JPH11246799A - Modifier for aqueous coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel modifier for an aqueous coating agent which improves the coating suitability of an aqueous coating agent and improves the coating quality after coating. SOLUTION: This modifier comprises, in 100 pts.wt. total amount of monomers, (1) from 25 to 90 pts.wt. methacrylic acid (salt), (2) from 1 to 30 pts.wt. monomer A of the formula: CH2 =C(R1 )-CO[OCH(R3 )CH(R3 )]n -OR4 (wherein R1 is H or CH3 ; R2 and R3 are each H or an 1-2C alkyl group; R4 is an 1-4C alkyl group; and n is from 3 to 100) and (3) a copolymer of from 1 to 60 pts.wt. monomer B of the formula: CH2 =C(R5 )-COOR6 (wherein R5 is H or CH3 ; and R6 is an 1-2C alkyl group) and from 0 to 30 pts.wt. other ethylenically unsaturated monomers C which are copolymerizable therewith.

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 in the production of coated paper, it can be used for water-retaining agents for paper coating agents, water-based emulsions and water-based emulsion paints that can impart high operability and high coated paper properties and printability. For example, the present invention relates to a water-based emulsion and a modifier for a water-based coating agent such as a thickener for a water-based emulsion paint, which can impart a thickening property, a thixotropic property, and high coating 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. Also, in recent years, acrylic and urethane-based synthetic products have been known.

[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. There were drawbacks that adversely affected coating operability, coated paper properties, and printability, such as increasing the viscosity of the coating material and decreasing the concentration of the paper coating coating. That is, the conventional additives cannot stably operate and improve the quality in high-speed coating, which is an obstacle to high-speed coating. Also, if it is used for aqueous emulsions and aqueous emulsion paints, the required thickening,
In order to impart thixotropy and water retention, a large amount of additives must be added due to the poor effect of these functions.In such a case, the concentration of the aqueous emulsion and the aqueous emulsion paint decreases, the water resistance decreases, and It had the disadvantage of adversely affecting the film properties.

[0004]

Means for Solving the Problems The present inventors overcame the above-mentioned drawbacks, and as a result of intensive studies on techniques for imparting high water retention, thickening, and thixotropy, came to the present invention. The present inventors, when applied to paper coatings, show high water retention, and increase the viscosity at low shear rate of the paper coatings,
If the viscosity at high shear rate is kept low and it is used for water-based emulsions and water-based emulsion paints, a limited number of specific compounds are required to increase the viscosity at low shear rates and impart thixotropic properties and water retention. The present invention has been found to be effective and has led to the present invention.

That is, the present invention relates to (1) 25 to 90 parts by weight of methacrylic acid (salt) based on 100 parts by weight of a total of monomers;
(2) The following general formula (I) (Wherein, R ₁ is H or CH ₃ , R ₂ and R ₃ are H or one or more selected from the group consisting of alkyl groups having 1 to 2 carbon atoms, and R ₄ has 1 or more carbon atoms.) And the alkyl group (n) is 3 to 100.)
1 to 30 parts by weight, and (3) the following general formula (J) (Wherein, R ₅ is H or CH ₃ , and R ₆ has 1 carbon atom.
To 2 alkyl groups. ) Monomers B1 to 6
A copolymer of 0 parts by weight and 0 to 30 parts by weight of another ethylenically unsaturated monomer C copolymerizable therewith, wherein the weight ratio of monomer C / monomer B is less than 0.5 And 2% of a 5% by weight aqueous solution of a polymer completely neutralized with sodium hydroxide.
A modifier for an aqueous coating agent comprising a polymer having a viscosity of 100 to 3,000 mPa · s at 5 ° C., for a paper coating paint containing a modifier mainly as a pigment and a binder. A paper coating composition comprising 0.001 to 10 parts by weight based on 100 parts by weight of a pigment, wherein 100 parts by weight of a filler is added to an aqueous emulsion paint containing a modifier and a binder as a main component. 0.001 to 10 per part
A water-based emulsion coating composition characterized in that it is blended in parts by weight, wherein the water-based emulsion composition is characterized in that a modifier is incorporated in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the water-based emulsion.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a specific example of the monomer A used in the present invention, an alkoxypolyoxyalkylene glycol represented by the general formula (I) (the number of moles of alkylene oxide added n = 3 to 100) (meth) acrylic acid Is an ester,
More specifically, in the formula (I), R ₄ has an alkyl group having 1 to ₄ carbon atoms, and in the formula (I), n is 3 to 100. I will give it. These can be used alone or in combination of two or more. In the formula (I), R ₄ includes a methyl group, an ethyl group, a propyl group and a butyl group. Of these, preferred are those having a methyl group, an ethyl group, a propyl group and a butyl group, and in the formula (I),
Is 3 to 100, and the relationship between the number of moles of addition of ethylene glycol n1 and the number of moles of addition of propylene glycol n2 is
n1> n2, n2 is 0 or a positive number of 1 or more (meta)
Acrylic ester.

Specific examples of the monomer B used in the present invention include methyl (meth) acrylate and ethyl (meth) acrylate wherein R ₆ is an alkyl group having 1 to 2 carbon atoms in the formula (J). These can be used alone or in combination of two or more.

Specific examples of other copolymerizable ethylenically unsaturated monomers C include butyl (meth) acrylate,
Pentyl (meth) acrylate and hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Lauryl acrylate, tridecyl (meth) acrylate, (meth)
Alkyl (meth) acrylate having an alkyl group having 4 to 22 carbon atoms, such as tetradecyl acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate, acrylonitrile, styrene, and acrylic acid (Salts), unsaturated monocarboxylic acids (salts) such as crotonic acid (salt), and unsaturated dicarboxylic acids (salts) such as maleic acid (salt) and fumaric acid (salt). One or two or more of them can be used. Of these, preferred are hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, (meth) Tridecyl acrylate, stearyl (meth) acrylate and acrylonitrile are more preferred, and 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate and lauryl (meth) acrylate are more preferred. Which is an alkyl (meth) acrylate having an alkyl group having 8 to 12 carbon atoms.

In the modifier for a water-based coating agent of the present invention, the ratio of methacrylic acid (salt), monomer A, monomer B and monomer C is methacrylic acid in 100 parts by weight of the total monomer. 25 to 90 parts by weight of an acid (salt), 1 to 30 parts by weight of a monomer A, 1 to 60 parts by weight of a monomer B, and 0 to 30 parts of another ethylenically unsaturated monomer C copolymerizable therewith. Parts by weight. The weight ratio of monomer C / monomer B is less than 0.5. Preferably, methacrylic acid (salt) is 27 to 85 parts by weight, monomer A is 3 to 25 parts by weight, and monomer B is 3 to 85 parts by weight.
55 parts by weight, and the weight ratio of monomer C / monomer B is 0.4
Methacrylic acid (salt) is more preferably 3
0 to 80 parts by weight, 5 to 20 parts by weight of monomer A and 5 to 50 parts by weight of monomer B, and the weight ratio of monomer C / monomer B is less than 0.3. When the amount of methacrylic acid (salt) is less than 25 parts by weight, the obtained water retention decreases, and when it exceeds 90 parts by weight, the viscosity increases, especially the viscosity under high shearing at a shear rate of 10 ⁶ / sec or more, In addition, thixotropic properties are undesirably reduced. When the amount of the monomer A is less than 1 part by weight, the effect of increasing the viscosity, thixotropic property and water retention becomes poor. When the amount of the monomer A exceeds 30 parts by weight, the viscosity under a high shear rate of not less than 10 ⁶ / sec. Is too high. Monomer B is 1
When the amount is less than part by weight, the emulsion polymerization is difficult, an agglomerate is 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. When the amount of the monomer C exceeds 30 parts by weight, water retention, viscosity increase, and thixotropy decrease. If the weight ratio of monomer C / monomer B is more than 0.5, the viscosity and thixotropy decrease, especially at a low shear rate, and the thixotropy 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 metal salts (such as magnesium and calcium salts), ammonium salts and amine salts. (Monoethanolamine, diethanolamine, triethanolamine, alkyl (C1-C4) amine salts, etc.). One or two or more selected from these groups may be used. Particularly, sodium salts and potassium salts are preferred.

The modifier for an aqueous coating agent of the present invention comprises:
It is a copolymer, which 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 the solution polymerization, methacrylic acid (salt), monomer A, monomer B and / or monomer C are converted to a conventional polymerization initiator in the presence of water or / and an alcohol (methanol, Polymerization in a solvent such as ethanol and isopropyl alcohol) at 40 to 130 ° C. for 1 to 15 hours, followed by neutralization with a base, if necessary, can easily obtain the compound. As for the acidic groups such as methacrylic acid and the unsaturated monocarboxylic acid and unsaturated dicarboxylic acid of the monomer D, a method of neutralizing with a base before, during and after the polymerization, if necessary, is also possible. As the method of polymerization, methacrylic acid (salt),
The total amount of monomers such as monomer A, monomer B and / or monomer C may be charged and polymerized in a polymerization tank, or may be charged dropwise 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, and may be used in combination at an arbitrary 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 the polymerization may be performed dropwise while charging. 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.

Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis (4-methoxy-2,2
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,
Azo-based catalysts such as 2′-azobis [2- (hydroxymethyl) propionitrile] and 1,1′-azobis (1-acetoxy-1-phenylethane); persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; Examples include inorganic peroxides such as perborate and hydrogen peroxide, redox catalysts such as ascorbic acid-hydrogen peroxide, and organic peroxides such as benzoyl peroxide. One or two or more selected from these groups may be used.

For example, in the emulsion polymerization, methacrylic acid (salt), monomer A, monomer B and / or monomer C may be added to an anionic surfactant, a nonionic surfactant and, if necessary, to adjust the degree of polymerization. For this purpose, a known chain transfer agent, an additive such as acetaldehyde, isopropyl alcohol, dodecyl mercaptan or hexadecyl mercaptan is added to water, dispersed and emulsified, and the presence of a usual polymerization initiator is added.
After polymerization at ~ 130 ° C for 1-15 hours, it can be easily obtained by neutralizing with a base if necessary. As for the acidic groups such as methacrylic acid and unsaturated monocarboxylic acid and unsaturated dicarboxylic acid of the monomer C, a method of neutralizing with a base before, during and after the polymerization may be used, if necessary. As a method of polymerization, methacrylic acid (salt), monomer A, monomer B and / or
Alternatively, the entire amount of the monomer C may be charged into the polymerization tank for polymerization, or the polymerization may be performed dropwise while charging. 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.

Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 4,4′-azobis-4-cyanovaleric acid, and 2,2′-azobis (4-methoxy-2,2
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,
Azo-based catalysts such as 2′-azobis [2- (hydroxymethyl) propionitrile] and 1,1′-azobis (1-acetoxy-1-phenylethane); persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; Examples include inorganic peroxides such as perborate and hydrogen peroxide, redox catalysts such as ascorbic acid-hydrogen peroxide, and organic peroxides such as benzoyl peroxide. One or two or more selected from these groups may be used.

The anionic surfactant used in synthesizing the modifier for an aqueous coating agent of the present invention includes:
Sulfate alkali such as polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether sulfate, α-olefin sulfate, higher alcohol sulfate, fatty acid sulfate, fatty acid ester sulfate, polyoxyethylene alkyl propenyl phenyl ether sulfate, and fats and wax sulfates. Metal salts, ammonium salts or amine salts, mono, di, tripolyoxyethylene alkyl phenyl ether phosphate, mono, di,
Alkali metal salts, ammonium salts or amine salts of phosphate esters such as tripolyoxyethylene alkyl ether phosphate esters and higher alcohol phosphate esters, paraffin sulfonates, α-olefin sulfonates, α-sulfonated fatty acids and α-sulfonated fatty acids Anionic surfactants represented by alkali metal salts, ammonium salts or amine salts of sulfonates such as esters, alkali metal salts of higher fatty acids, and the like are included. Among these, preferred are polyoxyethylene (ethylene oxide added mole number 2 to 100) octyl phenyl ether sulfate, polyoxyethylene (ethylene oxide added mole number 2 to 100) nonyl phenyl ether sulfate, polyoxyethylene (ethylene oxide added mole number) An alkali metal salt, an ammonium salt or an amine salt of 2 to 100) alkyl (C6 to C22) ether sulfate, polyoxyethylene (ethylene oxide addition mole number of 2 to 100) alkyl (C6 to C22) propenyl phenyl ether sulfate, Mono, di, tripolyoxyethylene (ethylene oxide added mole number 2 to 100) octyl phenyl ether phosphate, mono, di, tripolyoxyethylene (ethylene oxide added mole) 2-100) nonylphenyl ether phosphate and mono-, di-, Tripoli oxyethylene (ethylene oxide addition molar number 2 to 10
0) alkali metal, ammonium or amine salts of alkyl (C6-22) ether phosphates;
More preferably, polyoxyethylene (2 to 50 ethylene oxide addition moles) octyl phenyl ether sulfate, polyoxyethylene (2 to 50 ethylene oxide addition moles) nonyl phenyl ether sulfate, polyoxyethylene (2 to 50 ethylene oxide addition moles) alkyl (C6-18) ether sulfate, polyoxyethylene (ethylene oxide added mole number 2-50) alkyl (C6-18) propenyl phenyl ether sulfate, mono, di, tripolyoxyethylene (ethylene oxide added mole number 2-50) )
Octyl phenyl ether phosphate, mono, di,
Tripolyoxyethylene (ethylene oxide added mole number 2-50) nonyl phenyl ether phosphate and mono, di, alkali metal of tripolyoxyethylene (ethylene oxide added mole number 2-50) alkyl (C8-18) ether phosphate , Ammonium and amine salts.

Nonionic surfactants used in synthesizing the modifier for aqueous coating agent 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 type and / or a mixture of two or more types selected from the group consisting of these anionic surfactants and nonionic surfactants may be used.

The total amount of the anionic surfactant and 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 ~
15 parts by weight. The amount of anionic surfactant used is 1
If the amount is less than parts by weight, aggregates are generated in the emulsion polymerization, and the stability of the obtained aqueous dispersion of the emulsion polymerization product is reduced. 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 5% aqueous solution obtained by neutralizing the aqueous coating agent modifier of the present invention with sodium hydroxide is 100 to 3,000 mPa · s. 100-1,500mPa · s
, Preferably 110 to 1,400 mPa · s, more preferably 120 to 1,300 mPa · s. When it is applied to an aqueous emulsion or an aqueous emulsion paint, it is 300 to 3,000 mPa · s, preferably 40 to 3,000 mPa · s.
0 to 2,900 mPa · s, more preferably 500 to 2.8
00 mPa · s. In any case, if the viscosity is less than 50 mPa · s, the water retention, thickening, and thixotropy decrease, and
If the viscosity exceeds mPa · s, the viscosity becomes extremely high, and the water retention, viscosity increase, and thixotropic properties cannot be balanced.

The water-based coating agent modifier of the present invention comprises:
In the case of a water-soluble modifier, it can be added as it is to the aqueous coating agent with stirring, and in the case of an alkali-sensitive emulsion, in the case of a water-insoluble modifier, the pH is usually adjusted with an arbitrary base.
It can be added to the water-based coating agent in a state of being neutralized to 6 to 13 and made water-soluble. Examples of the base include alkali metal salts (eg, sodium, potassium, lithium salts), alkaline earth metal salts (eg, magnesium and calcium salts), ammonium salts and amine salts (eg, monoethanolamine, diethanolamine, triethanolamine, alkyl (C1 to C1)).
C4) amine salts and the like. Using one or more selected from these groups, usually at pH 6 to 13
Adjust and provide for use. 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 for high-speed coating of implants such as ceramic siding boards, which is a technical trend in the water-based emulsion paint industry.

Examples of pigments in these aqueous 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 may be used alone or in combination.

The binder in these aqueous coating agents includes natural binders such as starch, modified starch, casein, and modified soybean protein, and 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 (in terms of solid content) of the water-based coating agent modifier of the present invention is usually from 0.001 to 1 based on 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 0.05 to 3 parts by weight. The amount is usually 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, more preferably 0.05 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 mainly composed of a pigment and a binder, the amount used (in terms of solid content) is determined in the aqueous paper coating composition. Is usually 0.00
It is 1 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.05 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, and if it exceeds 10 parts by weight, the viscosity under a high shear rate is undesirably too high. 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 thickener for an aqueous emulsion paint mainly containing a filler and a binder, or when it is used as a thickener for an aqueous emulsion mainly containing 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 0.05 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 substrate by a known method, for example, by brush coating, spray coating, roll coating, curtain flow coater coating, airless coating, electrostatic coating, or the like.

[0031]

EXAMPLES The present invention will be further described with reference to examples below, 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 and 169.
9 parts, methoxypolyoxyethylene glycol (ethylene oxide 90 mol adduct) acrylate
6 parts, 58.5 parts of ethyl methacrylate, 5.6 parts of lauryl acrylate, and 21.2 parts of sodium salt of polyoxyethylene (25 mol adduct of ethylene oxide) stearyl ether sulfate were added, and the mixture was stirred at 0. 100 parts of a 2% aqueous solution was allowed to react by dropping from a dropping funnel over 3 hours. The reaction temperature was kept at 80-100 ° C. After maintaining the same temperature for 3 hours after the completion of dropping (referred to as aging)
Take out after cooling to 30 ° C, concentration 30%, viscosity 20mPa · S
A water-based coating agent modifier as a 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 144.9 parts, methoxypolyoxyethylene glycol (ethylene oxide 25 mol adduct) methacrylate 27.8 parts, ethyl acrylate 31.2 parts, methyl methacrylate 46.8 parts, acrylic acid 2- 27.8 parts of ethylhexyl, 7.3 parts of polyoxyethylene (ethylene oxide 15 mol adduct) nonylphenyl ether phosphoric acid monoester disodium salt and 13.9 parts of polyoxyethylene (ethylene oxide 25 mol adduct) lauryl ether were charged. Then, 100 parts of a 0.2% aqueous solution of potassium persulfate was added dropwise with stirring, followed by reaction, aging, and cooling to obtain a water-based coating agent modifier as a white emulsion having a concentration of 30% and a viscosity of 10 mPa · S.

Example 3 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 112.6 parts, methoxy polyoxyethylene glycol (ethylene oxide 10 mol adduct) acrylate 8.2 parts, ethoxy polyoxyethylene glycol (ethylene oxide 25 mol adduct) methacrylic ester 11.0 parts, 71.4 parts of ethyl acrylate, 71.4 parts of ethyl methacrylate and polyoxyethylene (ethylene oxide 18 mol adduct)
Nonyl phenyl ether sulfate potassium salt 18.
7 parts and polyoxyethylene (ethylene oxide 25
Mole adduct) 6.5 parts of potassium octylphenyl ether phosphoric acid diester were charged, 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% and a viscosity of 10 mPa · S. A water-based coating agent modifier as a white emulsion was obtained.

Example 4 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, 76.1 parts of methacrylic acid, butoxypolyoxyethylene / propylene glycol (ethylene oxide 3
0 mol adduct / propylene oxide 20 mol adduct) 40.5 parts of methacrylic acid ester, ethoxy polyoxyethylene / propylene glycol (ethylene oxide 60
30.0 parts of acrylate, 28.2 parts of methyl acrylate
Parts, 62.0 parts of methyl methacrylate, 45.1 parts of 2-ethylhexyl acrylate, 4.0 parts of polyoxyethylene (22 mol adduct of ethylene oxide) octyl ether sulfate sodium salt, and polyoxyethylene (48 mol adduct of ethylene oxide) 13.9 parts of octyl ether was added, and 0.2 g of ammonium persulfate was added with stirring.
100% aqueous solution was dropped, reacted, aged and cooled to a concentration of 3
An aqueous coating agent modifier as a white emulsion having a viscosity of 12% and a viscosity of 12 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 225.1 parts, methoxypolyoxyethylene / propylene glycol (ethylene oxide 30 mol adduct / propylene oxide 10 mol adduct)
5.4 parts of methacrylic acid ester, ethoxypolyoxyethylene / propylene glycol (ethylene oxide 25
Mole adduct / propylene oxide 15 mole adduct) 2.7 parts of methacrylic acid ester, 24.1 ethyl acrylate
Part, lauryl methacrylate 10.7 parts, polyoxyethylene (ethylene oxide 41 mol adduct) octyl phenyl ether sulfate sodium salt 16.0 parts and polyoxyethylene (ethylene oxide 25 mol adduct) octyl phenyl ether phosphoric acid diester sodium salt 16 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 29 mPa · S.

COMPARATIVE EXAMPLE 1 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 56.4 parts, methoxypolyoxyethylene glycol (ethylene oxide 25 mol adduct) methacrylate 56.4 parts, ethyl methacrylate 112.8 parts, lauryl methacrylate 56.4 parts,
Polyoxyethylene (ethylene oxide 25 mol adduct) octyl ether sulfate sodium salt 9.0
And 9.1 parts of polyoxyethylene (48 mol adduct of ethylene oxide) octyl ether, 100 parts of a 0.2% aqueous solution of potassium persulfate was added dropwise with stirring, reacted, aged, and cooled to a concentration of 30% and a viscosity of 10 mPa · A water-based coating agent modifier as a white emulsion of S was obtained.

Comparative Example 2 In the same manner as in Example 1, water 6
00 parts, 254.3 parts of methacrylic acid, 5.4 parts of ethyl acrylate, 8.0 parts of 2-ethylhexyl methacrylate and polyoxyethylene (ethylene oxide 40 mol adduct) octyl ether sulfate sodium salt 3
2.1 parts of the solution 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. 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.
Liquid, 1.0 part of ethyl acrylate, 1.5 parts of 2-ethylhexyl methacrylate and 0.2% of potassium persulfate
An aqueous solution (15 parts) was dropped at a constant rate over 5 hours to cause a reaction. The reaction temperature was maintained at 85 to 100 ° C. After maintaining the same temperature for 3 hours after completion of the dropping (referred to as aging), the isopropyl alcohol was removed while adding water, and the mixture was cooled to 30 ° C. and cooled to 30 ° C. to give a water-based coating agent modifier having a concentration of 5% and a viscosity of 4500 mPa · S. I got

Comparative Example 3 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, methacrylic acid 88.3 parts, methoxypolyoxyethylene glycol (ethylene oxide 10 mol adduct) acrylate 1.4 parts, ethoxypolyoxyethylene propylene glycol (ethylene oxide 6
0 mol adduct / 30 mol propylene oxide adduct) 1.4 parts of methacrylic acid ester, ethyl acrylate
7 parts, ethyl methacrylate 85.4 parts, acrylic acid 2-
8.5 parts of ethylhexyl, 12.5 parts of polyoxyethylene (ethylene oxide 15 mol adduct) nonylphenyl ether phosphate monoester disodium salt and 12.5 parts of polyoxyethylene (ethylene oxide 25 mol adduct) lauryl phenyl ether Then, 100 parts of a 0.3% 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 10 mPa · S.

Comparative Example 4 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, 141.7 parts of methacrylic acid, 27.84 parts of methoxypolyoxyethylene (90 mol adduct of ethylene oxide) acrylate, 13.9 parts of methyl acrylate
Parts, 13.9 parts of ethyl acrylate, 38.9 parts of 2-ethylhexyl acrylate, 41.7 parts of lauryl acrylate
10.3 parts of polyoxyethylene (ethylene oxide 15 mol adduct) nonylphenyl ether phosphoric acid monoester disodium salt 10.3 parts and polyoxyethylene (ethylene oxide 25 mol adduct) lauryl ether
7 parts were added, and 100 parts of a 0.2% aqueous solution of ammonium persulfate was added dropwise with stirring, followed by reaction, aging, and cooling to a concentration of 30%.
An aqueous coating agent modifier as a white emulsion having a viscosity of 12 mPa · S was obtained.

Comparative Example 5 In the same manner as in Example 1, water 6 was added to a glass reaction vessel.
00 parts, 85.4 parts of methacrylic acid, 42.7 parts of methacrylic acid ester of ethoxypolyoxyethylene (ethylene oxide 25 mol adduct), ethoxypolyoxyethylene / propylene (60 mol adduct of ethylene oxide / 30 mol adduct of propylene oxide) acrylic Acid ester 5
7.0 parts, 42.7 parts of 2-ethylhexyl acrylate,
57.0 parts of 2-ethylhexyl methacrylate, 24.4 parts of disodium salt of polyoxyethylene (41 mol adduct of ethylene oxide) octylphenyl ether phosphate monoester and sodium salt of stearyl ether sulfate of polyoxyethylene (61 mol adduct of ethylene oxide) 21.4 parts were charged, and 100 parts of a 0.2% aqueous solution of ammonium persulfate was added dropwise with stirring, followed by reaction, aging, and cooling to obtain a water-based coating agent modifier as a white emulsion having a concentration of 30% and a viscosity of 10 mPa · S. Was.

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

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

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

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

[0046]

[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: In terms of solid content, means 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 twice,
It was conditioned and measured. Print gloss, dry pick, wet pick, water-absorbing ink depositability: Printed with Mei Seisakusho's RI-1 type printability tester. The dry pick, the wet pick, and the ink-adhesiveness of the ink were evaluated by a five-point method. The larger the value, the better. Smoothness: Measured by Oken type smoothness tester. The larger the value, the higher the smoothness and the better.

[0050]

[Table 2]

Evaluation Example 2 (1) Formulation of aqueous emulsion (part: solid content conversion, meaning part 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 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 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.

[0053]

[Table 3]

Evaluation Example 3 (1) Formulation of Water-Based Emulsion Paint (Part: Meaning of Formulation Ratio) Titanium Dioxide (JR-600A, manufactured by Teica Co., Ltd.) 35
0 parts, calcium carbonate [Escalon, manufactured by Sankyo Flour Milling Co., Ltd.
# 2000] 100 parts, dispersant [manufactured by San Nopco Co., Ltd.
Nopcospars 44-C] 4 parts, defoamer [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 manufactured by Tokyo Keiki Co., Ltd., 60 rp
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 occurred, ×: Many coating unevenness mud track: Mud crack (crack) of the coating film of the object was visually judged. ○: No mud cracks, △: Slight mud cracks generated, ×: Many mud cracks

[0056]

[Table 4]

[0057]

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. When scraping,
It has the effect of reducing streaks, bleeding, blade wear and coating suitability, and is capable of adjusting coating materials such as water-based paper 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 mainly composed of a binder, the viscosity of the aqueous emulsion under low shear is increased so as to be easily adjusted, and the shear is increased. Under high shear at a speed 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 which has not been known in the art, and has high water retention. . 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 effects such as ease of shear between emulsion particles and easy adjustment of viscosity based on the function of imparting viscosity, thixotropy and water retention, and Even with a base material through which water easily penetrates, a uniform coating layer without coating unevenness can be formed.
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, which has not been known in this field. It has the effect. ADVANTAGE OF THE INVENTION The modifier for water-based coating agents of the present invention can easily adjust the viscosity of a water-based emulsion paint, is excellent in coating suitability, and exerts an effect on the physical properties of a material to be coated. 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. Due to the above effects, the water-based coating agent modifier of the present invention has the effect of adjusting the water-based emulsion paint having physical properties suitable for high-speed coating in line-coating of the water-based emulsion paint, and has an effect of improving productivity. Improvement,
Realize high-speed line coating with implants, which is a coating technology trend in the paint industry, from the viewpoints of quality improvement, cost reduction, energy saving, etc., and impart good emulsion paint physical properties, high operability and high coated physical properties. It is suitable for application of a water-based emulsion paint.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 3/00 103 C09K 3/00 103G D21H 19/44 D21H 1/28 Z 19/20 1/34 F

Claims (8)

[Claims] 1. A total of 100 parts by weight of a monomer, (1) 25 to 90 parts by weight of methacrylic acid (salt), and (2) the following general formula (I) (Wherein, R ₁ is H or CH ₃ , R ₂ and R ₃ are H or one or more selected from the group consisting of alkyl groups having 1 to 2 carbon atoms, and R ₄ has 1 or more carbon atoms.) And the alkyl group (n) is 3 to 100.)
1 to 30 parts by weight, and (3) the following general formula (J) (Wherein, R ₅ is H or CH ₃ , and R ₆ has 1 carbon atom.
To 2 alkyl groups. ) Monomers B1 to 6
A copolymer of 0 parts by weight and 0 to 30 parts by weight of another ethylenically unsaturated monomer C copolymerizable therewith, wherein the weight ratio of monomer C / monomer B is less than 0.5 And 2% of a 5% by weight aqueous solution of a polymer completely neutralized with sodium hydroxide.
A modifier for a water-based coating agent, comprising a polymer having a viscosity at 5 ° C of 100 to 3,000 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. One or more selected from the group consisting of an alkyl ether phosphate ester salt and a polyoxyethylene alkylpropenyl phenyl ether sulfate salt and / or as a nonionic emulsifier polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether and One or more selected from the group consisting of polyoxyethylene alkylpropenyl phenyl ethers is used in an amount of 1 to 25 parts by weight based on 100 parts by weight of the total monomers. The modifier for an aqueous coating agent according to claim 1 or 2, which is subjected to emulsion polymerization. 4. A 5% by weight aqueous solution of a polymer completely neutralized with sodium hydroxide has a viscosity at 25.degree.
A modifier for a paper coating agent comprising the modifier according to any one of claims 1 to 3 at 500 mPa · s. 5. A paper coating composition containing the modifying agent according to claim 4 mainly containing a pigment and a binder.
A paper coating composition comprising 0.001 to 10 parts by weight per part by weight. 6. A 5% by weight aqueous solution of a polymer completely neutralized with sodium hydroxide having a viscosity at 25 ° C. of 300 to 3,
An aqueous emulsion paint modifier and an aqueous emulsion modifier comprising the modifier according to any one of claims 1 to 3 at 000 mPa · s. 7. An aqueous emulsion paint containing the modifier according to claim 6 mainly containing a filler and a binder, in an amount of from 0.001 to 1 based on 100 parts by weight of the filler.
A water-based emulsion coating composition, which is added in an amount of 0 parts by weight. 8. An aqueous emulsion composition comprising the modifier according to claim 6 in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the aqueous emulsion.