# US 10,865,365 B2 · Phosphate-free polymer detergent composition

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- Number: US 10,865,365 B2
- Document ID: US10865365B2
- Status: Granted
- Kind: B2
- Application number: 16/306,630
- Filed: 2017-06-09
- Published: 2019-06-13
- Granted: 2020-12-15
- Earliest claimed: 2016-06-13
- Assignees: Coatex
- Applicants: Coatex
- Inventors: Yves Kensicher
- Web page: https://patentgrep.com/patent/US10865365B2

## CPC

- C11D 3/3757: {(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions}
- C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL

## Abstract

The invention relates to the field of detergent compositions, in particular detergent compositions for automatic washing, especially for automatic dishwashing. Thus, the invention provides a phosphate-free detergent composition comprising at least one non-sulfonated nonionic surfactant compound and a non-sulfonated water-soluble copolymer prepared especially by polymerization reaction of acrylic or methacrylic acid, of an acrylic or methacrylic acid, itaconic acid or maleic acid ester and of a compound of formula (I): The invention also relates to the use of this non-sulfonated water-soluble copolymer as a scale-inhibiting agent or anti-spotting agent, and also to a cleaning process.

## Claims

### Claim 1

A phosphate-free detergent composition comprising:
at least one non-sulfonated water-soluble copolymer chosen from:
(i) a non-sulfonated water-soluble copolymer prepared by polymerization reaction:
a) of 55 mol % to 93 mol % of at least one acid chosen from acrylic acid and methacrylic acid, mixtures thereof and salts thereof,
b) of 2 mol % to 25 mol % of at least one ester of a compound derived from an acid chosen from acrylic acid, methacrylic acid, itaconic acid and maleic acid, and
c) of 5 mol % to 20 mol % of at least one compound of formula (I):
wherein:
R1 represents H or CH3,
R2 represents H,
L1 independently represents a group chosen from C(O), CH2, CH2—CH2 and O—CH2CH2—CH2—CH2,
L2 independently represents a group chosen from (CH2-CH2O)x, (CH2CH(CH3)O)y, (CH(CH3)CH2O)z and combinations thereof, and
x, y and z, which may be identical or different, independently represent an integer or decimal number between 0 and 150, x is strictly greater than y+z and the sum x+y+z is between 10 and 150, and
(ii) a non-sulfonated water-soluble copolymer prepared by polymerization reaction:
a) of 55% to 93% by weight of at least one acid chosen from acrylic acid and methacrylic acid, mixtures thereof and salts thereof,
b) of 2% to 25% by weight of at least one ester of a compound derived from an acid chosen from acrylic acid, methacrylic acid, itaconic acid and maleic acid, and
c) of 5% to 20% by weight of at least one compound of formula (I):
wherein:
R1 represents H or CH3,
R2 represents H,
L1 independently represents a group chosen from C(O), CH2, CH2—CH2 and O—CH2CH2—CH2—CH2,
L2 independently represents a group chosen from (CH2—CH2O)x, (CH2CH(CH3)O)y, (CH(CH3)CH2O)z and combinations thereof, and
x, y and z, which may be identical or different, independently represent an integer or decimal number between 0 and 150, x is strictly greater than y+z and the sum x+y+z is between 10 and 150; and
at least one non-sulfonated nonionic surfactant compound.

### Claim 2 (depends on 1)

The detergent composition as claimed in claim 1, wherein:
the acid (a) is acrylic acid or an acrylic acid salt or
the copolymer is prepared by reacting from 55 mol % to 90 mol % of acid (a) or
the copolymer is prepared by reacting from 55% to 90% by weight of acid (a).

### Claim 3 (depends on 1)

The detergent composition as claimed in claim 1, wherein:
the ester (b) is an anionic or nonionic ester or is a hydrophilic ester or a hydrophobic ester, or
the copolymer is prepared by reacting from 5 mol % to 20 mol % of ester (b) or
the copolymer is prepared by reacting from 5% to 20% by weight of ester (b).

### Claim 4 (depends on 1)

The detergent composition as claimed in claim 1, wherein the compound (c) of formula (I) is a compound wherein:
R1 represents H.

### Claim 5 (depends on 1)

The detergent composition as claimed in claim 1, wherein compound (c) of formula (I) is a compound wherein:
R1 and R2 represent H,
L1 represents a group chosen from C(O) and CH2,
L2 represents a group combining (CH2—CH2O)x and (CH2CH(CH3)O)y or (CH2(CH3)CH2O)z,
x represents an integer or decimal number between 10 and 140,
y+z represents an integer or decimal number between 10 and 140, and
x is strictly greater than y+z and the sum x+y+z is between 20 and 150.

### Claim 6 (depends on 1)

The detergent composition as claimed in claim 1, wherein compound (c) is:
a compound of formula (I) for which x represents an integer or decimal number between 15 and 80 and y+z represents an integer or decimal number between 10 and 65.

### Claim 7 (depends on 1)

The detergent composition as claimed in claim 1, wherein compound (c) is chosen from:
a compound of formula (I) in which R1 represents CH3, R2 represents H, L1 represents a C(O) group, L2 represents a group combining (CH2—CH2O)x and (CH2CH(CH3)O)y, or (CH(CH3)CH2O)z, x represents an integer or decimal number between 10 and 140, y+z represents an integer or decimal number between 10 and 140 and x is strictly greater than y+z and the sum x+y+z is between 20 and 150,
a compound of formula (I) in which R1 and R2 represent H, L′ represents C(O), L2 represents (CH2CH2O)x and x represents 1,
a compound of formula (I) in which R1 and R2 represent H, L′ represents C(O), L2 represents (CH2CH(CH3)O)x or (CH(CH3)CH2O)z and y+z represents 1,
a compound of formula (I) in which R′ represents CH3, R2 represents H, L′ represents C(O), L2 represents a group (CH2—CH2O)x and x represents 1,
a compound of formula (I) in which R′ represents CH3, R2 represents H, L′ represents C(O), L2 represents a group (CH2—CH(CH3)O)y or (CH(CH3)CH2O)z and y+z represents 1,
a compound of formula (I) in which R1 represents CH3, R2 represents H, L1 represents CH)2, L2 represents a group combining (CH2—CH2O)x and (CH2CH(CH3)O)y or (CH(CH3)CH2O)z, x represents an integer or decimal number between 10 and 140, y+z represents an integer or decimal number between 10 and 140 and x is strictly greater than y+z and the sum x+y+z is between 10 and 150,
a compound of formula (I) in which R1 represents CH3, R2 represent H, L′ represents CH2, L2 represents (CH2—CH2O)x and x represents an integer or decimal number between 10 and 140, and
a compound of formula (I) in which R1 and R2 represent H, L1 represents O—CH2—CH2—CH2—CH2, L2 represents (CH2—CH2O)x and x represents an integer or decimal number between 10 and 140.

### Claim 8 (depends on 1)

The detergent composition as claimed in claim 1, wherein,
the copolymer is prepared by reacting 7 mol % to 18 mol % of compound (c) of formula (I) or
the copolymer is prepared by reacting 7% to 18% by weight of compound (c) of formula (I).

### Claim 9 (depends on 1)

The detergent composition as claimed in claim 1, wherein the non-sulfonated water-soluble copolymer is prepared by polymerization reaction also using a monomer (d) chosen from maleic acid, itaconic acid and crotonic acid, mixtures thereof and salts thereof, in a weight amount ranging from 1/20 to ⅓ relative to the amount of monomer (a).

### Claim 10 (depends on 1)

The detergent composition as claimed in claim 1, comprising from 1% to 15% by weight of non-sulfonated water-soluble copolymer.

### Claim 11 (depends on 1)

A scale-inhibiting and/or anti-spotting agent, comprising the detergent composition as claimed in claim 1, wherein the at least one non-sulfonated nonionic surfactant is selected from the group consisting of synthetic alcohol ethoxylates, alcohol ethoxylates of natural origin, tributyl phenol ethoxylates, nonyl phenol ethoxylates, block polymers of ethylene oxide and of propylene oxide, adducts of ethoxylated-propoxylated alcohols, fatty acid ethoxylates, fatty amine ethoxylates, castor oil ethoxylates, tristyryl phenol ethoxylates, alkyl polyglycosides, adducts of C10-C12 ethoxylated-propoxylated fatty alcohols, adducts of C12-C14 ethoxylated-propoxylated fatty alcohols, adducts of C12-C15 ethoxylated-propoxylated oxo-alcohols, adducts of C12-C18 ethoxylated-propoxylated oxo-alcohols, C12-C14 fatty alcohol ethoxylates comprising 10 ethylene oxide groups and bearing a butyl end function C12-C18 fatty alcohol ethoxylates comprising 5 ethylene oxide groups and bearing a butyl end function, C12-C18 fatty alcohol ethoxylates comprising 10 ethylene oxide groups and bearing a butyl end function, C12-C15 oxo-alcohol ethoxylates comprising 8 ethylene oxide groups, C12-C15 oxo-alcohol ethoxylates comprising 8 ethylene oxide groups, C12-C15 oxo-alcohol ethoxylates comprising 10 ethylene oxide groups, poly(C6-hexyl glycosides) and poly(C8-alkyl glucosides).

### Claim 12 (depends on 1)

A cleaning process comprising:
washing with water and at least one detergent composition as claimed in claim 1;
rinsing; and
drying.

### Claim 13 (depends on 12)

The cleaning process as claimed in claim 12, wherein the washing or cleaning is chosen from the group consisting of washing a vehicle, detergency, laundry washing, washing or cleaning tableware, washing assistance, and surface cleaning.

### Claim 14 (depends on 1)

The detergent composition as claimed in claim 1, wherein the compound (c) of formula (I) is a compound wherein:
L1 represents a group chosen from C(O) and CH2.

### Claim 15 (depends on 1)

The detergent composition as claimed in claim 1, wherein the compound (c) of formula (I) is a compound wherein:
L2 represents a group combining (CH2—CH2O)x and (CH2CH(CH3)O)y or (CH(CH3)CH2O)z.

### Claim 16 (depends on 1)

The detergent composition as claimed in claim 1, wherein the compound (c) of formula (I) is a compound wherein:
x represents an integer or decimal number between 10 and 140.

### Claim 17 (depends on 1)

The detergent composition as claimed in claim 1, wherein the compound (c) of formula (I) is a compound wherein:
y+z represents an integer or decimal number between 10 and 140.

### Claim 18 (depends on 1)

The detergent composition as claimed in claim 1, wherein the compound (c) of formula (I) is a compound wherein:
x is strictly greater than y+z and the sum x+y+z is between 20 and 150.

### Claim 19 (depends on 1)

The detergent composition as claimed in claim 1, wherein the compound (c) of formula (I) is a compound wherein:
R1 represents CH3.