Machine dishwashing detergents containing surfactants with specific diffusion coefficients

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation under 35 U.S.C. § 365 (c) and 35 U.S.C. § 120 of international application PCT/EP02/07820, filed Jul. 13, 2002. This application also claims priority under 35 U.S.C. § 119 of DE 101 36 002.9, filed Jul. 24, 2003, which is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

The present invention relates to machine dishwashing detergents and methods of using these compositions. Specifically, the invention relates to machine dishwashing detergents which comprise nonionic surfactants which have particularly low viscosities in aqueous solution.

Machine dishwashing in domestic dishwashing machines is a process which differs fundamentally from laundry washing in domestic washing machines. Whereas in a washing machine the item to be washed is permanently agitated in the liquor and, in this way, the washing is mechanically assisted, in a dishwashing machine, the rinse liquor is applied by a spraying system to the surfaces to be cleaned. There, the cleaning liquor must itself counteract even stubborn soilings without assistance by mechanical influences. The performance level of machine dishwashing detergents must therefore be much higher than that of conventional textile detergents.

In addition, there is a trend in machine dishwashing toward ever lower temperatures, ever shorter rinse cycles and a reduced dosing of detergents for ecological reasons, in some countries it also being necessary to observe restrictions with regard to the use of certain ingredients (for example phosphates).

The performance requirements of modern machine dishwashing detergents are continually increasing under the abovementioned framework conditions. As a result of these increased performance requirements, there is a continual need for performance-enhanced machine dishwashing detergents which achieve high cleaning performances at a lower concentration, also at lower temperatures and short wash times.

The object of the present invention was to provide machine dishwashing detergents which meet the increased performance requirements. The compositions to be provided should be superior to conventional compositions, even when compared at a lower concentration, in particular on greasy soilings. In addition, the compositions should be able to be prepared as conventional machine dishwashing detergents (“cleaners”) in powder or granule form or as tablets or in pourable supply form, and also in the form of a combination product (“2in1” products which combine detergent and rinse aid, and also “3in1” products, which combine detergent, rinse aid and salt replacement).

It has now been found that machine dishwashing detergents which satisfy the profile of requirements given above can be provided if they comprise builders and certain nonionic surfactants, and also optionally further ingredients of cleaning compositions.

The present invention provides machine dishwashing detergents which comprise builder(s), surfactant(s), and optionally further ingredients which comprise 0.1 to 50% by weight of one or more nonionic surfactants which, at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 9·10⁻¹¹m²s⁻¹.

The diffusion coefficient can be determined here in accordance with the theory by Fainerman et al. (Colloids and Surfaces A, 90 (1994) 213–224) from the measurement of the dynamic surface tension.

According to the Fainerman theory, which, for short surface ages and low concentrations, models the surface film as an ideal gas, the surface pressure P(t)=s₀−s(t) for short surface ages and low surface concentrations is calculated as

Π ⁡ ( t ) = σ 0 - σ ⁡ ( t ) = 2 ⁢ RTc ⁢ Dt π
From this it is possible to calculate the diffusion coefficient by the equation

D = π ⁡ ( m 2 ⁢ RTc ) 2
where m is the increase in the straight lines in a plot of P against t^1/2.
In the above formulae, the following apply:

• t: surface age
• s(t): surface tension as a function of surface age
• s₀: surface tension of water
• P(t): surface pressure=s₀−s(t)
• R: gas constant
• c: molar concentration
• T: temperature
• D: diffusion coefficient

The larger diffusion coefficients of the surfactant at high concentrations brings about a significantly improved run-off behavior of the overall formulation from surfaces treated with the cleaning compositions. The surfactants used according to the invention wet the surfaces rapidly and, in particular, uniformly, so that the film of the rinse aid solution on the ware runs off uniformly and does not rupture prematurely. In this way, spot- and smear-free surfaces and thus improved clear-rinse results are obtained.

In preferred embodiments of the present invention, the surfactant has still higher diffusion coefficients in a high concentrated aqueous solution. Preference is given here to compositions according to the invention in which the nonionic surfactant(s), at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 9.5·10⁻¹¹m²s⁻¹, preferably of at least 1·10⁻¹⁰m²s⁻¹ and in particular of at least 2.5·10⁻¹⁰m²s⁻¹.

Particularly preferred machine dishwashing detergents according to the invention comprise one or more nonionic surfactant(s) which, at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 5·10⁻¹⁰m²s⁻¹, preferably of at least 1·10⁻⁹m²s⁻¹ and in particular of at least 5·10⁻⁹m²s⁻¹.

Irrespective of the diffusion coefficient of the surfactants present according to the invention in the compositions in aqueous solutions, it may be advantageous for certain formulations if the surfactants are liquid at room temperature. As well as the easier processability for compositions in the form of powders or granules, this has the additional advantage that the surfactants do not have to be melted during processing, as a result of which the production costs can be further reduced.

Nonionic surfactants which, at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 9·10⁻¹¹m²s⁻¹ can be of varying molecular structure. Depending on the nature and length of the hydrophobic and of the hydrophilic radical in the molecule, the properties of the surfactants can be controlled to give desirable properties.

The nonionic surfactants with the above-described properties are used in the compositions according to the invention in amounts of from 0.1 to 50% by weight, in each case based on the total composition. Preferred machine dishwashing detergents according to the invention comprise the nonionic surfactant(s) in amounts of from 0.5 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.

For the purposes of the present invention, particularly preferred nonionic surfactants have proven to be low-foam nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Of these, preference is in turn given to surfactants with EO-AO-EO-AO blocks, where in each case one to ten EO and/or AO groups are bonded to one another before a block from the other groups in each case follows. Preference is given here to machine dishwashing detergents according to the invention which comprise, as nonionic surfactant(s), surfactants of the general formula I

in which R¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C_6-24-alkyl or -alkenyl radical; each group R² and R³, independently of one another, is chosen from —CH₃, —CH₂CH₃, —CH₂CH₂—CH₃, CH(CH₃)₂ and the indices w, x, y, z, independently of one another, are integers from 1 to 6.

The preferred nonionic surfactants of the formula I can be prepared by known methods from the corresponding alcohols R¹—OH and ethylene oxide or alkylene oxide. The radical R¹ in the above formula I can vary depending on the origin of the alcohol. If native sources are used, the radical R¹ has an even number of carbon atoms and is usually unbranched, where the linear radicals from alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow fatty or oleyl alcohol, are preferred. Alcohols obtainable from synthetic sources are, for example, the Guerbet alcohols or radicals which are methyl-branched in the 2 position or linear and methyl-branched in the mixture, as are customarily present in oxo alcohol radicals. Irrespective of the nature of the alcohol used for the preparation of the nonionic surfactants present according to the invention in the compositions, preference is given to machine dishwashing detergents according to the invention in which R¹ in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

A suitable alkylene oxide unit which is present in alternating manner relative to the ethylene oxide unit in the preferred nonionic surfactants is, in particular, butylene oxide, as well as propylene oxide. However, further alkylene oxides in which R² and R³, independently of one another, are chosen from —CH₂CH₂—CH₃ and CH(CH₃)₂ are also suitable. Preferred machine dishwashing detergents are CH₂CH₂—CH₃ and CH(CH₃)₂ are suitable. Preferred machine dishwashing detergents are characterized in that R² and R³ are a radical —CH₃, w and x, independently of one another, are values of 3 or 4 and y and z, independently of one another, are values of 1 or 2.

In summary, particular preference is given to using nonionic surfactants in the compositions according to the invention which have a C_9-15-alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required high diffusion coefficients in aqueous solution and can be used particularly advantageously according to the invention.

The given carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation are statistical average values which may be an integer or a fraction for a specific product. Due to the preparation process, commercial products of said formulae consist mostly not of an individual representative, but of mixtures, giving rise to average values and consequently fractional values both for the carbon chain lengths and also for the degrees of ethoxylation or degrees of alkoxylation. In the table below, nonionic surfactants which are particularly preferably present in the compositions according to the invention are characterized with regard to the radical R¹, the radicals R² and R³, and the indices w, x, y and z. Preferred compositions according to the invention comprise one or more surfactants from the table below or mixtures thereof.

No.	R1	R2	R3	w	x	y	z

1	CH3—(CH2)8—	CH3—	CH3—	1	1	1	1
2	CH3—(CH2)8—	CH3—	CH3—	2	1	1	1
3	CH3—(CH2)8—	CH3—	CH3—	1	2	1	1
4	CH3—(CH2)8—	CH3—	CH3—	1	1	2	1
5	CH3—(CH2)8—	CH3—	CH3—	1	1	1	2
6	CH3—(CH2)8—	CH3—	CH3—	3	1	1	1
7	CH3—(CH2)8—	CH3—	CH3—	1	3	1	1
8	CH3—(CH2)8—	CH3—	CH3—	1	1	3	1
9	CH3—(CH2)8—	CH3—	CH3—	1	1	1	3
10	CH3—(CH2)8—	CH3—	CH3—	4	1	1	1
11	CH3—(CH2)8—	CH3—	CH3—	1	4	1	1
12	CH3—(CH2)8—	CH3—	CH3—	1	1	4	1
13	CH3—(CH2)8—	CH3—	CH3—	1	1	1	4
14	CH3—(CH2)8—	CH3—	CH3—	1	2	2	1
15	CH3—(CH2)8—	CH3—	CH3—	1	2	1	2
16	CH3—(CH2)8—	CH3—	CH3—	1	1	2	2
17	CH3—(CH2)8—	CH3—	CH3—	2	2	1	1
18	CH3—(CH2)8—	CH3—	CH3—	2	1	2	1
19	CH3—(CH2)8—	CH3—	CH3—	2	1	1	2
20	CH3—(CH2)8—	CH3—	CH3—	1	3	3	1
21	CH3—(CH2)8—	CH3—	CH3—	1	3	1	3
22	CH3—(CH2)8—	CH3—	CH3—	1	1	3	3
23	CH3—(CH2)8—	CH3—	CH3—	3	3	1	1
24	CH3—(CH2)8—	CH3—	CH3—	3	1	3	1
25	CH3—(CH2)8—	CH3—	CH3—	3	1	1	3
26	CH3—(CH2)8—	CH3—	CH3—	1	4	4	1
27	CH3—(CH2)8—	CH3—	CH3—	1	4	1	4
28	CH3—(CH2)8—	CH3—	CH3—	1	1	4	4
29	CH3—(CH2)8—	CH3—	CH3—	4	4	1	1
30	CH3—(CH2)8—	CH3—	CH3—	4	1	4	1
31	CH3—(CH2)8—	CH3—	CH3—	4	1	1	4
32	CH3—(CH2)8—	CH3—	CH3—	1	1	2	3
33	CH3—(CH2)8—	CH3—	CH3—	1	1	3	2
34	CH3—(CH2)8—	CH3—	CH3—	1	2	3	1
35	CH3—(CH2)8—	CH3—	CH3—	1	3	2	1
36	CH3—(CH2)8—	CH3—	CH3—	1	2	1	3
37	CH3—(CH2)8—	CH3—	CH3—	1	3	1	2
38	CH3—(CH2)8—	CH3—	CH3—	2	1	1	3
39	CH3—(CH2)8—	CH3—	CH3—	2	1	3	1
40	CH3—(CH2)8—	CH3—	CH3—	2	3	1	1
41	CH3—(CH2)8—	CH3—	CH3—	3	1	1	2
42	CH3—(CH2)8—	CH3—	CH3—	3	1	2	1
43	CH3—(CH2)8—	CH3—	CH3—	3	2	1	1
44	CH3—(CH2)8—	CH3—	CH3—	1	1	2	4
45	CH3—(CH2)8—	CH3—	CH3—	1	1	4	2
46	CH3—(CH2)8—	CH3—	CH3—	1	2	4	1
47	CH3—(CH2)8—	CH3—	CH3—	1	4	2	1
48	CH3—(CH2)8—	CH3—	CH3—	1	2	1	4
49	CH3—(CH2)8—	CH3—	CH3—	1	4	1	2
50	CH3—(CH2)8—	CH3—	CH3—	2	1	1	4
51	CH3—(CH2)8—	CH3—	CH3—	2	1	4	1
52	CH3—(CH2)8—	CH3—	CH3—	2	4	1	1
53	CH3—(CH2)8—	CH3—	CH3—	4	1	1	2
54	CH3—(CH2)8—	CH3—	CH3—	4	1	2	1
55	CH3—(CH2)8—	CH3—	CH3—	4	2	1	1
56	CH3—(CH2)8—	CH3—	CH3—	1	1	4	3
57	CH3—(CH2)8—	CH3—	CH3—	1	1	3	4
58	CH3—(CH2)8—	CH3—	CH3—	1	4	3	1
59	CH3—(CH2)8—	CH3—	CH3—	1	3	4	1
60	CH3—(CH2)8—	CH3—	CH3—	1	4	1	3
61	CH3—(CH2)8—	CH3—	CH3—	1	3	1	4
62	CH3—(CH2)8—	CH3—	CH3—	4	1	1	3
63	CH3—(CH2)8—	CH3—	CH3—	4	1	3	1
64	CH3—(CH2)8—	CH3—	CH3—	4	3	1	1
65	CH3—(CH2)8—	CH3—	CH3—	3	1	1	4
66	CH3—(CH2)8—	CH3—	CH3—	3	1	4	1
67	CH3—(CH2)8—	CH3—	CH3—	3	4	1	1
68	CH3—(CH2)8—	CH3—	CH3—	1	2	2	2
69	CH3—(CH2)8—	CH3—	CH3—	2	1	2	2
70	CH3—(CH2)8—	CH3—	CH3—	2	2	1	2
71	CH3—(CH2)8—	CH3—	CH3—	2	2	2	1
72	CH3—(CH2)8—	CH3—	CH3—	1	3	3	3
73	CH3—(CH2)8—	CH3—	CH3—	3	1	3	3
74	CH3—(CH2)8—	CH3—	CH3—	3	3	1	3
75	CH3—(CH2)8—	CH3—	CH3—	3	3	3	1
76	CH3—(CH2)8—	CH3—	CH3—	1	4	4	4
77	CH3—(CH2)8—	CH3—	CH3—	4	1	4	4
78	CH3—(CH2)8—	CH3—	CH3—	4	4	1	4
79	CH3—(CH2)8—	CH3—	CH3—	4	4	4	1
80	CH3—(CH2)8—	CH3—	CH3—	2	2	1	3
81	CH3—(CH2)8—	CH3—	CH3—	2	2	3	1
82	CH3—(CH2)8—	CH3—	CH3—	2	1	2	3
83	CH3—(CH2)8—	CH3—	CH3—	2	3	2	1
84	CH3—(CH2)8—	CH3—	CH3—	2	1	3	2
85	CH3—(CH2)8—	CH3—	CH3—	2	3	1	2
86	CH3—(CH2)8—	CH3—	CH3—	1	2	2	3
87	CH3—(CH2)8—	CH3—	CH3—	1	2	3	2
88	CH3—(CH2)8—	CH3—	CH3—	1	3	2	2
89	CH3—(CH2)8—	CH3—	CH3—	3	2	2	1
90	CH3—(CH2)8—	CH3—	CH3—	3	2	1	2
91	CH3—(CH2)8—	CH3—	CH3—	3	1	2	2
92	CH3—(CH2)8—	CH3—	CH3—	2	2	1	4
93	CH3—(CH2)8—	CH3—	CH3—	2	2	4	1
94	CH3—(CH2)8—	CH3—	CH3—	2	1	2	4
95	CH3—(CH2)8—	CH3—	CH3—	2	4	2	1
96	CH3—(CH2)8—	CH3—	CH3—	2	1	4	2
97	CH3—(CH2)8—	CH3—	CH3—	2	4	1	2
98	CH3—(CH2)8—	CH3—	CH3—	1	2	2	4
99	CH3—(CH2)8—	CH3—	CH3—	1	2	4	2
100	CH3—(CH2)8—	CH3—	CH3—	1	4	2	2
101	CH3—(CH2)8—	CH3—	CH3—	4	2	2	1
102	CH3—(CH2)8—	CH3—	CH3—	4	2	1	2
103	CH3—(CH2)8—	CH3—	CH3—	4	1	2	2
104	CH3—(CH2)8—	CH3—	CH3—	2	2	4	3
105	CH3—(CH2)8—	CH3—	CH3—	2	2	3	4
106	CH3—(CH2)8—	CH3—	CH3—	2	4	2	3
107	CH3—(CH2)8—	CH3—	CH3—	2	3	2	4
108	CH3—(CH2)8—	CH3—	CH3—	2	4	3	2
109	CH3—(CH2)8—	CH3—	CH3—	2	3	4	2
110	CH3—(CH2)8—	CH3—	CH3—	4	2	2	3
111	CH3—(CH2)8—	CH3—	CH3—	4	2	3	2
112	CH3—(CH2)8—	CH3—	CH3—	4	3	2	2
113	CH3—(CH2)8—	CH3—	CH3—	3	2	2	4
114	CH3—(CH2)8—	CH3—	CH3—	3	2	4	2
115	CH3—(CH2)8—	CH3—	CH3—	3	4	2	2
116	CH3—(CH2)8—	CH3—	CH3—	3	3	1	2
117	CH3—(CH2)8—	CH3—	CH3—	3	3	2	1
118	CH3—(CH2)8—	CH3—	CH3—	3	1	3	2
119	CH3—(CH2)8—	CH3—	CH3—	3	2	3	1
120	CH3—(CH2)8—	CH3—	CH3—	3	1	2	3
121	CH3—(CH2)8—	CH3—	CH3—	3	2	1	3
122	CH3—(CH2)8—	CH3—	CH3—	1	3	3	2
123	CH3—(CH2)8—	CH3—	CH3—	1	3	2	3
124	CH3—(CH2)8—	CH3—	CH3—	1	2	3	3
125	CH3—(CH2)8—	CH3—	CH3—	2	3	3	1
126	CH3—(CH2)8—	CH3—	CH3—	2	3	1	3
127	CH3—(CH2)8—	CH3—	CH3—	2	1	3	3
128	CH3—(CH2)8—	CH3—	CH3—	3	3	1	4
129	CH3—(CH2)8—	CH3—	CH3—	3	3	4	1
130	CH3—(CH2)8—	CH3—	CH3—	3	1	3	4
131	CH3—(CH2)8—	CH3—	CH3—	3	4	3	1
132	CH3—(CH2)8—	CH3—	CH3—	3	1	4	3
133	CH3—(CH2)8—	CH3—	CH3—	3	4	1	3
134	CH3—(CH2)8—	CH3—	CH3—	1	3	3	4
135	CH3—(CH2)8—	CH3—	CH3—	1	3	4	3
136	CH3—(CH2)8—	CH3—	CH3—	1	4	3	3
137	CH3—(CH2)8—	CH3—	CH3—	4	3	3	1
138	CH3—(CH2)8—	CH3—	CH3—	4	3	1	3
139	CH3—(CH2)8—	CH3—	CH3—	4	1	3	3
140	CH3—(CH2)8—	CH3—	CH3—	3	3	4	2
141	CH3—(CH2)8—	CH3—	CH3—	3	3	2	4
142	CH3—(CH2)8—	CH3—	CH3—	3	4	3	2
143	CH3—(CH2)8—	CH3—	CH3—	3	2	3	4
144	CH3—(CH2)8—	CH3—	CH3—	3	4	2	3
145	CH3—(CH2)8—	CH3—	CH3—	3	2	4	3
146	CH3—(CH2)8—	CH3—	CH3—	4	3	3	2
147	CH3—(CH2)8—	CH3—	CH3—	4	3	2	3
148	CH3—(CH2)8—	CH3—	CH3—	4	2	3	3
149	CH3—(CH2)8—	CH3—	CH3—	2	3	3	4
150	CH3—(CH2)8—	CH3—	CH3—	2	3	4	3
151	CH3—(CH2)8—	CH3—	CH3—	2	4	3	3
152	CH3—(CH2)8—	CH3—	CH3—	4	4	1	2
153	CH3—(CH2)8—	CH3—	CH3—	4	4	2	1
154	CH3—(CH2)8—	CH3—	CH3—	4	1	4	2
155	CH3—(CH2)8—	CH3—	CH3—	4	2	4	1
156	CH3—(CH2)8—	CH3—	CH3—	4	1	2	4
157	CH3—(CH2)8—	CH3—	CH3—	4	2	1	4
158	CH3—(CH2)8—	CH3—	CH3—	1	4	4	2
159	CH3—(CH2)8—	CH3—	CH3—	1	4	2	4
160	CH3—(CH2)8—	CH3—	CH3—	1	2	4	4
161	CH3—(CH2)8—	CH3—	CH3—	2	4	4	1
162	CH3—(CH2)8—	CH3—	CH3—	2	4	1	4
163	CH3—(CH2)8—	CH3—	CH3—	2	1	4	4
164	CH3—(CH2)8—	CH3—	CH3—	4	4	1	3
165	CH3—(CH2)8—	CH3—	CH3—	4	4	3	1
166	CH3—(CH2)8—	CH3—	CH3—	4	1	4	3
167	CH3—(CH2)8—	CH3—	CH3—	4	3	4	1
168	CH3—(CH2)8—	CH3—	CH3—	4	1	3	4
169	CH3—(CH2)8—	CH3—	CH3—	4	3	1	4
170	CH3—(CH2)8—	CH3—	CH3—	1	4	4	3
171	CH3—(CH2)8—	CH3—	CH3—	1	4	3	4
172	CH3—(CH2)8—	CH3—	CH3—	1	3	4	4
173	CH3—(CH2)8—	CH3—	CH3—	3	4	4	1
174	CH3—(CH2)8—	CH3—	CH3—	3	4	1	4
175	CH3—(CH2)8—	CH3—	CH3—	3	1	4	4
176	CH3—(CH2)8—	CH3—	CH3—	4	4	3	2
177	CH3—(CH2)8—	CH3—	CH3—	4	4	2	3
178	CH3—(CH2)8—	CH3—	CH3—	4	3	4	2
179	CH3—(CH2)8—	CH3—	CH3—	4	2	4	3
180	CH3—(CH2)8—	CH3—	CH3—	4	3	2	4
181	CH3—(CH2)8—	CH3—	CH3—	4	2	3	4
182	CH3—(CH2)8—	CH3—	CH3—	3	4	4	2
183	CH3—(CH2)8—	CH3—	CH3—	3	4	2	4
184	CH3—(CH2)8—	CH3—	CH3—	3	2	4	4
185	CH3—(CH2)8—	CH3—	CH3—	2	4	4	3
186	CH3—(CH2)8—	CH3—	CH3—	2	4	3	4
187	CH3—(CH2)8—	CH3—	CH3—	2	3	4	4
188	CH3—(CH2)8—	CH3—	CH3—	1	2	3	4
189	CH3—(CH2)8—	CH3—	CH3—	1	2	4	3
190	CH3—(CH2)8—	CH3—	CH3—	1	3	2	4
191	CH3—(CH2)8—	CH3—	CH3—	1	3	4	2
192	CH3—(CH2)8—	CH3—	CH3—	1	4	2	3
193	CH3—(CH2)8—	CH3—	CH3—	1	4	3	2
194	CH3—(CH2)8—	CH3—	CH3—	2	1	3	4
195	CH3—(CH2)8—	CH3—	CH3—	2	1	4	3
196	CH3—(CH2)8—	CH3—	CH3—	2	3	1	4
197	CH3—(CH2)8—	CH3—	CH3—	2	3	4	1
198	CH3—(CH2)8—	CH3—	CH3—	2	4	1	3
199	CH3—(CH2)8—	CH3—	CH3—	2	4	3	1
200	CH3—(CH2)8—	CH3—	CH3—	3	1	2	4
201	CH3—(CH2)8—	CH3—	CH3—	3	1	4	2
202	CH3—(CH2)8—	CH3—	CH3—	3	2	1	4
203	CH3—(CH2)8—	CH3—	CH3—	3	2	4	1
204	CH3—(CH2)8—	CH3—	CH3—	3	4	1	2
205	CH3—(CH2)8—	CH3—	CH3—	3	4	2	1
206	CH3—(CH2)8—	CH3—	CH3—	4	1	2	3
207	CH3—(CH2)8—	CH3—	CH3—	4	1	3	2
208	CH3—(CH2)8—	CH3—	CH3—	4	2	1	3
209	CH3—(CH2)8—	CH3—	CH3—	4	2	3	1
210	CH3—(CH2)8—	CH3—	CH3—	4	3	1	2
211	CH3—(CH2)8—	CH3—	CH3—	4	3	2	1
212	CH3—(CH2)8—	CH3—	CH3—	2	3	3	2
213	CH3—(CH2)8—	CH3—	CH3—	2	3	2	3
214	CH3—(CH2)8—	CH3—	CH3—	2	2	3	3
215	CH3—(CH2)8—	CH3—	CH3—	3	3	2	2
216	CH3—(CH2)8—	CH3—	CH3—	3	2	3	2
217	CH3—(CH2)8—	CH3—	CH3—	3	2	2	3
218	CH3—(CH2)8—	CH3—	CH3—	2	4	4	2
219	CH3—(CH2)8—	CH3—	CH3—	2	4	2	4
220	CH3—(CH2)8—	CH3—	CH3—	2	2	4	4
221	CH3—(CH2)8—	CH3—	CH3—	4	4	2	2
222	CH3—(CH2)8—	CH3—	CH3—	4	2	4	2
223	CH3—(CH2)8—	CH3—	CH3—	4	2	2	4
224	CH3—(CH2)8—	CH3—	CH3—	3	4	4	3
225	CH3—(CH2)8—	CH3—	CH3—	3	4	3	4
226	CH3—(CH2)8—	CH3—	CH3—	3	3	4	4
227	CH3—(CH2)8—	CH3—	CH3—	4	4	3	3
228	CH3—(CH2)8—	CH3—	CH3—	4	3	4	3
229	CH3—(CH2)8—	CH3—	CH3—	4	3	3	4
230	CH3—(CH2)9—	CH3—	CH3—	1	1	1	1
231	CH3—(CH2)9—	CH3—	CH3—	2	1	1	1
232	CH3—(CH2)9—	CH3—	CH3—	1	2	1	1
233	CH3—(CH2)9—	CH3—	CH3—	1	1	2	1
234	CH3—(CH2)9—	CH3—	CH3—	1	1	1	2
235	CH3—(CH2)9—	CH3—	CH3—	3	1	1	1
236	CH3—(CH2)9—	CH3—	CH3—	1	3	1	1
237	CH3—(CH2)9—	CH3—	CH3—	1	1	3	1
238	CH3—(CH2)9—	CH3—	CH3—	1	1	1	3
239	CH3—(CH2)9—	CH3—	CH3—	4	1	1	1
240	CH3—(CH2)9—	CH3—	CH3—	1	4	1	1
241	CH3—(CH2)9—	CH3—	CH3—	1	1	4	1
242	CH3—(CH2)9—	CH3—	CH3—	1	1	1	4
243	CH3—(CH2)9—	CH3—	CH3—	1	2	2	1
244	CH3—(CH2)9—	CH3—	CH3—	1	2	1	2
245	CH3—(CH2)9—	CH3—	CH3—	1	1	2	2
246	CH3—(CH2)9—	CH3—	CH3—	2	2	1	1
247	CH3—(CH2)9—	CH3—	CH3—	2	1	2	1
248	CH3—(CH2)9—	CH3—	CH3—	2	1	1	2
249	CH3—(CH2)9—	CH3—	CH3—	1	3	3	1
250	CH3—(CH2)9—	CH3—	CH3—	1	3	1	3
251	CH3—(CH2)9—	CH3—	CH3—	1	1	3	3
252	CH3—(CH2)9—	CH3—	CH3—	3	3	1	1
253	CH3—(CH2)9—	CH3—	CH3—	3	1	3	1
254	CH3—(CH2)9—	CH3—	CH3—	3	1	1	3
255	CH3—(CH2)9—	CH3—	CH3—	1	4	4	1
256	CH3—(CH2)9—	CH3—	CH3—	1	4	1	4
257	CH3—(CH2)9—	CH3—	CH3—	1	1	4	4
258	CH3—(CH2)9—	CH3—	CH3—	4	4	1	1
259	CH3—(CH2)9—	CH3—	CH3—	4	1	4	1
260	CH3—(CH2)9—	CH3—	CH3—	4	1	1	4
261	CH3—(CH2)9—	CH3—	CH3—	1	1	2	3
262	CH3—(CH2)9—	CH3—	CH3—	1	1	3	2
263	CH3—(CH2)9—	CH3—	CH3—	1	2	3	1
264	CH3—(CH2)9—	CH3—	CH3—	1	3	2	1
265	CH3—(CH2)9—	CH3—	CH3—	1	2	1	3
266	CH3—(CH2)9—	CH3—	CH3—	1	3	1	2
267	CH3—(CH2)9—	CH3—	CH3—	2	1	1	3
268	CH3—(CH2)9—	CH3—	CH3—	2	1	3	1
269	CH3—(CH2)9—	CH3—	CH3—	2	3	1	1
270	CH3—(CH2)9—	CH3—	CH3—	3	1	1	2
271	CH3—(CH2)9—	CH3—	CH3—	3	1	2	1
272	CH3—(CH2)9—	CH3—	CH3—	3	2	1	1
273	CH3—(CH2)9—	CH3—	CH3—	1	1	2	4
274	CH3—(CH2)9—	CH3—	CH3—	1	1	4	2
275	CH3—(CH2)9—	CH3—	CH3—	1	2	4	1
276	CH3—(CH2)9—	CH3—	CH3—	1	4	2	1
277	CH3—(CH2)9—	CH3—	CH3—	1	2	1	4
278	CH3—(CH2)9—	CH3—	CH3—	1	4	1	2
279	CH3—(CH2)9—	CH3—	CH3—	2	1	1	4
280	CH3—(CH2)9—	CH3—	CH3—	2	1	4	1
281	CH3—(CH2)9—	CH3—	CH3—	2	4	1	1
282	CH3—(CH2)9—	CH3—	CH3—	4	1	1	2
283	CH3—(CH2)9—	CH3—	CH3—	4	1	2	1
284	CH3—(CH2)9—	CH3—	CH3—	4	2	1	1
285	CH3—(CH2)9—	CH3—	CH3—	1	1	4	3
286	CH3—(CH2)9—	CH3—	CH3—	1	1	3	4
287	CH3—(CH2)9—	CH3—	CH3—	1	4	3	1
288	CH3—(CH2)9—	CH3—	CH3—	1	3	4	1
289	CH3—(CH2)9—	CH3—	CH3—	1	4	1	3
290	CH3—(CH2)9—	CH3—	CH3—	1	3	1	4
291	CH3—(CH2)9—	CH3—	CH3—	4	1	1	3
292	CH3—(CH2)9—	CH3—	CH3—	4	1	3	1
293	CH3—(CH2)9—	CH3—	CH3—	4	3	1	1
294	CH3—(CH2)9—	CH3—	CH3—	3	1	1	4
295	CH3—(CH2)9—	CH3—	CH3—	3	1	4	1
296	CH3—(CH2)9—	CH3—	CH3—	3	4	1	1
297	CH3—(CH2)9—	CH3—	CH3—	1	2	2	2
298	CH3—(CH2)9—	CH3—	CH3—	2	1	2	2
299	CH3—(CH2)9—	CH3—	CH3—	2	2	1	2
300	CH3—(CH2)9—	CH3—	CH3—	2	2	2	1
301	CH3—(CH2)9—	CH3—	CH3—	1	3	3	3
302	CH3—(CH2)9—	CH3—	CH3—	3	1	3	3
303	CH3—(CH2)9—	CH3—	CH3—	3	3	1	3
304	CH3—(CH2)9—	CH3—	CH3—	3	3	3	1
305	CH3—(CH2)9—	CH3—	CH3—	1	4	4	4
306	CH3—(CH2)9—	CH3—	CH3—	4	1	4	4
307	CH3—(CH2)9—	CH3—	CH3—	4	4	1	4
308	CH3—(CH2)9—	CH3—	CH3—	4	4	4	1
309	CH3—(CH2)9—	CH3—	CH3—	2	2	1	3
310	CH3—(CH2)9—	CH3—	CH3—	2	2	3	1
311	CH3—(CH2)9—	CH3—	CH3—	2	1	2	3
312	CH3—(CH2)9—	CH3—	CH3—	2	3	2	1
313	CH3—(CH2)9—	CH3—	CH3—	2	1	3	2
314	CH3—(CH2)9—	CH3—	CH3—	2	3	1	2
315	CH3—(CH2)9—	CH3—	CH3—	1	2	2	3
316	CH3—(CH2)9—	CH3—	CH3—	1	2	3	2
317	CH3—(CH2)9—	CH3—	CH3—	1	3	2	2
318	CH3—(CH2)9—	CH3—	CH3—	3	2	2	1
319	CH3—(CH2)9—	CH3—	CH3—	3	2	1	2
320	CH3—(CH2)9—	CH3—	CH3—	3	1	2	2
321	CH3—(CH2)9—	CH3—	CH3—	2	2	1	4
322	CH3—(CH2)9—	CH3—	CH3—	2	2	4	1
323	CH3—(CH2)9—	CH3—	CH3—	2	1	2	4
324	CH3—(CH2)9—	CH3—	CH3—	2	4	2	1
325	CH3—(CH2)9—	CH3—	CH3—	2	1	4	2
326	CH3—(CH2)9—	CH3—	CH3—	2	4	1	2
327	CH3—(CH2)9—	CH3—	CH3—	1	2	2	4
328	CH3—(CH2)9—	CH3—	CH3—	1	2	4	2
329	CH3—(CH2)9—	CH3—	CH3—	1	4	2	2
330	CH3—(CH2)9—	CH3—	CH3—	4	2	2	1
331	CH3—(CH2)9—	CH3—	CH3—	4	2	1	2
332	CH3—(CH2)9—	CH3—	CH3—	4	1	2	2
333	CH3—(CH2)9—	CH3—	CH3—	2	2	4	3
334	CH3—(CH2)9—	CH3—	CH3—	2	2	3	4
335	CH3—(CH2)9—	CH3—	CH3—	2	4	2	3
336	CH3—(CH2)9—	CH3—	CH3—	2	3	2	4
337	CH3—(CH2)9—	CH3—	CH3—	2	4	3	2
338	CH3—(CH2)9—	CH3—	CH3—	2	3	4	2
339	CH3—(CH2)9—	CH3—	CH3—	4	2	2	3
340	CH3—(CH2)9—	CH3—	CH3—	4	2	3	2
341	CH3—(CH2)9—	CH3—	CH3—	4	3	2	2
342	CH3—(CH2)9—	CH3—	CH3—	3	2	2	4
343	CH3—(CH2)9—	CH3—	CH3—	3	2	4	2
344	CH3—(CH2)9—	CH3—	CH3—	3	4	2	2
345	CH3—(CH2)9—	CH3—	CH3—	3	3	1	2
346	CH3—(CH2)9—	CH3—	CH3—	3	3	2	1
347	CH3—(CH2)9—	CH3—	CH3—	3	1	3	2
348	CH3—(CH2)9—	CH3—	CH3—	3	2	3	1
349	CH3—(CH2)9—	CH3—	CH3—	3	1	2	3
350	CH3—(CH2)9—	CH3—	CH3—	3	2	1	3
351	CH3—(CH2)9—	CH3—	CH3—	1	3	3	2
352	CH3—(CH2)9—	CH3—	CH3—	1	3	2	3
353	CH3—(CH2)9—	CH3—	CH3—	1	2	3	3
354	CH3—(CH2)9—	CH3—	CH3—	2	3	3	1
355	CH3—(CH2)9—	CH3—	CH3—	2	3	1	3
356	CH3—(CH2)9—	CH3—	CH3—	2	1	3	3
357	CH3—(CH2)9—	CH3—	CH3—	3	3	1	4
358	CH3—(CH2)9—	CH3—	CH3—	3	3	4	1
359	CH3—(CH2)9—	CH3—	CH3—	3	1	3	4
360	CH3—(CH2)9—	CH3—	CH3—	3	4	3	1
361	CH3—(CH2)9—	CH3—	CH3—	3	1	4	3
362	CH3—(CH2)9—	CH3—	CH3—	3	4	1	3
363	CH3—(CH2)9—	CH3—	CH3—	1	3	3	4
364	CH3—(CH2)9—	CH3—	CH3—	1	3	4	3
365	CH3—(CH2)9—	CH3—	CH3—	1	4	3	3
366	CH3—(CH2)9—	CH3—	CH3—	4	3	3	1
367	CH3—(CH2)9—	CH3—	CH3—	4	3	1	3
368	CH3—(CH2)9—	CH3—	CH3—	4	1	3	3
369	CH3—(CH2)9—	CH3—	CH3—	3	3	4	2
370	CH3—(CH2)9—	CH3—	CH3—	3	3	2	4
371	CH3—(CH2)9—	CH3—	CH3—	3	4	3	2
372	CH3—(CH2)9—	CH3—	CH3—	3	2	3	4
373	CH3—(CH2)9—	CH3—	CH3—	3	4	2	3
374	CH3—(CH2)9—	CH3—	CH3—	3	2	4	3
375	CH3—(CH2)9—	CH3—	CH3—	4	3	3	2
376	CH3—(CH2)9—	CH3—	CH3—	4	3	2	3
377	CH3—(CH2)9—	CH3—	CH3—	4	2	3	3
378	CH3—(CH2)9—	CH3—	CH3—	2	3	3	4
379	CH3—(CH2)9—	CH3—	CH3—	2	3	4	3
380	CH3—(CH2)9—	CH3—	CH3—	2	4	3	3
381	CH3—(CH2)9—	CH3—	CH3—	4	4	1	2
382	CH3—(CH2)9—	CH3—	CH3—	4	4	2	1
383	CH3—(CH2)9—	CH3—	CH3—	4	1	4	2
384	CH3—(CH2)9—	CH3—	CH3—	4	2	4	1
385	CH3—(CH2)9—	CH3—	CH3—	4	1	2	4
386	CH3—(CH2)9—	CH3—	CH3—	4	2	1	4
387	CH3—(CH2)9—	CH3—	CH3—	1	4	4	2
388	CH3—(CH2)9—	CH3—	CH3—	1	4	2	4
389	CH3—(CH2)9—	CH3—	CH3—	1	2	4	4
390	CH3—(CH2)9—	CH3—	CH3—	2	4	4	1
391	CH3—(CH2)9—	CH3—	CH3—	2	4	1	4
392	CH3—(CH2)9—	CH3—	CH3—	2	1	4	4
393	CH3—(CH2)9—	CH3—	CH3—	4	4	1	3
394	CH3—(CH2)9—	CH3—	CH3—	4	4	3	1
395	CH3—(CH2)9—	CH3—	CH3—	4	1	4	3
396	CH3—(CH2)9—	CH3—	CH3—	4	3	4	1
397	CH3—(CH2)9—	CH3—	CH3—	4	1	3	4
398	CH3—(CH2)9—	CH3—	CH3—	4	3	1	4
399	CH3—(CH2)9—	CH3—	CH3—	1	4	4	3
400	CH3—(CH2)9—	CH3—	CH3—	1	4	3	4
401	CH3—(CH2)9—	CH3—	CH3—	1	3	4	4
402	CH3—(CH2)9—	CH3—	CH3—	3	4	4	1
403	CH3—(CH2)9—	CH3—	CH3—	3	4	1	4
404	CH3—(CH2)9—	CH3—	CH3—	3	1	4	4
405	CH3—(CH2)9—	CH3—	CH3—	4	4	3	2
406	CH3—(CH2)9—	CH3—	CH3—	4	4	2	3
407	CH3—(CH2)9—	CH3—	CH3—	4	3	4	2
408	CH3—(CH2)9—	CH3—	CH3—	4	2	4	3
409	CH3—(CH2)9—	CH3—	CH3—	4	3	2	4
410	CH3—(CH2)9—	CH3—	CH3—	4	2	3	4
411	CH3—(CH2)9—	CH3—	CH3—	3	4	4	2
412	CH3—(CH2)9—	CH3—	CH3—	3	4	2	4
413	CH3—(CH2)9—	CH3—	CH3—	3	2	4	4
414	CH3—(CH2)9—	CH3—	CH3—	2	4	4	3
415	CH3—(CH2)9—	CH3—	CH3—	2	4	3	4
416	CH3—(CH2)9—	CH3—	CH3—	2	3	4	4
417	CH3—(CH2)9—	CH3—	CH3—	1	2	3	4
418	CH3—(CH2)9—	CH3—	CH3—	1	2	4	3
419	CH3—(CH2)9—	CH3—	CH3—	1	3	2	4
420	CH3—(CH2)9—	CH3—	CH3—	1	3	4	2
421	CH3—(CH2)9—	CH3—	CH3—	1	4	2	3
422	CH3—(CH2)9—	CH3—	CH3—	1	4	3	2
423	CH3—(CH2)9—	CH3—	CH3—	2	1	3	4
424	CH3—(CH2)9—	CH3—	CH3—	2	1	4	3
425	CH3—(CH2)9—	CH3—	CH3—	2	3	1	4
426	CH3—(CH2)9—	CH3—	CH3—	2	3	4	1
427	CH3—(CH2)9—	CH3—	CH3—	2	4	1	3
428	CH3—(CH2)9—	CH3—	CH3—	2	4	3	1
429	CH3—(CH2)9—	CH3—	CH3—	3	1	2	4
430	CH3—(CH2)9—	CH3—	CH3—	3	1	4	2
431	CH3—(CH2)9—	CH3—	CH3—	3	2	1	4
432	CH3—(CH2)9—	CH3—	CH3—	3	2	4	1
433	CH3—(CH2)9—	CH3—	CH3—	3	4	1	2
434	CH3—(CH2)9—	CH3—	CH3—	3	4	2	1
435	CH3—(CH2)9—	CH3—	CH3—	4	1	2	3
436	CH3—(CH2)9—	CH3—	CH3—	4	1	3	2
437	CH3—(CH2)9—	CH3—	CH3—	4	2	1	3
438	CH3—(CH2)9—	CH3—	CH3—	4	2	3	1
439	CH3—(CH2)9—	CH3—	CH3—	4	3	1	2
440	CH3—(CH2)9—	CH3—	CH3—	4	3	2	1
441	CH3—(CH2)9—	CH3—	CH3—	2	3	3	2
442	CH3—(CH2)9—	CH3—	CH3—	2	3	2	3
443	CH3—(CH2)9—	CH3—	CH3—	2	2	3	3
444	CH3—(CH2)9—	CH3—	CH3—	3	3	2	2
445	CH3—(CH2)9—	CH3—	CH3—	3	2	3	2
446	CH3—(CH2)9—	CH3—	CH3—	3	2	2	3
447	CH3—(CH2)9—	CH3—	CH3—	2	4	4	2
448	CH3—(CH2)9—	CH3—	CH3—	2	4	2	4
449	CH3—(CH2)9—	CH3—	CH3—	2	2	4	4
450	CH3—(CH2)9—	CH3—	CH3—	4	4	2	2
451	CH3—(CH2)9—	CH3—	CH3—	4	2	4	2
452	CH3—(CH2)9—	CH3—	CH3—	4	2	2	4
453	CH3—(CH2)9—	CH3—	CH3—	3	4	4	3
454	CH3—(CH2)9—	CH3—	CH3—	3	4	3	4
455	CH3—(CH2)9—	CH3—	CH3—	3	3	4	4
456	CH3—(CH2)9—	CH3—	CH3—	4	4	3	3
457	CH3—(CH2)9—	CH3—	CH3—	4	3	4	3
458	CH3—(CH2)9—	CH3—	CH3—	4	3	3	4
459	CH3—(CH2)10—	CH3—	CH3—	1	1	1	1
460	CH3—(CH2)10—	CH3—	CH3—	2	1	1	1
461	CH3—(CH2)10—	CH3—	CH3—	1	2	1	1
462	CH3—(CH2)10—	CH3—	CH3—	1	1	2	1
463	CH3—(CH2)10—	CH3—	CH3—	1	1	1	2
464	CH3—(CH2)10—	CH3—	CH3—	3	1	1	1
465	CH3—(CH2)10—	CH3—	CH3—	1	3	1	1
466	CH3—(CH2)10—	CH3—	CH3—	1	1	3	1
467	CH3—(CH2)10—	CH3—	CH3—	1	1	1	3
468	CH3—(CH2)10—	CH3—	CH3—	4	1	1	1
469	CH3—(CH2)10—	CH3—	CH3—	1	4	1	1
470	CH3—(CH2)10—	CH3—	CH3—	1	1	4	1
471	CH3—(CH2)10—	CH3—	CH3—	1	1	1	4
472	CH3—(CH2)10—	CH3—	CH3—	1	2	2	1
473	CH3—(CH2)10—	CH3—	CH3—	1	2	1	2
474	CH3—(CH2)10—	CH3—	CH3—	1	1	2	2
475	CH3—(CH2)10—	CH3—	CH3—	2	2	1	1
476	CH3—(CH2)10—	CH3—	CH3—	2	1	2	1
477	CH3—(CH2)10—	CH3—	CH3—	2	1	1	2
478	CH3—(CH2)10—	CH3—	CH3—	1	3	3	1
479	CH3—(CH2)10—	CH3—	CH3—	1	3	1	3
480	CH3—(CH2)10—	CH3—	CH3—	1	1	3	3
481	CH3—(CH2)10—	CH3—	CH3—	3	3	1	1
482	CH3—(CH2)10—	CH3—	CH3—	3	1	3	1
483	CH3—(CH2)10—	CH3—	CH3—	3	1	1	3
484	CH3—(CH2)10—	CH3—	CH3—	1	4	4	1
485	CH3—(CH2)10—	CH3—	CH3—	1	4	1	4
486	CH3—(CH2)10—	CH3—	CH3—	1	1	4	4
487	CH3—(CH2)10—	CH3—	CH3—	4	4	1	1
488	CH3—(CH2)10—	CH3—	CH3—	4	1	4	1
489	CH3—(CH2)10—	CH3—	CH3—	4	1	1	4
490	CH3—(CH2)10—	CH3—	CH3—	1	1	2	3
491	CH3—(CH2)10—	CH3—	CH3—	1	1	3	2
492	CH3—(CH2)10—	CH3—	CH3—	1	2	3	1
493	CH3—(CH2)10—	CH3—	CH3—	1	3	2	1
494	CH3—(CH2)10—	CH3—	CH3—	1	2	1	3
495	CH3—(CH2)10—	CH3—	CH3—	1	3	1	2
496	CH3—(CH2)10—	CH3—	CH3—	2	1	1	3
497	CH3—(CH2)10—	CH3—	CH3—	2	1	3	1
498	CH3—(CH2)10—	CH3—	CH3—	2	3	1	1
499	CH3—(CH2)10—	CH3—	CH3—	3	1	1	2
500	CH3—(CH2)10—	CH3—	CH3—	3	1	2	1
501	CH3—(CH2)10—	CH3—	CH3—	3	2	1	1
502	CH3—(CH2)10—	CH3—	CH3—	1	1	2	4
503	CH3—(CH2)10—	CH3—	CH3—	1	1	4	2
504	CH3—(CH2)10—	CH3—	CH3—	1	2	4	1
505	CH3—(CH2)10—	CH3—	CH3—	1	4	2	1
506	CH3—(CH2)10—	CH3—	CH3—	1	2	1	4
507	CH3—(CH2)10—	CH3—	CH3—	1	4	1	2
508	CH3—(CH2)10—	CH3—	CH3—	2	1	1	4
509	CH3—(CH2)10—	CH3—	CH3—	2	1	4	1
510	CH3—(CH2)10—	CH3—	CH3—	2	4	1	1
511	CH3—(CH2)10—	CH3—	CH3—	4	1	1	2
512	CH3—(CH2)10—	CH3—	CH3—	4	1	2	1
513	CH3—(CH2)10—	CH3—	CH3—	4	2	1	1
514	CH3—(CH2)10—	CH3—	CH3—	1	1	4	3
515	CH3—(CH2)10—	CH3—	CH3—	1	1	3	4
516	CH3—(CH2)10—	CH3—	CH3—	1	4	3	1
517	CH3—(CH2)10—	CH3—	CH3—	1	3	4	1
518	CH3—(CH2)10—	CH3—	CH3—	1	4	1	3
519	CH3—(CH2)10—	CH3—	CH3—	1	3	1	4
520	CH3—(CH2)10—	CH3—	CH3—	4	1	1	3
521	CH3—(CH2)10—	CH3—	CH3—	4	1	3	1
522	CH3—(CH2)10—	CH3—	CH3—	4	3	1	1
523	CH3—(CH2)10—	CH3—	CH3—	3	1	1	4
524	CH3—(CH2)10—	CH3—	CH3—	3	1	4	1
525	CH3—(CH2)10—	CH3—	CH3—	3	4	1	1
526	CH3—(CH2)10—	CH3—	CH3—	1	2	2	2
527	CH3—(CH2)10—	CH3—	CH3—	2	1	2	2
528	CH3—(CH2)10—	CH3—	CH3—	2	2	1	2
529	CH3—(CH2)10—	CH3—	CH3—	2	2	2	1
530	CH3—(CH2)10—	CH3—	CH3—	1	3	3	3
531	CH3—(CH2)10—	CH3—	CH3—	3	1	3	3
532	CH3—(CH2)10—	CH3—	CH3—	3	3	1	3
533	CH3—(CH2)10—	CH3—	CH3—	3	3	3	1
534	CH3—(CH2)10—	CH3—	CH3—	1	4	4	4
535	CH3—(CH2)10—	CH3—	CH3—	4	1	4	4
536	CH3—(CH2)10—	CH3—	CH3—	4	4	1	4
537	CH3—(CH2)10—	CH3—	CH3—	4	4	4	1
538	CH3—(CH2)10—	CH3—	CH3—	2	2	1	3
539	CH3—(CH2)10—	CH3—	CH3—	2	2	3	1
540	CH3—(CH2)10—	CH3—	CH3—	2	1	2	3
541	CH3—(CH2)10—	CH3—	CH3—	2	3	2	1
542	CH3—(CH2)10—	CH3—	CH3—	2	1	3	2
543	CH3—(CH2)10—	CH3—	CH3—	2	3	1	2
544	CH3—(CH2)10—	CH3—	CH3—	1	2	2	3
545	CH3—(CH2)10—	CH3—	CH3—	1	2	3	2
546	CH3—(CH2)10—	CH3—	CH3—	1	3	2	2
547	CH3—(CH2)10—	CH3—	CH3—	3	2	2	1
548	CH3—(CH2)10—	CH3—	CH3—	3	2	1	2
549	CH3—(CH2)10—	CH3—	CH3—	3	1	2	2
550	CH3—(CH2)10—	CH3—	CH3—	2	2	1	4
551	CH3—(CH2)10—	CH3—	CH3—	2	2	4	1
552	CH3—(CH2)10—	CH3—	CH3—	2	1	2	4
553	CH3—(CH2)10—	CH3—	CH3—	2	4	2	1
554	CH3—(CH2)10—	CH3—	CH3—	2	1	4	2
555	CH3—(CH2)10—	CH3—	CH3—	2	4	1	2
556	CH3—(CH2)10—	CH3—	CH3—	1	2	2	4
557	CH3—(CH2)10—	CH3—	CH3—	1	2	4	2
558	CH3—(CH2)10—	CH3—	CH3—	1	4	2	2
559	CH3—(CH2)10—	CH3—	CH3—	4	2	2	1
560	CH3—(CH2)10—	CH3—	CH3—	4	2	1	2
561	CH3—(CH2)10—	CH3—	CH3—	4	1	2	2
562	CH3—(CH2)10—	CH3—	CH3—	2	2	4	3
563	CH3—(CH2)10—	CH3—	CH3—	2	2	3	4
564	CH3—(CH2)10—	CH3—	CH3—	2	4	2	3
565	CH3—(CH2)10—	CH3—	CH3—	2	3	2	4
566	CH3—(CH2)10—	CH3—	CH3—	2	4	3	2
567	CH3—(CH2)10—	CH3—	CH3—	2	3	4	2
568	CH3—(CH2)10—	CH3—	CH3—	4	2	2	3
569	CH3—(CH2)10—	CH3—	CH3—	4	2	3	2
570	CH3—(CH2)10—	CH3—	CH3—	4	3	2	2
571	CH3—(CH2)10—	CH3—	CH3—	3	2	2	4
572	CH3—(CH2)10—	CH3—	CH3—	3	2	4	2
573	CH3—(CH2)10—	CH3—	CH3—	3	4	2	2
574	CH3—(CH2)10—	CH3—	CH3—	3	3	1	2
575	CH3—(CH2)10—	CH3—	CH3—	3	3	2	1
576	CH3—(CH2)10—	CH3—	CH3—	3	1	3	2
577	CH3—(CH2)10—	CH3—	CH3—	3	2	3	1
578	CH3—(CH2)10—	CH3—	CH3—	3	1	2	3
579	CH3—(CH2)10—	CH3—	CH3—	3	2	1	3
580	CH3—(CH2)10—	CH3—	CH3—	1	3	3	2
581	CH3—(CH2)10—	CH3—	CH3—	1	3	2	3
582	CH3—(CH2)10—	CH3—	CH3—	1	2	3	3
583	CH3—(CH2)10—	CH3—	CH3—	2	3	3	1
584	CH3—(CH2)10—	CH3—	CH3—	2	3	1	3
585	CH3—(CH2)10—	CH3—	CH3—	2	1	3	3
586	CH3—(CH2)10—	CH3—	CH3—	3	3	1	4
587	CH3—(CH2)10—	CH3—	CH3—	3	3	4	1
588	CH3—(CH2)10—	CH3—	CH3—	3	1	3	4
589	CH3—(CH2)10—	CH3—	CH3—	3	4	3	1
590	CH3—(CH2)10—	CH3—	CH3—	3	1	4	3
591	CH3—(CH2)10—	CH3—	CH3—	3	4	1	3
592	CH3—(CH2)10—	CH3—	CH3—	1	3	3	4
593	CH3—(CH2)10—	CH3—	CH3—	1	3	4	3
594	CH3—(CH2)10—	CH3—	CH3—	1	4	3	3
595	CH3—(CH2)10—	CH3—	CH3—	4	3	3	1
596	CH3—(CH2)10—	CH3—	CH3—	4	3	1	3
597	CH3—(CH2)10—	CH3—	CH3—	4	1	3	3
598	CH3—(CH2)10—	CH3—	CH3—	3	3	4	2
599	CH3—(CH2)10—	CH3—	CH3—	3	3	2	4
600	CH3—(CH2)10—	CH3—	CH3—	3	4	3	2
601	CH3—(CH2)10—	CH3—	CH3—	3	2	3	4
602	CH3—(CH2)10—	CH3—	CH3—	3	4	2	3
603	CH3—(CH2)10—	CH3—	CH3—	3	2	4	3
604	CH3—(CH2)10—	CH3—	CH3—	4	3	3	2
605	CH3—(CH2)10—	CH3—	CH3—	4	3	2	3
606	CH3—(CH2)10—	CH3—	CH3—	4	2	3	3
607	CH3—(CH2)10—	CH3—	CH3—	2	3	3	4
608	CH3—(CH2)10—	CH3—	CH3—	2	3	4	3
609	CH3—(CH2)10—	CH3—	CH3—	2	4	3	3
610	CH3—(CH2)10—	CH3—	CH3—	4	4	1	2
611	CH3—(CH2)10—	CH3—	CH3—	4	4	2	1
612	CH3—(CH2)10—	CH3—	CH3—	4	1	4	2
613	CH3—(CH2)10—	CH3—	CH3—	4	2	4	1
614	CH3—(CH2)10—	CH3—	CH3—	4	1	2	4
615	CH3—(CH2)10—	CH3—	CH3—	4	2	1	4
616	CH3—(CH2)10—	CH3—	CH3—	1	4	4	2
617	CH3—(CH2)10—	CH3—	CH3—	1	4	2	4
618	CH3—(CH2)10—	CH3—	CH3—	1	2	4	4
619	CH3—(CH2)10—	CH3—	CH3—	2	4	4	1
620	CH3—(CH2)10—	CH3—	CH3—	2	4	1	4
621	CH3—(CH2)10—	CH3—	CH3—	2	1	4	4
622	CH3—(CH2)10—	CH3—	CH3—	4	4	1	3
623	CH3—(CH2)10—	CH3—	CH3—	4	4	3	1
624	CH3—(CH2)10—	CH3—	CH3—	4	1	4	3
625	CH3—(CH2)10—	CH3—	CH3—	4	3	4	1
626	CH3—(CH2)10—	CH3—	CH3—	4	1	3	4
627	CH3—(CH2)10—	CH3—	CH3—	4	3	1	4
628	CH3—(CH2)10—	CH3—	CH3—	1	4	4	3
629	CH3—(CH2)10—	CH3—	CH3—	1	4	3	4
630	CH3—(CH2)10—	CH3—	CH3—	1	3	4	4
631	CH3—(CH2)10—	CH3—	CH3—	3	4	4	1
632	CH3—(CH2)10—	CH3—	CH3—	3	4	1	4
633	CH3—(CH2)10—	CH3—	CH3—	3	1	4	4
634	CH3—(CH2)10—	CH3—	CH3—	4	4	3	2
635	CH3—(CH2)10—	CH3—	CH3—	4	4	2	3
636	CH3—(CH2)10—	CH3—	CH3—	4	3	4	2
637	CH3—(CH2)10—	CH3—	CH3—	4	2	4	3
638	CH3—(CH2)10—	CH3—	CH3—	4	3	2	4
639	CH3—(CH2)10—	CH3—	CH3—	4	2	3	4
640	CH3—(CH2)10—	CH3—	CH3—	3	4	4	2
641	CH3—(CH2)10—	CH3—	CH3—	3	4	2	4
642	CH3—(CH2)10—	CH3—	CH3—	3	2	4	4
643	CH3—(CH2)10—	CH3—	CH3—	2	4	4	3
644	CH3—(CH2)10—	CH3—	CH3—	2	4	3	4
645	CH3—(CH2)10—	CH3—	CH3—	2	3	4	4
646	CH3—(CH2)10—	CH3—	CH3—	1	2	3	4
647	CH3—(CH2)10—	CH3—	CH3—	1	2	4	3
648	CH3—(CH2)10—	CH3—	CH3—	1	3	2	4
649	CH3—(CH2)10—	CH3—	CH3—	1	3	4	2
650	CH3—(CH2)10—	CH3—	CH3—	1	4	2	3
651	CH3—(CH2)10—	CH3—	CH3—	1	4	3	2
652	CH3—(CH2)10—	CH3—	CH3—	2	1	3	4
653	CH3—(CH2)10—	CH3—	CH3—	2	1	4	3
654	CH3—(CH2)10—	CH3—	CH3—	2	3	1	4
655	CH3—(CH2)10—	CH3—	CH3—	2	3	4	1
656	CH3—(CH2)10—	CH3—	CH3—	2	4	1	3
657	CH3—(CH2)10—	CH3—	CH3—	2	4	3	1
658	CH3—(CH2)10—	CH3—	CH3—	3	1	2	4
659	CH3—(CH2)10—	CH3—	CH3—	3	1	4	2
660	CH3—(CH2)10—	CH3—	CH3—	3	2	1	4
661	CH3—(CH2)10—	CH3—	CH3—	3	2	4	1
662	CH3—(CH2)10—	CH3—	CH3—	3	4	1	2
663	CH3—(CH2)10—	CH3—	CH3—	3	4	2	1
664	CH3—(CH2)10—	CH3—	CH3—	4	1	2	3
665	CH3—(CH2)10—	CH3—	CH3—	4	1	3	2
666	CH3—(CH2)10—	CH3—	CH3—	4	2	1	3
667	CH3—(CH2)10—	CH3—	CH3—	4	2	3	1
668	CH3—(CH2)10—	CH3—	CH3—	4	3	1	2
669	CH3—(CH2)10—	CH3—	CH3—	4	3	2	1
670	CH3—(CH2)10—	CH3—	CH3—	2	3	3	2
671	CH3—(CH2)10—	CH3—	CH3—	2	3	2	3
672	CH3—(CH2)10—	CH3—	CH3—	2	2	3	3
673	CH3—(CH2)10—	CH3—	CH3—	3	3	2	2
674	CH3—(CH2)10—	CH3—	CH3—	3	2	3	2
675	CH3—(CH2)10—	CH3—	CH3—	3	2	2	3
676	CH3—(CH2)10—	CH3—	CH3—	2	4	4	2
677	CH3—(CH2)10—	CH3—	CH3—	2	4	2	4
678	CH3—(CH2)10—	CH3—	CH3—	2	2	4	4
679	CH3—(CH2)10—	CH3—	CH3—	4	4	2	2
680	CH3—(CH2)10—	CH3—	CH3—	4	2	4	2
681	CH3—(CH2)10—	CH3—	CH3—	4	2	2	4
682	CH3—(CH2)10—	CH3—	CH3—	3	4	4	3
683	CH3—(CH2)10—	CH3—	CH3—	3	4	3	4
684	CH3—(CH2)10—	CH3—	CH3—	3	3	4	4
685	CH3—(CH2)10—	CH3—	CH3—	4	4	3	3
686	CH3—(CH2)10—	CH3—	CH3—	4	3	4	3
687	CH3—(CH2)10—	CH3—	CH3—	4	3	3	4
688	CH3—(CH2)11—	CH3—	CH3—	1	1	1	1
689	CH3—(CH2)11—	CH3—	CH3—	2	1	1	1
690	CH3—(CH2)11—	CH3—	CH3—	1	2	1	1
691	CH3—(CH2)11—	CH3—	CH3—	1	1	2	1
692	CH3—(CH2)11—	CH3—	CH3—	1	1	1	2
693	CH3—(CH2)11—	CH3—	CH3—	3	1	1	1
694	CH3—(CH2)11—	CH3—	CH3—	1	3	1	1
695	CH3—(CH2)11—	CH3—	CH3—	1	1	3	1
696	CH3—(CH2)11—	CH3—	CH3—	1	1	1	3
697	CH3—(CH2)11—	CH3—	CH3—	4	1	1	1
698	CH3—(CH2)11—	CH3—	CH3—	1	4	1	1
699	CH3—(CH2)11—	CH3—	CH3—	1	1	4	1
700	CH3—(CH2)11—	CH3—	CH3—	1	1	1	4
701	CH3—(CH2)11—	CH3—	CH3—	1	2	2	1
702	CH3—(CH2)11—	CH3—	CH3—	1	2	1	2
703	CH3—(CH2)11—	CH3—	CH3—	1	1	2	2
704	CH3—(CH2)11—	CH3—	CH3—	2	2	1	1
705	CH3—(CH2)11—	CH3—	CH3—	2	1	2	1
706	CH3—(CH2)11—	CH3—	CH3—	2	1	1	2
707	CH3—(CH2)11—	CH3—	CH3—	1	3	3	1
708	CH3—(CH2)11—	CH3—	CH3—	1	3	1	3
709	CH3—(CH2)11—	CH3—	CH3—	1	1	3	3
710	CH3—(CH2)11—	CH3—	CH3—	3	3	1	1
711	CH3—(CH2)11—	CH3—	CH3—	3	1	3	1
712	CH3—(CH2)11—	CH3—	CH3—	3	1	1	3
713	CH3—(CH2)11—	CH3—	CH3—	1	4	4	1
714	CH3—(CH2)11—	CH3—	CH3—	1	4	1	4
715	CH3—(CH2)11—	CH3—	CH3—	1	1	4	4
716	CH3—(CH2)11—	CH3—	CH3—	4	4	1	1
717	CH3—(CH2)11—	CH3—	CH3—	4	1	4	1
718	CH3—(CH2)11—	CH3—	CH3—	4	1	1	4
719	CH3—(CH2)11—	CH3—	CH3—	1	1	2	3
720	CH3—(CH2)11—	CH3—	CH3—	1	1	3	2
721	CH3—(CH2)11—	CH3—	CH3—	1	2	3	1
722	CH3—(CH2)11—	CH3—	CH3—	1	3	2	1
723	CH3—(CH2)11—	CH3—	CH3—	1	2	1	3
724	CH3—(CH2)11—	CH3—	CH3—	1	3	1	2
725	CH3—(CH2)11—	CH3—	CH3—	2	1	1	3
726	CH3—(CH2)11—	CH3—	CH3—	2	1	3	1
727	CH3—(CH2)11—	CH3—	CH3—	2	3	1	1
728	CH3—(CH2)11—	CH3—	CH3—	3	1	1	2
729	CH3—(CH2)11—	CH3—	CH3—	3	1	2	1
730	CH3—(CH2)11—	CH3—	CH3—	3	2	1	1
731	CH3—(CH2)11—	CH3—	CH3—	1	1	2	4
732	CH3—(CH2)11—	CH3—	CH3—	1	1	4	2
733	CH3—(CH2)11—	CH3—	CH3—	1	2	4	1
734	CH3—(CH2)11—	CH3—	CH3—	1	4	2	1
735	CH3—(CH2)11—	CH3—	CH3—	1	2	1	4
736	CH3—(CH2)11—	CH3—	CH3—	1	4	1	2
737	CH3—(CH2)11—	CH3—	CH3—	2	1	1	4
738	CH3—(CH2)11—	CH3—	CH3—	2	1	4	1
739	CH3—(CH2)11—	CH3—	CH3—	2	4	1	1
740	CH3—(CH2)11—	CH3—	CH3—	4	1	1	2
741	CH3—(CH2)11—	CH3—	CH3—	4	1	2	1
742	CH3—(CH2)11—	CH3—	CH3—	4	2	1	1
743	CH3—(CH2)11—	CH3—	CH3—	1	1	4	3
744	CH3—(CH2)11—	CH3—	CH3—	1	1	3	4
745	CH3—(CH2)11—	CH3—	CH3—	1	4	3	1
746	CH3—(CH2)11—	CH3—	CH3—	1	3	4	1
747	CH3—(CH2)11—	CH3—	CH3—	1	4	1	3
748	CH3—(CH2)11—	CH3—	CH3—	1	3	1	4
749	CH3—(CH2)11—	CH3—	CH3—	4	1	1	3
750	CH3—(CH2)11—	CH3—	CH3—	4	1	3	1
751	CH3—(CH2)11—	CH3—	CH3—	4	3	1	1
752	CH3—(CH2)11—	CH3—	CH3—	3	1	1	4
753	CH3—(CH2)11—	CH3—	CH3—	3	1	4	1
754	CH3—(CH2)11—	CH3—	CH3—	3	4	1	1
755	CH3—(CH2)11—	CH3—	CH3—	1	2	2	2
756	CH3—(CH2)11—	CH3—	CH3—	2	1	2	2
757	CH3—(CH2)11—	CH3—	CH3—	2	2	1	2
758	CH3—(CH2)11—	CH3—	CH3—	2	2	2	1
759	CH3—(CH2)11—	CH3—	CH3—	1	3	3	3
760	CH3—(CH2)11—	CH3—	CH3—	3	1	3	3
761	CH3—(CH2)11—	CH3—	CH3—	3	3	1	3
762	CH3—(CH2)11—	CH3—	CH3—	3	3	3	1
763	CH3—(CH2)11—	CH3—	CH3—	1	4	4	4
764	CH3—(CH2)11—	CH3—	CH3—	4	1	4	4
765	CH3—(CH2)11—	CH3—	CH3—	4	4	1	4
766	CH3—(CH2)11—	CH3—	CH3—	4	4	4	1
767	CH3—(CH2)11—	CH3—	CH3—	2	2	1	3
768	CH3—(CH2)11—	CH3—	CH3—	2	2	3	1
769	CH3—(CH2)11—	CH3—	CH3—	2	1	2	3
770	CH3—(CH2)11—	CH3—	CH3—	2	3	2	1
771	CH3—(CH2)11—	CH3—	CH3—	2	1	3	2
772	CH3—(CH2)11—	CH3—	CH3—	2	3	1	2
773	CH3—(CH2)11—	CH3—	CH3—	1	2	2	3
774	CH3—(CH2)11—	CH3—	CH3—	1	2	3	2
775	CH3—(CH2)11—	CH3—	CH3—	1	3	2	2
776	CH3—(CH2)11—	CH3—	CH3—	3	2	2	1
777	CH3—(CH2)11—	CH3—	CH3—	3	2	1	2
778	CH3—(CH2)11—	CH3—	CH3—	3	1	2	2
779	CH3—(CH2)11—	CH3—	CH3—	2	2	1	4
780	CH3—(CH2)11—	CH3—	CH3—	2	2	4	1
781	CH3—(CH2)11—	CH3—	CH3—	2	1	2	4
782	CH3—(CH2)11—	CH3—	CH3—	2	4	2	1
783	CH3—(CH2)11—	CH3—	CH3—	2	1	4	2
784	CH3—(CH2)11—	CH3—	CH3—	2	4	1	2
785	CH3—(CH2)11—	CH3—	CH3—	1	2	2	4
786	CH3—(CH2)11—	CH3—	CH3—	1	2	4	2
787	CH3—(CH2)11—	CH3—	CH3—	1	4	2	2
788	CH3—(CH2)11—	CH3—	CH3—	4	2	2	1
789	CH3—(CH2)11—	CH3—	CH3—	4	2	1	2
790	CH3—(CH2)11—	CH3—	CH3—	4	1	2	2
791	CH3—(CH2)11—	CH3—	CH3—	2	2	4	3
792	CH3—(CH2)11—	CH3—	CH3—	2	2	3	4
793	CH3—(CH2)11—	CH3—	CH3—	2	4	2	3
794	CH3—(CH2)11—	CH3—	CH3—	2	3	2	4
795	CH3—(CH2)11—	CH3—	CH3—	2	4	3	2
796	CH3—(CH2)11—	CH3—	CH3—	2	3	4	2
797	CH3—(CH2)11—	CH3—	CH3—	4	2	2	3
798	CH3—(CH2)11—	CH3—	CH3—	4	2	3	2
799	CH3—(CH2)11—	CH3—	CH3—	4	3	2	2
800	CH3—(CH2)11—	CH3—	CH3—	3	2	2	4
801	CH3—(CH2)11—	CH3—	CH3—	3	2	4	2
802	CH3—(CH2)11—	CH3—	CH3—	3	4	2	2
803	CH3—(CH2)11—	CH3—	CH3—	3	3	1	2
804	CH3—(CH2)11—	CH3—	CH3—	3	3	2	1
805	CH3—(CH2)11—	CH3—	CH3—	3	1	3	2
806	CH3—(CH2)11—	CH3—	CH3—	3	2	3	1
807	CH3—(CH2)11—	CH3—	CH3—	3	1	2	3
808	CH3—(CH2)11—	CH3—	CH3—	3	2	1	3
809	CH3—(CH2)11—	CH3—	CH3—	1	3	3	2
810	CH3—(CH2)11—	CH3—	CH3—	1	3	2	3
811	CH3—(CH2)11—	CH3—	CH3—	1	2	3	3
812	CH3—(CH2)11—	CH3—	CH3—	2	3	3	1
813	CH3—(CH2)11—	CH3—	CH3—	2	3	1	3
814	CH3—(CH2)11—	CH3—	CH3—	2	1	3	3
815	CH3—(CH2)11—	CH3—	CH3—	3	3	1	4
816	CH3—(CH2)11—	CH3—	CH3—	3	3	4	1
817	CH3—(CH2)11—	CH3—	CH3—	3	1	3	4
818	CH3—(CH2)11—	CH3—	CH3—	3	4	3	1
819	CH3—(CH2)11—	CH3—	CH3—	3	1	4	3
820	CH3—(CH2)11—	CH3—	CH3—	3	4	1	3
821	CH3—(CH2)11—	CH3—	CH3—	1	3	3	4
822	CH3—(CH2)11—	CH3—	CH3—	1	3	4	3
823	CH3—(CH2)11—	CH3—	CH3—	1	4	3	3
824	CH3—(CH2)11—	CH3—	CH3—	4	3	3	1
825	CH3—(CH2)11—	CH3—	CH3—	4	3	1	3
826	CH3—(CH2)11—	CH3—	CH3—	4	1	3	3
827	CH3—(CH2)11—	CH3—	CH3—	3	3	4	2
828	CH3—(CH2)11—	CH3—	CH3—	3	3	2	4
829	CH3—(CH2)11—	CH3—	CH3—	3	4	3	2
830	CH3—(CH2)11—	CH3—	CH3—	3	2	3	4
831	CH3—(CH2)11—	CH3—	CH3—	3	4	2	3
832	CH3—(CH2)11—	CH3—	CH3—	3	2	4	3
833	CH3—(CH2)11—	CH3—	CH3—	4	3	3	2
834	CH3—(CH2)11—	CH3—	CH3—	4	3	2	3
835	CH3—(CH2)11—	CH3—	CH3—	4	2	3	3
836	CH3—(CH2)11—	CH3—	CH3—	2	3	3	4
837	CH3—(CH2)11—	CH3—	CH3—	2	3	4	3
838	CH3—(CH2)11—	CH3—	CH3—	2	4	3	3
839	CH3—(CH2)11—	CH3—	CH3—	4	4	1	2
840	CH3—(CH2)11—	CH3—	CH3—	4	4	2	1
841	CH3—(CH2)11—	CH3—	CH3—	4	1	4	2
842	CH3—(CH2)11—	CH3—	CH3—	4	2	4	1
843	CH3—(CH2)11—	CH3—	CH3—	4	1	2	4
844	CH3—(CH2)11—	CH3—	CH3—	4	2	1	4
845	CH3—(CH2)11—	CH3—	CH3—	1	4	4	2
846	CH3—(CH2)11—	CH3—	CH3—	1	4	2	4
847	CH3—(CH2)11—	CH3—	CH3—	1	2	4	4
848	CH3—(CH2)11—	CH3—	CH3—	2	4	4	1
849	CH3—(CH2)11—	CH3—	CH3—	2	4	1	4
850	CH3—(CH2)11—	CH3—	CH3—	2	1	4	4
851	CH3—(CH2)11—	CH3—	CH3—	4	4	1	3
852	CH3—(CH2)11—	CH3—	CH3—	4	4	3	1
853	CH3—(CH2)11—	CH3—	CH3—	4	1	4	3
854	CH3—(CH2)11—	CH3—	CH3—	4	3	4	1
855	CH3—(CH2)11—	CH3—	CH3—	4	1	3	4
856	CH3—(CH2)11—	CH3—	CH3—	4	3	1	4
857	CH3—(CH2)11—	CH3—	CH3—	1	4	4	3
858	CH3—(CH2)11—	CH3—	CH3—	1	4	3	4
859	CH3—(CH2)11—	CH3—	CH3—	1	3	4	4
860	CH3—(CH2)11—	CH3—	CH3—	3	4	4	1
861	CH3—(CH2)11—	CH3—	CH3—	3	4	1	4
862	CH3—(CH2)11—	CH3—	CH3—	3	1	4	4
863	CH3—(CH2)11—	CH3—	CH3—	4	4	3	2
864	CH3—(CH2)11—	CH3—	CH3—	4	4	2	3
865	CH3—(CH2)11—	CH3—	CH3—	4	3	4	2
866	CH3—(CH2)11—	CH3—	CH3—	4	2	4	3
867	CH3—(CH2)11—	CH3—	CH3—	4	3	2	4
868	CH3—(CH2)11—	CH3—	CH3—	4	2	3	4
869	CH3—(CH2)11—	CH3—	CH3—	3	4	4	2
870	CH3—(CH2)11—	CH3—	CH3—	3	4	2	4
871	CH3—(CH2)11—	CH3—	CH3—	3	2	4	4
872	CH3—(CH2)11—	CH3—	CH3—	2	4	4	3
873	CH3—(CH2)11—	CH3—	CH3—	2	4	3	4
874	CH3—(CH2)11—	CH3—	CH3—	2	3	4	4
875	CH3—(CH2)11—	CH3—	CH3—	1	2	3	4
876	CH3—(CH2)11—	CH3—	CH3—	1	2	4	3
877	CH3—(CH2)11—	CH3—	CH3—	1	3	2	4
878	CH3—(CH2)11—	CH3—	CH3—	1	3	4	2
879	CH3—(CH2)11—	CH3—	CH3—	1	4	2	3
880	CH3—(CH2)11—	CH3—	CH3—	1	4	3	2
881	CH3—(CH2)11—	CH3—	CH3—	2	1	3	4
882	CH3—(CH2)11—	CH3—	CH3—	2	1	4	3
883	CH3—(CH2)11—	CH3—	CH3—	2	3	1	4
884	CH3—(CH2)11—	CH3—	CH3—	2	3	4	1
885	CH3—(CH2)11—	CH3—	CH3—	2	4	1	3
886	CH3—(CH2)11—	CH3—	CH3—	2	4	3	1
887	CH3—(CH2)11—	CH3—	CH3—	3	1	2	4
888	CH3—(CH2)11—	CH3—	CH3—	3	1	4	2
889	CH3—(CH2)11—	CH3—	CH3—	3	2	1	4
890	CH3—(CH2)11—	CH3—	CH3—	3	2	4	1
891	CH3—(CH2)11—	CH3—	CH3—	3	4	1	2
892	CH3—(CH2)11—	CH3—	CH3—	3	4	2	1
893	CH3—(CH2)11—	CH3—	CH3—	4	1	2	3
894	CH3—(CH2)11—	CH3—	CH3—	4	1	3	2
895	CH3—(CH2)11—	CH3—	CH3—	4	2	1	3
896	CH3—(CH2)11—	CH3—	CH3—	4	2	3	1
897	CH3—(CH2)11—	CH3—	CH3—	4	3	1	2
898	CH3—(CH2)11—	CH3—	CH3—	4	3	2	1
899	CH3—(CH2)11—	CH3—	CH3—	2	3	3	2
900	CH3—(CH2)11—	CH3—	CH3—	2	3	2	3
901	CH3—(CH2)11—	CH3—	CH3—	2	2	3	3
902	CH3—(CH2)11—	CH3—	CH3—	3	3	2	2
903	CH3—(CH2)11—	CH3—	CH3—	3	2	3	2
904	CH3—(CH2)11—	CH3—	CH3—	3	2	2	3
905	CH3—(CH2)11—	CH3—	CH3—	2	4	4	2
906	CH3—(CH2)11—	CH3—	CH3—	2	4	2	4
907	CH3—(CH2)11—	CH3—	CH3—	2	2	4	4
908	CH3—(CH2)11—	CH3—	CH3—	4	4	2	2
909	CH3—(CH2)11—	CH3—	CH3—	4	2	4	2
910	CH3—(CH2)11—	CH3—	CH3—	4	2	2	4
911	CH3—(CH2)11—	CH3—	CH3—	3	4	4	3
912	CH3—(CH2)11—	CH3—	CH3—	3	4	3	4
913	CH3—(CH2)11—	CH3—	CH3—	3	3	4	4
914	CH3—(CH2)11—	CH3—	CH3—	4	4	3	3
915	CH3—(CH2)11—	CH3—	CH3—	4	3	4	3
916	CH3—(CH2)11—	CH3—	CH3—	4	3	3	4
917	CH3—(CH2)12—	CH3—	CH3—	1	1	1	1
918	CH3—(CH2)12—	CH3—	CH3—	2	1	1	1
919	CH3—(CH2)12—	CH3—	CH3—	1	2	1	1
920	CH3—(CH2)12—	CH3—	CH3—	1	1	2	1
921	CH3—(CH2)12—	CH3—	CH3—	1	1	1	2
922	CH3—(CH2)12—	CH3—	CH3—	3	1	1	1
923	CH3—(CH2)12—	CH3—	CH3—	1	3	1	1
924	CH3—(CH2)12—	CH3—	CH3—	1	1	3	1
925	CH3—(CH2)12—	CH3—	CH3—	1	1	1	3
926	CH3—(CH2)12—	CH3—	CH3—	4	1	1	1
927	CH3—(CH2)12—	CH3—	CH3—	1	4	1	1
928	CH3—(CH2)12—	CH3—	CH3—	1	1	4	1
929	CH3—(CH2)12—	CH3—	CH3—	1	1	1	4
930	CH3—(CH2)12—	CH3—	CH3—	1	2	2	1
931	CH3—(CH2)12—	CH3—	CH3—	1	2	1	2
932	CH3—(CH2)12—	CH3—	CH3—	1	1	2	2
933	CH3—(CH2)12—	CH3—	CH3—	2	2	1	1
934	CH3—(CH2)12—	CH3—	CH3—	2	1	2	1
935	CH3—(CH2)12—	CH3—	CH3—	2	1	1	2
936	CH3—(CH2)12—	CH3—	CH3—	1	3	3	1
937	CH3—(CH2)12—	CH3—	CH3—	1	3	1	3
938	CH3—(CH2)12—	CH3—	CH3—	1	1	3	3
939	CH3—(CH2)12—	CH3—	CH3—	3	3	1	1
940	CH3—(CH2)12—	CH3—	CH3—	3	1	3	1
941	CH3—(CH2)12—	CH3—	CH3—	3	1	1	3
942	CH3—(CH2)12—	CH3—	CH3—	1	4	4	1
943	CH3—(CH2)12—	CH3—	CH3—	1	4	1	4
944	CH3—(CH2)12—	CH3—	CH3—	1	1	4	4
945	CH3—(CH2)12—	CH3—	CH3—	4	4	1	1
946	CH3—(CH2)12—	CH3—	CH3—	4	1	4	1
947	CH3—(CH2)12—	CH3—	CH3—	4	1	1	4
948	CH3—(CH2)12—	CH3—	CH3—	1	1	2	3
949	CH3—(CH2)12—	CH3—	CH3—	1	1	3	2
950	CH3—(CH2)12—	CH3—	CH3—	1	2	3	1
951	CH3—(CH2)12—	CH3—	CH3—	1	3	2	1
952	CH3—(CH2)12—	CH3—	CH3—	1	2	1	3
953	CH3—(CH2)12—	CH3—	CH3—	1	3	1	2
954	CH3—(CH2)12—	CH3—	CH3—	2	1	1	3
955	CH3—(CH2)12—	CH3—	CH3—	2	1	3	1
956	CH3—(CH2)12—	CH3—	CH3—	2	3	1	1
957	CH3—(CH2)12—	CH3—	CH3—	3	1	1	2
958	CH3—(CH2)12—	CH3—	CH3—	3	1	2	1
959	CH3—(CH2)12—	CH3—	CH3—	3	2	1	1
960	CH3—(CH2)12—	CH3—	CH3—	1	1	2	4
961	CH3—(CH2)12—	CH3—	CH3—	1	1	4	2
962	CH3—(CH2)12—	CH3—	CH3—	1	2	4	1
963	CH3—(CH2)12—	CH3—	CH3—	1	4	2	1
964	CH3—(CH2)12—	CH3—	CH3—	1	2	1	4
965	CH3—(CH2)12—	CH3—	CH3—	1	4	1	2
966	CH3—(CH2)12—	CH3—	CH3—	2	1	1	4
967	CH3—(CH2)12—	CH3—	CH3—	2	1	4	1
968	CH3—(CH2)12—	CH3—	CH3—	2	4	1	1
969	CH3—(CH2)12—	CH3—	CH3—	4	1	1	2
970	CH3—(CH2)12—	CH3—	CH3—	4	1	2	1
971	CH3—(CH2)12—	CH3—	CH3—	4	2	1	1
972	CH3—(CH2)12—	CH3—	CH3—	1	1	4	3
973	CH3—(CH2)12—	CH3—	CH3—	1	1	3	4
974	CH3—(CH2)12—	CH3—	CH3—	1	4	3	1
975	CH3—(CH2)12—	CH3—	CH3—	1	3	4	1
976	CH3—(CH2)12—	CH3—	CH3—	1	4	1	3
977	CH3—(CH2)12—	CH3—	CH3—	1	3	1	4
978	CH3—(CH2)12—	CH3—	CH3—	4	1	1	3
979	CH3—(CH2)12—	CH3—	CH3—	4	1	3	1
980	CH3—(CH2)12—	CH3—	CH3—	4	3	1	1
981	CH3—(CH2)12—	CH3—	CH3—	3	1	1	4
982	CH3—(CH2)12—	CH3—	CH3—	3	1	4	1
983	CH3—(CH2)12—	CH3—	CH3—	3	4	1	1
984	CH3—(CH2)12—	CH3—	CH3—	1	2	2	2
985	CH3—(CH2)12—	CH3—	CH3—	2	1	2	2
986	CH3—(CH2)12—	CH3—	CH3—	2	2	1	2
987	CH3—(CH2)12—	CH3—	CH3—	2	2	2	1
988	CH3—(CH2)12—	CH3—	CH3—	1	3	3	3
989	CH3—(CH2)12—	CH3—	CH3—	3	1	3	3
990	CH3—(CH2)12—	CH3—	CH3—	3	3	1	3
991	CH3—(CH2)12—	CH3—	CH3—	3	3	3	1
992	CH3—(CH2)12—	CH3—	CH3—	1	4	4	4
993	CH3—(CH2)12—	CH3—	CH3—	4	1	4	4
994	CH3—(CH2)12—	CH3—	CH3—	4	4	1	4
995	CH3—(CH2)12—	CH3—	CH3—	4	4	4	1
996	CH3—(CH2)12—	CH3—	CH3—	2	2	1	3
997	CH3—(CH2)12—	CH3—	CH3—	2	2	3	1
998	CH3—(CH2)12—	CH3—	CH3—	2	1	2	3
999	CH3—(CH2)12—	CH3—	CH3—	2	3	2	1
1000	CH3—(CH2)12—	CH3—	CH3—	2	1	3	2
1001	CH3—(CH2)12—	CH3—	CH3—	2	3	1	2
1002	CH3—(CH2)12—	CH3—	CH3—	1	2	2	3
1003	CH3—(CH2)12—	CH3—	CH3—	1	2	3	2
1004	CH3—(CH2)12—	CH3—	CH3—	1	3	2	2
1005	CH3—(CH2)12—	CH3—	CH3—	3	2	2	1
1006	CH3—(CH2)12—	CH3—	CH3—	3	2	1	2
1007	CH3—(CH2)12—	CH3—	CH3—	3	1	2	2
1008	CH3—(CH2)12—	CH3—	CH3—	2	2	1	4
1009	CH3—(CH2)12—	CH3—	CH3—	2	2	4	1
1010	CH3—(CH2)12—	CH3—	CH3—	2	1	2	4
1011	CH3—(CH2)12—	CH3—	CH3—	2	4	2	1
1012	CH3—(CH2)12—	CH3—	CH3—	2	1	4	2
1013	CH3—(CH2)12—	CH3—	CH3—	2	4	1	2
1014	CH3—(CH2)12—	CH3—	CH3—	1	2	2	4
1015	CH3—(CH2)12—	CH3—	CH3—	1	2	4	2
1016	CH3—(CH2)12—	CH3—	CH3—	1	4	2	2
1017	CH3—(CH2)12—	CH3—	CH3—	4	2	2	1
1018	CH3—(CH2)12—	CH3—	CH3—	4	2	1	2
1019	CH3—(CH2)12—	CH3—	CH3—	4	1	2	2
1020	CH3—(CH2)12—	CH3—	CH3—	2	2	4	3
1021	CH3—(CH2)12—	CH3—	CH3—	2	2	3	4
1022	CH3—(CH2)12—	CH3—	CH3—	2	4	2	3
1023	CH3—(CH2)12—	CH3—	CH3—	2	3	2	4
1024	CH3—(CH2)12—	CH3—	CH3—	2	4	3	2
1025	CH3—(CH2)12—	CH3—	CH3—	2	3	4	2
1026	CH3—(CH2)12—	CH3—	CH3—	4	2	2	3
1027	CH3—(CH2)12—	CH3—	CH3—	4	2	3	2
1028	CH3—(CH2)12—	CH3—	CH3—	4	3	2	2
1029	CH3—(CH2)12—	CH3—	CH3—	3	2	2	4
1030	CH3—(CH2)12—	CH3—	CH3—	3	2	4	2
1031	CH3—(CH2)12—	CH3—	CH3—	3	4	2	2
1032	CH3—(CH2)12—	CH3—	CH3—	3	3	1	2
1033	CH3—(CH2)12—	CH3—	CH3—	3	3	2	1
1034	CH3—(CH2)12—	CH3—	CH3—	3	1	3	2
1035	CH3—(CH2)12—	CH3—	CH3—	3	2	3	1
1036	CH3—(CH2)12—	CH3—	CH3—	3	1	2	3
1037	CH3—(CH2)12—	CH3—	CH3—	3	2	1	3
1038	CH3—(CH2)12—	CH3—	CH3—	1	3	3	2
1039	CH3—(CH2)12—	CH3—	CH3—	1	3	2	3
1040	CH3—(CH2)12—	CH3—	CH3—	1	2	3	3
1041	CH3—(CH2)12—	CH3—	CH3—	2	3	3	1
1042	CH3—(CH2)12—	CH3—	CH3—	2	3	1	3
1043	CH3—(CH2)12—	CH3—	CH3—	2	1	3	3
1044	CH3—(CH2)12—	CH3—	CH3—	3	3	1	4
1045	CH3—(CH2)12—	CH3—	CH3—	3	3	4	1
1046	CH3—(CH2)12—	CH3—	CH3—	3	1	3	4
1047	CH3—(CH2)12—	CH3—	CH3—	3	4	3	1
1048	CH3—(CH2)12—	CH3—	CH3—	3	1	4	3
1049	CH3—(CH2)12—	CH3—	CH3—	3	4	1	3
1050	CH3—(CH2)12—	CH3—	CH3—	1	3	3	4
1051	CH3—(CH2)12—	CH3—	CH3—	1	3	4	3
1052	CH3—(CH2)12—	CH3—	CH3—	1	4	3	3
1053	CH3—(CH2)12—	CH3—	CH3—	4	3	3	1
1054	CH3—(CH2)12—	CH3—	CH3—	4	3	1	3
1055	CH3—(CH2)12—	CH3—	CH3—	4	1	3	3
1056	CH3—(CH2)12—	CH3—	CH3—	3	3	4	2
1057	CH3—(CH2)12—	CH3—	CH3—	3	3	2	4
1058	CH3—(CH2)12—	CH3—	CH3—	3	4	3	2
1059	CH3—(CH2)12—	CH3—	CH3—	3	2	3	4
1060	CH3—(CH2)12—	CH3—	CH3—	3	4	2	3
1061	CH3—(CH2)12—	CH3—	CH3—	3	2	4	3
1062	CH3—(CH2)12—	CH3—	CH3—	4	3	3	2
1063	CH3—(CH2)12—	CH3—	CH3—	4	3	2	3
1064	CH3—(CH2)12—	CH3—	CH3—	4	2	3	3
1065	CH3—(CH2)12—	CH3—	CH3—	2	3	3	4
1066	CH3—(CH2)12—	CH3—	CH3—	2	3	4	3
1067	CH3—(CH2)12—	CH3—	CH3—	2	4	3	3
1068	CH3—(CH2)12—	CH3—	CH3—	4	4	1	2
1069	CH3—(CH2)12—	CH3—	CH3—	4	4	2	1
1070	CH3—(CH2)12—	CH3—	CH3—	4	1	4	2
1071	CH3—(CH2)12—	CH3—	CH3—	4	2	4	1
1072	CH3—(CH2)12—	CH3—	CH3—	4	1	2	4
1073	CH3—(CH2)12—	CH3—	CH3—	4	2	1	4
1074	CH3—(CH2)12—	CH3—	CH3—	1	4	4	2
1075	CH3—(CH2)12—	CH3—	CH3—	1	4	2	4
1076	CH3—(CH2)12—	CH3—	CH3—	1	2	4	4
1077	CH3—(CH2)12—	CH3—	CH3—	2	4	4	1
1078	CH3—(CH2)12—	CH3—	CH3—	2	4	1	4
1079	CH3—(CH2)12—	CH3—	CH3—	2	1	4	4
1080	CH3—(CH2)12—	CH3—	CH3—	4	4	1	3
1081	CH3—(CH2)12—	CH3—	CH3—	4	4	3	1
1082	CH3—(CH2)12—	CH3—	CH3—	4	1	4	3
1083	CH3—(CH2)12—	CH3—	CH3—	4	3	4	1
1084	CH3—(CH2)12—	CH3—	CH3—	4	1	3	4
1085	CH3—(CH2)12—	CH3—	CH3—	4	3	1	4
1086	CH3—(CH2)12—	CH3—	CH3—	1	4	4	3
1087	CH3—(CH2)12—	CH3—	CH3—	1	4	3	4
1088	CH3—(CH2)12—	CH3—	CH3—	1	3	4	4
1089	CH3—(CH2)12—	CH3—	CH3—	3	4	4	1
1090	CH3—(CH2)12—	CH3—	CH3—	3	4	1	4
1091	CH3—(CH2)12—	CH3—	CH3—	3	1	4	4
1092	CH3—(CH2)12—	CH3—	CH3—	4	4	3	2
1093	CH3—(CH2)12—	CH3—	CH3—	4	4	2	3
1094	CH3—(CH2)12—	CH3—	CH3—	4	3	4	2
1095	CH3—(CH2)12—	CH3—	CH3—	4	2	4	3
1096	CH3—(CH2)12—	CH3—	CH3—	4	3	2	4
1097	CH3—(CH2)12—	CH3—	CH3—	4	2	3	4
1098	CH3—(CH2)12—	CH3—	CH3—	3	4	4	2
1099	CH3—(CH2)12—	CH3—	CH3—	3	4	2	4
1100	CH3—(CH2)12—	CH3—	CH3—	3	2	4	4
1101	CH3—(CH2)12—	CH3—	CH3—	2	4	4	3
1102	CH3—(CH2)12—	CH3—	CH3—	2	4	3	4
1103	CH3—(CH2)12—	CH3—	CH3—	2	3	4	4
1104	CH3—(CH2)12—	CH3—	CH3—	1	2	3	4
1105	CH3—(CH2)12—	CH3—	CH3—	1	2	4	3
1106	CH3—(CH2)12—	CH3—	CH3—	1	3	2	4
1107	CH3—(CH2)12—	CH3—	CH3—	1	3	4	2
1108	CH3—(CH2)12—	CH3—	CH3—	1	4	2	3
1109	CH3—(CH2)12—	CH3—	CH3—	1	4	3	2
1110	CH3—(CH2)12—	CH3—	CH3—	2	1	3	4
1111	CH3—(CH2)12—	CH3—	CH3—	2	1	4	3
1112	CH3—(CH2)12—	CH3—	CH3—	2	3	1	4
1113	CH3—(CH2)12—	CH3—	CH3—	2	3	4	1
1114	CH3—(CH2)12—	CH3—	CH3—	2	4	1	3
1115	CH3—(CH2)12—	CH3—	CH3—	2	4	3	1
1116	CH3—(CH2)12—	CH3—	CH3—	3	1	2	4
1117	CH3—(CH2)12—	CH3—	CH3—	3	1	4	2
1118	CH3—(CH2)12—	CH3—	CH3—	3	2	1	4
1119	CH3—(CH2)12—	CH3—	CH3—	3	2	4	1
1120	CH3—(CH2)12—	CH3—	CH3—	3	4	1	2
1121	CH3—(CH2)12—	CH3—	CH3—	3	4	2	1
1122	CH3—(CH2)12—	CH3—	CH3—	4	1	2	3
1123	CH3—(CH2)12—	CH3—	CH3—	4	1	3	2
1124	CH3—(CH2)12—	CH3—	CH3—	4	2	1	3
1125	CH3—(CH2)12—	CH3—	CH3—	4	2	3	1
1126	CH3—(CH2)12—	CH3—	CH3—	4	3	1	2
1127	CH3—(CH2)12—	CH3—	CH3—	4	3	2	1
1128	CH3—(CH2)12—	CH3—	CH3—	2	3	3	2
1129	CH3—(CH2)12—	CH3—	CH3—	2	3	2	3
1130	CH3—(CH2)12—	CH3—	CH3—	2	2	3	3
1131	CH3—(CH2)12—	CH3—	CH3—	3	3	2	2
1132	CH3—(CH2)12—	CH3—	CH3—	3	2	3	2
1133	CH3—(CH2)12—	CH3—	CH3—	3	2	2	3
1134	CH3—(CH2)12—	CH3—	CH3—	2	4	4	2
1135	CH3—(CH2)12—	CH3—	CH3—	2	4	2	4
1136	CH3—(CH2)12—	CH3—	CH3—	2	2	4	4
1137	CH3—(CH2)12—	CH3—	CH3—	4	4	2	2
1138	CH3—(CH2)12—	CH3—	CH3—	4	2	4	2
1139	CH3—(CH2)12—	CH3—	CH3—	4	2	2	4
1140	CH3—(CH2)12—	CH3—	CH3—	3	4	4	3
1141	CH3—(CH2)12—	CH3—	CH3—	3	4	3	4
1142	CH3—(CH2)12—	CH3—	CH3—	3	3	4	4
1143	CH3—(CH2)12—	CH3—	CH3—	4	4	3	3
1144	CH3—(CH2)12—	CH3—	CH3—	4	3	4	3
1145	CH3—(CH2)12—	CH3—	CH3—	4	3	3	4
1146	CH3—(CH2)13—	CH3—	CH3—	1	1	1	1
1147	CH3—(CH2)13—	CH3—	CH3—	2	1	1	1
1148	CH3—(CH2)13—	CH3—	CH3—	1	2	1	1
1149	CH3—(CH2)13—	CH3—	CH3—	1	1	2	1
1150	CH3—(CH2)13—	CH3—	CH3—	1	1	1	2
1151	CH3—(CH2)13—	CH3—	CH3—	3	1	1	1
1152	CH3—(CH2)13—	CH3—	CH3—	1	3	1	1
1153	CH3—(CH2)13—	CH3—	CH3—	1	1	3	1
1154	CH3—(CH2)13—	CH3—	CH3—	1	1	1	3
1155	CH3—(CH2)13—	CH3—	CH3—	4	1	1	1
1156	CH3—(CH2)13—	CH3—	CH3—	1	4	1	1
1157	CH3—(CH2)13—	CH3—	CH3—	1	1	4	1
1158	CH3—(CH2)13—	CH3—	CH3—	1	1	1	4
1159	CH3—(CH2)13—	CH3—	CH3—	1	2	2	1
1160	CH3—(CH2)13—	CH3—	CH3—	1	2	1	2
1161	CH3—(CH2)13—	CH3—	CH3—	1	1	2	2
1162	CH3—(CH2)13—	CH3—	CH3—	2	2	1	1
1163	CH3—(CH2)13—	CH3—	CH3—	2	1	2	1
1164	CH3—(CH2)13—	CH3—	CH3—	2	1	1	2
1165	CH3—(CH2)13—	CH3—	CH3—	1	3	3	1
1166	CH3—(CH2)13—	CH3—	CH3—	1	3	1	3
1167	CH3—(CH2)13—	CH3—	CH3—	1	1	3	3
1168	CH3—(CH2)13—	CH3—	CH3—	3	3	1	1
1169	CH3—(CH2)13—	CH3—	CH3—	3	1	3	1
1170	CH3—(CH2)13—	CH3—	CH3—	3	1	1	3
1171	CH3—(CH2)13—	CH3—	CH3—	1	4	4	1
1172	CH3—(CH2)13—	CH3—	CH3—	1	4	1	4
1173	CH3—(CH2)13—	CH3—	CH3—	1	1	4	4
1174	CH3—(CH2)13—	CH3—	CH3—	4	4	1	1
1175	CH3—(CH2)13—	CH3—	CH3—	4	1	4	1
1176	CH3—(CH2)13—	CH3—	CH3—	4	1	1	4
1177	CH3—(CH2)13—	CH3—	CH3—	1	1	2	3
1178	CH3—(CH2)13—	CH3—	CH3—	1	1	3	2
1179	CH3—(CH2)13—	CH3—	CH3—	1	2	3	1
1180	CH3—(CH2)13—	CH3—	CH3—	1	3	2	1
1181	CH3—(CH2)13—	CH3—	CH3—	1	2	1	3
1182	CH3—(CH2)13—	CH3—	CH3—	1	3	1	2
1183	CH3—(CH2)13—	CH3—	CH3—	2	1	1	3
1184	CH3—(CH2)13—	CH3—	CH3—	2	1	3	1
1185	CH3—(CH2)13—	CH3—	CH3—	2	3	1	1
1186	CH3—(CH2)13—	CH3—	CH3—	3	1	1	2
1187	CH3—(CH2)13—	CH3—	CH3—	3	1	2	1
1188	CH3—(CH2)13—	CH3—	CH3—	3	2	1	1
1189	CH3—(CH2)13—	CH3—	CH3—	1	1	2	4
1190	CH3—(CH2)13—	CH3—	CH3—	1	1	4	2
1191	CH3—(CH2)13—	CH3—	CH3—	1	2	4	1
1192	CH3—(CH2)13—	CH3—	CH3—	1	4	2	1
1193	CH3—(CH2)13—	CH3—	CH3—	1	2	1	4
1194	CH3—(CH2)13—	CH3—	CH3—	1	4	1	2
1195	CH3—(CH2)13—	CH3—	CH3—	2	1	1	4
1196	CH3—(CH2)13—	CH3—	CH3—	2	1	4	1
1197	CH3—(CH2)13—	CH3—	CH3—	2	4	1	1
1198	CH3—(CH2)13—	CH3—	CH3—	4	1	1	2
1199	CH3—(CH2)13—	CH3—	CH3—	4	1	2	1
1200	CH3—(CH2)13—	CH3—	CH3—	4	2	1	1
1201	CH3—(CH2)13—	CH3—	CH3—	1	1	4	3
1202	CH3—(CH2)13—	CH3—	CH3—	1	1	3	4
1203	CH3—(CH2)13—	CH3—	CH3—	1	4	3	1
1204	CH3—(CH2)13—	CH3—	CH3—	1	3	4	1
1205	CH3—(CH2)13—	CH3—	CH3—	1	4	1	3
1206	CH3—(CH2)13—	CH3—	CH3—	1	3	1	4
1207	CH3—(CH2)13—	CH3—	CH3—	4	1	1	3
1208	CH3—(CH2)13—	CH3—	CH3—	4	1	3	1
1209	CH3—(CH2)13—	CH3—	CH3—	4	3	1	1
1210	CH3—(CH2)13—	CH3—	CH3—	3	1	1	4
1211	CH3—(CH2)13—	CH3—	CH3—	3	1	4	1
1212	CH3—(CH2)13—	CH3—	CH3—	3	4	1	1
1213	CH3—(CH2)13—	CH3—	CH3—	1	2	2	2
1214	CH3—(CH2)13—	CH3—	CH3—	2	1	2	2
1215	CH3—(CH2)13—	CH3—	CH3—	2	2	1	2
1216	CH3—(CH2)13—	CH3—	CH3—	2	2	2	1
1217	CH3—(CH2)13—	CH3—	CH3—	1	3	3	3
1218	CH3—(CH2)13—	CH3—	CH3—	3	1	3	3
1219	CH3—(CH2)13—	CH3—	CH3—	3	3	1	3
1220	CH3—(CH2)13—	CH3—	CH3—	3	3	3	1
1221	CH3—(CH2)13—	CH3—	CH3—	1	4	4	4
1222	CH3—(CH2)13—	CH3—	CH3—	4	1	4	4
1223	CH3—(CH2)13—	CH3—	CH3—	4	4	1	4
1224	CH3—(CH2)13—	CH3—	CH3—	4	4	4	1
1225	CH3—(CH2)13—	CH3—	CH3—	2	2	1	3
1226	CH3—(CH2)13—	CH3—	CH3—	2	2	3	1
1227	CH3—(CH2)13—	CH3—	CH3—	2	1	2	3
1228	CH3—(CH2)13—	CH3—	CH3—	2	3	2	1
1229	CH3—(CH2)13—	CH3—	CH3—	2	1	3	2
1230	CH3—(CH2)13—	CH3—	CH3—	2	3	1	2
1231	CH3—(CH2)13—	CH3—	CH3—	1	2	2	3
1232	CH3—(CH2)13—	CH3—	CH3—	1	2	3	2
1233	CH3—(CH2)13—	CH3—	CH3—	1	3	2	2
1234	CH3—(CH2)13—	CH3—	CH3—	3	2	2	1
1235	CH3—(CH2)13—	CH3—	CH3—	3	2	1	2
1236	CH3—(CH2)13—	CH3—	CH3—	3	1	2	2
1237	CH3—(CH2)13—	CH3—	CH3—	2	2	1	4
1238	CH3—(CH2)13—	CH3—	CH3—	2	2	4	1
1239	CH3—(CH2)13—	CH3—	CH3—	2	1	2	4
1240	CH3—(CH2)13—	CH3—	CH3—	2	4	2	1
1241	CH3—(CH2)13—	CH3—	CH3—	2	1	4	2
1242	CH3—(CH2)13—	CH3—	CH3—	2	4	1	2
1243	CH3—(CH2)13—	CH3—	CH3—	1	2	2	4
1244	CH3—(CH2)13—	CH3—	CH3—	1	2	4	2
1245	CH3—(CH2)13—	CH3—	CH3—	1	4	2	2
1246	CH3—(CH2)13—	CH3—	CH3—	4	2	2	1
1247	CH3—(CH2)13—	CH3—	CH3—	4	2	1	2
1248	CH3—(CH2)13—	CH3—	CH3—	4	1	2	2
1249	CH3—(CH2)13—	CH3—	CH3—	2	2	4	3
1250	CH3—(CH2)13—	CH3—	CH3—	2	2	3	4
1251	CH3—(CH2)13—	CH3—	CH3—	2	4	2	3
1252	CH3—(CH2)13—	CH3—	CH3—	2	3	2	4
1253	CH3—(CH2)13—	CH3—	CH3—	2	4	3	2
1254	CH3—(CH2)13—	CH3—	CH3—	2	3	4	2
1255	CH3—(CH2)13—	CH3—	CH3—	4	2	2	3
1256	CH3—(CH2)13—	CH3—	CH3—	4	2	3	2
1257	CH3—(CH2)13—	CH3—	CH3—	4	3	2	2
1258	CH3—(CH2)13—	CH3—	CH3—	3	2	2	4
1259	CH3—(CH2)13—	CH3—	CH3—	3	2	4	2
1260	CH3—(CH2)13—	CH3—	CH3—	3	4	2	2
1261	CH3—(CH2)13—	CH3—	CH3—	3	3	1	2
1262	CH3—(CH2)13—	CH3—	CH3—	3	3	2	1
1263	CH3—(CH2)13—	CH3—	CH3—	3	1	3	2
1264	CH3—(CH2)13—	CH3—	CH3—	3	2	3	1
1265	CH3—(CH2)13—	CH3—	CH3—	3	1	2	3
1266	CH3—(CH2)13—	CH3—	CH3—	3	2	1	3
1267	CH3—(CH2)13—	CH3—	CH3—	1	3	3	2
1268	CH3—(CH2)13—	CH3—	CH3—	1	3	2	3
1269	CH3—(CH2)13—	CH3—	CH3—	1	2	3	3
1270	CH3—(CH2)13—	CH3—	CH3—	2	3	3	1
1271	CH3—(CH2)13—	CH3—	CH3—	2	3	1	3
1272	CH3—(CH2)13—	CH3—	CH3—	2	1	3	3
1273	CH3—(CH2)13—	CH3—	CH3—	3	3	1	4
1274	CH3—(CH2)13—	CH3—	CH3—	3	3	4	1
1275	CH3—(CH2)13—	CH3—	CH3—	3	1	3	4
1276	CH3—(CH2)13—	CH3—	CH3—	3	4	3	1
1277	CH3—(CH2)13—	CH3—	CH3—	3	1	4	3
1278	CH3—(CH2)13—	CH3—	CH3—	3	4	1	3
1279	CH3—(CH2)13—	CH3—	CH3—	1	3	3	4
1280	CH3—(CH2)13—	CH3—	CH3—	1	3	4	3
1281	CH3—(CH2)13—	CH3—	CH3—	1	4	3	3
1282	CH3—(CH2)13—	CH3—	CH3—	4	3	3	1
1283	CH3—(CH2)13—	CH3—	CH3—	4	3	1	3
1284	CH3—(CH2)13—	CH3—	CH3—	4	1	3	3
1285	CH3—(CH2)13—	CH3—	CH3—	3	3	4	2
1286	CH3—(CH2)13—	CH3—	CH3—	3	3	2	4
1287	CH3—(CH2)13—	CH3—	CH3—	3	4	3	2
1288	CH3—(CH2)13—	CH3—	CH3—	3	2	3	4
1289	CH3—(CH2)13—	CH3—	CH3—	3	4	2	3
1290	CH3—(CH2)13—	CH3—	CH3—	3	2	4	3
1291	CH3—(CH2)13—	CH3—	CH3—	4	3	3	2
1292	CH3—(CH2)13—	CH3—	CH3—	4	3	2	3
1293	CH3—(CH2)13—	CH3—	CH3—	4	2	3	3
1294	CH3—(CH2)13—	CH3—	CH3—	2	3	3	4
1295	CH3—(CH2)13—	CH3—	CH3—	2	3	4	3
1296	CH3—(CH2)13—	CH3—	CH3—	2	4	3	3
1297	CH3—(CH2)13—	CH3—	CH3—	4	4	1	2
1298	CH3—(CH2)13—	CH3—	CH3—	4	4	2	1
1299	CH3—(CH2)13—	CH3—	CH3—	4	1	4	2
1300	CH3—(CH2)13—	CH3—	CH3—	4	2	4	1
1301	CH3—(CH2)13—	CH3—	CH3—	4	1	2	4
1302	CH3—(CH2)13—	CH3—	CH3—	4	2	1	4
1303	CH3—(CH2)13—	CH3—	CH3—	1	4	4	2
1304	CH3—(CH2)13—	CH3—	CH3—	1	4	2	4
1305	CH3—(CH2)13—	CH3—	CH3—	1	2	4	4
1306	CH3—(CH2)13—	CH3—	CH3—	2	4	4	1
1307	CH3—(CH2)13—	CH3—	CH3—	2	4	1	4
1308	CH3—(CH2)13—	CH3—	CH3—	2	1	4	4
1309	CH3—(CH2)13—	CH3—	CH3—	4	4	1	3
1310	CH3—(CH2)13—	CH3—	CH3—	4	4	3	1
1311	CH3—(CH2)13—	CH3—	CH3—	4	1	4	3
1312	CH3—(CH2)13—	CH3—	CH3—	4	3	4	1
1313	CH3—(CH2)13—	CH3—	CH3—	4	1	3	4
1314	CH3—(CH2)13—	CH3—	CH3—	4	3	1	4
1315	CH3—(CH2)13—	CH3—	CH3—	1	4	4	3
1316	CH3—(CH2)13—	CH3—	CH3—	1	4	3	4
1317	CH3—(CH2)13—	CH3—	CH3—	1	3	4	4
1318	CH3—(CH2)13—	CH3—	CH3—	3	4	4	1
1319	CH3—(CH2)13—	CH3—	CH3—	3	4	1	4
1320	CH3—(CH2)13—	CH3—	CH3—	3	1	4	4
1321	CH3—(CH2)13—	CH3—	CH3—	4	4	3	2
1322	CH3—(CH2)13—	CH3—	CH3—	4	4	2	3
1323	CH3—(CH2)13—	CH3—	CH3—	4	3	4	2
1324	CH3—(CH2)13—	CH3—	CH3—	4	2	4	3
1325	CH3—(CH2)13—	CH3—	CH3—	4	3	2	4
1326	CH3—(CH2)13—	CH3—	CH3—	4	2	3	4
1327	CH3—(CH2)13—	CH3—	CH3—	3	4	4	2
1328	CH3—(CH2)13—	CH3—	CH3—	3	4	2	4
1329	CH3—(CH2)13—	CH3—	CH3—	3	2	4	4
1330	CH3—(CH2)13—	CH3—	CH3—	2	4	4	3
1331	CH3—(CH2)13—	CH3—	CH3—	2	4	3	4
1332	CH3—(CH2)13—	CH3—	CH3—	2	3	4	4
1333	CH3—(CH2)13—	CH3—	CH3—	1	2	3	4
1334	CH3—(CH2)13—	CH3—	CH3—	1	2	4	3
1335	CH3—(CH2)13—	CH3—	CH3—	1	3	2	4
1336	CH3—(CH2)13—	CH3—	CH3—	1	3	4	2
1337	CH3—(CH2)13—	CH3—	CH3—	1	4	2	3
1338	CH3—(CH2)13—	CH3—	CH3—	1	4	3	2
1339	CH3—(CH2)13—	CH3—	CH3—	2	1	3	4
1340	CH3—(CH2)13—	CH3—	CH3—	2	1	4	3
1341	CH3—(CH2)13—	CH3—	CH3—	2	3	1	4
1342	CH3—(CH2)13—	CH3—	CH3—	2	3	4	1
1343	CH3—(CH2)13—	CH3—	CH3—	2	4	1	3
1344	CH3—(CH2)13—	CH3—	CH3—	2	4	3	1
1345	CH3—(CH2)13—	CH3—	CH3—	3	1	2	4
1346	CH3—(CH2)13—	CH3—	CH3—	3	1	4	2
1347	CH3—(CH2)13—	CH3—	CH3—	3	2	1	4
1348	CH3—(CH2)13—	CH3—	CH3—	3	2	4	1
1349	CH3—(CH2)13—	CH3—	CH3—	3	4	1	2
1350	CH3—(CH2)13—	CH3—	CH3—	3	4	2	1
1351	CH3—(CH2)13—	CH3—	CH3—	4	1	2	3
1352	CH3—(CH2)13—	CH3—	CH3—	4	1	3	2
1353	CH3—(CH2)13—	CH3—	CH3—	4	2	1	3
1354	CH3—(CH2)13—	CH3—	CH3—	4	2	3	1
1355	CH3—(CH2)13—	CH3—	CH3—	4	3	1	2
1356	CH3—(CH2)13—	CH3—	CH3—	4	3	2	1
1357	CH3—(CH2)13—	CH3—	CH3—	2	3	3	2
1358	CH3—(CH2)13—	CH3—	CH3—	2	3	2	3
1359	CH3—(CH2)13—	CH3—	CH3—	2	2	3	3
1360	CH3—(CH2)13—	CH3—	CH3—	3	3	2	2
1361	CH3—(CH2)13—	CH3—	CH3—	3	2	3	2
1362	CH3—(CH2)13—	CH3—	CH3—	3	2	2	3
1363	CH3—(CH2)13—	CH3—	CH3—	2	4	4	2
1364	CH3—(CH2)13—	CH3—	CH3—	2	4	2	4
1365	CH3—(CH2)13—	CH3—	CH3—	2	2	4	4
1366	CH3—(CH2)13—	CH3—	CH3—	4	4	2	2
1367	CH3—(CH2)13—	CH3—	CH3—	4	2	4	2
1368	CH3—(CH2)13—	CH3—	CH3—	4	2	2	4
1369	CH3—(CH2)13—	CH3—	CH3—	3	4	4	3
1370	CH3—(CH2)13—	CH3—	CH3—	3	4	3	4
1371	CH3—(CH2)13—	CH3—	CH3—	3	3	4	4
1372	CH3—(CH2)13—	CH3—	CH3—	4	4	3	3
1373	CH3—(CH2)13—	CH3—	CH3—	4	3	4	3
1374	CH3—(CH2)13—	CH3—	CH3—	4	3	3	4
1375	CH3—(CH2)14—	CH3—	CH3—	1	1	1	1
1376	CH3—(CH2)14—	CH3—	CH3—	2	1	1	1
1377	CH3—(CH2)14—	CH3—	CH3—	1	2	1	1
1378	CH3—(CH2)14—	CH3—	CH3—	1	1	2	1
1379	CH3—(CH2)14—	CH3—	CH3—	1	1	1	2
1380	CH3—(CH2)14—	CH3—	CH3—	3	1	1	1
1381	CH3—(CH2)14—	CH3—	CH3—	1	3	1	1
1382	CH3—(CH2)14—	CH3—	CH3—	1	1	3	1
1383	CH3—(CH2)14—	CH3—	CH3—	1	1	1	3
1384	CH3—(CH2)14—	CH3—	CH3—	4	1	1	1
1385	CH3—(CH2)14—	CH3—	CH3—	1	4	1	1
1386	CH3—(CH2)14—	CH3—	CH3—	1	1	4	1
1387	CH3—(CH2)14—	CH3—	CH3—	1	1	1	4
1388	CH3—(CH2)14—	CH3—	CH3—	1	2	2	1
1389	CH3—(CH2)14—	CH3—	CH3—	1	2	1	2
1390	CH3—(CH2)14—	CH3—	CH3—	1	1	2	2
1391	CH3—(CH2)14—	CH3—	CH3—	2	2	1	1
1392	CH3—(CH2)14—	CH3—	CH3—	2	1	2	1
1393	CH3—(CH2)14—	CH3—	CH3—	2	1	1	2
1394	CH3—(CH2)14—	CH3—	CH3—	1	3	3	1
1395	CH3—(CH2)14—	CH3—	CH3—	1	3	1	3
1396	CH3—(CH2)14—	CH3—	CH3—	1	1	3	3
1397	CH3—(CH2)14—	CH3—	CH3—	3	3	1	1
1398	CH3—(CH2)14—	CH3—	CH3—	3	1	3	1
1399	CH3—(CH2)14—	CH3—	CH3—	3	1	1	3
1400	CH3—(CH2)14—	CH3—	CH3—	1	4	4	1
1401	CH3—(CH2)14—	CH3—	CH3—	1	4	1	4
1402	CH3—(CH2)14—	CH3—	CH3—	1	1	4	4
1403	CH3—(CH2)14—	CH3—	CH3—	4	4	1	1
1404	CH3—(CH2)14—	CH3—	CH3—	4	1	4	1
1405	CH3—(CH2)14—	CH3—	CH3—	4	1	1	4
1406	CH3—(CH2)14—	CH3—	CH3—	1	1	2	3
1407	CH3—(CH2)14—	CH3—	CH3—	1	1	3	2
1408	CH3—(CH2)14—	CH3—	CH3—	1	2	3	1
1409	CH3—(CH2)14—	CH3—	CH3—	1	3	2	1
1410	CH3—(CH2)14—	CH3—	CH3—	1	2	1	3
1411	CH3—(CH2)14—	CH3—	CH3—	1	3	1	2
1412	CH3—(CH2)14—	CH3—	CH3—	2	1	1	3
1413	CH3—(CH2)14—	CH3—	CH3—	2	1	3	1
1414	CH3—(CH2)14—	CH3—	CH3—	2	3	1	1
1415	CH3—(CH2)14—	CH3—	CH3—	3	1	1	2
1416	CH3—(CH2)14—	CH3—	CH3—	3	1	2	1
1417	CH3—(CH2)14—	CH3—	CH3—	3	2	1	1
1418	CH3—(CH2)14—	CH3—	CH3—	1	1	2	4
1419	CH3—(CH2)14—	CH3—	CH3—	1	1	4	2
1420	CH3—(CH2)14—	CH3—	CH3—	1	2	4	1
1421	CH3—(CH2)14—	CH3—	CH3—	1	4	2	1
1422	CH3—(CH2)14—	CH3—	CH3—	1	2	1	4
1423	CH3—(CH2)14—	CH3—	CH3—	1	4	1	2
1424	CH3—(CH2)14—	CH3—	CH3—	2	1	1	4
1425	CH3—(CH2)14—	CH3—	CH3—	2	1	4	1
1426	CH3—(CH2)14—	CH3—	CH3—	2	4	1	1
1427	CH3—(CH2)14—	CH3—	CH3—	4	1	1	2
1428	CH3—(CH2)14—	CH3—	CH3—	4	1	2	1
1429	CH3—(CH2)14—	CH3—	CH3—	4	2	1	1
1430	CH3—(CH2)14—	CH3—	CH3—	1	1	4	3
1431	CH3—(CH2)14—	CH3—	CH3—	1	1	3	4
1432	CH3—(CH2)14—	CH3—	CH3—	1	4	3	1
1433	CH3—(CH2)14—	CH3—	CH3—	1	3	4	1
1434	CH3—(CH2)14—	CH3—	CH3—	1	4	1	3
1435	CH3—(CH2)14—	CH3—	CH3—	1	3	1	4
1436	CH3—(CH2)14—	CH3—	CH3—	4	1	1	3
1437	CH3—(CH2)14—	CH3—	CH3—	4	1	3	1
1438	CH3—(CH2)14—	CH3—	CH3—	4	3	1	1
1439	CH3—(CH2)14—	CH3—	CH3—	3	1	1	4
1440	CH3—(CH2)14—	CH3—	CH3—	3	1	4	1
1441	CH3—(CH2)14—	CH3—	CH3—	3	4	1	1
1442	CH3—(CH2)14—	CH3—	CH3—	1	2	2	2
1443	CH3—(CH2)14—	CH3—	CH3—	2	1	2	2
1444	CH3—(CH2)14—	CH3—	CH3—	2	2	1	2
1445	CH3—(CH2)14—	CH3—	CH3—	2	2	2	1
1446	CH3—(CH2)14—	CH3—	CH3—	1	3	3	3
1447	CH3—(CH2)14—	CH3—	CH3—	3	1	3	3
1448	CH3—(CH2)14—	CH3—	CH3—	3	3	1	3
1449	CH3—(CH2)14—	CH3—	CH3—	3	3	3	1
1450	CH3—(CH2)14—	CH3—	CH3—	1	4	4	4
1451	CH3—(CH2)14—	CH3—	CH3—	4	1	4	4
1452	CH3—(CH2)14—	CH3—	CH3—	4	4	1	4
1453	CH3—(CH2)14—	CH3—	CH3—	4	4	4	1
1454	CH3—(CH2)14—	CH3—	CH3—	2	2	1	3
1455	CH3—(CH2)14—	CH3—	CH3—	2	2	3	1
1456	CH3—(CH2)14—	CH3—	CH3—	2	1	2	3
1457	CH3—(CH2)14—	CH3—	CH3—	2	3	2	1
1458	CH3—(CH2)14—	CH3—	CH3—	2	1	3	2
1459	CH3—(CH2)14—	CH3—	CH3—	2	3	1	2
1460	CH3—(CH2)14—	CH3—	CH3—	1	2	2	3
1461	CH3—(CH2)14—	CH3—	CH3—	1	2	3	2
1462	CH3—(CH2)14—	CH3—	CH3—	1	3	2	2
1463	CH3—(CH2)14—	CH3—	CH3—	3	2	2	1
1464	CH3—(CH2)14—	CH3—	CH3—	3	2	1	2
1465	CH3—(CH2)14—	CH3—	CH3—	3	1	2	2
1466	CH3—(CH2)14—	CH3—	CH3—	2	2	1	4
1467	CH3—(CH2)14—	CH3—	CH3—	2	2	4	1
1468	CH3—(CH2)14—	CH3—	CH3—	2	1	2	4
1469	CH3—(CH2)14—	CH3—	CH3—	2	4	2	1
1470	CH3—(CH2)14—	CH3—	CH3—	2	1	4	2
1471	CH3—(CH2)14—	CH3—	CH3—	2	4	1	2
1472	CH3—(CH2)14—	CH3—	CH3—	1	2	2	4
1473	CH3—(CH2)14—	CH3—	CH3—	1	2	4	2
1474	CH3—(CH2)14—	CH3—	CH3—	1	4	2	2
1475	CH3—(CH2)14—	CH3—	CH3—	4	2	2	1
1476	CH3—(CH2)14—	CH3—	CH3—	4	2	1	2
1477	CH3—(CH2)14—	CH3—	CH3—	4	1	2	2
1478	CH3—(CH2)14—	CH3—	CH3—	2	2	4	3
1479	CH3—(CH2)14—	CH3—	CH3—	2	2	3	4
1480	CH3—(CH2)14—	CH3—	CH3—	2	4	2	3
1481	CH3—(CH2)14—	CH3—	CH3—	2	3	2	4
1482	CH3—(CH2)14—	CH3—	CH3—	2	4	3	2
1483	CH3—(CH2)14—	CH3—	CH3—	2	3	4	2
1484	CH3—(CH2)14—	CH3—	CH3—	4	2	2	3
1485	CH3—(CH2)14—	CH3—	CH3—	4	2	3	2
1486	CH3—(CH2)14—	CH3—	CH3—	4	3	2	2
1487	CH3—(CH2)14—	CH3—	CH3—	3	2	2	4
1488	CH3—(CH2)14—	CH3—	CH3—	3	2	4	2
1489	CH3—(CH2)14—	CH3—	CH3—	3	4	2	2
1490	CH3—(CH2)14—	CH3—	CH3—	3	3	1	2
1491	CH3—(CH2)14—	CH3—	CH3—	3	3	2	1
1492	CH3—(CH2)14—	CH3—	CH3—	3	1	3	2
1493	CH3—(CH2)14—	CH3—	CH3—	3	2	3	1
1494	CH3—(CH2)14—	CH3—	CH3—	3	1	2	3
1495	CH3—(CH2)14—	CH3—	CH3—	3	2	1	3
1496	CH3—(CH2)14—	CH3—	CH3—	1	3	3	2
1497	CH3—(CH2)14—	CH3—	CH3—	1	3	2	3
1498	CH3—(CH2)14—	CH3—	CH3—	1	2	3	3
1499	CH3—(CH2)14—	CH3—	CH3—	2	3	3	1
1500	CH3—(CH2)14—	CH3—	CH3—	2	3	1	3
1501	CH3—(CH2)14—	CH3—	CH3—	2	1	3	3
1502	CH3—(CH2)14—	CH3—	CH3—	3	3	1	4
1503	CH3—(CH2)14—	CH3—	CH3—	3	3	4	1
1504	CH3—(CH2)14—	CH3—	CH3—	3	1	3	4
1505	CH3—(CH2)14—	CH3—	CH3—	3	4	3	1
1506	CH3—(CH2)14—	CH3—	CH3—	3	1	4	3
1507	CH3—(CH2)14—	CH3—	CH3—	3	4	1	3
1508	CH3—(CH2)14—	CH3—	CH3—	1	3	3	4
1509	CH3—(CH2)14—	CH3—	CH3—	1	3	4	3
1510	CH3—(CH2)14—	CH3—	CH3—	1	4	3	3
1511	CH3—(CH2)14—	CH3—	CH3—	4	3	3	1
1512	CH3—(CH2)14—	CH3—	CH3—	4	3	1	3
1513	CH3—(CH2)14—	CH3—	CH3—	4	1	3	3
1514	CH3—(CH2)14—	CH3—	CH3—	3	3	4	2
1515	CH3—(CH2)14—	CH3—	CH3—	3	3	2	4
1516	CH3—(CH2)14—	CH3—	CH3—	3	4	3	2
1517	CH3—(CH2)14—	CH3—	CH3—	3	2	3	4
1518	CH3—(CH2)14—	CH3—	CH3—	3	4	2	3
1519	CH3—(CH2)14—	CH3—	CH3—	3	2	4	3
1520	CH3—(CH2)14—	CH3—	CH3—	4	3	3	2
1521	CH3—(CH2)14—	CH3—	CH3—	4	3	2	3
1522	CH3—(CH2)14—	CH3—	CH3—	4	2	3	3
1523	CH3—(CH2)14—	CH3—	CH3—	2	3	3	4
1524	CH3—(CH2)14—	CH3—	CH3—	2	3	4	3
1525	CH3—(CH2)14—	CH3—	CH3—	2	4	3	3
1526	CH3—(CH2)14—	CH3—	CH3—	4	4	1	2
1527	CH3—(CH2)14—	CH3—	CH3—	4	4	2	1
1528	CH3—(CH2)14—	CH3—	CH3—	4	1	4	2
1529	CH3—(CH2)14—	CH3—	CH3—	4	2	4	1
1530	CH3—(CH2)14—	CH3—	CH3—	4	1	2	4
1531	CH3—(CH2)14—	CH3—	CH3—	4	2	1	4
1532	CH3—(CH2)14—	CH3—	CH3—	1	4	4	2
1533	CH3—(CH2)14—	CH3—	CH3—	1	4	2	4
1534	CH3—(CH2)14—	CH3—	CH3—	1	2	4	4
1535	CH3—(CH2)14—	CH3—	CH3—	2	4	4	1
1536	CH3—(CH2)14—	CH3—	CH3—	2	4	1	4
1537	CH3—(CH2)14—	CH3—	CH3—	2	1	4	4
1538	CH3—(CH2)14—	CH3—	CH3—	4	4	1	3
1539	CH3—(CH2)14—	CH3—	CH3—	4	4	3	1
1540	CH3—(CH2)14—	CH3—	CH3—	4	1	4	3
1541	CH3—(CH2)14—	CH3—	CH3—	4	3	4	1
1542	CH3—(CH2)14—	CH3—	CH3—	4	1	3	4
1543	CH3—(CH2)14—	CH3—	CH3—	4	3	1	4
1544	CH3—(CH2)14—	CH3—	CH3—	1	4	4	3
1545	CH3—(CH2)14—	CH3—	CH3—	1	4	3	4
1546	CH3—(CH2)14—	CH3—	CH3—	1	3	4	4
1547	CH3—(CH2)14—	CH3—	CH3—	3	4	4	1
1548	CH3—(CH2)14—	CH3—	CH3—	3	4	1	4
1549	CH3—(CH2)14—	CH3—	CH3—	3	1	4	4
1550	CH3—(CH2)14—	CH3—	CH3—	4	4	3	2
1551	CH3—(CH2)14—	CH3—	CH3—	4	4	2	3
1552	CH3—(CH2)14—	CH3—	CH3—	4	3	4	2
1553	CH3—(CH2)14—	CH3—	CH3—	4	2	4	3
1554	CH3—(CH2)14—	CH3—	CH3—	4	3	2	4
1555	CH3—(CH2)14—	CH3—	CH3—	4	2	3	4
1556	CH3—(CH2)14—	CH3—	CH3—	3	4	4	2
1557	CH3—(CH2)14—	CH3—	CH3—	3	4	2	4
1558	CH3—(CH2)14—	CH3—	CH3—	3	2	4	4
1559	CH3—(CH2)14—	CH3—	CH3—	2	4	4	3
1560	CH3—(CH2)14—	CH3—	CH3—	2	4	3	4
1561	CH3—(CH2)14—	CH3—	CH3—	2	3	4	4
1562	CH3—(CH2)14—	CH3—	CH3—	1	2	3	4
1563	CH3—(CH2)14—	CH3—	CH3—	1	2	4	3
1564	CH3—(CH2)14—	CH3—	CH3—	1	3	2	4
1565	CH3—(CH2)14—	CH3—	CH3—	1	3	4	2
1566	CH3—(CH2)14—	CH3—	CH3—	1	4	2	3
1567	CH3—(CH2)14—	CH3—	CH3—	1	4	3	2
1568	CH3—(CH2)14—	CH3—	CH3—	2	1	3	4
1569	CH3—(CH2)14—	CH3—	CH3—	2	1	4	3
1570	CH3—(CH2)14—	CH3—	CH3—	2	3	1	4
1571	CH3—(CH2)14—	CH3—	CH3—	2	3	4	1
1572	CH3—(CH2)14—	CH3—	CH3—	2	4	1	3
1573	CH3—(CH2)14—	CH3—	CH3—	2	4	3	1
1574	CH3—(CH2)14—	CH3—	CH3—	3	1	2	4
1575	CH3—(CH2)14—	CH3—	CH3—	3	1	4	2
1576	CH3—(CH2)14—	CH3—	CH3—	3	2	1	4
1577	CH3—(CH2)14—	CH3—	CH3—	3	2	4	1
1578	CH3—(CH2)14—	CH3—	CH3—	3	4	1	2
1579	CH3—(CH2)14—	CH3—	CH3—	3	4	2	1
1580	CH3—(CH2)14—	CH3—	CH3—	4	1	2	3
1581	CH3—(CH2)14—	CH3—	CH3—	4	1	3	2
1582	CH3—(CH2)14—	CH3—	CH3—	4	2	1	3
1583	CH3—(CH2)14—	CH3—	CH3—	4	2	3	1
1584	CH3—(CH2)14—	CH3—	CH3—	4	3	1	2
1585	CH3—(CH2)14—	CH3—	CH3—	4	3	2	1
1586	CH3—(CH2)14—	CH3—	CH3—	2	3	3	2
1587	CH3—(CH2)14—	CH3—	CH3—	2	3	2	3
1588	CH3—(CH2)14—	CH3—	CH3—	2	2	3	3
1589	CH3—(CH2)14—	CH3—	CH3—	3	3	2	2
1590	CH3—(CH2)14—	CH3—	CH3—	3	2	3	2
1591	CH3—(CH2)14—	CH3—	CH3—	3	2	2	3
1592	CH3—(CH2)14—	CH3—	CH3—	2	4	4	2
1593	CH3—(CH2)14—	CH3—	CH3—	2	4	2	4
1594	CH3—(CH2)14—	CH3—	CH3—	2	2	4	4
1595	CH3—(CH2)14—	CH3—	CH3—	4	4	2	2
1596	CH3—(CH2)14—	CH3—	CH3—	4	2	4	2
1597	CH3—(CH2)14—	CH3—	CH3—	4	2	2	4
1598	CH3—(CH2)14—	CH3—	CH3—	3	4	4	3
1599	CH3—(CH2)14—	CH3—	CH3—	3	4	3	4
1600	CH3—(CH2)14—	CH3—	CH3—	3	3	4	4
1601	CH3—(CH2)14—	CH3—	CH3—	4	4	3	3
1602	CH3—(CH2)14—	CH3—	CH3—	4	3	4	3
1603	CH3—(CH2)14—	CH3—	CH3—	4	3	3	4

In addition to the nonionic surfactants with high diffusion coefficients present according to the invention in the compositions, the compositions according to the invention can comprise further surfactants from the groups of nonionic, anionic, cationic or amphoteric surfactants. The additional nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2 position, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, preference is given to alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut alcohol, palm alcohol, tallow fatty alcohol or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C_12-14-alcohols with 3 EO or 4 EO, C_9-11-alcohol with 7 EO, C_13-15-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C_12-18-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C_12-14-alcohol with 3 EO and C_12-18-alcohol with 5 EO. The stated degrees of ethoxylation represent statistical average values which, for a specific product, may be an integer or a fraction. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples thereof are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, further nonionic surfactants which may be used are also alkyl glycosides of the general formula RO(G)_x, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2 position, aliphatic radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which gives the distribution of monoglycosides and oligoglycosides, is any desired number between 1 and 10; preferably x is 1.2 to 1.4.

A further class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow-alkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamide type, may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (II)

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R¹ is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are customarily obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine, and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R¹ is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms, and R² is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, where C_1-4-alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of said radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The preferred additional surfactants used are low-foam nonionic surfactants. The machine dishwashing detergents according to the invention particularly advantageously comprise a nonionic surfactant which has a melting point above room temperature. Consequently, preferred compositions are characterized in that they comprise nonionic surfactant(s) which has/have a melting point above 20° C., preferably above 25° C., particularly preferably between 25 and 60° C. and in particular between 26.6 and 43.3° C.

In addition to the nonionic surfactants present according to the invention in the compositions, suitable nonionic surfactants which have melting points or softening points within the stated temperature range are, for example, low-foam nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, then it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas, and in particular above 40 Pas. Nonionic surfactants which have a wax-like consistency at room temperature are also preferred.

Preferred nonionic surfactants that are to be used in solid form at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with surfactants of more complex structure, such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) nonionic surfactants are distinguished, moreover, by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant originating from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 mol, of ethylene oxide per mole of alcohol or alkylphenol.

A particularly preferred nonionic surfactant to be used that is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C_16-20-alcohol), preferably a C₁₈-alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide. Of these, the so-called “narrow range ethoxylates” (see above) are particularly preferred.

Accordingly, particularly preferred products according to the invention comprise ethoxylated nonionic surfactant(s) which has/have been obtained from C_6-20-monohydroxyalkanols or C_6-20-alkylphenols or C_16-20-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol, of ethylene oxide per mole of alcohol.

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units constitute up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight, of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules constitutes preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight, of the total molar mass of such nonionic surfactants. Preferred rinse aids are characterized in that they comprise ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule constitute up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molar mass of the nonionic surfactant.

Further nonionic surfactants with melting points above room temperature which can particularly preferably be used comprise 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and comprising 24 mol of ethylene oxide and 99 mol of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants which can particularly preferably be used can be obtained, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred rinse aid according to the invention comprises nonionic surfactants of the formula
R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(OH)R²]
in which R¹ is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R² is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x represents values between 0.5 and 1.5 and y represents a value of at least 15.

Further nonionic surfactants which can preferably be used are the terminally capped poly(oxyalkylated) nonionic surfactants of the formula
R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²
in which R¹ and R² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R³ is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x represents values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5. If the value x is ≧2, each R³ in the above formula may be different. R¹ and R² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R³, H, —CH₃ or —CH₂CH₃ are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R³ in the above formula may be different if x is ≧2. By this means it is possible to vary the alkylene oxide unit in the square brackets. If x, for example, is 3, the radical R³ may be selected in order to form ethylene oxide (R³=H) or propylene oxide (R³=CH₃) units, which may be added onto one another in any sequence, examples being (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been chosen here by way of example and it is entirely possible for it to be larger, the scope for variation increasing with increasing values of x and embracing, for example, a large number of (EO) groups, combined with a small number of (PO) groups, or vice versa.

Particularly preferred terminally capped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1, thereby simplifying the above formula to
R¹O[CH₂CH(R³)O]_xCH₂CH(OH)CH₂OR²

In the last-mentioned formula, R¹, R² and R³ are as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R¹ and R² have 9 to 14 carbon atoms, R³ is H, and x assumes values from 6 to 15.

Summarizing the last-mentioned statements, preference is given to rinse aids according to the invention which comprise terminally capped poly(oxyalkylated) nonionic surfactants of the formula
R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²
in which R¹ and R² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R³ is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x represents values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, where surfactants of the type
R¹O[CH₂CH(R³)O]_xCH₂CH(OH)CH₂OR²
in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

It is also possible to use anionic, cationic and/or amphoteric surfactants in conjunction with said surfactants; due to their foaming behavior, the former are only of minor importance in machine dishwashing detergents and are in most cases used only in amounts below 10% by weight, in most cases even below 5% by weight, for example from 0.01 to 2.5% by weight, in each case based on the product. The products according to the invention may thus also comprise anionic, cationic and/or amphoteric surfactants as surfactant component.

The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are, preferably, C_9-13-alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonates, and disulfonates, as are obtained, for example, from C_12-18-monoolefins having a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtained from C_12-18-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, respectively. Likewise suitable are also the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are understood as meaning the monoesters, diesters and triesters, and mixtures thereof, as are obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters here are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example those of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Preferred alk(en)yl sulfates are the alkali metal salts, and in particular the sodium salts, of the sulfuric monoesters of C₁₂–C₁₈-fatty alcohols, for example those of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of C₁₀–C₂₀-oxo alcohols, and those monoesters of secondary alcohols of these chain lengths. Preference is also given to alk(en)yl sulfates of said chain length which contain a synthetic straight-chain alkyl radical prepared on a petrochemical basis, and which have a degradation behavior analogous to that of the corresponding compounds based on fatty-chemical raw materials. From a washing technology viewpoint, the C₁₂–C₁₆-alkyl sulfates and C₁₂–C₁₅-alkyl sulfates and also C₁₄–C₁₅-alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are suitable anionic surfactants.

Also suitable are the sulfuric monoesters of the straight-chain or branched C_7-21-alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C_9-11-alcohols containing, on average, 3.5 mol of ethylene oxide (EO) or C_12-18-fatty alcohols having 1 to 4 EO. Due to their high foaming behavior, they are used in cleaning compositions only in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of the alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates comprise C_8-18-fatty alcohol radicals or mixtures of these. Particularly preferred sulfosuccinates comprise a fatty alcohol radical derived from ethoxylated fatty alcohols, which themselves represent nonionic surfactants (for description see below). Here, particular preference is in turn given to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrowed homolog distribution. It is likewise also possible to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.

Further suitable anionic surfactants are, in particular, soaps. Suitable soaps include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular mixtures of soaps derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

As cationic active substances, the products according to the invention may, for example, comprise cationic compounds of the formulae IV, V or VI,

in which each group R¹, independently of one another, is chosen from C_1-6-alkyl, -alkenyl or -hydroxyalkyl groups; each group R², independently of one another, is chosen from C_8-28-alkyl or -alkenyl groups; R³=R¹ or (CH₂)_n-T-R²; R⁴=R¹ or R² or (CH₂)_n-T-R²; T=—CH₂—, —O—CO— or —CO—O— and n is an integer from 0 to 5.

As a further ingredient, the compositions according to the invention comprise one or more builder(s). Builders are used in the compositions according to the invention primarily to bind calcium and magnesium. Customary builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates. For the cleaning compositions according to the invention, preference is given to using trisodium citrate and/or pentasodium tripolyphosphate and silicatic builders from the class of alkali metal disilicates. In general, with the alkali metal salts, the potassium salts are preferred over the sodium salts since they often have a greater solubility in water. Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium waterglasses.

Particularly preferred machine dishwashing detergents comprise, as builders, phosphates, preferably alkali metal phosphates, particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

Alkali metal phosphates is the collective term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, among which metaphosphoric acids (HPO₃)_n and orthophosphoric acid H₃PO₄, in addition to higher molecular weight representatives, may be differentiated. The phosphates combine a number of advantages: they act as alkali carriers, prevent limescale deposits and additionally contribute to the cleaning performance.

Sodium dihydrogenphosphate, NaH₂PO₄, exists as the dihydrate (density 1.91 gcm⁻³, melting point 60°) and as the monohydrate (density 2.04 gcm⁻³). Both salts are white powders which are very readily soluble in water, which lose the water of crystallization upon heating and undergo conversion at 200° C. into the weakly acidic diphosphate (disodium hydrogendiphosphate, Na₂H₂P₂O₇), at a higher temperature into sodium trimetaphosphate (Na₃P₃O₉) and Maddrell's salt (see below). NaH₂PO₄ is acidic; it is formed if phosphoric acid is adjusted to a pH of 4.5 using sodium hydroxide solution and the slurry is sprayed. Potassium dihydrogenphosphate (primary or monobasic potassium phosphate, potassium biphosphate, PDP), KH₂PO₄, is a white salt of density 2.33 gcm⁻³, has a melting point of 253° [decomposition with the formation of potassium polyphosphate (KPO₃)_x] and is readily soluble in water.

Disodium hydrogenphosphate (secondary sodium phosphate), Na₂HPO₄, is a colorless, very readily water-soluble crystalline salt. It exists in anhydrous form and with 2 mol of water (density 2.066 gcm⁻³, water loss at 95°), 7 mol of water (density 1.68 gcm⁻³, melting point 48° with loss of 5 H₂O) and 12 mol of water (density 1.52 gcm⁻³, melting point 35° with loss of 5 H₂O), becomes anhydrous at 100° and converts to the diphosphate Na₄P₂O₇ upon more severe heating. Disodium hydrogenphosphate is prepared by neutralizing phosphoric acid with soda solution using phenol-phthalein as indicator. Dipotassium hydrogenphosphate (secondary or dibasic potassium phosphate), K₂HPO₄, is an amorphous white salt which is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na₃PO₄, are colorless crystals which as the dodecahydrate have a density of 1.62 gcm⁻³ and a melting point of 73–76° C. (decomposition), as the decahydrate (corresponding to 19–20% of P₂O₅) have a melting point of 100° C. and in anhydrous form (corresponding to 39–40% of P₂O₅) have a density of 2.536 gcm⁻³. Trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporative concentration of a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K₃PO₄, is a white, deliquescent, granular powder of density 2.56 gcm⁻³, has a melting point of 1340° and is readily soluble in water with an alkaline reaction. It is produced, for example, when Thomas slag is heated with charcoal and potassium sulfate. Despite the relatively high price, the more readily soluble and therefore highly effective potassium phosphates are often preferred in the cleaners industry over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na₄P₂O₇, exists in anhydrous form (density 2.534 gcm⁻³, melting point 988°, 880° also reported) and as the decahydrate (density 1.815–1.836 gcm⁻³, melting point 94° with loss of water). Both substances are colorless crystals which are soluble in water with an alkaline reaction. Na₄P₂O₇ is formed when disodium phosphate is heated at >200° or by reacting phosphoric acid with soda in the stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and water hardness constituents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K₄P₂O₇, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm⁻³ which is soluble in water, the pH of the 1% strength solution at 25° being 10.4.

Condensation of the NaH₂PO₄ or of the KH₂PO₄ gives rise to higher molecular weight sodium and potassium phosphates, among which it is possible to differentiate between cyclic representatives, the sodium and potassium metaphosphates, and catenated types, the sodium and potassium polyphosphates. For the latter, in particular, a large number of names are in use: fused or high-temperature phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are referred to collectively as condensed phosphates.

The industrially important pentasodium triphosphate, Na₅P₃O₁₀ (sodium tripolyphosphate), is a nonhygroscopic, white, water-soluble salt which is anhydrous or crystallizes with 6 H₂O and has the general formula NaO—[P(O)(ONa)—O]_n—Na where n=3. About 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, about 20 g dissolve at 60°, and about 32 g dissolve at 100°; after heating the solution for 2 hours at 100°, about 8% orthophosphate and 15% diphosphate are produced by hydrolysis. In the case of the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in the stoichiometric ratio and the solution is dewatered by spraying. Similarly to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K₅P₃O₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (>23% P₂O₅, 25% K₂O). The potassium polyphosphates are widely used in the detergents and cleaners industry.

Further important builders are, in particular, the carbonates, citrates and silicates. Preference is given to using trisodium citrate and/or pentasodium tripolyphosphate and/or sodium carbonate and/or sodium bicarbonate and/or gluconates and/or silicatic builders from the class of disilicates and/or metasilicates.

Further constituents which may be present are alkali carriers. Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal metasilicates, and mixtures of the abovementioned substances, preference being given, for the purposes of this invention, to using alkali metal carbonates, in particular sodium carbonate, sodium hydrogencarbonate or sodium sesquicarbonate.

Particular preference is given to a builder system comprising a mixture of tripolyphosphate and sodium carbonate.

A builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is likewise particularly preferred.

The compositions according to the invention can comprise the builder or builders in varying amounts depending on the intended use. Preference is given here to machine dishwashing detergents according to the invention which comprise the builder(s) in amounts of from 5 to 90% by weight, preferably from 7.5 to 85% by weight and in particular from 10 to 80% by weight, in each case based on the total composition.

As well as the builders, bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances etc. in particular are preferred ingredients of machine dishwashing detergents. In addition, further ingredients may be present, preference being given to machine dishwashing detergents according to the invention which additionally comprise one or more substances from the group of acidifying agents, chelate complexing agents or of deposit-inhibiting polymers.

Possible acidifiers are either inorganic acids or organic acids provided these are compatible with the other ingredients. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is in turn given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid, and polyacrylic acid. The anhydrides of these acids can also be used as acidifiers, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids, such as amidosulfonic acid can likewise be used. A product which is commercially available and which can likewise preferably be used as acidifier for the purposes of the present invention is Sokalan® DCS (trade mark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

A further possible group of ingredients are the chelate complexing agents. Chelate complexing agents are substances which form cyclic compounds with metal ions, where a single ligand occupies more than one coordination site on a central atom, i.e. is at least “bidentate”. In this case, stretched compounds are thus normally closed by complex formation via an ion to give rings. The number of bonded ligands depends on the coordination number of the central ion.

Chelate complexing agents which are customary and preferred for the purposes of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, i.e. polymers which carry functional groups either in the main chain itself or laterally relative to this, which can act as ligands and react with suitable metal atoms usually to form chelate complexes, can also be used according to the invention. The polymer-bonded ligands of the resulting metal complexes can originate from just one macromolecule or else belong to different polymer chains. The latter leads to crosslinking of the material, provided the complex-forming polymers have not already been crosslinked beforehand via covalent bonds.

Complexing groups (ligands) of customary complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals, some of which have very specific activities toward ions of different metals. Basis polymers of many complex-forming polymers, which are also commercially important, are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Natural polymers, such as cellulose, starch or chitin are also complex-forming polymers. Moreover, these may be provided with further ligand functionalities as a result of polymer-analogous modifications.

For the purposes of the present invention, particular preference is given to machine dishwashing detergents which comprise one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the dishwasher product.

For the purposes of the present invention, it is possible to use all complexing agents of the prior art. These may belong to different chemical groups. Preference is given to using the following, individually or in a mixture with one another:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N,N-di(β-hydroxyethyl)glycine, N-(1,2-dicarboxy-2-hydroxyethyl)glycine, N-(1,2-dicarboxy-2-hydroxyethyl)aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids, such as 1-hydroxyethane1,1-diphosphonic acid (HEDP), higher homologs thereof having up to 8 carbon atoms, and hydroxy or amino group-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid, higher homologs thereof having up to 8 carbon atoms, and hydroxy or amino group-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) or nitrilotri(methylenephosphonic acid),
• e) phosphonopolycarboxylic acids, such as 2-phosphonobutane-1,2,4-tricarboxylic acid, and
• f) cyclodextrins.

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids—including monocarboxylic acids—in which the sum of carboxyl and the hydroxyl groups present in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially in the form of anions. It is unimportant whether they are introduced in the form of acids or in the form of salts. In the case of using salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Deposit-inhibiting polymers may likewise be present in the products according to the invention. These substances, which may have chemically different structures, originate, for example, from the groups of low molecular weight polyacrylates with molar masses between 1000 and 20 000 daltons, preference being given to polymers with molar masses below 15 000 daltons.

Deposit-inhibiting polymers may also have cobuilder properties. Organic cobuilders which may be used in the machine dishwashing detergents according to the invention are, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. These classes of substance are described below.

Organic builder substances which can be used are, for example, the polycarboxylic acids usable in the form of their sodium salts, the term polycarboxylic acids meaning carboxylic acids which carry more than one acid function. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such a use is not objectionable on ecological grounds, and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids per se may also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH of detergents or cleaners. In this connection, particular mention is made of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

Also suitable as builders or deposit inhibitors are polymeric polycarboxylates; these are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70 000 g/mol.

The molar masses given for polymeric polycarboxylates are, for the purposes of this specification, weight-average molar masses M_w of the respective acid form, determined fundamentally by means of gel permeation chromatography (GPC) using a UV detector. The measurement was made against an external polyacrylic acid standard which, owing to its structural similarity to the polymers under investigation, provides realistic molecular weight values. These figures differ considerably from the molecular weight values obtained using polystyrenesulfonic acids as the standard. The molar masses measured against polystyrenesulfonic acids are usually considerably higher than the molar masses given in this specification.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of from 500 to 20 000 g/mol. Owing to their superior solubility, preference in this group may be given in turn to the short-chain polyacrylates which have molar masses of from 1000 to 10 000 g/mol and particularly preferably from 1000 to 4000 g/mol.

Particular preference is given to using both polyacrylates and also copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups, and optionally further ionic or nonionogenic monomers in the compositions according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers which have proven to be particularly suitable are those of acrylic acid with maleic acid which contain from 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally 2000 to 70 000 g/mol, preferably 20 000 to 50 000 g/mol and in particular 30 000 to 40 000 g/mol.

The (co)polymeric polycarboxylates can either be used as powders or as aqueous solutions. The (co)polymeric polycarboxylate content of the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Particular preference is also given to biodegradable polymers of more than two different monomer units, for example those which contain, as monomers, salts of acrylic acid or of maleic acid, and vinyl alcohol or vinyl alcohol derivatives, or those which contain, as monomers, salts of acrylic acid and of 2-alkylallylsulfonic acid, and sugar derivatives. Further preferred copolymers are those which preferably have, as monomers, acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate.

Further preferred builder substances which are likewise to be mentioned are polymeric aminodicarboxylic acids, salts thereof or precursor substances thereof. Particular preference is given to polyaspartic acids or salts and derivatives thereof, which also have a bleach-stabilizing effect as well as cobuilder properties.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthalaldehyde, and mixtures thereof and from polyolcarboxylic acids, such as gluconic acid and/or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out in accordance with customary processes, for example acid-catalyzed or enzyme-catalyzed processes. The hydrolysis products preferably have average molar masses in the range from 400 to 500 000 g/mol. Preference is given here to a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared with dextrose, which has a DE of 100. It is also possible to use maltodextrins with a DE between 3 and 20 and dried glucose syrups with a DE between 20 and 37, and also so-called yellow dextrins and white dextrins with relatively high molar masses in the range from 2000 to 30 000 g/mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized on the C₆ of the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminedisuccinate, are also further suitable cobuilders. Here, ethylenediamine N,N′-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. In this connection, preference is also given to glycerol disuccinates and glycerol trisuccinates. Suitable use amounts in zeolite-containing and/or silicate-containing formulations are 3 to 15% by weight.

Further organic cobuilders which can be used are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups.

A further class of substances with cobuilder properties is the phosphonates. These are, in particular, hydroxyalkane- and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as cobuilder. It is preferably used as the sodium salt, the disodium salt giving a neutral reaction and the tetrasodium salt giving an alkaline reaction (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. Here, preference is given to using HEDP as builder from the class of phosphonates. In addition, the aminoalkanephosphonates have a marked heavy metal-binding capacity. Accordingly, particularly if the agents also comprise bleaches, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or mixtures of said phosphonates.

In addition to the substances from the classes of substance given, the products according to the invention can comprise further customary ingredients of cleaning compositions, where bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances in particular are of importance. These substances are described below.

Among the compounds which serve as bleaches and liberate H₂O₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Examples of further bleaches which may be used are sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H₂O₂-supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaners according to the invention can also comprise bleaches from the group of organic bleaches. Typical organic bleaches are the diacyl peroxides, such as, for example, dibenzoyl peroxide. Further typical organic bleaches are the peroxy acids, particular examples being the alkylperoxy acids and the arylperoxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyl-di(6-aminopercaproic acid) can be used.

Bleaches which may be used in the cleaners according to the invention for machine dishwashing may also be substances which liberate chlorine or bromine. Among the suitable materials which liberate chlorine or bromine, suitable examples include heterocyclic N-bromoamides and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or salts thereof with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin, are likewise suitable.

Preferred machine dishwashing detergents according to the invention additionally comprise bleaches in amounts of from 1 to 40% by weight, preferably from 2.5 to 30% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.

Bleach activators, which assist the action of the bleaches, have already been mentioned above as a possible ingredient of the rinse aid particles. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, of esters, of imides and of acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances which carry O-acyl and/or N-acyl groups of said number of carbon atoms and/or optionally substituted benzoyl groups are suitable. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methylmorpholinium acetonitrile methylsulfate (MMA), and enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated, glucamine and gluconolactone, and/or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are likewise preferably used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators, or instead of them, so-called bleach catalysts may also be incorporated into the rinse aid particles. These substances are bleach-boosting transition metal salts or transition metal complexes, such as, for example, Mn-, Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands, and Co-, Fe-, Cu- and Ru-ammine complexes can also be used as bleach catalysts.

Preference is given to using bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methylmorpholinium acetonitrile methylsulfate (MMA), preferably in amounts up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total agent.

Bleach-boosting transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferably chosen from the group of manganese and/or cobalt salts and/or complexes, particularly preferably the cobalt (ammine) complexes, cobalt (acetato) complexes, cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in customary amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total agent. However, in special cases, more bleach activator can also be used.

Suitable enzymes in the cleaners according to the invention are, in particular, those from the classes of hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases contribute to the removal of soilings such as protein-, grease- or starch-containing stains. For bleaching, it is also possible to use oxidoreductases. Especially suitable enzymatic active ingredients are those obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, and from genetically modified variants thereof. Preference is given to using proteases of the subtilisin type and in particular to proteases obtained from Bacillus lentus. Of particular interest here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes, or of protease, amylase and lipase or lipolytic enzymes, or protease, lipase or lipolytic enzymes, but in particular protease and/or lipase-containing mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proven suitable in some cases. Suitable amylases include, in particular, alpha-amylases, isoamylases, pullulanases and pectinases.

The enzymes can be adsorbed on carrier substances or embedded in coating substances in order to protect them from premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, be about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

For the purposes of the present invention, particular preference is given to the use of liquid enzyme formulations. Preference is given here to machine dishwashing detergents according to the invention which additionally comprise enzymes in amounts of from 0.01 to 15% by weight, preferably from 0.1 to 10 and in particular from 0.5 to 6% by weight, in each case based on the total product.

Dyes and fragrances can be added to the machine dishwashing detergents according to the invention in order to improve the esthetic impression of the resulting products and to provide the consumer with performance coupled with a visually and sensorily “typical and unmistakable” product. Perfume oils or fragrances which may be used are individual odorant compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Odorant compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclohexylpropionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, and the aldehydes include, for example, the linear alkanals having 8–18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the ionones, α-isomethylionone and methyl cedryl ketone, and the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, and the hydrocarbons include primarily the terpenes, such as limonene and pinene. Preference is, however, given to using mixtures of different odorants which together produce a pleasing scent note. Such perfume oils can also contain natural odorant mixtures, as are obtainable from plant sources, e.g. pine oil, citrus oil, jasmine oil, patchouli oil, rose oil and ylang ylang oil. Likewise suitable are muscatel, sage oil, camomile oil, oil of cloves, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning compositions according to the invention, although it may also be advantageous to apply the fragrances to carriers which enhance the adhesion of the perfume to the laundry and, by virtue of slower fragrance release, ensure long-lasting fragrance of the textiles. Materials which have become established as such carrier materials are, for example, cyclodextrins, in which the cyclodextrin perfume complexes can additionally be coated with further auxiliaries.

In order to improve the esthetic impression of the compositions prepared according to the invention, it (or parts thereof) may be colored with suitable dyes. Preferred dyes, the choice of which does not present any problems at all to the person skilled in the art, have high storage stability and high insensitivity toward the other ingredients of the composition and toward light, and do not have marked substantivity toward the substrates to be treated with the compositions, such as glass, ceramic or plastic dishware, in order not to dye these.

The cleaning compositions according to the invention can comprise corrosion inhibitors to protect the ware or the machine, particular importance in the field of machine dishwashing being attached to silver protectants. It is possible to use the known substances of the prior art. In general, it is possible to use, in particular, silver protectants chosen from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or transition metal complexes. Particular preference is given to the use of benzotriazole and/or alkylaminotriazole. Frequently encountered in cleaning formulations, moreover, are agents containing active chlorine, which can significantly reduce corrosion of the silver surface. In chlorine-free cleaners, use is made in particular of oxygen- and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, and derivatives of these classes of compounds. Inorganic compounds in the form of salts and complexes, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also often used. Preference is given here to the transition metal salts chosen from the group of manganese and/or cobalt salts and/or complexes, particularly preferably the cobalt(ammine) complexes, the cobalt(acetato) complexes, the cobalt(carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. It is likewise possible to use zinc compounds to prevent corrosion on the ware.

The requirements placed on dishes washed by machine are often nowadays higher than those placed on dishes washed manually. For example, even dishes which have been completely cleaned of food residues will not be evaluated as being perfect if, after machine dishwashing, they still have whitish marks based on water hardness or other mineral salts which, due to a lack of wetting agent, originate from dried-on water drops. In order to obtain sparkling and stain-free dishes, a rinse aid is therefore used. The addition of a rinse aid at the end of the wash program ensures that water runs off as completely as possible from the ware so that, at the end of the wash program, the various surfaces are residue-free and mark-free and sparkling. Machine dishwashing in domestic dishwashing machines usually includes a prerinse cycle, a main wash cycle and a clear-rinse cycle, which are interrupted by intermediate rinsing cycles. In most machines, the prerinse cycle can be included for heavily soiled dishes, but is only chosen by the consumer in exceptional cases, meaning that in most machines a main wash cycle, an intermediate rinse cycle with clean water and a clear-rinse cycle are carried out. The temperature of the main cycle varies between 40 and 65° C. depending on the type of machine and the program chosen. In the clear-rinse cycle, rinse aids, which usually comprise nonionic surfactants as the main constituent, are added from a dosing compartment within the machine. Such rinse aids are in liquid form and are widely described in the prior art. Their task is primarily to prevent lime marks and films on the dishes.

The compositions according to the invention can be formulated as “normal” cleaners which are used together with standard commercial supplementary agents (rinse aids, regeneration salts). However, it is particularly advantageous with the products according to the invention to dispense with the additional dosing of rinse aids since the surfactants with high diffusion coefficients present in the compositions lead to excellent run-off properties of the wash liquor and significantly reduced films on the dishes compared to conventional surfactants. These so-called “2in1” products lead to easier handling and take away the burden for the consumer of additionally dosing two different products (detergent and rinse aid).

Even in the case of “2in1” products, two dosing operations are periodically required to operate a domestic dishwashing machine since the regeneration salt must be topped up in the water softening system of the machine after a certain number of wash operations. These water softening systems consist of ion exchanger polymers which soften the hard water flowing into the machine and, after the wash program, are regenerated by rinsing with salt water.

It is, however, also possible to provide products according to the invention which, in the form of so-called “3in1” products, combine the conventional detergents, rinse aid and salt replacement function. In this respect, preference is given to machine dishwashing detergents according to the invention which additionally comprise 0.1 to 70% by weight of copolymers of

• • i) unsaturated carboxylic acids
  • ii) monomers containing sulfonic acid groups
  • iii) optionally further ionic or nonionogenic monomers.

These copolymers result in parts of dishes treated with such compositions becoming significantly cleaner in subsequent cleaning operations than parts of dishes which have been washed with conventional compositions.

An additional positive effect is the shortening of the drying time of the parts of dishes treated with the cleaning composition, i.e. the consumer can take the dishes from the machine earlier and reuse them after the wash program is finished.

The invention is characterized by an improved “cleanability” of the treated substrate during later washing operations and by a considerable shortening of the drying time compared with comparable compositions without the use of polymers containing sulfonic acid groups.

For the purposes of the teaching according to the invention, drying time is generally understood as having the literal meaning, i.e. the time which elapses until a surface of the dishes treated in a dishwasher machine has dried, but in particular the time which elapses until 90% of a surface treated with a cleaning composition or rinse aid in concentrated or dilute form has dried.

For the purposes of the present invention, unsaturated carboxylic acids of the formula VII are preferred as monomer,
R¹(R²)C═C(R³)COOH  (VII),
in which R¹ to R³, independently of one another, are —H—CH₃, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above and substituted by —NH₂, —OH or —COOH, or —COOH or —COOR⁴, where R⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula I, particular preference is given to acrylic acid (R¹=R²=R³=H), methacrylic acid (R¹=R²=H; R³=CH₃) and/or maleic acid (R¹=COOH; R²=R³=H).

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula VIII,
R⁵(R⁶)C═C(R⁷)—X—SO₃H  (VIII),
in which R⁵ to R⁷, independently of one another, are —H—CH₃, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above and substituted by —NH₂, —OH or —COOH, or —COOH or —COOR⁴, where R⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is chosen from —(CH₂)_n—, where n=0 to 4, —COO—(CH₂)_k— where k=1 to 6, —C(O)—NH—C(CH₃)₂— and —C(O)—NH—CH(CH₂CH₃)—.

Among these monomers, preference is given to those of the formulae VIIIa, VIIIb and/or VIIIc,
H₂C═CH—X—SO₃H  (VIIIa),
H₂C═C(CH₃)—X—SO₃H  (VIIIb),
HO₃S—X—(R⁶)C═C(R⁷)—X—SO₃H  (VIIIc),
in which R⁶ and R⁷, independently of one another, are chosen from —H, —CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂ and X is an optionally present spacer group which is chosen from —(CH₂)_n—, where n=0 to 4, —COO—(CH₂)_k— where k=1 to 6, —C(O)—NH—C(CH₃)₂— and —C(O)—NH—CH(CH₂CH₃)—.

Particularly preferred monomers containing sulfonic acid groups here are 1-acrylamido-1-propanesulfonic acid (X=—C(O)NH—CH(CH₂CH₃) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X=—C(O)NH—C(CH₃)₂ in formula VIIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X=—C(O)NH—CH(CH₃)CH₂— in formula VIIIa), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X=—C(O)NH—CH(CH₃)CH₂— in formula VIIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X=—C(O)NH—CH₂CH(OH)CH₂— in formula VIIIb), allylsulfonic acid (X=CH₂ in formula VIIIa), methallylsulfonic acid (X=CH₂ in formula VIIIb), allyloxybenzenesulfonic acid (X=—CH₂—O—C₆H₄— in formula VIIIa), methallyloxybenzenesulfonic acid (X=—CH₂—O—C₆H₄— in formula VIIIb), 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X=CH₂ in formula VIIIb), styrenesulfonic acid (X=C₆H₄ in formula VIIIa), vinylsulfonic acid (X not present in formula VIIIa), 3-sulfopropyl acrylate (X=—C(O)NH—CH₂CH₂CH₂— in formula VIIIa), 3-sulfopropyl methacrylate (X=—C(O)NH—CH₂CH₂CH₂— in formula VIIIb), sulfomethacrylamide (X=—C(O)NH— in formula VIIIb), sulfomethyl methacrylamide (X=—C(O)NH—CH₂— in formula VIIIb) and water-soluble salts of said acids.

Suitable further ionic or nonionogenic monomers are, in particular, ethylenically unsaturated compounds. Preferably the content of the monomers of group iii) in the polymers used according to the invention is less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist merely of monomers of groups i) and ii).

In summary, copolymers of

• i) unsaturated carboxylic acids of the formula VII
  R¹(R²)C═C(R³)COOH  (VII),
•  in which R¹ to R³, independently of one another, are —H, —CH₃, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above and substituted by —NH₂, —OH or —COOH, or —COOH or —COOR⁴, where R⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) monomers of the formula VIII containing sulfonic acid groups
  R⁵(R⁶)C═C(R⁷)—X—SO₃H  (VIII),
•  in which R⁵ to R⁷, independently of one another, are —H, —CH₃, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above and substituted by —NH₂, —OH or —COOH, or —COOH or —COOR⁴, where R⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is chosen from —(CH₂)_n—, where n=0 to 4, —COO—(CH₂)_k— where k=1 to 6, —C(O)—NH—C(CH₃)₂— and —C(O)—NH—CH(CH₂CH₃)—
• iii) optionally further ionic or nonionogenic monomers
  are particularly preferred.

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and/or maleic acid
• ii) one or more monomers containing sulfonic acid groups and of the formulae VIIIa, VIIIb and/or VIIIc:
  H₂C═CH—X—SO₃H  (VIIIa),
  H₂C═C(CH₃)—X—SO₃H  (VIIIb),
  HO₃S—X—(R⁶)C═C(R⁷)—X—SO₃H  (VIIIc),
•  in which R⁶ and R⁷, independently of one another, are chosen from —H, —CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂ and X is an optionally present spacer group which is chosen from —(CH₂)_n—, where n=0 to 4, —COO—(CH₂)_k— where k=1 to 6, —C(O)—NH—C(CH₃)₂— and —C(O)—NH—CH(CH₂CH₃)—
• iii) optionally further ionic or nonionogenic monomers.

The copolymers present according to the invention in the products can comprise the monomers from groups i) and ii), and optionally iii) in varying amounts, where all of the representatives from group i) can be combined with all of the representatives from group ii) and all of the representatives from group iii). Particularly preferred polymers have certain structural units which are described below.

Thus, for example, preference is given to products according to the invention which are characterized in that they comprise one or more copolymers which contain structural units of the formula IX
—[CH₂—CHCOOH]_m—[CH₂—CHC(O)—Y—SO₃H]_p—  (IX),
in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH₂)_n— where n=0 to 4, is —O—(C₆H₄)—, is —NH—C(CH₃)₂— or —NH—CH(CH₂CH₃)— are preferred.

These polymers are prepared by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. Copolymerizing the acrylic acid derivative containing sulfonic acid groups with methacrylic acid leads to another polymer which is likewise used with preference in the products according to the invention and is characterized in that the products comprise one or more copolymers which contain structural units of the formula X
—[CH₂—C(CH₃)COOH]_m—[CH₂—CHC(O)—Y—SO₃H]_p—  (X),
in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group which is chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH₂)_n—, where n=0 to 4, is —O—(C₆H₄)—, is —NH—C(CH₃)₂— or —NH—CH(CH₂CH₃)— are preferred.

Entirely analogously, acrylic acid and/or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. For example, products according to the invention which comprise one or more copolymers which contain structural units of the formula XI
—[CH₂—CHCOOH]_m—[CH₂—C(CH₃)C(O)—Y—SO₃H]_p—  (XI),
in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group which is chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH₂)_n—, where n=0 to 4, is —O—(C₆H₄)—, is —NH—C(CH₃)₂— or —NH—CH(CH₂CH₃)— are preferred, are likewise a preferred embodiment of the present invention, just as preference is also given to products which are characterized in that they comprise one or more copolymers which contain structural units of the formula XII
—[CH₂—C(CH₃)COOH]_m—[CH₂—C(CH₃)C(O)—Y—SO₃H]_p—  (XII),
in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group which is chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH₂)_n—, where n=0 to 4, is —O—(C₆H₄)—, is —NH—C(CH₃)₂— or —NH—CH(CH₂CH₃)— are preferred.

In place of acrylic acid and/or methacrylic acid, or in addition thereto, it is also possible to use maleic acid as particularly preferred monomer from group i). This gives products preferred according to the invention which are characterized in that they comprise one or more copolymers which contain structural units of the formula XIII
—[HOOCCH—CHCOOH]_m—[CH₂—CHC(O)—Y—SO₃H]_p—  (XIII),
in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group which is chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH₂)_n—, where n=0 to 4, is —O—(C₆H₄)—, is —NH—C(CH₃)₂— or —NH—CH(CH₂CH₃)— are preferred, and gives products which are characterized in that they comprise one or more copolymers which contain structural units of the formula XIV
—[HOOCCH—CHCOOH]_m—[CH₂—C(CH₃)C(O)O—Y—SO₃H]_p—  (XIV),
in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group which is chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH₂)_n—, where n=0 to 4, is —O—(C₆H₄)—, is —NH—C(CH₃)₂— or —NH—CH(CH₂CH₃)— are preferred.

In summary, machine dishwashing detergents according to the invention are preferred which comprise, as ingredient b), one or more copolymers which contain structural units of the formulae IX and/or X and/or XI and/or XII and/or XIII and/or XIV
—[CH₂—CHCOOH]_m—[CH₂—CHC(O)—Y—SO₃H]_p—  (IX),
—[CH₂—C(CH₃)COOH]_m—[CH₂—CHC(O)—Y—SO₃H]_p—  (X),
—[CH₂—CHCOOH]_m—[CH₂—C(CH₃)C(O)—Y—SO₃H]_p—  (XI),
—[CH₂—C(CH₃)COOH]_m—[CH₂—C(CH₃)C(O)—Y—SO₃H]_p—  (XII),
—[HOOCCH—CHCOOH]_m—[CH₂—CHC(O)—Y—SO₃H]_p—  (XIII),
—[HOOCCH—CHCOOH]_m—[CH₂—C(CH₃)C(O)O—Y—SO₃H]_p—  (XIV),
in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group which is chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is —O—(CH₂)_n— where n=0 to 4, is —O—(C₆H₄)—, is —NH—C(CH₃)₂— or —NH—CH(CH₂CH₃)— are preferred.

In the polymers, all or some of the sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced with metal ions, preferably alkali metal ions and in particular with sodium ions. Corresponding products which are characterized in that the sulfonic acid groups in the copolymer are in partially or completely neutralized form are preferred in accordance with the invention.

The monomer distribution of the copolymers used in the products according to the invention is, in the case of copolymers which comprise only monomers from groups i) and ii), preferably in each case 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those which comprise 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii), and 5 to 30% by weight of monomer from group iii).

The molar mass of the polymers used in the products according to the invention can be varied in order to match the properties of the polymers to the desired intended use. Preferred machine dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200 000 gmol⁻¹, preferably from 4000 to 25 000 gmol⁻¹ and in particular from 5000 to 15 000 gmol⁻¹.

The content of one or more copolymers in the products according to the invention can vary depending on the intended use and desired product performance, preferred machine dishwashing detergents according to the invention being characterized in that the copolymer or copolymers is/are present in amounts of from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.

As already mentioned above, particular preference is given to using both polyacrylates and also the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups, and optionally further ionic or nonionogenic monomers in the compositions according to the invention. The polyacrylates have been described above in detail. Particular preference is given to combinations of the above-described copolymers containing sulfonic acid groups with polyacrylates of low molar mass, for example in the range between 1000 and 4000 daltons. Such polyacrylates are available commercially under the trade name Sokalan® PA15 and Sokalan® PA25 (BASF).

EXAMPLES

A mixture of the surfactants 575 and 673 from the table in the description text was prepared by ethoxylating an unbranched and saturated C₁₁-alcohol with ethylene oxide in the presence of KOH as catalyst in an autoclave at 150° C. After the ethylene oxide had fully reacted, propylene oxide was fed into the autoclave and, after its reaction, the procedure was repeated with ethylene oxide and then with propylene oxide. The resulting surfactant mixture can be described by the formula
CH₃(CH₂)₁₀—O—(CH₂—CH₂—O)₃—(CH₂—CH(CH₃)—O)₃—(CH₂—CH₂—O)₂—(CH₂—CH(CH₃)—O)_1.5—H

The surfactant mixture has, at a concentration of 0.01 g/l in distilled water, a diffusion coefficient of 9.1·10⁻¹¹m²s⁻¹.

By means of granulation in a 130 liter plowshare mixer from Lödige, granular machine dishwashing detergents of the composition given in Table 1 were prepared.

TABLE 1
Granular machine dishwashing
detergents [% by weight]

		in accordance
		with the	comparative
		invention	example
		I1	C1
	Trisodium phosphate	30.44%	30.44%
	Sodium perborate	3.00%	3.00%
	TAED	1.07%	1.07%
	Nonionic surfactant*	5.27%	5.27%
	Sodium carbonate	54.11%	54.11%
	Polymeric cobuilder	3.78%	3.78%
	Enzymes	2.22%	2.22%
	Perfume	0.11%	0.11%
	*In Example I1 according to the invention, the nonionic surfactant described above was used; in the comparative example C1 Poly Tergent ®. SLF 18 B-45 from Olin was used, which, at a concentration of 0.01 g/l in distilled water, has a diffusion coefficient of 5 · 10−11 m2s−1.

Performance Assessment
a) Film Test
To assess the performance of formulations I1 (use of the composition according to the invention) and C1, a film test is carried out in a 65° C. universal wash program in a Miele dishwasher converted to operate continuously. For this, the program was carried out without standard commercial rinse aid (storage compartment of the dishwasher empty) and with water hardened to 21° German hardness (bypassing the ion exchanger).
Test Conditions

• Dishwasher: Miele Konti
• Detergent: 45 g metered into the main wash cycle
• Water hardness: 21° German hardness
• Program: Universal 65° C.
• Cycles: 30
• Soiling: 50 g of liquid soling metered into the main wash cycle
  • Composition:
    • 30% protein
    • 30% starch
    • 30% fat
    • 10% water/emulsifier

TABLE 2
Two-phase detergent tablets for
machine dishwashing [% by weight]

		in accordance
		with the	Comparative
		invention	example
		I2	C2

	Upper phase
	Sodium perborate	10.44%	10.44%
	TAED	2.01%	2.01%
	Nonionic surfactant*	7.23%	7.23%
	Hydroxyethane-1,1-	0.68%	0.68%
	diphosphonic acid,
	Na salt
	Sodium carbonate	10.04%	10.04%
	Benzotriazole	0.12%	0.12%
	Polymeric cobuilder	16.06%	16.06%
	Phyllosilicate	1.61%	1.61%
	(SKS6 ®)
	Trisodium citrate	16.06%	16.06%
	Sodium	6.02%	6.02%
	hydrogencarbonate
	Lower phase
	Trisodium phosphate	25.42%	25.42%
	Enzymes	2.85%	2.85%
	Perfume	0.08%	0.08%
	Nonionic surfactant	1.37%	1.37%
	*In the Example I2 in accordance with the invention the nonionic surfactant described above was used; in the comparative example C2 Poly Tergent ® SLF 18 B-45 from Olin was used which, at a concentration of 0.01 g/l in distilled water, has a diffusion coefficient of 5 · 10−11 m2s−1.

b) Clear-rinse Test
To assess the clear-rinse effect, the compositions I2 and C2 were used in a universal wash program. For this, the program was carried out without standard commercial rinse aid (storage compartment of the dishwasher empty) and with water hardened to 21° German hardness (bypassing the ion exchanger).
Test Conditions

• Dishwasher: Miele G575
• Detergent: 24.9 g metered into the main wash cycle
• Water hardness: 21° German hardness
• Program: Universal 55° C.
• Cycles: 3
• Soiling: 50 g of minced meat soiling
  The clear-rinse effect is assessed by visual inspection in a box whose walls are lined with black velvet, and the grades 0–4 are awarded separately for spotting and filming. The assessment is made in accordance with the following scheme:

	Spotting:	4 = no spots
		3 = 1–4 spots
		2 = more than 4 spots, up to 25% of the
		surface coated with spots
		1 = 25–50% of the surface covered with
		spots
		0 = more than 50% of the surface covered
		with spots
	Filming:	4 = no film to 0 = very considerable film

	Spotting	Filming	Spotting	Filming	Spotting	Filming

Glass

Stainless steel

Porcelain

I2	3.7	2.3	3.8	2.8	3.8	4
C2	3.2	1.0	3.2	1.3	3.8	3.7

Melamine

PE

SAN

I2	3	3	2.2	3.0	2.0	2.3
C2	3	2.3	2.2	1.7	2.0	1.0

The table shows that the formulation I2 is at times significantly superior to formulation C2 with regard to filming, and is at least equivalent with regard to spotting.