JP2000313846A - Modifier for aqueous coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modifier which increases the viscosity of and improves the thixotropic properties and water retention of an aqueous coating agent by incorporating a copolymer prepared from methacrylic acid or its salt, specific monomers and an ethylenically unsaturated monomer and having a specified viscosity into the same. SOLUTION: This modifier for an aqueous coating agent contains a copolymer which is prepared by the emulsion copolymerization of (A) 25-90 pts.wt. methacrylic acid (salt), (B) 1-40 pts.wt. monomer of formula I, (C) 1-40 pts.wt. monomer of formula II, (D) 1-30 pts.wt. monomer of formula III, (E) 1-60 pts.wt. monomer of formula IV and (F) 0-18 pts.wt. ethylenically unsaturated monomer copolymerizable with these monomers in a wt. ratio of monomer F/monomer E of 0.3 or lower and which, when completely neutralized with sodium hydroxide, gives a 2 wt.% aqueous solution having a viscosity at 25 deg.C of 50-20,000 mPa.s. In the formulas, R1, R5, R9 and R13 are each H or CH3; R2, R3, R6, R7, R10 and R11 are each H, CH3 or C2H5; R4 is an 8-20C alkyl; R8 is a 6-30C aromatic residue; R12 is a 1-4C alkyl; R14 is CH3 or C2H5; (m) and (p) are each 3-100; and (n) is 3-50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based coating agent modifier mainly comprising a pigment, a filler and / or a binder. More specifically, if it is used for the production of coated paper, it can be used as a water retention agent for paper coating paints, water-based emulsions or water-based emulsion paints, which can impart high operability, high physical properties of coated paper, and printability. The present invention relates to a water-based emulsion or a modifier for a water-based coating agent that can be used as a thickener for a water-based emulsion paint capable of imparting high viscosity, thixotropy, water retention and high film properties.

[0002]

2. Description of the Related Art Among water-based coating agent modifiers, sodium alginate, carboxymethylcellulose, methylcellulose, ethylcellulose, polyvinyl alcohol and the like are known as water retention agents and thickeners. Further, an alkali-thickened copolymer having a specific composition and a polyol compound (JP-A-2-53996), a specific anion-modified polyvinyl alcohol, or a specific water-soluble polyurethane resin (JP-A-6-57695) have been proposed. ing.

[0003]

However, with these conventional additives, productivity improvement, quality improvement, cost reduction,
It was not satisfactory for energy saving and other improvements. In the production of coated paper, in order to impart the required water retention to the paper coating paint, it is necessary to add a large amount of additives because the effect of imparting water retention is poor. It has the drawback of adversely affecting coating operability, physical properties of coated paper, and printability, such as increasing the viscosity of the coating material and decreasing the concentration of the paper coating material. That is, the conventional additives cannot stably operate and improve the quality in high-speed coating, which is an obstacle to high-speed coating. In addition, if provided for an aqueous emulsion or an aqueous emulsion paint, in order to impart the required high viscosity, thixotropy and water retention,
Due to the poor effect of these functions, it is necessary to add a large amount of additives.In this case, the concentration of the aqueous emulsion or the aqueous emulsion paint decreases, the water resistance decreases, the stability is poor such as floating, and the physical properties of the coating film are adversely affected. Had the disadvantage of producing

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to overcome the above-mentioned problems. As a result, when the present invention is applied to a paper coating material, it exhibits high water retention and low shearing of the paper coating material. The viscosity at high speed is greatly increased, the viscosity at high shear rate is kept low, and when used for water-based emulsions or water-based emulsion paints, it shows high water retention, greatly increasing the viscosity at low shear rates, The present inventors have found that limited specific compounds are effective for suppressing the viscosity at a shear rate to be low, and have reached the present invention.

That is, in the present invention, methacrylic acid (salt) [methacrylic acid (salt) means methacrylic acid or a methacrylic acid salt in 100 parts by weight of the total of monomers. same as below. 25 to 90 parts by weight, a monomer A1 to 40 parts by weight represented by the following general formula (I),

Embedded image (Wherein, R ₁ is H or CH ₃ , R ₂
And R ₃ is H or one or more selected from alkyl groups having 1 to 2 carbon atoms, R ₄ is an alkyl group having 8 to 20 carbon atoms, and n is an integer of 3 to 100. ) A monomer B1 to 40 parts by weight represented by the following general formula (J),

Embedded image (Wherein, R ₅ is H or CH ₃ , R ₆ and R ₇ are H or one or more selected from alkyl groups having 1 to 2 carbon atoms, and R ₈ is an aromatic group having 6 to 30 carbon atoms) And m is an integer of 3 to 50.) A monomer C1 to 30 parts by weight represented by the following general formula (K),

Embedded image (Wherein, R ₉ is H or CH ₃ , R ₁₀ and R ₁₁ are H or one or more selected from alkyl groups having 1 to 2 carbon atoms, and R ₁₂ is an alkyl group having 1 to 4 carbon atoms. And p is an integer of 3 to 100.) A monomer D1 to 60 parts by weight represented by the following general formula (L),

Embedded image (Wherein, R ₁₃ is H or CH ₃ ;
₁₄ is an alkyl group having 1 to 2 carbon atoms. ) A copolymer of these with other ethylenically unsaturated monomers E0 to 18 parts by weight copolymerizable, wherein the weight ratio of monomer E / monomer D is less than 0.3, A modifier for an aqueous coating agent comprising a polymer having a viscosity at 25 ° C. of a 2% by weight aqueous solution of a polymer completely neutralized with sodium oxide having a viscosity of 50 to 20,000 mPa · s. To the paper coating composition containing a pigment and a binder as main components in an amount of 0.001 to 1 with respect to 100 parts by weight of the pigment.
It is a paper coating composition characterized by being blended in an amount of 0 part by weight, wherein 0.001 to 10 parts by weight per 100 parts by weight of a filler is added to an aqueous emulsion paint containing a modifier and a filler as a main component. A water-based emulsion coating composition characterized by being blended with 0.001 part by weight of a modifier based on 100 parts by weight of the water-based emulsion.
To 10 parts by weight of a water-based emulsion composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As a specific example of the monomer A used in the present invention, an alkoxypolyalkylene glycol represented by (I) (the number of moles of alkylene oxide added n = 3 to 10)
0) (meth) acrylic acid [(meth) acrylic acid means acrylic acid or methacrylic acid. same as below. And the like. More specifically, in the formula (I),
R ₄ has an alkyl group having 8 to 20 carbon atoms, and (I)
In the formula, (meth) acrylic acid esters of alkylene glycol wherein n is 3 to 100, and from these, 1
More than one species can be used. In the formula (I), R ₄ is an alkyl group having 8 to 20 carbon atoms such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, and heptadecyl. Octadecyl group, nonadecyl group, aralkyl group and the like. Preferred of these are:
It has an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a cetyl group, an octadecyl group and the like, and in the formula (I), n is from 3 to 100, and The relationship of the number of moles of glycol addition n2 is such that n1> n2 and n2 is a (meth) acrylate ester in which 0 or an integer of 1 or more.

Specific examples of the monomer B used in the present invention include a polyalkylene glycol having an aromatic residue having a benzene ring and / or a condensed cyclic structure represented by (J) at the terminal (an alkylene oxide addition mole). Number m = 3-5
0) (meth) acrylate and the like. More specifically, in the formula of (J), R ₈ is a benzene derivative having 6 to 30 carbon atoms, an indene derivative, a naphthalene derivative,
Alkylene glycol (meth) having an aromatic compound such as a tetralin derivative, an anthracene derivative or a phenanthrene derivative, and wherein m is 3 to 50 in the formula (J).
Acrylic esters and the like can be mentioned. One or more selected from these can be used. Of these, preferred are phenoxy polyalkylene glycol (alkylene oxide addition moles 3 to 50) (meth) acrylic acid ester and alkylphenoxy polyalkylene glycol (alkylene oxide addition moles 3 to 50).
(Meth) acrylic acid ester, phenylphenoxy polyalkylene glycol (alkylene oxide addition mole number 3-50) (meth) acrylic acid ester, phenoxyphenoxy polyalkylene glycol (alkylene oxide addition mole number 3-50) (meth) acrylic acid ester ,
Alkylphenoxyphenoxypolyalkylene glycol (alkylene oxide addition moles 3 to 50) (meth)
Acrylic acid ester, phenylalkylphenoxypolyalkylene glycol (alkylene oxide added mole number 3 to 50) (meth) acrylic acid ester, alkylphenylalkylphenoxypolyalkylene glycol (alkylene oxide added mole number 3 to 50) (meth) acrylic acid ester , Styrenated phenoxy polyalkylene glycol (alkylene oxide addition mole number 3 to 50)
(Meth) acrylic acid ester, naphthoxy polyalkylene glycol (alkylene oxide addition mole number 3 to 5)
0) (meth) acrylic acid ester, tetraoxypolyalkylene glycol (alkylene oxide added mole number 3
To 50) (meth) acrylic acid ester, anthraloxypolyalkylene glycol (alkylene oxide addition mole number 3 to 50) (meth) acrylic acid ester, phenanthroxypolyalkylene glycol (alkylene oxide addition mole number 3 to 50) (meta) ) An acrylic ester or the like, and in the formula (J), m is 3 to 50, and the relationship between the number of moles of ethylene glycol added m1 and the number of moles of propylene glycol added m2 is m1 <m2, m1 is 0 or (Meth) acrylic acid ester which is an integer of 1 or more.

Specific examples of the monomer C used in the present invention include an alkoxypolyalkylene glycol represented by (K) (alkylene oxide addition mole number p = 3 to 100)
(Meth) acrylic acid ester, more specifically, in the formula (K), R ₁₂ has an alkyl group having 1 to 4 carbon atoms, and p is 3 to 100 in the formula (K). (Meth) acrylic acid esters of alkylene glycols. One or more selected from these can be used. In the formula (K), R ₁₂ includes a methyl group, an ethyl group, a propyl group and a butyl group. Among these, preferred are those having a methyl group, an ethyl group, a propyl group and a butyl group, and in the formula (K), p is 3 to 100, and the number of moles of ethylene glycol added p
The relationship between 1 and the addition mole number p2 of propylene glycol is p
1> p2 and p2 are (meth) acrylates which are 0 or a positive number of 1 or more.

Specific examples of the monomer D used in the present invention include methyl (meth) acrylate and ethyl (meth) acrylate in which R ₁₄ is an alkyl group having 1 to 2 carbon atoms in the formula (L). And at least one selected from these can be used.

Specific examples of other copolymerizable ethylenically unsaturated monomers E include butyl (meth) acrylate,
Pentyl (meth) acrylate and hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, (meth) ) Decyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate,
Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, aralkyl (meth) acrylate Unsaturated monocarboxylic acid (salt) such as alkyl (meth) acrylate having an alkyl group having 4 to 20 carbon atoms, acrylonitrile, styrene, acrylic acid (salt), crotonic acid (salt), and maleic acid (salt) ), Fumaric acid (salt), unsaturated dicarboxylic acid (salt) such as itaconic acid (salt), and at least one selected from these can be used. Of these, preferred are hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, and (meth) acrylate.
Decyl acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate and acrylonitrile, more preferably 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate , (Meth) acrylic acid alkyl esters having an alkyl group having 8 to 12 carbon atoms, which are composed of decyl (meth) acrylate and dodecyl (meth) acrylate.

In the modifier for a water-based coating agent of the present invention, the proportions of methacrylic acid (salt), monomer A, monomer B, monomer C, monomer D and monomer E are as follows: 25 to 90 parts by weight of methacrylic acid (salt) and 1 to 40 parts by weight of monomer A, 1 to 40 parts by weight of monomer B,
The monomer C is 1 to 30 parts by weight, the monomer D is 1 to 60 parts by weight, and the other ethylenically unsaturated monomer E copolymerizable therewith is 0 to 18 parts by weight. The weight ratio of monomer E / monomer D is less than 0.3. Preferably, methacrylic acid (salt) is 27 to 85 parts by weight, monomer A is 3 to 35 parts by weight, monomer B is 3 to 35 parts by weight and monomer C3 to 25 parts.
Parts by weight, 3-55 parts by weight of monomer D, and a weight ratio of monomer E / monomer D of less than 0.2, more preferably 30-80 parts by weight of methacrylic acid (salt), Body A is 5
30 parts by weight, monomer B is 5 to 30 parts by weight, monomer C5 to 5 parts by weight.
20 weight and monomer D5-50 weight, and monomer E /
The weight ratio of monomer D is less than 0.1. Water retention methacrylic acid (salt) is obtained in the case of less than 25 parts by weight decreases, the viscosity at high shear of a thixotropic property is lowered, more particularly the shear rate of 10 6 ^/ sec if it exceeds 90 parts by weight It is undesirably high. When the amount of the monomer A is less than 1 part by weight, the viscosity increase becomes poor, and when it exceeds 40 parts by weight, the viscosity particularly under high shear at a shear rate of 10 ⁶ / sec or more becomes too high, which is not preferable. When the amount of the monomer B is less than 1 part by weight, the thickening becomes poor, and when it exceeds 40 parts by weight, the viscosity particularly under high shearing at a shear rate of 10 ⁶ / sec or more becomes too high, which is not preferable. When the amount of the monomer C is less than 1 part by weight, the effects of imparting water retention, thickening and thixotropy are poor, and
If the amount is more than 10 parts by weight, the viscosity under high shear at a shear rate of 10 ⁶ / sec or more is undesirably too high. Monomer D
Is less than 1 part by weight, emulsion polymerization is difficult, agglomerates are generated during the polymerization, and the mechanical stability of the obtained emulsion is poor. If the amount exceeds 60 parts by weight, water retention, viscosity increase, and thixotropic properties decrease. Monomer E is 1
If it exceeds 8 parts by weight, water retention, viscosity increase, and thixotropic properties decrease. When the weight ratio of monomer E / monomer D is more than 0.3, the viscosity and thixotropy decrease, and the viscosity especially at a low shear rate decreases, and the thixotropy also decreases, which is not preferable.

The base forming the salt of the modifier for an aqueous coating agent includes alkali metal salts (such as sodium, potassium and lithium salts), alkaline earth metals (such as magnesium and calcium salts), ammonium salts and amine salts ( Monoethanolamine, diethanolamine, triethanolamine, and alkyl (C1-C4) amine salts). One or more selected from these can be used. Particularly, sodium salts and potassium salts are preferred.

The modifier for an aqueous coating agent of the present invention comprises:
It contains a copolymer, and the copolymer may be used alone or as a mixture.

In synthesizing the modifier for water-based coating agent of the present invention, it is possible to use ordinary methods such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization. Preferably, a solution polymerization method and an emulsion polymerization method are used, and more preferably, an emulsion polymerization method is used.

For example, in solution polymerization, methacrylic acid (salt), monomer A, monomer B, monomer C, monomer D and / or monomer E are converted into a conventional polymerization initiator. , Water or / and an alcohol-based solvent (such as methanol, ethanol and isopropyl alcohol).
After polymerization at 30 ° C. for 1 to 15 hours, it can be easily obtained by neutralizing with a base as required.
As for the acidic groups such as methacrylic acid and unsaturated monocarboxylic acid and unsaturated dicarboxylic acid of the monomer E, a method of neutralizing with a base before, during and after the polymerization is also possible if necessary. As a method of polymerization,
Methacrylic acid (salt), monomer A, monomer B, monomer C,
The total amount of the monomers such as the monomer D and / or the monomer E may be charged into the polymerization tank for polymerization, or may be charged while dropping and polymerized. Further, a part of the monomers may be charged into the polymerization tank and the polymerization may be performed while dropping some of the monomers. The polymerization initiator may be charged in its entirety in a polymerization tank for polymerization, or may be charged dropwise and polymerized. The solvent may be a combination of water and an alcohol, or may be used in combination at any ratio. Particularly preferred is a system in which the weight ratio of water to the total amount of the solvent is higher than that of alcohol. Further, the entire amount of the solvent may be charged into the polymerization tank for polymerization, or may be charged while dropping or polymerization may be performed. on the other hand,
The polymerization may be performed while charging the entire amount of the solvent into the polymerization tank and removing the solvent during the polymerization.

As the polymerization initiator, 2,2'-azobisisobutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (4-methoxy-2,
4-dimethylvaleronitrile, 2,2′-azobis (2
-Methylbutyronitrile), 1,1'-azobis (cyclohexane-1-alkonitrile), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,
2′-azobis (2-methylpropionate), 2,
2′-azobis [2- (hydroxymethyl) propionitrile] and 1,1′-azobis (1-acetoxy-
Azo catalysts such as 1-phenylethane), persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; inorganic peroxides such as perborate and hydrogen peroxide; and ascorbic acid-hydrogen peroxide. Examples include redox catalysts and organic peroxides such as benzoyl peroxide. One or more selected from these can be used.

For example, in emulsion polymerization, methacrylic acid (salt), monomer A, monomer B, monomer C, monomer D, and / or monomer E are anionic surfactant, nonionic surfactant Surfactant, known chain transfer agent for adjusting the degree of polymerization if necessary, acetaldehyde, isopropyl alcohol,
An additive such as dodecyl mercaptan or hexadecyl mercaptan is added to water, dispersed and emulsified to make a normal polymerization initiator exist, and polymerized at 40 to 130 ° C. for 1 to 15 hours. It can be easily obtained by summing. As for the acidic groups such as methacrylic acid and unsaturated monocarboxylic acid and unsaturated dicarboxylic acid of the monomer E, a method of neutralizing with a base before, during and after the polymerization is also possible if necessary. As a method of polymerization, methacrylic acid (salt), monomer A, monomer B, monomer C, monomer D and / or monomer E may be charged in a polymerization tank and polymerized. The polymerization may be carried out while being dropped well. Further, a part of the monomers may be charged into the polymerization tank and the polymerization may be performed while dropping some of the monomers. The polymerization initiator may be charged in its entirety in a polymerization tank for polymerization, or may be charged dropwise and polymerized.

As the polymerization initiator, 2,2'-azobisisobutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (4-methoxy-2,
4-dimethylvaleronitrile, 2,2′-azobis (2
-Methylbutyronitrile), 1,1'-azobis (cyclohexane-1-alkonitrile), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,
2′-azobis (2-methylpropionate), 2,
2′-azobis [2- (hydroxymethyl) propionitrile] and 1,1′-azobis (1-acetoxy-
Azo catalysts such as 1-phenylethane), persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; inorganic peroxides such as perborate and hydrogen peroxide; and ascorbic acid-hydrogen peroxide. Examples include redox catalysts and organic peroxides such as benzoyl peroxide. One or more selected from these can be used.

The anionic surfactant used in synthesizing the modifier for an aqueous coating agent of the present invention includes polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether sulfate, α-olefin sulfate, higher alcohol sulfate, and the like. Alkali metal salts, ammonium salts or amine salts of sulfates such as fatty acid sulfates, fatty acid ester sulfates, polyoxyethylene alkylpropenyl phenyl ether sulfate and fats and oils sulfates, mono-, di-, tripolyoxyethylene alkyl phenyl ether phosphates, mono- ,
Alkali metal salts, ammonium salts or amine salts of phosphate esters such as di, tripolyoxyethylene alkyl ether phosphate esters and higher alcohol phosphate esters, paraffin sulfonates, α-olefin sulfonates, α-sulfonated fatty acids and α-sulfones And anionic surfactants represented by alkali metal salts, ammonium salts or amine salts of sulfonates such as hydrogenated fatty acid esters, and alkali metal salts of higher fatty acids. Of these, preferred are polyoxyethylene (ethylene oxide addition mole number 2 to 10).
0) Octyl phenyl ether sulfate, polyoxyethylene (2 to 100 moles of ethylene oxide added)
Nonyl phenyl ether sulfate, polyoxyethylene (ethylene oxide added mole number 2 to 100) alkyl (C6 to C22) ether sulfate, polyoxyethylene (ethylene oxide added mole number 2 to 100)
Alkali (C6-22) propenyl phenyl ether sulfate alkali metal salt, ammonium salt or amine salt, mono, di, tripolyoxyethylene (ethylene oxide addition mole number 2 to 100) octyl phenyl ether phosphate, mono, di, Tripolyoxyethylene (ethylene oxide added mole number 2 to 100) nonyl phenyl ether phosphate and mono, di, tripolyoxyethylene (ethylene oxide added mole number 2)
Alkali metal, ammonium or amine salts of alkyl (C.sub.6 to C.sub.22) ether phosphates, more preferably polyoxyethylene (ethylene oxide addition mole number: 2 to 50) octyl phenyl ether sulfate, polyoxyethylene ( Ethylene oxide addition mole number 2 to 50) nonylphenyl ether sulfate, polyoxyethylene (ethylene oxide addition mole number 2 to 50) alkyl (C6 to C18) ether sulfate, polyoxyethylene (ethylene oxide addition mole number 2 to 50) alkyl ( C6-C18 propenyl phenyl ether sulfate, mono-, di-, tripolyoxyethylene (ethylene oxide added mole number 2-5
0) octyl phenyl ether phosphate, mono,
Di, tripolyoxyethylene (ethylene oxide added mole number 2 to 50) nonylphenyl ether phosphate and mono, di, tripolyoxyethylene (ethylene oxide added mole number 2 to 50) alkyl (carbon number 8 to 1)
8) Alkali metal, ammonium and amine salts of ether phosphates.

Nonionic surfactants used in synthesizing the modifier for water-based coating agents of the present invention include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl propenyl phenyl ether, and fatty acid polyethylene glycol. Esters, polyoxyethylene-type nonionic surfactants such as ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, fatty acid amide ethylene oxide adducts and ethylene oxide / propylene oxide copolymers, and fatty acid esters of glycerin;
Polyhydric alcohol type nonionic surfactants such as fatty acid esters of sorbitol, fatty acid esters of sorbitan, alkyl ethers of polyhydric alcohols and fatty acid amides of alkanolamines are exemplified. Among these, preferred are polyoxyethylene (2 to 100 ethylene oxide addition moles) octyl phenyl ether,
Polyoxyethylene (2 to 2 moles of ethylene oxide added)
100) Nonyl phenyl ether and polyoxyethylene (ethylene oxide addition mole number 2 to 100) alkyl (C6 to C22) ether, polyoxyethylene (ethylene oxide addition mole number 2 to 100) alkyl (C6 to C22) propenyl phenyl Ether and ethylene oxide (ethylene oxide addition mole number 2-1)
And polyoxyethylene type nonionic surfactant such as propylene oxide (propylene oxide added mole number 2 to 100) copolymer, and more preferably polyoxyethylene (ethylene oxide added mole number 2 to 5).
0) octyl phenyl ether, polyoxyethylene (2 to 50 ethylene oxide addition moles) nonyl phenyl ether, polyoxyethylene (2 to 50 ethylene oxide addition moles) alkyl (6 to 18 carbon atoms) ether, polyoxyethylene (ethylene oxide addition Examples thereof include an alkyl (2 to 50) alkyl (6 to 18 carbon atoms) propenyl phenyl ether and an ethylene oxide (ethylene oxide added 2 to 50) / propylene oxide (propylene oxide added 2 to 50) copolymer. One or more selected from these anionic surfactants and nonionic surfactants may be used.

The total amount of the anionic surfactant and the nonionic surfactant used is 1 to 25 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of the total monomers of the modifier for an aqueous coating agent of the present invention. ~ 20 parts by weight, more preferably 5
１５15 parts by weight. If the amount of the anionic surfactant is less than 1 part by weight, aggregates are generated in the emulsion polymerization,
Further, the stability of the obtained aqueous dispersion of the emulsion polymer decreases. If the amount exceeds 25 parts by weight, the water resistance of the emulsion polymer is lowered and bubbles of the water-based coating agent are undesirably generated.

The viscosity at 25 ° C. of a 2% aqueous solution obtained by neutralizing the water-based coating agent modifier of the present invention with sodium hydroxide is 50 to 20,000 mPa · s, and is used as a water retention agent for paper coating paint. , 50 to 10,000 mPa · s, preferably 60 to 8,000, more preferably 7 to 10,000 mPa · s.
0 to 6,000 mPa · s. When used in aqueous emulsions and aqueous emulsion paints,
20,000 mPa · s, preferably 2,500 to 1
5,000 mPa · s, more preferably 3,000 to 1
It is 000 mPa · s. In any case, viscosity is 50mP
If it is less than a · s, the water retention, viscosity increase, and thixotropic properties decrease, and
If it exceeds 000 mPa · s, the viscosity becomes extremely high, and the water retention, viscosity increase, and thixotropic properties cannot be balanced, which is not preferable.

The water-based coating agent modifier of the present invention comprises:
In the case of a water-soluble modifier, it can be added to the water-based coating agent with stirring as it is, and in the case of a water-insoluble modifier such as an alkali-sensitive emulsion, the pH is usually adjusted to pH 6 to 13 with an arbitrary base. It can be added to a water-based coating agent in a state of being made water-soluble. Bases include alkali metal salts (eg, sodium, potassium, lithium salts), alkaline earth metal salts (eg, magnesium, calcium salts), ammonium salts and amine salts (eg, monoethanolamine,
Diethanolamine, triethanolamine, and alkyl (C1-C4) amine salts). The pH is usually adjusted to 6 to 13 using one or more selected from these, and the mixture is used. The method of pH adjustment may be such that the aqueous coating agent modifier of the present invention is adjusted to the desired pH with a base in advance and added to the aqueous coating agent, or the aqueous coating agent is adjusted to the desired pH in advance. A necessary amount of a base may be added, and the modifier for an aqueous coating agent of the present invention may be added thereto with stirring.

The modifier for an aqueous coating agent of the present invention comprises:
Effective for imparting water retention, thickening, and thixotropy of water-based coating agents mainly containing pigments or fillers and / or binders, and water-holding agents for water-based paper coating paints, water-based emulsions and water-based emulsion paints, thickeners and thixotropes It is particularly effective as an agent. Specifically, it is optimal for high-speed coating of water-based paper coating paints, which is a technical trend in the papermaking industry. It is ideal for high-speed coating of water-based emulsions and high-speed paint coating with implants such as ceramic siding boards, which is a technical trend in the water-based emulsion paint industry.

Examples of pigments in these water-based coating agents include inorganic pigments such as clay, calcium carbonate, titanium oxide, satin white, barium sulfate, talc, zinc oxide, gypsum, silica, ferrite, and organic pigments such as polystyrene plastic pigment. Pigments.

The binder in these aqueous coating agents includes natural binders such as starch, modified starch, casein, modified soy protein, styrene butadiene latex, carboxyl modified styrene butadiene latex, acrylic resin emulsion, vinyl acetate resin emulsion, and vinyl chloride. Resin emulsion, acrylic styrene resin emulsion, silicone resin emulsion, urethane resin emulsion, epoxy resin emulsion, fluororesin emulsion, ABS latex,
Synthetic binders such as NBR latex and CR latex are exemplified.

The amount of the modifier (in terms of solid content) of the water-based coating agent modifier of the present invention is usually from 0.001 to 1 per 100 parts by weight of the pigment or filler in the water-based coating agent.
0 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight. The amount is usually 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, and more preferably 0.02 to 6 parts by weight, based on 100 parts by weight of the binder. If the amount is less than 0.001 part by weight, the effect of imparting water retention, thickening and thixotropic properties is poor, and
If it exceeds 0 parts by weight, the viscosity under a high shear rate becomes too high, which is not preferable.

The modifier for an aqueous coating agent of the present invention comprises:
An antioxidant, an ultraviolet absorber, a water-proofing agent, an antiseptic / antifungal agent, a defoamer, a dispersant, a deodorant, a fragrance, a dye, a pigment, and the like may be contained or used in combination.

When the modifier for an aqueous coating composition of the present invention is used as a modifier for an aqueous paper coating composition containing a pigment and a binder as a main component, the amount used (in terms of solid content) is determined by the amount of Is usually 0.00
The amount is 1 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight. 0.0
If the amount is less than 01 parts by weight, the effect of imparting water retention and the effect of increasing the viscosity are poor. The paper coating composition using the water-based coating agent modifier of the present invention is usually used in the form of an aqueous dispersion, and if necessary, other additives, for example, a dispersant such as sodium polyacrylate, a fatty acid ester. Antifoaming agents such as, lubricating agents such as calcium stearate,
Water-proofing agents such as glyoxal, urea resin or polyamide polyamine resin, wetting agents, preservatives and fluorescent dyes are added. Water retention agents and thickeners other than the water-based coating agent modifier of the present invention, for example, sodium alginate, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, polyvinyl alcohol and the like can be used in combination, but the amount of these used Preferably, it is used in less than 50% by weight, more preferably 10% by weight or less, of the modifier for water-based coating agent of the present invention. When the content is 50% by weight or more, the characteristics of the modifier for a water-based coating agent of the present invention are not utilized, and the effect of imparting water retention and increasing viscosity is significantly reduced.

The paper coating composition can be coated on the paper by a known method, for example, with an air knife coater, curtain flow coater, blade coater, roll coater, rod coater or the like. After coating, it is dried and finished with a calender ring or super calender ring as required. The coating temperature is usually 10-60 ° C,
The drying temperature is usually 90 to 150 ° C, and the temperature of the calender ring, super calender ring or soft nip calender ring is usually 30 to 200 ° C.

When the modifier for an aqueous coating agent of the present invention is used as a modifier for an aqueous emulsion paint mainly composed of a filler and a binder, or when it is used as a modifier for an aqueous emulsion mainly composed of a binder, The amount (in terms of solid content) of the modifier for an aqueous coating agent of the present invention is usually 0.0 with respect to 100 parts by weight of a binder in an aqueous emulsion paint and an aqueous emulsion.
The amount is from 0.01 to 10 parts by weight, preferably from 0.01 to 8 parts by weight, more preferably from 0.02 to 6 parts by weight. 0.0
If it is less than 01 parts by weight, the effect of imparting viscosity, thixotropy and water retention is poor, and if it exceeds 10 parts by weight, the viscosity under a high shear rate becomes too high and the water resistance is undesirably reduced. Aqueous emulsion paint and aqueous emulsion using the aqueous coating agent modifier of the present invention,
Usually used in the form of an aqueous dispersion, if necessary, other solvents, antifreezing agents, dispersants, defoamers, wetting agents, film-forming aids, lubricants, thickeners, water-proofing agents, preservatives And a fluorescent dye. Thickeners other than the aqueous coating agent modifier of the present invention, for example, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose,
Ethyl cellulose, sodium alginate, polyvinyl alcohol, and the like can be used in combination, but the amount of these used is preferably less than 50% by weight, more preferably 10% by weight of the aqueous coating agent modifier of the present invention. It is used below. When the content is 50% by weight or more, the characteristics of the modifier for a water-based coating agent of the present invention are not utilized, and the effects of increasing viscosity, thixotropy and water retention are remarkably reduced.

The water-based emulsion paint can be coated on the object by a known method, for example, by brush coating, spray coating, roll coating, curtain flow coater coating, airless coating, electrostatic coating and the like.

[0033]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following examples, "part" means "part by weight" and "%" means "% by weight".

Example 1 In a glass reaction vessel equipped with a dropping funnel, a reflux condenser, a stirrer and a thermometer, 600 parts of water, methacrylic acid 164.
6 parts, polyethylene / propylene glycol (ethylene oxide 50 mol adduct / propylene oxide 5 mol adduct) tetradecyl ether acrylate
2 parts, nonylphenoxy polyethylene / propylene glycol (ethylene oxide 5 mol adduct / propylene oxide 15 mol adduct) methacrylate 13.5
Part, butoxypolyoxyethylene / propylene glycol (ethylene oxide 30 mol adduct / propylene oxide 20 mol adduct) methacrylate 18.9
Parts, 29.7 parts of ethyl methacrylate, 15.0 parts of sodium salt of polyoxyethylene (25 mol adduct of ethylene oxide) octadecyl ether sulfate, and potassium salt of dioxyethylene (15 mol adduct of ethylene oxide) nonylphenyl ether phosphate diester 1
5.0 parts of ammonium persulfate 0.2
100 parts of a 100% aqueous solution was dropped from the dropping funnel at a constant rate over 3 hours to cause a reaction. The reaction temperature was kept at 60-100C. After the dropping was completed, the temperature was kept at the same temperature for 3 hours (ripening), cooled to 30 ° C, taken out, and the concentration was 30% and the viscosity was 10 mP.
An aqueous coating agent modifier as an a · S white emulsion was obtained.

Example 2 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 140.3 parts, polyethylene propylene glycol (ethylene oxide 50 mol adduct / propylene oxide 5 mol adduct) decyl ether methacrylate 13.5 parts, styrenated phenoxy polyethylene glycol propylene glycol (ethylene oxide 10 mol) Adduct, propylene oxide 20 adduct)
24.3 parts of methacrylic acid ester, 13.5 parts of methoxypolyethylene glycol (ethylene oxide 25 mol adduct) acrylate, 37.5 parts of ethyl acrylate
Parts, 37.5 parts of ethyl methacrylate, 5.4 parts of 2-ethylhexyl acrylate, 15.0 parts of polyoxyethylene (25 mol adduct of ethylene oxide) dodecyl ether and octyl phenyl ether of polyoxyethylene (25 mol adduct of ethylene oxide) 15.0 parts of phosphoric acid monoester disodium salt were added, and 100 parts of a 0.2% aqueous solution of ammonium persulfate was added dropwise with stirring, followed by reaction, aging,
Upon cooling, a water-based coating agent modifier as a white emulsion having a concentration of 30% and a viscosity of 15 mPa · S was obtained.

Example 3 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 110.6 parts, polyethylene / propylene glycol (ethylene oxide 25 mol adduct / propylene oxide 5 mol adduct) octadecyl ether methacrylate 27.0 parts, naphthoxy polypropylene glycol (propylene oxide 10 mol adduct) Acrylic acid ester 10.8 parts, methoxypolyethylene glycol (ethylene oxide 90 mol adduct)
32.4 parts of acrylic ester, ethyl acrylate 5
4.0 parts, methyl methacrylate 27.0 parts, 2-ethylhexyl acrylate 8.1 parts, polyoxyethylene (ethylene oxide 25 mol adduct) octadecyl ether phosphate monoester disodium salt 20.0 parts and polyoxyethylene (Ethylene oxide 15 mol adduct)
Nonylphenyl ether phosphoric acid diester sodium salt (10.0 parts) was added, and ammonium persulfate (0.2%) was added with stirring.
100% aqueous solution was dropped, reacted, aged and cooled to a concentration of 3
A water-based coating agent modifier as a white emulsion having a viscosity of 10% and a viscosity of 10 mPa · S was obtained.

Example 4 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, 70.1 parts of methacrylic acid, polyethylene propylene glycol (ethylene oxide 25 mol adduct
Propylene oxide 5 mol adduct) 54.0 parts of dodecyl ether methacrylate, phenylphenoxy polyethylene / propylene glycol (ethylene oxide 10 mol adduct / propylene oxide 20 mol adduct)
13.5 parts of methacrylic acid ester, 13.5 parts of ethoxy polyethylene glycol (addition product of 25 mol of ethylene oxide) methacrylic acid ester, ethyl acrylate
8 parts, ethyl methacrylate 27.0 parts, methacrylic acid 2
27.0 parts of ethylhexyl, 10.0 parts of sodium salt of polyoxyethylene (ethylene oxide 20 mol adduct) nonylpropenyl phenyl ether sulfate and sodium salt of polyoxyethylene (25 mol adduct of ethylene oxide) dodecyl ether sulfate 20.
0 parts, and 100 parts of a 0.2% aqueous solution of ammonium persulfate was added dropwise with stirring, reacted, aged, and cooled to a concentration of 30%.
A modifier for an aqueous coating agent as a white emulsion having a viscosity of 30 mPa · S was obtained.

Example 5 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 226.6 parts, polyethylene glycol (ethylene oxide 70 mol adduct) octyl ether methacrylate 13.5 parts, benzylphenoxypolyethylene propylene glycol (ethylene oxide 5 mol adduct / propylene oxide 15 mol adduct) methacryl Acid ester 13.5 parts, ethoxy polyethylene propylene glycol (ethylene oxide 3
0 mol adduct / 10 mol propylene oxide adduct) 8.1 parts of methacrylic acid ester, ethyl methacrylate
1 part, polyoxyethylene (40 mol of ethylene oxide adduct) octyl ether sulfate sodium salt 2
5.0 parts of polyoxyethylene (25 mol adduct of ethylene oxide) octyl phenyl ether phosphate monoester disodium salt (5.0 parts) were added, and 100 parts of a 0.2% aqueous solution of ammonium persulfate was added dropwise with stirring.
After aging and cooling, a water-based coating agent modifier as a white emulsion having a concentration of 30% and a viscosity of 35 mPa · S was obtained.

Comparative Example 1 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 54.0 parts, polyethylene propylene glycol (ethylene oxide 25 mol adduct
Propylene oxide 5 mol adduct) 54.0 parts of octyl ether methacrylate, nonylphenoxypolyethylene propylene glycol (ethylene oxide 5
27.0 parts of methacrylic acid ester, 27.0 parts of methacrylic acid ester of ethoxy polyethylene glycol (25 mol of ethylene oxide adduct), 27.0 parts of ethyl acrylate
12. parts, 27.0 parts of ethyl methacrylate, 40.5 parts of 2-ethylhexyl acrylate, dodecyl methacrylate
5 parts, 5.0 parts of polyoxyethylene (ethylene oxide 25 mol adduct) octadecyl ether sulfate sodium salt and 15.0 parts of polyoxyethylene (ethylene oxide 25 mol adduct) nonylphenyl ether monophosphate diester sodium salt were added, and the mixture was stirred. 100 parts of a 0.2% aqueous solution of ammonium persulfate was dropped, reacted, aged, and cooled to obtain a water-based coating agent modifier as a white emulsion having a concentration of 30% and a viscosity of 10 mPa · S.

Comparative Example 2 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 246.8 parts, methoxypolyethylene glycol (ethylene oxide 25 mol adduct) methacrylic acid ester 5.2 parts, methyl acrylate 2.6
Parts, 2-ethylhexyl acrylate 5.2 parts, polyoxyethylene (ethylene oxide 40 mol adduct) octyl ether sulfate sodium salt 20.0 parts and polyoxyethylene (ethylene oxide addition mole 1
0) 20.0 parts of nonylpropenyl phenyl ether were added, and 100 parts of a 0.2% aqueous solution of potassium persulfate was added dropwise with stirring, and the reaction was carried out. However, the reaction was stopped because a large amount of aggregates was generated during the polymerization. Next, solution polymerization was attempted. 700 parts of water and 200 parts of isopropyl alcohol are charged into a dropping funnel, a reflux condenser, a distillation apparatus, a stirring apparatus, and a glass reaction vessel equipped with a thermometer, and 47.5 parts of methacrylic acid is stirred.
Part, methoxypolyoxyethylene glycol (ethylene oxide 25 mol adduct) methacrylate 1.0
, A mixture of 0.5 parts of methyl acrylate and 1.0 part of 2-ethylhexyl acrylate and 15 parts of a 0.2% aqueous solution of potassium persulfate were added dropwise at a constant rate over 5 hours to cause a reaction. The reaction temperature was kept at 60-100C. After dropping 3
After maintaining at the same temperature for a period of time (referred to as aging), isopropyl alcohol was removed while adding water, and the mixture was cooled to 30 ° C. to obtain a transparent liquid-based coating agent modifier having a concentration of 2% and a viscosity of 1900 mPa · S. .

Comparative Example 3 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 83.6 parts, polyethylene propylene glycol (ethylene oxide 50 mol adduct.
Propylene oxide 5 mol adduct) decyl ether methacrylate 5.4 parts, naphthoxy polyethylene
Propylene glycol (ethylene oxide 5 mol adduct / propylenoxide 15 mol adduct) methacrylic acid ester 5.4 parts, butoxy polyethylene propylene glycol (ethylene oxide 30 mol adduct / propylene oxide 20 mol adduct) methacrylic acid ester 86.
3 parts, ethyl acrylate 18.9 parts, methyl methacrylate 27.0 parts, 2-ethylhexyl acrylate 27.0 parts
Parts, 16.2 parts of octadecyl acrylate, 10.0 parts of polyoxyethylene (ethylene oxide 25 mol adduct) dodecyl ether and 10.0 parts of polyoxyethylene (ethylene oxide 15 mol adduct) nonylphenyl ether phosphate monoester dipotassium salt And 100 parts of a 0.2% aqueous solution of ammonium persulfate are added dropwise with stirring, followed by reaction, aging and cooling to give a concentration of 30% and a viscosity of 35 mP.
An aqueous coating agent modifier as an a · S white emulsion was obtained.

Comparative Example 4 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, 137.6 parts of methacrylic acid, polyethylene / propylene glycol (ethylene oxide 25 mol adduct / propylene oxide 5 mol adduct) dodecyl ether methacrylate 27.0 parts, styrenated phenoxy polyethylene glycol (ethylene oxide 20 mol adduct) Acrylic ester 21.6 parts, methoxypolyethylene glycol (ethylene oxide 90 mol adduct) acrylate 5.4 parts, methyl acrylate 2
4.3 parts, ethyl acrylate 54.0 parts, polyoxyethylene (ethylene oxide 25 mol adduct) dodecyl ether sulfate sodium salt 10.0 parts and polyoxyethylene (ethylene oxide 25 mol adduct) octyl phenyl ether phosphate sodium diester 10.0 parts of salt and 100 parts of a 0.2% aqueous solution of ammonium persulfate are added dropwise with stirring, and the mixture is reacted, aged and cooled to modify a water-based coating agent as a white emulsion having a concentration of 30% and a viscosity of 15 mPa · S. Agent was obtained.

Comparative Example 5 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, 80.9 parts of methacrylic acid, 121.4 parts of polyethylene glycol (addition product of 20 moles of ethylene oxide) dodecyl ether methacrylate, octylphenoxypolyethylene / propylene glycol (addition product of 30 moles of ethylene oxide and 10 moles of propylene oxide) methacryl Acid ester 27.0 parts, methoxypolyethylene glycol (ethylene oxide 25 mol adduct) acrylate 13.5 parts, decyl acrylate 13.5 parts, dodecyl methacrylate 13.5 parts, polyoxyethylene (ethylene oxide addition mole 20 ) Nonylpropenyl phenyl ether 10.0 parts and polyoxyethylene (ethylene oxide 25 mol adduct) octyl phenyl ether sulfate potassium salt 20.0 parts
Then, 100 parts of a 0.2% aqueous solution of ammonium persulfate was added dropwise with stirring, reacted, aged, and cooled to obtain a water-based coating agent modifier as a white emulsion having a concentration of 30% and a viscosity of 45 mPa · S.

Comparative Example 6 Sodium alginate (Kimitsu Algin L manufactured by Kimitsu Kasei Co., Ltd.)
A 5% aqueous solution of -2) was prepared to obtain a modifier for a water-based coating agent.

Comparative Example 7 A 5% aqueous solution of carboxymethylcellulose (Cerogen PR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was prepared to obtain a modifier for an aqueous coating agent.

Comparative Example 8 Hydroxyethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.
P-800) was prepared to obtain a water-based coating agent modifier.

Table 1 shows the relative viscosities of 2% aqueous solutions of Examples 1 to 5 and Comparative Examples 1 to 5, which were adjusted to pH 9 with sodium hydroxide and measured at 25 ° C. using an Ubbelohde viscometer.

[0048]

[Table 1]

The performance of Examples 1 to 5 and Comparative Examples 1 to 8 was evaluated by the following methods. The results are shown in Tables 2, 3 and 4.

Evaluation Example 1 (1) Formulation of Paper Coating Paint (Parts: Mean solid parts, parts by weight) 1 Pre-dispersed clay [ENGELHARD MINERA
70 parts of L & CHEMICALS, UW-90], heavy calcium carbonate [FMT-90], manufactured by FIMATECH, Inc. 15
Parts, light calcium carbonate (manufactured by Okutama Industry Co., Ltd., Tamapearl TP-222-HS) 15 parts, dispersant (manufactured by San Nopco, SN dispersant 5040) 0.2 part,
0.1 to 0.3 parts of sodium hydroxide, 3 parts of phosphoric acid-modified starch (manufactured by Japan Food Processing Co., Ltd., MS-4600), 3 parts of SBR latex (manufactured by Nippon Synthetic Rubber Co., Ltd., JSR0696) 1
2 parts, lubricant [Nopcoat C-1 manufactured by San Nopco Co., Ltd.]
04-HS] and 0.2 parts of a modifier for water-based coating agents at a pH of 9.0 and paint concentrations of 63 and 65.
% Paper coatings were made.

(2) Physical properties of paper coating paint Low shear viscosity: BM type viscometer, 60 rp, manufactured by Tokyo Keiki Co., Ltd.
m, measured at 25 ° C. The higher the viscosity, the better. High shear viscosity: Hercules viscometer manufactured by Kumagai Riki, 880
Measured at 0 rpm and 25 ° C. The lower the viscosity, the better. Water retention: Caltech Scientific Co., Ltd.
, A gravimetric water retention meter, a pressure of 0.5 kg / m ² , and a dehydration amount for a pressurization time of 30 seconds. The smaller the numerical value, the better. Coating aptitude: Coating concentration a63% and b65 at a coating speed of 1,500 m / min using CLC-6000 manufactured by Waferuser.
% Paper coating paint and dried. It is preferable that the coating amount does not increase as much as possible even when the paper coating concentration increases. That is, the smaller the coating amount ratio of b / a, the better. in this case,
Since coating can be performed without increasing the blade pressure, there is no occurrence of paper breakage, and a bulky coating layer is obtained,
Improves white paper gloss, smoothness, print gloss, and water-absorbing ink adhesion after super calendering. Coating unevenness: The coating unevenness of paper coated with a coating concentration b of 65% was visually determined. ：: no coating unevenness, △: slight coating unevenness, ×: many coating unevenness White paper gloss: coated paper having a coating amount of 10 gr / m ² at 60 ° C. and a linear pressure of 80 kg / cm using a super calender. After passing the paper twice, the humidity was adjusted and measured. Printing gloss, dry pick, wet pick, water-absorbing ink inking property: Printed by Mei Seisakusho's RI-1 type printability tester. The dry pick, wet pick, and water-absorbing ink deposition were evaluated by a five-point method. The higher the value, the better. Smoothness: Measured by Oken type smoothness tester. The larger the value, the higher the smoothness and the better.

[0052]

[Table 2]

Evaluation Example 2 (1) Formulation of aqueous emulsion (part: solid content, meaning parts by weight) Acrylic emulsion [commercial product: concentration 48%] 100
Part, defoamer [Dehydran 1 manufactured by Henkel KGaA Co., Ltd.]
620] A water-based emulsion having a solid content of 43% was prepared by mixing 0.1 part and a water-based coating agent modifier 0.5 part. With the above composition, 30 with a tabletop homogenizer
After stirring at 00 rpm for 5 minutes, the mixture was allowed to stand for 12 hours.

(2) Physical Properties of Aqueous Emulsion Low Shear Viscosity: BM viscometer, 60 rp, manufactured by Tokyo Keiki Co., Ltd.
m, measured at 25 ° C. The higher the viscosity, the better. High shear viscosity: Hercules viscometer manufactured by Kumagai Riki 440
Measured at 0 rpm and 25 ° C. The lower the viscosity, the better. Water retention: Caltech Scientific Co., Ltd.
, A gravimetric water retention meter, a pressure of 0.5 kg / m ² , and a dehydration amount for a pressurization time of 30 seconds. The smaller the numerical value, the better.

[0055]

[Table 3]

Evaluation Example 3 (1) Formulation of Water-Based Emulsion Paint (Part: Meaning of Formulation Ratio) Titanium Dioxide 35 (manufactured by Teica Co., Ltd., JR-600A)
0 parts, calcium carbonate [Escalon, manufactured by Sankyo Flour Milling Co., Ltd.
# 2000] 100 parts, dispersant [manufactured by San Nopco Co., Ltd.
Nopco Spars 44-C] 4 parts, antifoaming agent [Henkel K
3 parts of Dehydran 1620 manufactured by GaAs Co., Ltd., preservative [Nopcoside SN-215 manufactured by San Nopco Co., Ltd.]
2.4 parts, water 100 parts, emulsion [Mitsubishi Chemical BAS
F. Co., Ltd., Acronal 295DN] 605 parts, propylene glycol 30 parts, film-forming aid (Texanol, Eastman Chemical Company, 15 parts) and water-based coating agent modifier 12 parts for line coating of building materials Aqueous emulsion paint was prepared.

(2) Physical properties of water-based emulsion paint Low shear viscosity: BM type viscometer, 60 rp, manufactured by Tokyo Keiki Co., Ltd.
m, measured at 25 ° C. The higher the viscosity, the better. Water retention: Caltech Scientific Co., Ltd.
, A gravimetric water retention meter, a pressure of 0.5 kg / m ² , and a dehydration amount for a pressurization time of 30 seconds. The smaller the numerical value, the better. Coating aptitude: Adjusted to a coating specific gravity of 1.2 at a coating speed of 40 m / sec by curtain flow coater coating, and a viscosity of about 1
After applying the water-based emulsion paint adjusted to 0 mPa · s, 8
Force dry at 0 ° C. for 10 minutes. At this time, it is preferable that there is no curtain break, foam, uneven coating, uneven color, and the like, and that the coating film after forced drying has no mud cracks (cracks). Uneven coating: The uneven coating of the object to be coated was visually determined. ：: no coating unevenness, Δ: slight coating unevenness, ×: many coating unevenness Mad crack: Mud crack (crack) of the coating film of the object was visually judged. ○: No mud cracks, △: Slight mud cracks generated, ×: Many mud cracks

[0058]

[Table 4]

[0059]

When the modifier for an aqueous coating composition of the present invention is used as a modifier for an aqueous paper coating composition mainly composed of a pigment and a binder, the viscosity of the aqueous paper coating composition under low shear can be reduced. Viscosity can be increased, and the viscosity of the water-based paper coating composition can be kept low under high shear at a shear rate of 10 ⁶ / sec or more. In addition, it has an effect that has not been known so far, that it has excellent high water retention. By these functions, the modifier for water-based coating agent of the present invention can easily apply to the base paper at the time of applying the water-based paper coating paint, can make the profile uniform, and can easily adjust the coating amount. At the time of scraping, it has an effect of being able to adjust a water-based paper coating material having excellent coating suitability such as reduction of streak, bleeding and blade abrasion and having physical properties suitable for high-speed coating. Further, the water-based coating agent modifier of the present invention suppresses migration of a binder or the like based on the function of imparting water retention, reduces the blade pressure based on the function of reducing viscosity under high shear, or coats after application and scraping. It has the effect of accelerating the immobilization of paint, and can form a uniform and bulky coating layer without coating unevenness, and is excellent in smoothness, glossiness of white paper, print gloss, and adhesion of water-absorbing ink. A coated paper can be obtained. Due to the above effects, the water-based coating agent modifier of the present invention is used in the coating technology trend of the paper manufacturing industry from the viewpoint of improving productivity in production of coated paper, improving quality, reducing costs, saving energy, and the like. It realizes high-speed coating of a certain water-based paper coating paint and can impart good coating paint physical properties, high operability, high coated paper physical properties, and printability, and is suitable for the production of coated paper.

When the modifier for an aqueous coating agent of the present invention is used as a modifier for an aqueous emulsion containing a binder as a main component, the aqueous emulsion is thickened so that the viscosity of the aqueous emulsion under low shear can be easily adjusted. Under high shear at a shear rate of 10 ⁴ / sec or more, the aqueous emulsion has a thixotropy so that the viscosity of the emulsion can be reduced, and has an effect that has not been known in this field of having high water retention. I have. ADVANTAGE OF THE INVENTION The modifier for aqueous coating agents of the present invention can easily adjust the viscosity of an aqueous emulsion, is excellent in coating suitability, and has the effect of adjusting an aqueous emulsion having physical properties suitable for high-speed coating. Furthermore, the modifier for an aqueous coating agent of the present invention has an effect of facilitating viscosity adjustment, relaxation of shear between emulsion particles based on the function of imparting thixotropic properties and water retention, and easy adjustment of viscosity. Can form a uniform coating layer without coating unevenness even with a base material that easily penetrates water. Due to the above effects, the water-based coating agent modifier of the present invention has an effect of adjusting a water-based emulsion having physical properties suitable for high-speed coating in a line coating of a water-based emulsion, thereby improving productivity. High-speed line coating with implants, which is a technical trend in the adhesive industry from the viewpoints of quality improvement, cost reduction, energy saving, etc., realizes good emulsion physical properties, high operability and high coated physical properties It is suitable for coating water-based emulsions.

On the other hand, when the modifier for an aqueous coating agent of the present invention is used as a modifier for an aqueous emulsion paint mainly composed of a filler and a binder, the viscosity of the aqueous emulsion paint under low shear can be easily adjusted. The aqueous emulsion paint has a thixotropic property so that the viscosity of the aqueous emulsion paint can be reduced under a high shearing rate of 10 ⁴ / sec or more, and has a high water retention property. It has the effect. The modifier for an aqueous coating agent of the present invention can easily adjust the viscosity of an aqueous emulsion paint, has excellent toning stability, has excellent stability without water floating, and has excellent coating aptitude. Also exerts an effect on paint properties. In addition, it has the effect of promoting the immobilization of coated paints, such as slow release of solvent based on water retention function, suppression of migration of binders, etc., and easy viscosity adjustment based on thickening function. In addition, it is possible to obtain an excellent object to be coated, which is uniform, free of bubbles, uneven coating, uneven color, and has no mud cracks (cracks) in the coating film. Because of the above effects, the water-based coating agent modifier of the present invention,
It has the effect of adjusting water-based emulsion paints with physical properties suitable for high-speed coating in water-based emulsion paint line coating. From the viewpoint of improving productivity, quality improvement, cost reduction, energy saving, etc., the paint industry It realizes high-speed line coating with implants, which is a trend in coating technology, and can impart good emulsion paint physical properties, high operability and high physical properties to be coated, and is suitable for coating water-based emulsion paints.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D21H 19/62 D21H 19/62

Claims (8)

[Claims] 1. A total of 100 parts by weight of a monomer, 25 to 90 parts by weight of methacrylic acid (salt), 1 to 50 parts by weight of a monomer A represented by the following general formula (I), and (Wherein, R ₁ is H or CH ₃ , R ₂
And R ₃ is H or one or more selected from alkyl groups having 1 to 2 carbon atoms, R ₄ is an alkyl group having 8 to 20 carbon atoms, and n is an integer of 3 to 100. And 1 to 40 parts by weight of a monomer B represented by the following general formula (J): (Wherein, R ₅ is H or CH ₃ , R ₆ and R ₇ are H or one or more selected from alkyl groups having 1 to 2 carbon atoms, and R ₈ is an aromatic group having 6 to 30 carbon atoms) And m is an integer of 3 to 50.) 1 to 30 parts by weight of a monomer C represented by the following general formula (K): (Wherein, R ₉ is H or CH ₃ , R ₁₀ and R ₁₁ are H or one or more selected from alkyl groups having 1 to 2 carbon atoms, and R ₁₂ is an alkyl group having 1 to 4 carbon atoms. And p is an integer of 3 to 100.) 1 to 60 parts by weight of a monomer D represented by the following general formula (L): (Wherein, R ₁₃ is H or CH ₃ ;
₁₄ is an alkyl group having 1 to 2 carbon atoms. ) A copolymer of these with other ethylenically unsaturated monomers E0 to 18 parts by weight copolymerizable, wherein the weight ratio of monomer E / monomer D is less than 0.3, A modifier for a water-based coating agent, comprising a polymer having a viscosity at 25 ° C. of a 2% by weight aqueous solution of a polymer completely neutralized with sodium oxide having a viscosity of 50 to 20,000 mPa · s. 2. The modifier for an aqueous coating agent according to claim 1, wherein the polymer is in the form of an emulsion. 3. The emulsion according to claim 1, wherein said emulsion is an anionic emulsifier such as polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether sulfate, mono, di, tripolyoxyethylene alkyl phenyl ether phosphate, mono, di, tripolyoxyethylene. At least one selected from alkyl ether phosphoric acid ester salts and polyoxyethylene alkylpropenyl phenyl ether sulfate salts and / or as a nonionic emulsifier polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether and polyoxyethylene alkyl propenyl phenyl The aqueous system according to claim 2, which is obtained by emulsion polymerization of 1 to 25 parts by weight of at least one selected from ethers based on 100 parts by weight of the total of monomers. Modifier for coating agent. 4. A 2% by weight aqueous solution of a polymer completely neutralized with sodium hydroxide having a viscosity at 25.degree.
A modifier for a paper coating composition comprising the modifier according to any one of claims 1 to 3 at 000 mPa · s. 5. A paper coating composition containing the modifier according to claim 1 as a main component containing a pigment and a binder, in an amount of from 0.001 to 10 parts by weight per 100 parts by weight of the pigment.
A paper coating composition characterized by being mixed in parts by weight. 6. A 2% by weight aqueous solution of a polymer completely neutralized with sodium hydroxide having a viscosity at 25 ° C. of 2,000 to
A modifier for an aqueous emulsion paint or a modifier for an aqueous emulsion comprising the modifier according to any one of claims 1 to 3 at 20,000 mPa · s. 7. A water-based emulsion paint containing the modifier according to any one of claims 1 to 3 and 6 mainly containing a filler and a binder, in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the filler. An aqueous emulsion paint composition characterized by being blended. 8. An aqueous emulsion composition comprising the modifier according to claim 1 in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the aqueous emulsion.