This invention relates to a cleaning composition comprising at least one surfacatant or at least one cosmetic vehicle and a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
##STR00001##
|
0. 23. A process for cleaning ceramics, tilings, baths and sinks, comprising the step of cleaning said ceramics, tilings, baths and sinks with an efficient cleaning amount of a composition comprising:
from 0.02 to 5% by weight with respect to the total weight of said composition of water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00036##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0 to 30%, by weight of at least one nonionic surfactant;
from 0 to 30%, by weight of at least one anionic surfactant, the total amount of surfactants representing from 1.5 to 50%, by weight, with respect to the total weight of the composition;
from 0.1 to 25% by weight with respect to the total weight of the composition of at least one organic or inorganic builder; and
optionally a foam modifier,
said composition exhibiting a pH of between 3 and 1 and an a/b molar ratio of between 30/70 and 60/40.
0. 25. A process for rinsing shower walls, comprising the step of rinsing said shower walls with a rinsing efficient amount of a composition comprising:
from 0.02 to 5% by weight, of water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00038##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C3-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.5 to 5% by weight of a nonionic surfactant; and
optionally from 0.01 to 5% by weight of a metal-chelating agent.
0. 20. A process for rinsing dishes in an automatic dishwasher, comprising the step of treating said dishes with an efficient rinsing amount of a composition comprising:
from 0.02 to 10%, by weight of water-soluble or water-dispersible copolymer, with respect to the total weight of the composition, said copolymer comprising
from 0.001 to 10%, by weight of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00033##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.2 to 15%, by weight with respect to the total weight of said composition of a nonionic surfactant or a mixture of nonionic and anionic surfactants;
from 0 to 40%, by weight with respect to the total weight of dry matter of a calcium-sequestering organic acid; and
from 0 to 15%, by weight with respect to the total weight of said composition, expressed as dry matter, of an auxiliary agent of copolymer of acrylic acid and of maleic anhydride or acrylic acid homopolymers.
0. 17. A process for cleaning windows, comprising the step of treating said windows with a an efficient cleaning amount of a composition comprising:
from 0.001 to 10%, by weight of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00031##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.005 to 20%, by weight of at least one nonionic and/or anionic surfactant;
the remainder being formed of water, or solvents.
0. 21. A process for washing dishes by hand comprising the step of treating said dishes with an efficient cleaning amount of a composition comprising:
from 0.1 to 5 parts by weight with respect to the total weight of said composition of water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00034##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 5 to 50, parts by weight of at least one surfactant;
at least one noncationic bactericide or disinfectant;
at least one synthetic cationic polymer agent;
a polymer for controling the viscosity of the mixture or the stability of the foams;
a hydrotropic agent;
a hydrating or moisturizing agent or an agent for protecting the skin; and
a dye or fragrance, and a preservative.
0. 19. A process for washing dishes in an automatic dishwasher, comprising the step of treating said dishes with an efficient washing amount of a composition comprising:
from 0.001 to 10%, by weight of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00032##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.2 to 10%, by weight with respect to the total weight of dry matter of a surfactant, and, optionally;
from 30 to 95% by weight with respect to the total weight of detergent composition, expressed as dry matter, of builders; and
from 3 to 25% by weight with respect to the total weight of the composition of an oxidizing system.
0. 69. A water-soluble or water-dispersible copolymer which comprises the copolymerizate of:
(a) at least one monomer compound of general formula I:
##STR00068##
in which:
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6 which are identical or different, are linear or branched C1-C6 alkyl, hydroxyalkyl or aminoalkyl groups;
m is 0 or 2;
n is an integer ranging from 1 to 6;
Z is a —C(O)O— or —C(O)NH— group or an oxygen atom;
A is a (CH2)p group, p being an integer ranging from 1 to 6;
B is a linear or branched C1-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in a cleaning/rinsing medium.
0. 30. A process for the treatment of hard surfaces, comprising the step of treating said surfaces with an efficient cleaning or rinsing amount of a composition comprising at least one water-soluble or water dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
##STR00039##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium.
0. 54. A process for rinsing shower walls, comprising the step of rinsing said shower walls with a rinsing efficient amount of a composition comprising:
from 0.02 to 5% by weight, of water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00057##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.5 to 5% by weight of a nonionic surfactant; and
optionally from 0.01 to 5% by weight of a metal-chelating agent.
0. 46. A process for cleaning windows, comprising the step of treating said windows with a an efficient cleaning amount of a composition comprising: from 0.001 to 10%, by weight of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
##STR00050##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.005 to 20%, by weight of at least one nonionic and/or anionic surfactant;
the remainder being formed of water, or solvents.
0. 59. A cleaning/rinsing composition, comprising at least one surfactant and/or at least one cleaning additive or vehicle and at least one water-soluble or water dispersible copolymer which comprises the copolymerizate of:
(a) at least one monomer compound of general formula I:
e####
##STR00058##
in which:
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkl groups;
m is an integer ranging from 0 to 10;
n is an integer ranging from 1 to 6;
Z is a —C(O)O— or —C(O)NH— group or an oxygen atom;
A is a (CH2)p group, p being an integer ranging from 1 to 6;
B is a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in a cleaning/rinsing medium; the at least one monomer (a) being effective to enable anchoring of said copolymer to a surface to be cleaned and the at least one monomer (b) being effective to confer hydrophilic characteristics thereon.
0. 48. A process for washing dishes in an automatic dishwasher, comprising the step of treating said dishes with an efficient washing amount of a composition comprising: from 0.001 to 10%, by weight of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
##STR00051##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.2 to 10%, by weight with respect to the total weight of dry matter of a surfactant, and, optionally;
from 30 to 95% by weight with respect to the total weight of detergent composition, expressed as dry matter, of builders; and
from 3 to 25% by weight with respect to the total weight of the composition of an oxidizing system.
0. 51. A process for the external cleaning of motor vehicles, comprising the step of cleaning said motor vehicles with an efficient cleaning amount of a composition comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
##STR00054##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0 to 30%, by weight of the formulation of at least one nonionic surfactant;
from 0 to 30%, by weight of the formulation of at least one anionic surfactant;
from 0 to 30%, by weight of an amphoteric and/or zwitterionic surfactant;
from 0 to 30%, by weight of a cationic surfactant; the minimum amount of surfactant being at least 1%;
an inorganic or organic builder; and
optionally, a hydrotropic agent, filler or pH modifier.
0. 50. A process for washing dishes by hand comprising the step of treating said dishes with an efficient cleaning amount of a composition comprising:
from 0.1 to 5 parts by weight with respect to the total weight of said composition of water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
##STR00053##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 5 to 50, parts by weight of at least one surfactant;
at least one noncationic bactericide or disinfectant;
at least one synthetic cationic polymer agent;
a polymer for controling the viscosity of the mixture or the stability of the foams;
a hydrotropic agent;
a hydrating or moisturizing agent or an agent for protecting the skin; and
a dye or fragrance, and a preservative.
0. 53. A process for cleaning toilet bowls, comprising the step of cleaning said toilet bowls with a cleaning efficient amount of a composition comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
##STR00056##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.1 to 40% by weight with respect to the total weight of the composition of an inorganic acid cleaning agent selected from the group consisting of phosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and sodium bisulfate;
from 0.5 to 10% by weight of a surfactant;
from 0.1 to 3% by weight of a thickener; and
a preservative intended to prevent the growth of microorganisms; said composition exhibiting a pH of between 0.5 and 4.
0. 52. A process for cleaning ceramics, tilings, baths and sinks, comprising the step of cleaning said ceramics, tilings, baths and sinks with an efficient cleaning amount of a composition comprising:
from 0.02 to 5% by weight with respect to the total weight of said composition of water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
e####
(a) at least one monomer compound of general formula I:
##STR00055##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0 to 30%, by weight of at least one nonionic surfactant;
from 0 to 30%, by weight of at least one anionic surfactant, the total amount of surfactants representing
from 1.5 to 50%, by weight, with respect to the total weight of the composition;
from 0.1 to 25% by weight with respect to the total weight of the composition of at least one organic or inorganic builder; and
optionally a foam modifier,
said composition exhibiting a pH of between 3 and 1 and an a/b molar ratio of between 30/70 and 60/40.
0. 49. A process for rinsing dishes in an automatic dishwasher, comprising the step of treating said dishes with an efficient rinsing amount of a composition comprising:
from 0.02 to 10%, by weight of water-soluble or water-dispersible copolymer, with respect to the total weight of the composition, said copolymer comprising
from 0.001 to 10%, by weight of a water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
##STR00052##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.2 to 15%, by weight with respect to the total weight of said composition of a nonionic surfactant or a mixture of nonionic and anionic surfactants;
from 0 to 40%, by weight with respect to the total weight of dry matter of a calcium-sequestering organic acid; and
from 0 to 15%, by weight with respect to the total weight of said composition, expressed as dry matter, of an auxiliary agent of copolymer of acrylic acid and of maleic anhydride or acrylic acid homopolymers.
0. 1. A process for the treatment of hard surfaces, comprising the step of treating said surfaces with an efficient cleaning or rinsing amount of a composition comprising at least one water-soluble or water dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
e####
##STR00020##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium.
0. 2. The process according to Z represents C(O)O, C(O)NH or O;
n is equal to 2 or 3;
m ranges from 0 to 2;
B represents
e####
##STR00021##
with q from 1 to 4; and
R1 to R6, which are identical or different, represent a methyl or ethyl group.
0. 3. The process according to
##STR00022##
wherein p=2 to 4.
0. 4. The process according to
##STR00023##
X− representing a chloride ion.
0. 5. The process according to
(c) at least one monomer compound with ethylenic unsaturation with a neutral charge which is copolymerizable with (a) and (b).
0. 6. The process according to
0. 7. The process according to
0. 8. The process according to
0. 9. The process according to
0. 10. The process according to
0. 11. The process according to
of 3 to 80 mol %, of the monomer (a);
of 10 to 95 mol %, of the monomer (b);
of 0 to 50 mol %, of the monomer (c).
0. 12. The process according to
0. 13. The process according to
0. 14. The process according to
##STR00024##
wherein x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%,
z having a mean value of 3 to 80%, and
with x+y+z=100%, x, y and z representing the mol % of units derived from acrylamide, acrylic acid (sodium salt) and from Diquat respectively;
##STR00025##
wherein x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00026##
wherein x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00027##
wherein x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00028##
wherein x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00029##
wherein x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%, or
##STR00030##
wherein x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%.
0. 15. The process according to
0. 16. The process according to
0. 18. The process according to
0. 22. A process for the external cleaning of motor vehicles, comprising the step of cleaning said motor vehicles with an efficient cleaning amount of a composition comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
e####
##STR00035##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O)O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0 to 30%, by weight of the formulation of at least one nonionic surfactant;
from 0 to 30%, by weight of the formulation of at least one anionic surfactant;
from 0 to 30%, by weight of an amphoteric and/or zwitterionic surfactant;
from 0 to 30%, by weight of a cationic surfactant; the minimum amount of surfactant being at least 1%;
an inorganic or organic builder; and
optionally, a hydrotropic agent, filler or pH modifier.
0. 24. A process for cleaning toilet bowls, comprising the step of cleaning said toilet bowls with a cleaning efficient amount of a composition comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I:
e####
##STR00037##
in which
R1 is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a —C(O))O— or —C(O)NH— group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2-C12, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, and optionally substituted by one or more hydroxyl or amino groups;
X, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which is copolymerizable with (a) and which is capable of being ionized in the application medium;
from 0.1 to 40% by weight with respect to the total weight of the composition of an inorganic acid cleaning agent selected from the group consisting of phosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and sodium bisulfate;
from 0.5 to 10% by weight of a surfactant;
from 0.1 to 3% by weight of a thickener; and
a preservative intended to prevent the growth of microorganisms; said composition exhibiting a pH of between 0.5 and 4.
0. 26. A process for cleaning a hard surface according to
0. 27. The process according to
0. 28. The process according to
0. 29. The process according to
0. 31. The process according to claim 30, wherein, in the general formula I:
Z represents C(O)O, C(O)NH or O;
n is equal to 2 or 3;
m ranges from 0 to 2;
B represents
##STR00040##
with q from 1 to 4; and
R1 to R6, which are identical or different, represent a methyl or ethyl group.
0. 32. The process according to claim 30, in which the monomer (a) is represented by the following formula:
##STR00041##
wherein p=2 to 4.
0. 33. The process according to claim 30, in which the monomer (a) is:
##STR00042##
X− representing a chloride ion.
0. 34. The process according to claim 30, wherein said polymer further comprising:
(c) at least one monomer compound with ethylenic unsaturation with a neutral charge which is copolymerizable with (a) and (b).
0. 35. The process according to claim 34, wherein (c) is a hydrophilic monomer compound with ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic groups, which is copolymerizable with (a) and (b).
0. 36. The process according to claim 30, wherein (b) is a C3-C8 carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids with monoethylenic unsaturation.
0. 37. The process according to claim 34, wherein the monomer (b) is acrylic acid, methacrylic acid, α-ethacrylic acid, β,β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-(methacroyl)alanine, N-(acryloyl)hydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl acrylate, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate, or phophonopropyl methacrylate.
0. 38. The process according to claim 34, wherein the monomer (c) is acrylamide, vinyl alcohol, C1-C4 alkyl ester of acrylic acid and of methacrylic acid, C1-C4 hydroxyalkyl ester of acrylic acid and of methacrylic acid, polyalkoxylated ester of acrylic acid and of methacrylic acid, ester of acrylic acid, ester of methacrylic acid and of polyethylene glycol, polypropylene glycol C1-C25 monoalkyl ether, vinyl acetate, vinylpyrrolidone or methyl vinyl ether.
0. 39. The process according to claim 30, wherein X is halogen, sulfonate, sulfate, hydrogensulfate, phosphate, phosphanate, citrate, formate or an acetate anion.
0. 40. The process according to claim 34, wherein the water-soluble or water-dispersible copolymer is obtained by copolymerization
of 3 to 80 mol %, of the monomer (a);
of 10 to 95 mol %, of the monomer (b);
of 0 to 50 mol %, of the monomer (c).
0. 41. The process according to claim 30, wherein the monomers (a) and the monomers (b) have a molar ratio by weight of the total of the monomers (a) to the total of the monomers (b) between 80/20 and 5/95.
0. 42. The process according to claim 30, wherein the copolymer has a molecular mass of at least 1000.
0. 43. The process according to claim 30, wherein the copolymer has the following formula:
##STR00043##
wherein
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%,
z having a mean value of 3 to 80%, and
with x+y+z=100%, x, y and z representing the mol % of units derived from acrylamide, acrylic acid (sodium salt) and from Diquat respectively;
##STR00044##
wherein
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00045##
wherein
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00046##
wherein
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00047##
wherein
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%,
##STR00048##
wherein
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%, or
##STR00049##
wherein
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%.
0. 44. The process according to claim 30, wherein the copolymer of formula I represents from 0.0005 to 10% by weight with respect to the total weight of said composition.
0. 45. The process according to claim 30, wherein said composition further comprises a surfactant, with a copolymer/surfactant ratio by weight of between 1/2 and 1/100.
0. 47. The process according to claim 46, wherein said composition further comprises an amine oxide as nonionic surfactant.
0. 55. A process for cleaning a hard surface according to claim 30, thereby conferring hydrophilization properties on said hard surface.
0. 56. The process according to claim 55, wherein the hydrophilization properties are “resistance to running”, “resistance to condensation”, “resistance to stains” or “resistance to marks”.
0. 57. The process according to claim 30, wherein from 0.0001 to 6 g/m2, of said water-soluble or water-dispersible copolymer are deposited on said surface.
0. 58. The process according to claim 57, wherein the surface is a glass, a ceramic, a tile, a sink, a toilet bowl, a window, a shower wall, or a motor vehicle.
0. 60. The cleaning/rinsing composition as defined by claim 59, wherein, in the general formula I:
Z is C(O)O, C(O)NH or O;
n is equal to 2 or 3;
m ranges from 0 to 2;
B is
##STR00059##
with q from 1 to 4; and
R1 to R6, which are identical or different, represent a methyl or ethyl group.
0. 61. The cleaning/rinsing composition as defined by claim 59, in which the monomer (a) is:
##STR00060##
X− representing a chloride ion.
0. 62. The cleaning/rinsing composition as defined by claim 59, said at least one water-soluble or water-dispersible copolymer further comprising:
(c) at least one monomer compound with ethylenic unsaturation with a neutral charge which is copolymerizable with (a) and (b).
0. 63. The cleaning/rinsing composition as defined by claim 59, wherein (c) is a hydrophilic monomer compound with ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic groups, which is copolymerizable with (a) and (b).
0. 64. The cleaning/rinsing composition as defined by claim 59, wherein (b) is a C3-C8 carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids with monoethylenic unsaturation.
0. 65. The cleaning/rinsing composition as defined by claim 59, wherein the monomer (b) is acrylic acid, methacrylic acid, α-ethacrylic acid, β,β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-(methacroyl)alanine, N-(acryloyl)hydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl acrylate, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate, or phosphonopropyl methacrylate.
0. 66. The cleaning/rinsing composition as defined by claim 62, wherein the monomer (c) is acrylamide, vinyl alcohol, C1-C4 alkyl ester of acrylic acid and of methacrylic acid, C1-C4 hydroxyalkyl ester of acrylic acid and of methacrylic acid, polyalkoxylated ester of acrylic acid and of methacrylic acid, ester of acrylic acid, ester of methacrylic acid and of polyethylene glycol, polypropylene glycol C1-C25 monoalkyl ether, vinyl acetate, vinylpyrrolidone or methyl vinyl ether.
0. 67. The cleaning/rinsing composition as defined by claim 59, wherein X is halogen, sulfonate, sulfate, hydrogensulfate, phosphate, phosphonate, citrate, formate or an acetate anion.
0. 68. The cleaning/rinsing composition as defined by claim 59, comprising at least one water-soluble or water-dispersible copolymer having at least one of the following formulae:
##STR00061##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%,
z having a mean value of 3 to 80%, and
with x+y+z=100%, x, y and z representing the mol % of units derived from acrylamide, acrylic acid (sodium salt) and from Diquat respectively;
##STR00062##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00063##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00064##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00065##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00066##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%; or
##STR00067##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%.
0. 70. The water-soluble or water-dispersible copolymer as defined by claim 69, wherein, in the general formula I:
Z represents C(O)O, C(O)NH or O;
n is equal to 2 or 3;
m ranges from 0 to 2;
B is
##STR00069##
with q from 1 to 4; and
R1 to R6, which are identical or different, represent a methyl or ethyl group.
0. 71. The water-soluble or water-dispersible copolymer as defined by claim 69, further comprising:
(c) at least one monomer compound with ethylenic unsaturation with a neutral charge which is copolymerizable with (a) and (b).
0. 72. The water-soluble or water-dispersible copolymer as defined by claim 71, wherein (c) is a hydrophilic monomer compound with ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic groups, which is copolymerizable with (a) and (b).
0. 73. The water-soluble or water-dispersible copolymer as defined by claim 69, wherein (b) is a C3-C8 carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids with monoethylenic unsaturation.
0. 74. The water-soluble or water-dispersible copolymer as defined by claim 69, wherein the monomer (b) is acrylic acid, methacrylic acid, α-ethacrylic acid, β,β-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-(methacroyl)alanine, N-(acryloyl)hydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl acrylate, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate, or phophonopropyl methacrylate.
0. 75. The water-soluble or water-dispersible copolymer as defined by claim 71, wherein the monomer (c) is acrylamide, vinyl alcohol, C1-C4 alkyl ester of acrylic acid and of methacrylic acid, C1-C4 hydroxyalkyl ester of acrylic acid and of methacrylic acid, polyalkoxylated ester of acrylic acid and of methacrylic acid, ester of acrylic acid, ester of methacrylic acid and of polyethylene glycol, polypropylene glycol C1-C25 monoalkyl ether, vinyl acetate, vinylpyrrolidone or methyl vinyl ether.
0. 76. The water-soluble or water-dispersible copolymer as defined by claim 69, said water-soluble or water-dispersible copolymer having one of the following formulae:
##STR00070##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%,
z having a mean value of 3 to 80%, and
with x+y+z=100%, x, y and z representing the mol % of units derived from acrylamide, acrylic acid (sodium salt) and from Diquat respectively;
##STR00071##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00072##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00073##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00074##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%;
##STR00075##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%; or
##STR00076##
wherein:
x having a mean value of 0 to 50%,
y having a mean value of 10 to 95%, and
z having a mean value of 3 to 80%.
0. 77. A hydrophilized hard surface having at least one water-soluble or water-dispersible copolymer as defined by claim 69 deposited thereon and anchored thereto.
0. 78. The cleaning/rinsing composition as defined by claim 59, wherein m is 0 or 2.
|
|||||||||||||||||||||||||||||||||||||||||||||
Examples of zwitterionic surfactants comprise aliphatic quaternary ammonium derivatives, in particular 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate.
Examples of amphoteric surfactants comprise betaines, sulfobetaines and carboxylates and sulfonates of fatty acids and of imidazole.
The following surfactants are preferred:
Additional examples of suitable surfactants are compounds generally used as surfactants denoted in the well-known texts “Surface Active Agents”, volume I, by Schwartz and Perry, and “Surface Active Agents and Detergents”, volume II, by Schwartz, Perry and Berth.
The surfactants can be present, if necessary, in a proportion of 0.005 to 60%, in particular of 0.5 to 40%, by weight, depending on the nature of the surfactant(s) and on the destination of the cleaning or rinsing composition.
Mention may be made, among the other common additives which are part of the formulation of detergent compositions, of:
In Particular for Washing in a Dishwasher
The compositions according to the invention can be diluted (in water) from 1- to 10,000-fold, preferably from 1- to 1000-fold, before use.
The cleaning composition according to the invention is applied to the surface to be treated in an amount such that it allows, after rinsing, if necessary, and after drying, a deposit of copolymer according to the invention of 0.0001 to 1 g/m2, preferably 0.001 to 0.1 g/m2, of surface to be treated.
According to a particularly advantageous form, the cleaning composition according to the invention is employed for the treatment of glass surfaces, in particular windows. This treatment can be carried out by the various known techniques. Mention may be made in particular of the techniques for cleaning windows by spraying with a jet of water using devices of Karcher® type.
The amount of polymer introduced will generally be such that, during the use of the cleaning composition, after optional dilution, the concentration is between 0.001 g/l and 2 g/l, preferably from 0.005 g/l and 0.5 g/l.
Except when otherwise indicated, the proportions are shown by weight.
The composition for cleaning windows according to the invention comprises:
The formulations for cleaning windows comprising said polymer can also comprise:
The composition of the invention is also advantageous for cleaning dishes by hand or in an automatic device. In the latter case, said copolymer can be present either in the detergent formula used in the washing cycle or in the rinsing liquid.
Detergent formulations for washing dishes in automatic dishwashers advantageously comprise from 0.1 to 5%, preferably 0.2 to 3%, by weight of water-soluble or water-dispersible copolymer with respect to the total weight of dry matter of the composition.
The detergent compositions for dishwashers also comprise at least one surfactant, preferably a nonionic surfactant, in an amount ranging from 0.2 to 10%, preferably from 0.5 to 5%, of the weight of said detergent composition, expressed as dry matter, the remainder being composed of various additives and of fillers, as already mentioned above. These formulae generally comprise 30 to 95% of a builder, which builders are chosen from silicates, phosphates or carbonates. It also comprise an oxidizing system introduced at a content of between 3 and 25%.
It has been discovered, surprisingly, that the use of a copolymer according to the invention in a composition for washing in a dishwasher protects the glass and the dishes against corrosion by the washing medium during repeated washing operations.
Formulations for rinsing dishes in an automatic dishwasher advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5%, by weight of copolymer with respect to the total weight of the composition.
They also comprise from 0.2 to 15%, preferably 0.5 to 5%, by weight with respect to the total weight of said composition of a surfactant, preferably a nonionic surfactant or a mixture of nonionic and anionic surfactant.
Mention may be made, among preferred nonionic surfactants, of surfactants of the following type: polyoxyethylenated C6-C12 alkylpbenols, polyoxyethylenated and/or polyoxypropylenated C8-C22 aliphatic alcohols, ethylene oxide/propylene oxide block copolymers, optionally polyoxyethylenated carboxamides, and the like.
They also comprise from 0 to 40%, preferably from 3 to 30%, by weight with respect to the total weight of the composition of a calcium-sequestering organic acid, preferably citric acid.
They can also comprise an auxiliary agent of copolymer of acrylic acid and of maleic anhydride or acrylic acid homopolymers type, in a proportion of 0 to 15%, preferably 0 to 10%, by weight with respect to the total weight of said composition.
Another subject-matter of the invention is a cleaning composition for washing up dishes by hand.
Preferred detergent formulations of this type comprise from 0.1 to 5 parts by weight of copolymer of the invention per 100 parts by weight of said composition and comprise from 3 to 50, preferably from 10 to 40, parts by weight of at least one surfactant, preferably an anionic surfactant, chosen in particular from sulfates of saturated C5-C24, preferably C10-C16, aliphatic alcohols, optionally condensed with approximately 0.5 to 30, preferably 0.5 to 5, particularly 0.5 to 3, mol of ethylene oxide, in acid form or in the form of a salt, in particular an alkali metal (sodium) or alkaline earth metal (calcium, magnesium) salt, and the like.
The present invention is aimed more particularly at lathering liquid aqueous detergent formulations for washing up dishes by hand.
Said formulations can also comprise other additives, in particular other surfactants, such as:
Another subject-matter of the invention is a cleaning composition for the external cleaning, in particular of the bodywork, of motor vehicles.
In this case also, the copolymer according to the invention can be present either in a detergent formula used for the washing operation or in a rinsing product.
The cleaning composition for motor vehicles advantageously comprises from 0.05 to 5% by weight of copolymer according to the invention with respect to the total weight of said composition, as well as:
The minimum amount of surfactant present in of type of composition can be at least 1% of the formulation).
The composition of the invention is also particularly suitable for cleaning hard surfaces other than those described above, in particular ceramics (tiling, baths, sinks, and the like).
In this case, the cleaning formulation advantageously comprises from 0.02 to 5% by weight of copolymer with respect to the total weight of said composition, as well as at least one surfactant.
Preference is given, as surfactants, to nonionic surfactants, in particular the compounds produced by condensation of alkylene oxide groups as described above, which are of hydrophilic nature, with a hydrophobic organic compound, which can be of aliphatic or alkylaromatic nature.
The length of the hydrophilic chain or of the polyoxyalkylene radical condensed with any hydrophobic group can be readily adjusted in order to obtain a water-soluble compound which has the desired degree of hydrophilic/hydrophobic balance (HBL).
The amount of nonionic surfactants in the composition of the invention is generally from 0 to 30% by weight, preferably from 0 to 20% by weight.
An anionic surfactant can optionally be present in an amount of 0 to 30%, advantageously 0 to 20%, by weight.
It is also possible, but not obligatory, to add amphoteric, cationic or zwitterionic detergents to the composition of the present invention for cleaning hard surfaces.
The total amount of surfactants employed in this type of composition is generally between 1.5 and 50%, preferably between 5 and 30%, by weight and more particularly between 10 and 20% by weight, with respect to the total weight of the composition.
The composition for cleaning hard surfaces of the present invention can also comprise other minor ingredients which are cleaning additives.
For example, the composition can comprise organic or inorganic detergency adjuvants (builders) as mentioned above.
In general, the detergency adjuvant is employed in an amount of between 0.1 and 25% by weight with respect to the total weight of the composition.
Another optional ingredient in the compositions for cleaning hard surfaces of the invention is a foam modifier, which can be employed in compositions which have a tendency to produce an excess of lather during their use. An example of these materials are soaps. Soaps are fatty acid salts and comprise alkali metal, in particular the sodium or potassium salts, ammonium and alkanolammonium soaps of higher fatty acids comprising approximately from 8 to 24 carbon atoms and preferably from approximately 10 to approximately 20 carbon atoms. Particularly useful are the mono-, di- and triethanolamine salts, the sodium and potassium salts or of mixtures of fatty acids derived from coconut oil and from ground walnut oil. The amount of soap can be at least 0.005% by weight, preferably from 0.5% to 2% by weight, with respect to the total weight of the composition. Additional examples of foam modifiers are organic solvents, hydrophobic silica, silicone oil and hydrocarbons.
In addition to the ingredients mentioned above, the compositions for cleaning hard surfaces of the present invention can also comprise other optional ingredients, such as pH modifiers, dyes, optical brighteners, agents for suspending material from dirty marks, detergent enzymes, compatible bleaching agents, agents for controlling gel formation, freezing-thawing stabilizers, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents, fragrances, opacifiers or pearlescent agents.
The composition of the invention can also be employed by cleaning toilet bowls.
One composition which is particularly suitable for this purpose comprises from 0.05 to 5% by weight of copolymer according to the invention.
The composition for cleaning toilet bowls according to the invention also comprises an acid cleaning agent which can comprise an inorganic acid, such as phosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid or chromic acid and mixtures thereof, or an organic acid, in particular acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and tartaric acid and mixtures thereof, acid salts, such as sodium bisulfate, and mixtures thereof.
The amount of acid ingredients is preferably between 0.1 to approximately 40% and preferably between 0.5 and approximately 15% by weight, with respect to the total weight of the composition.
The preferred amount depends on the type of acid cleaning agent used: for example, with sulfamic acid. It is between approximately 0.2 and approximately 1%, with hydrochloric acid between approximately 1 and approximately 5%, with citric acid between approximately 2 and approximately 10%, with formic acid between approximately 5 and approximately 15% and with phosphoric acid between approximately 5 and approximately 30%, by weight.
The amount of acid agent is generally such that the final pH of the composition is from approximately 0.5 to about 4, preferably 1 to 3.
The composition for cleaning toilet bowls also comprises from 0.5 to 10% by weight of a surfactant, so as to contribute towards removing dirty marks or so as to give foaming or wetting characteristics, or in order to increase the cleaning efficacy of the composition. The surfactant is preferably an anionic or nonionic surfactant.
Cationic surfactants can also be added to the composition for cleaning toilet bowls according to the invention in order to provide germicidal properties. A person skilled in the art will see that amphoteric surfactants can also be used. Mixtures of various surfactants can be employed, if so desired.
The composition for cleaning toilet bowls according to the invention can also comprise a thickener of gum type, in particular a xanthan gum, introduced at a concentration of 0.1 to 3%, as well as one or more of the following minor ingredients: a preservative intended to prevent the growth of microorganisms in the product, a dye, a fragrance and/or an abrasive.
The composition according to the invention is also suitable for rinsing shower walls.
The aqueous compositions for rinsing shower walls comprise from 0.02% to 5% by weight, advantageously from 0.05 to 1%, of the copolymer of the invention.
The other main active components of the aqueous compositions for rinsing showers of the present invention are at least one surfactant, present in an amount ranging from 0.5 to 5% by weight, and optionally a metal-chelating agent, present in an amount ranging from 0.01 to 5% by weight.
The preferred metal-chelating agents are ethylenediaminetetraacetic acid (EDTA) and its analogues.
The aqueous rinsing compositions for showers advantageously comprise water with, optionally, a major proportion of at least one lower alcohol and a minor proportion of additives (between approximately 0.1 and approximately 5% by weight, more advantageously between approximately 0.5% and approximately 3% by weight and even more preferably between approximately 1% and approximately 2% by weight).
Certain surfactants which can be used in this type of application are disclosed in U.S. Pat. Nos. 5,536,452 and 5,587,022, the content of which is incorporated in the present description by way of reference.
Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan monooleates and polyethoxylated castor oil. Specific examples of such surfactants are the condensation products of 20 mol of ethylene oxide and of sorbitan monooleate (sold by Rhodia Inc. under the name Alkamuls PSMO-20® with an HLB of 15.0) and of 30 or 40 mol of ethylene oxide and of castor oil (sold by Rhodia Inc. under the name Alkamuls EL-620® (HLB of 12.0) and EL-719® (HLB of 13.6), respectively). The degree of ethoxylation is preferably sufficient to obtain a surfactant with an HLB of greater than 13. Other surfactants, such as alkylpolyglucosides, are also well suited to these compositions.
The composition according to the invention can also be employed for cleanings glass-ceramic plates.
Advantageously, the formulations for cleanings glass-ceramic plates of the invention comprise:
Another subject-matter of the invention is an aqueous biocidal cleaning composition for the treatment of hard surfaces comprising:
The biocide is preferably present in the aqueous biocidal cleaning composition at a concentration of the order of 0.1% to 20% by weight, preferably of the order of 0.5% to 5% by weight.
The copolymer according to the invention can be present in the aqueous biocidal cleaning composition at a concentration of the order of 0.01% to 20% by weight, preferably of the order of 0.05 to 5% by weight. Said copolymer does not in itself generally have a biocidal activity.
Mention may be made, among biocidal agents which may be present, of:
Mention may in particular be made, among possible surfactants, of:
These can be present in a proportion of 1 to 25%, preferably of the order of 2 to 10%, by weight of the aqueous biocidal cleaning composition.
According to the invention, in addition to the biocide and the copolymer according to the invention, which are the main constituents of the aqueous biocidal system of the invention, it is advantageously possible for other constituents to be present, such as chelating agents (for example aminocarboxylates (ethylenediaminetetraacetates, nitrilotriacetates or N,N-bis(carboxymethyl)glutamates or citrates), alcohols (ethanol, isopropanol or glycols), detergency adjuvants (phosphates or silicates), dyes, fragrances, and the like.
Said biocidal cleaning composition can be employed for disinfecting floors, walls, work surfaces, equipment, furniture, instruments, and the like in industry, the food processing field, the domestic sphere (kitchens, bathrooms, and the like) and communally.
Mention may be made, among the surfaces which can be treated, of those made of ceramic, glass, poly(vinyl chloride), formica or other hard organic polymer, stainless steel, aluminium, wood, and the like.
The cleaning and disinfecting operation consists in applying said biocidal cleaning composition, optionally diluted from 1- to 1000-fold, preferably from 1- to 100-fold, to the hard surface to be treated.
The amount of biocidal system which can be favorably employed is that corresponding to a deposition of 0.01 to 10 g, preferably of 0.1 to 1 g, of biocide per m2 of surface and to a deposition of 0.001 to 2 g, preferably of 0.01 to 0.5 g, of copolymer of the invention per m2 of surface.
Mention may be made, among the microorganisms whose proliferation can be controlled by employing the biocidal cleaning composition of the invention, of
The biocidal system of the invention is very particularly effective against the Gram negative microorganism Pseudomonas aeroginosa, the Gram positive microorganism Staphylococcus aureus or the fungus Aspergillus niger.
Another subject-matter of the invention is the use of a water-soluble or water-dispersible copolymer as defined above in the cleaning or rinsing of a hard surface, in particular in order to confer hydrophilization properties on a hard surface.
The hydrophilization properties conferred by the copolymer of the invention are in particular properties of “resistance to running”, “resistance to condensation”, “resistance to stains” and/or “resistance to marks”.
A subject-matter of the invention is likewise a process for improving the hydrophilicity of a hard surface by treating said surface using a cleaning composition comprising at least one copolymer according to the invention.
Another subject-matter of the invention is the use of a copolymer as defined above for decreasing the rate of drying of a hard surface to which the copolymer is applied.
Another subject-matter of the invention is the use, in a detergent composition for washing dishes in an automatic dishwasher, of a copolymer according to the invention as agent for eliminating or decreasing the corrosion of the glass and of the designs present on the glass or the dishes during repeated washing operations.
Finally, a subject-matter of the invention is a process for protecting the glass, dishes and designs by washing the glass and dishes in an automatic dishwasher using a cleaning composition comprising at least one copolymer according to the invention.
The examples below are intended to illustrate the invention.
Preparation of the copolymers according to the invention of formula:
##STR00016##
Viscosity of
the solution
x
y
z
in cps
Reference
(mol %)
(mol %)
(mol %)
dry matter %
pH
Polymer 1
20
40
40
29,500
cps
2.2 to 10%
20.5%
of dry matter
Polymer 2
0
10
10
840
cps
1.7 to 20.5%
20.5%
of dry matter
Polymer 3
0
20
10
8700
cps
1.6 to 20.0%
20.0%
of dry matter
Polymer 4
0
40
10
37,250
cps
3.5 to 37%
17%
of dry matter
Polymer 5
20
40
20
The following ingredients are added to a 1 liter reactor:
Polymer
Polymer
Polymer
Polymer
Polymer
1
2
3
4
5
Demineralized water
633
707
632.5
737
633
52% Acrylamide
29.3
0
0
0
29.3
Acrylic acid
30.9
33.5
55.5
89.1
30.9
65% Diquat monomer
236.7
256.2
212.3
170.6
118.35
Versene 100
0.2
0.2
0.2
0.2
0.2
(EDTA from Dow
Chemical)
The mixture obtained is heated gently to 75° C. at a pH of approximately 2.6 under a gentle nitrogen flow. After 30 minutes, when the temperature reaches 75° C., an initiator solution based on sodium persulfate (0.1 g in 1.0 g of demineralized water) is added to the reactor in a single step. Cooling is necessary in order to keep the temperature at 75° C. and the mixture becomes viscous after approximately 45 minutes. Two additional portions of initiating solution based on persulfate are added after reacting for one and two hours respectively. The reaction mixture is subsequently heated to a temperature of 85° C. and maintained at this temperature for an additional two hours before being cooled to 25° C. The viscosity of the resulting solution of Polymer 1 is approximately 29,500 cps with a total content of solids of approximately 20.5%. The pH of the 10% solution is approximately 2.2. The residual acrylamide is less than 0.1% by weight.
Preparation of the polymer of formula:
##STR00017##
with x=20, y=40, z=40 (Polymer 6).
The process is the same as that of Examples 1 to 5, apart from the fact that the acrylic acid is replaced with N-(1-sulfo-2-isobutyl)acrylamide.
The compositions of three cleaning formulations used for cleaning windows are recorded in the table below:
Formulations (by weight)
Example
Example
Example
Components
7
8
9
Isopropyl alcohol
7
7
15
Ethoxylated (7 EO) fatty (C12) alcohol
0
0
3
Sodium dodecylbenzenesulfonate
0.5
0.5
0
Ammonium hydroxide
0.3
0.3
0.3
Dipropylene glycol monomethyl ether
0.25
0.25
0.5
Copolymer No. 1 described in the
0.05
0.5
1
invention
Water
q.s.
q.s.
q.s.
for 100
for 100
for 100
The formulations of Examples 7 to 9 are used as is by spraying at the surface of the windows to be cleaned (6 to 8 sprayings, i.e. 3 to 5 g of formulation per m2 of surface.
Cleaning formulations for cleaning hard surfaces are given in the table below.
Formulations (by weight)
Example
Example
Components
10
11
Ethoxylated (7 EO) fatty (C12) alcohol
6
8
Sodium (C12)alkanesulfonate
3
2
Sodium hydroxide
such that
such that
pH = 10.4
pH = 10.4
Copolymer No. 2 described in the invention
1
0.5
Water
q.s.
q.s.
for 100
for 100
The formulations of Examples 10 and 11 are diluted before use in a proportion of 10 g of formulation in 1 liter of water.
A base detergent formula is prepared from the compounds given in the table below:
Compounds
weight %
Granulated sodium tripolyphosphate
45
Sodium carbonate
4
Granulated sodium disilicate
26
Sodium perborate monohydrate
7
TAED
2
Sodium sulfate
16
Three copolymers according to the invention (Copolymer No. 2, 3 and 4 above) or two other polymers (Copolymers No. 7 and No. 8 below), by way of comparison, are added to these compositions.
##STR00018##
##STR00019##
This simplified glass corrosion test reproduces certain washing conditions of dishwashers, in particular washing, rinsing and drying cycles.
Nature of the Glass
The glass used is composed of microscope slides with dimensions of 2.5×7.5 cm cleaned beforehand with ethanol, the composition of which slides, given below, is similar to that of table glasses:
200 ml of an aqueous washing solution comprising 6 g/l of product to be tested are introduced into a container. The container is introduced into and held in an oven at 65° C. for 1 hour.
A glass slide is completely immersed in this container in the inclined position. The container is then closed and then placed in an oven at 65° C. The slide is taken out of the container after 72 hours, rinsed twice on each face with deionized water using a wash bottle, touched lightly with the finger in order to remove the film which may have been formed and dried in the surrounding air for 2 hours.
At the end of the test, the slide is weighed after cooling to room temperature and the relative mass variation (as %×1000) is calculated. The test is repeated another time for confirmation of the results.
The corrosion visible to the eye is evaluated with respect to a reference slide which has not been subjected to the test.
The evaluation of corrosion is carried out visually by nine trained people with a scale ranging from 1 to 5 points, the glasses in the fresh state being taken as reference.
The points are distributed as follows:
Finally, the pH of the solutions is measured at room temperature before the immersion of the slide and at the end of the experiment.
This simplified test makes it possible to rapidly reproduce the various types of glass corrosion obtained by the repeated washing in a dishwasher, the sequence of the washing-rinsing-drying cycles, under concentration and temperature conditions similar to those used in dishwashers.
The results of the tests are given in the table below:
Example
Example
Example
Example
Examplc
Example
Example
12
13
14
15
16
17
Composition
Base
Base
Base
Base
Base
Base
formula: 98%
formula: 98%
formula: 98%
formula: 98%
formula: 98%
formula: 98%
Sodium
Polymer 7:
Polymer 7:
Polymer 2:
Polymer 3:
Polymer 4:
sulfate: 2%
2%
2%
2%
2%
2%
Final pH
10.33
10.35
10.35
10.32
10.33
10.35
Loss in mass
213
235
210
57
60
90
10−3 %
Visual assessment
4.5
4.5
4.5
1
1
15
Examples 12, 13 and 14 are given by way of comparison.
Examples 15, 16 and 17 show that the polymers of the invention introduce efficient protection of the glass against corrosion, which is not obtained with Examples 12, 13 and 14.
Formulations for rinsing dishes in an
automatic dishwasher
Example
Example
Example
Formulation
15
16
17
C13-3PO-7EO Nonionic surfactant
12
12
12
(EO/PO linear fatty alcohol)
Citric acid
3
3
3
Polymer
Polymer 3
Polymer 3
Polymer 5
(2%)
(2%)
(256)
Water
q.s.
q.s.
q.s.
for to
for to
for to
100
100
100
Formulation for washing dishes by hand
Example
Example
Formulation
18
19
Sodium (C14)alkylsulfonate
24
12
Ethoxylated C12 fatty alcohol - 1.5 EO
5
3
Ethoxylated C10 fatty alcohol - 7 EO
4
4
Polymer
Polymer 4
Polymer 6
(2%)
(2%)
Water
q.s.
q.s.
for to 100
for to 100
Detergent formulations for cleaning hard
surfaces (tilings, sinks, baths)
Example
Example
Formulation
20
21
Sodium (C12)alkylsulfonate
24
12
Ethoxylated C12 fatty alcohol - 6 EO
5
3
Ethanol
4
4
Polymer
Polymer 3
Polymer 5
(2%)
(2%)
Water
q.s.
q.s.
for to 100
for to 100
Detergent formulae for an automatic
dishwasher
Example
Example
Example
Example
Formulation example
22
23
24
25
Sodium tripolyphosphate
0
0
60
35
Sodium carbonate
35
30
0
20
Sodium disilicate
20
15
23
10
Sodium citrate
20
15
0
0
Sodium sulfate
0
20
0
19
Poly(sodium acrylate)
6
5
0
0
CP5 from BASF
Plurafac LF 403
2
1
2
2
Bleaching system
12
10
10
10
(perborate.1H2O + TAED**)
Other additives
3
3
3
3
(including benzatriazole,
enzymes, fragrance)
Polymer 3
2
1
2
1
Biocidal formulations
Example
Example
Example
26
27
28
Nonionic surfactant (C10 alcohol
5%
5%
5%
with 6 ethylene oxide units
Rhodaquat RP50 biocide
1.5%
1.5%
1.5%
% of active material
Polymer
Polymer 1
Polymer 3
Polymer 4
% of active material
0.15 or 0.2%
0.5%
0.2%
Water
The biocide Rhodaquat RP50 is an aqueous solution of (C12-C14 alkyl)benzyldimethylammonium chloride with an active material content of 50% sold by Rbodia.
The Formulation of Example 26 is Tested on a White Ceramic Tile According to the Following Protocol:
1. 3 g of dilute aqueous biocidal solution are added to the surface of the ceramic tile (5 cm×5 cm) sterilized beforehand by cleaning with isopropyl alcohol. The tile is dried at 45° C. in an oven.
2. The surface of the tile is positioned vertically and is sprayed with one gram of water using a hand sprayer. This corresponds to a washing operation without mechanical action. Between 0 and 15 washing operations are thus carried out before drying at 45° C.
3. 0.25 ml of an aqueous medium comprising approximately 108 CFU/ml of Gram negative bacterium, Pseudomonas aeruginosa, is added and is spread over the pretreated hard surface.
4. The tile is left at room temperature for 3 hours, in order to allow the biocide to migrate from the surface of the polymer and to kill the surface bacteria.
5. The tile is dried at 37° C. for at least 30 minutes.
6. The surviving microorganisms are recovered by using a sterile cottonwool pad moistened beforehand with a neutralizing solution. The entire surface is carefully cleaned by wiping 4 times in all directions.
7. The pad is introduced into 9 ml of neutralizing medium; the volume is adjusted to 10 ml with water. The bacterial suspension is transferred onto Nutrient Agar in Petri dishes by successive dilutions by a factor 10.
8. The dishes are incubated at 37° C. for 48 hours and the surviving microorganisms are counted.
The results of the above test appear in the following table.
Log10 for
Log10 for
reduction after
reduction after
0 washing
15 washing
Example
Polymer
operation
operation
26
Polymer 1: 0.15%
6
6
Without polymer
6
0
Without biocide and
0
0
0.15% of Polymer 1
The results show:
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