Copolymer having at least one alkoxy-or hydroxy-polyalkylene glycol grafted function, and use thereof
The present invention relates to the technical mineral matter suspension sector, and, before and/or after drying, their applications in the fields of paper, paint and, after drying, plastics. It also relates to the use of a copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as agent whose role is to enhance the gloss of the final product and, in particular, the gloss of the sheet of paper, irrespective of the viewing angle.
1. A gloss activator comprising a water-soluble and weakly ionic copolymer having least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer.
2. The gloss activator of claim 1 , wherein said copolymer comprises at least one monomer of formula (I):
where
m and p represent a number of alkylene oxide units less than or equal to 150,
n represents a number of ethylene oxide units less than or equal to 150,
q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150,
R 1 represents hydrogen or the methyl or ethyl radical,
R 2 represents hydrogen or the methyl or ethyl radical,
R represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms,
and wherein said copolymer has an intrinsic viscosity less than or equal to 100 ml/g determined in accordance with the method known as the intrinsic viscosity method.
3. The gloss activator according to claim 2 , wherein q in formula (I) represents an integer such that 15≦(m+n+p)q≦120.
4. The gloss activator according to claim 2 , wherein R′ in formula (I) represents a hydrocarbon radical having from 1 to 12 carbon atoms.
5. The gloss activator according to claim 2 , wherein R′ in formula (I) represents a hydrocarbon radical having from 1 to 4 carbon atoms.
6. The gloss activator according to claim 1 , characterized in that said copolymer comprises:
a) at least one anionic monomer with a carboxyl or dicarboxyl or sulfonic or phosphoric or phosphonic function or a mixture thereof,
b) at least one non-ionic monomer, the non-ionic monomer comprising at least one monomer of formula (I):
where
m and p represent a number of alkylene oxide units less than or equal to 150,
n represents a number of ethylene oxide units less than or equal to 150,
q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150,
R 1 represents hydrogen or the methyl or ethyl radical,
R 2 represents hydrogen or the methyl or ethyl radical,
R represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides, and
R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or a mixture of several monomers of formula (I),
c) at least one monomer of the acrylamide or methacrylamide type or their derivatives such as N-[3-(dimethylamino)propyl]acrylamide or N-[3-(dimethylamino)propyl]methacrylamide, and their mixtures, or at least one non water-soluble monomer such as the alkyl acrylates or methacrylates, unsaturated esters such as N-[2-(dimethylamino)ethyl]methacrylate, or N-[2-(dimethylamino)ethyl]acrylate, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one cationic monomer or quaternary ammonium such as [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride or sulphate, [2-(acryloyloxy)ethyl]trimethyl ammonium chloride or sulphate, [3-(acrylamido)propyl]trimethyl animonium chloride or sulphate, dimethyl diallyl ammonium chloride or sulphate, [3-(methacrylamido)propyl]trimethyl ammonium chloride or sulphate, or at least one organofluorinated or organosilylated monomer, or a mixture of several of these monomers,
d) at least one monomer having at least two ethylenic insaturations referred to as a crosslinking monomer,
the total of the proportions of components a), b), c) and d) being equal to 100%,
and wherein said copolymer has an intrinsic viscosity less than or equal to 100 ml/g determined in accordance with the method known as the intrinsic viscosity method.
7. The gloss activator according to claim 6 , wherein q in formula (I) represents an integer such that 15≦(m+n+p)q≦120.
8. The gloss activator according to claim 6 , wherein R′ in formula (I) represents a hydrocarbon radical having from 1 to 12 carbon atoms.
9. The gloss activator according to claim 6 , wherein R′ in formula (I) represents a hydrocarbon radical having from 1 to 4 carbon atoms.
10. The gloss activator according to claim 1 , wherein the organosilylated monomer is selected from among the molecules of formulae (IIa) or (IIb),
with formula (IIa):
where
m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150
n1 and n2 represent a number of ethylene oxide units less than or equal to 150
q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150,
r represents a number such that 1≦r≦200,
R 3 represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R 4 , R 5 , R 10 and R 11 represent hydrogen or the methyl or ethyl radical
R 6 , R 7 , R 8 and R 9 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof
R 12 represents a hydrocarbon radical having from 1 to 40 carbon atoms,
A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
with formula (IIb)
R-A-Si(OB) 3
where
R represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms,
B represents a hydrocarbon radical having from 1 to 4 carbon atoms,
or a mixture of several of said monomers,
and in that the crosslinking monomer is selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis- acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers prepared from polyols such as pentaerythritol, sorbitol, sucrose, or selected from among the molecules of formula (III):
where
m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150
n3 and n4 represent a number of ethylene oxide units less than or equal to 150
q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150,
r′ represents a number such that 1≦r′≦200,
R 13 represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R 14 , R 15 , R 20 and R 21 represent hydrogen or the methyl or ethyl radical
R 16 , R 17 , R 18 and R 19 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof
D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
or a mixture of several of said monomers.
11. The gloss activator of claim 1 , wherein the copolymer comprises, by weight:
a) from 2% to 95% of at least one ethylenically unsaturated anionic monomer having a monocarboxyl function selected from among the ethylenically unsaturated monomers having a monocarboxyl function such as acrylic or methacrylic acid or hemiesters of diacids such as C 1 to C 4 monoesters of maleic or itaconic acid, or mixtures thereof, or having a dicarboxyl function selected from among the ethylenically unsaturated monomers having a dicarboxyl function such as crotonic, isocrotonic, cinnamic, itaconic, maleic acid, or anhydrides of carboxyl acids, such as maleic anhydride or having a sulfonic function selected from among the ethylenically unsaturated monomers having a sulfonic function such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinylsulfonic acid and styrenesulfonic acid or having a phosphoric function selected from among the ethylenically unsaturated monomers having a phosphoric function such as vinylphosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and their ethoxylates or having a phosphonic function selected from among the ethylenically unsaturated monomers having a phosphonic function such as vinylphosphonic acid, or mixtures thereof,
a) from 2 to 95% of at least one non-ionic ethylenically unsaturated monomer of formula (I):
where
m and p represent a number of alkylene oxide units less than or equal to 150,
n represents a number of ethylene oxide units less than or equal to 150,
q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150,
R 1 represents hydrogen or the methyl or ethyl radical,
R 2 represents hydrogen or the methyl or ethyl radical,
R represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides, and
R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms,
or a mixture of several monomers of formula (I),
c) from 0% to 50% of at least one monomer of the acrylamide or methacrylamide type or their derivatives such as N-[3-(dimethylamino)propyl]acrylamide or N-[3-(dimethylamino)propyl]methacrylamide, and their mixtures, or at least one non water-soluble monomer such as the alkyl acrylates or methacrylates, unsaturated esters such as N-[2-(dimethylamino)ethyl]methacrylate, or N-[2-(dimethylamino)ethyl]acrylate, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one cationic monomer or quaternary ammonium such as [2-(methacryloyloxy) ethyl]trimethyl ammonium chloride or sulphate, [2-(acryloyloxy)ethyl]trimethyl ammonium chloride or sulphate, [3-(acrylamido)propyl]trimethyl ammonium chloride or sulphate, dimethyl diallyl ammonium chloride or sulphate, [3-(methacrylamido)propyl]trimethyl ammonium chloride or sulphate, or at least one organofluorinated or at least one organosilylated monomer, selected preferably from among molecules of formulae (IIa) or (IIb),
with formula (IIa):
where
m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150
n1 and n2 represent a number of ethylene oxide units less than or equal to 150
q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150,
r represents a number such that 1≦r≦200,
R 3 represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R 4 , R 5 , R 10 and R 11 represent hydrogen or the methyl or ethyl radical
R 6 , R 7 , R 8 and R 9 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof
R 12 represents a hydrocarbon radical having from 1 to 40 carbon atoms,
A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
with formula (IIb)
R-A-Si(OB) 3
where
R represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms,
B represents a hydrocarbon radical having from 1 to 4 carbon atoms,
or a mixture of several of said monomers,
d) from 0% to 3% of at least one crosslinking monomer selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers prepared from polyols such as pentaerythritol, sorbitol, sucrose, or selected from the molecules of formula (III):
where
m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150
n3 and n4 represent a number of ethylene oxide units less than or equal to 150
q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150,
r′ represents a number such that 1≦r′≦200
R 13 represents a radical containing a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R 14 , R 15 , R 20 and R 21 represent hydrogen or the methyl or ethyl radical
R 16 , R 17 , R 18 and R 19 represent straight or branched alkyl, aryl, alkylaryl or arylatkyl groups having from 1 to 20 carbon atoms, or a mixture thereof
D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
or a mixture of several of said monomers,
the total of the proportions of components a), b), c) and d) being equal to 100%, and wherein the copolymer has intrinsic viscosity less than or equal to 100 ml/g determined in accordance with the method known as the intrinsic viscosity method.
12. The gloss activator according to claim 11 , wherein said copolymer comprises from 5% to 90% of component a).
13. The gloss activator according to claim 11 , wherein said copolymer comprises from 5% to 90% of component b).
14. The gloss activator according to claim 11 , wherein q in formula (I) represents an integer such that 15≦(m+n+p)q≦120.
15. The gloss activator according to claim 11 , wherein R′ in formula (I) represent a hydrocarbon radical having from 1 to 12 carbon atoms.
16. The gloss activator according to claim 11 , wherein R′ in formula (I) represent a hydrocarbon radical having from 1 to 4 carbon atoms.
17. The gloss activator according to claim 1 , characterized in that said copolymer is in its acid form or fully or partially neutralized by one or more neutralizing agents having a monovalent neutralizing function or a polyvalent neutralizing function such as, for the monovalent function, those selected from among the group consisting of the alkaline cations, in particular sodium, potassium, lithium, ammonium or the primary, secondary or tertiary aliphatic and/or cyclic amines such as stearylamine, the ethanolamines (mono-, di-, triethanolamine), mono and diethylamine, cyclohexylamine, methylcyclohexylamine, aminomethylpropanol, morpholine or, for the polyvalent function, those selected from among the group consisting of alkaline earth divalent cations, in particular magnesium and calcium, or zinc, and of the trivalent cations, including in particular aluminium, or of certain cations of higher valency.
18. The gloss activator of claim 1 , wherein said copolymer has an intrinsic viscosity less than or equal to 100 ml/g determined in accordance with the method known as the intrinsic viscosity method.
19. A method for dispersing an aqueous suspension of mineral matter comprising the step of dispersing the mineral matter in the presence of the gloss activator according to claim 1 .
20. The method according to claim 19 , wherein said copolymer comprises 0.05% to 5% by dry weight with respect to the dry weight of the fillers and/or pigments.
21. The method according to claim 19 , wherein said copolymer comprises 0.1% to 2.5% by dry weight with respect to the dry weight of the fillers and/or pigments.
22. The method according to claim 19 , characterized in that the mineral matter is selected from among calcium carbonate, dolomites, kaolin, calcine kaolin, talc, gypsum, titanium oxide, satin white or aluminium trihydroxide, mica and the mixture of these fillers, such as talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminium trihydroxide, or mixtures with synthetic or natural fibres or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures.
23. The method according to claim 19 , characterized in that the mineral matter is calcium carbonate selected from marble, calcite, chalk or their mixtures.
24. An aqueous suspension of mineral matter comprising the gloss activator according to claim 1 .
25. The aqueous suspension of mineral matter according to claim 24 , characterized in that it contains from 0.05% to 5% of said copolymer by dry weight with respect to the dry weight of mineral matter.
26. The aqueous suspension of mineral matter according to claim 24 , characterized in that it contains from 0.1% to 2.5% of said copolymer by dry weight with respect to the dry weight of mineral matter.
27. The aqueous suspension of mineral matter according to claim 24 , characterized in that the mineral matter is selected from among calcium carbonate, dolomites, kaolin, calcine kaolin, talc, gypsum, titanium oxide, satin white or aluminium trihydroxide, mica and the mixture of these fillers, such as talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminium trihydroxide, or mixtures with synthetic or natural fibres or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures.
28. The aqueous suspension of mineral matter according to claim 24 , characterized in that the mineral matter is calcium carbonate selected from marble, calcite, chalk or their mixtures.
29. A method for grinding an aqueous suspension of mineral matter comprising the step of grinding the aqueous suspension of mineral matter in the presence of the gloss activator according to claim 1 .
30. The method according to claim 29 , characterized in that it contains from 0.05% to 5% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments.
31. The method according to claim 29 , characterized in that it contains from 0.1% to 2.5% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments.
32. The method according to claim 29 , characterized in that the mineral matter is selected from among calcium carbonate, dolomites, kaolin, calcine kaolin, talc, gypsum, titanium oxide, satin white or aluminium trihydroxide, mica and the mixture of these fillers, such as talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminium trihydroxide, or mixtures with synthetic or natural fibres or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures.
33. The aqueous suspension of mineral matter according to claim 29 , characterized in that the mineral matter is calcium carbonate selected from marble, calcite, chalk or their mixtures.
34. The aqueous suspension according to claim 29 , wherein the mineral matter is ground mineral matter.
35. Paper comprising a pigment prepared from the aqueous suspension of mineral matter according to claim 24 , wherein the pigment is included in the coating or surface treatment of the paper.
36. Paint comprising a pigment prepared from the aqueous suspension of mineral matter according to claim 24 .
37. Plastic comprising a pigment prepared from the aqueous suspension of mineral matter according to claim 24 .
38. A coating colour prepared from the gloss activator according to claim 1 .
39. The coating colour according to claim 38 , characterized in that it contains 0.05% to 5% of said copolymer by dry weight with respect to the dry weight of the mineral matter.
40. The coating colour according to claim 38 , characterized in that it contains 0.1% to 2.5% of said copolymer by dry weight with respect to the dry weight of mineral matter.
41. Paper comprising the gloss activator of claim 1 .
42. Paint comprising the gloss activator of claim 1 .
43. Plastic comprising the gloss activator of claim 1 .