JP2779611B2 - Thermoreversible thickening binder composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder composition, and more particularly to a binder composition having a temperature-sensitive gelling property capable of imparting high gloss and printability, particularly when applied to the production of coated paper. About things.

[0002]

2. Description of the Related Art Recently, the resin obtained by emulsion polymerization using an ethylenically unsaturated surfactant has a glass transition temperature of -30.
There has been proposed a temperature-sensitive gelling latex composition in which a heat-sensitive gelling agent is blended with a latex at ５０50 ° C. (JP-A-6-299000).

[0003]

However, although the above composition gels by heating, all of the exemplified heat-sensitive gelling agents are nonionic and have a gloss or gloss when applied to the production of coated paper. There is a problem that the effect of improving printability is low.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on a thermosensitive gelling binder composition having a high effect of improving gloss or printability when used in the production of coated paper. By combining the temperature-sensitive gelling agent and latex to be formed, a strong gel can be formed more quickly by heating, and when applied to the production of coated paper, the effect of improving gloss or printability is remarkable. And reached the present invention.

That is, the present invention relates to a cationic resin latex (A) and a thickening compound (B) having hydrophilicity and hydrophobicity reversibly changing at a certain temperature and containing an anionic group. Is a thermoreversible thickening binder composition characterized by comprising:

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The cationic resin latex (A) in the present invention is not particularly limited in the type of resin, and examples thereof include vinyl polymers (acrylic resin, styrene-acrylic resin, styrene-butadiene-based resin). Resin, butadiene-acrylonitrile resin, vinyl acetate resin,
Ethylene-vinyl acetate resin, ethylene / propylene resin, polybutadiene resin, etc.), polyurethane resin,
Anionic resin latex of a resin such as a polyurethane urea resin may be used. The (A) is required to be cationic, whereby a thickening compound (B) whose hydrophilicity and hydrophobicity are reversibly changed at a certain temperature and containing an anionic group is used. When combined, an ion complex can be formed to give high thermosensitive gelling properties.

In (A), the resin constituting the cationic resin latex of a vinyl polymer is a (co) polymer of various radically polymerizable monomers. As the radically polymerizable monomer, for example, an acrylic monomer [ Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylene glycol Mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acryloyloxy polyglycerol, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl ) Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, (meth) acrylamide, N, N-dibutyl (meth) Acrylamide, cyclohexyl (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, 2-cyanoethyl (meth) acrylate, (meth) acrylic acid, (meth) acrylsulfonic acid, (meth) acryloylpoly Oxyalkylene sulfate, 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-
Phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1,1-trimethylamine (meth)
Acrylimide, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
(Meth) acrylonitrile, etc.), styrene monomers (styrene, α-methylstyrene, vinyltoluene, p
-Aminostyrene, styrenesulfonic acid, vinylbenzoic acid, divinylbenzene, etc.), diene monomers (butadiene, isoprene, chloroprene, etc.), vinyl ester monomers (vinyl acetate, vinyl propionate, etc.) and other monomers [ethylene, propylene , Vinyl alcohol, vinyl chloride, vinyl alcohol, allyl alcohol, N-vinyl-2-pyrrolidone, vinyl imidazole, N-methylol-ε-caprolactam, N-methylol maleimide, N-vinyl succinimide, N-vinyl carbazole, 2-vinyl Pyridine, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, alkylallyl sulfosuccinic acid, etc.]
Combinations of more than one species are included.

[0008] The cationic resin latex of a vinyl polymer is obtained by adding the radical polymerizable monomer to a cationic emulsifier or a cationic water-soluble polymer [N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth). ) Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, p-aminostyrene, vinylimidazole, 2-vinylpyridine, etc. (Hydrochloric acid, formic acid, acetic acid, phosphoric acid, etc.) or quaternizing agent (alkyl halide, dimethylsulfuric acid, diethylsulfuric acid, etc.) containing 50% by weight or more as a structural unit
Emulsion polymerization under known conditions using a (partially cationized product), a polymer having a cationic functional group (dimethylamino group, piperidinoethyl group, etc.) in an organic solvent is synthesized by a known method, and if necessary, It is obtained by a method of neutralizing or quaternizing with an acid or a quaternizing agent, adding water, removing the solvent after emulsification, or the like. In the case of emulsion polymerization, when the cationic emulsifier (a) having a radical polymerizable group or the cationic water-soluble polymer is used, the amount of the emulsifier in the aqueous phase is reduced, so that the thermosensitive gelling property of the binder composition of the present invention is reduced. Is more preferable, and it is particularly preferable that the amount of the emulsifier in the aqueous phase is 0.01 mmol / g (resin) or less.

The amount of the emulsifier in the aqueous phase can be determined by analyzing and quantifying the aqueous phase obtained by removing the resin component from the resin latex by liquid chromatography or the like. As a method of removing the resin component from the resin latex, for example, a method of removing the resin component by coagulating and solidifying the resin component after freezing the resin latex, a method of removing the resin component by sedimentation and solidification by a centrifugal separator, an acid or an alkali. In addition, a method of removing and solidifying and removing the resin component may be used.

As the cationic emulsifier (a) having a radical polymerizable group, for example, the following general formulas (1) to (6)
(A1) Cationic (meth) acrylates [CH ₂ ＣC (R ¹ ) CO ₂ CH ₂ CH (OH) CH ₂ N (R ² ) ₃ ] X (1) [CH ₂ ＣC (R ¹ ) CO (AO) pN (R ² ) ₃ ] X (2), etc. (a2) Cationic (meth) acrylamides ア ミ ド [CH ₂ ＣC (R ¹ ) CONHCH ₂ CH (OH) CH ₂ N (R ² ) ₃ ] X (3) [CH ₂ ＣC (R ¹ ) CONH (AO) pN (R ² ) ₃ ] X (4) (A3) Cationic styrene derivatives ｛[CH ₂ ＣＨCHAr (CH ₂ ) qN (R ² ) ₃ ] X (5) [CH ₂ ＣＨCHAr (AO) pN (R ² ) ₃ ] X (6) And the like. In the above general formulas (1) to (6), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group, alkenyl group or aralkyl group having 1 to 21 carbon atoms, and AO is a C ² to C 4 An oxyalkylene group, p is an integer of 2 to 200, Ar is an aromatic ring, q is an integer of 4 to 24, and X is an anionic counterion. As the anionic counter ion, halogen, NO ₃ , HSO ₄ , CH ₃ OSO ₂ , (CH ₃ O) ₂
Each anion such as PO ₂ , CH ₃ CO _{2, and} HCO _{3 is} exemplified.

As the cationic emulsifier, those having the above-mentioned radically polymerizable group are preferable, but known cationic emulsifiers having no radically polymerizable group (laurieutrimethylammonium chloride, triethanolamine monostearate formate) , Diethylaminoethanol stearamide amide acetate, stearamidomethylpyridinium chloride, etc.) can also be used. Among the cationic emulsifiers (a) having a radical polymerizable group, (a1) is preferable in terms of good polymerization stability, and (meth) acrylate having a cationic group and a polyoxypropylene chain is particularly preferable.

The amount of the emulsifier (a) used is usually 0.1 to 20% by weight based on the total weight of (a) and the resin component.

In producing the cationic resin latex of a vinyl polymer, a known polymerization initiator is used. Examples of the polymerization initiator include organic polymerization initiators (peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, benzoyl peroxide, lauroyl peroxide, etc.), azo compounds (azobisisobutyrate). Lonitrile, azobisisovaleronitrile, etc.)] and inorganic polymerization initiators [persulfates (sodium persulfate, ammonium persulfate, potassium persulfate, etc.) and the like]. The amount of the polymerization initiator to be used is usually 0.01 to 5 based on the monomer mixture.
% By weight.

Known chain transfer agents can be used to adjust the molecular weight of the resin, the gel content of the latex, and the like. Examples of the chain transfer agent include α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene and the like), terpinolene, terpinene, dipentene, an alkyl mercaptan having 8 to 18 carbon atoms, and an alkylene having 8 to 18 carbon atoms. Examples thereof include dithiol, alkyl thioglycolate, dialkylxanthogen disulfide, tetraalkylthiuram disulfide, carbon tetrachloride and the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0 to 15% by weight based on the total amount of the monomer mixture.

Further, a reducing agent [sodium pyrobisulfite,
Sodium sulfite, sodium hydrogen sulfate, ferrous sulfate,
Glucose, sodium formaldehyde sodium sulfoxylate, L-ascorbic acid (salt)], chelating agents (glycine, alanine, sodium ethylenediaminetetraacetate, etc.), pH buffers (sodium tripolyphosphate, potassium tetrapolyphosphate, etc.). You may make it contain during manufacture of (A).

As the cationic latex of polyurethane resin or polyurethane urea resin, for example, Japanese Patent Publication No. Sho 4
The thing described in 3-9076 can be used. Examples of the cationic latex of a polyurethane resin include a latex of an addition polymer of a polyol component containing a cationic polyol (N, N-dimethylaminoethoxy-2,3-dihydroxypropane, N-methyldiethanolamine, etc.) and a diisocyanate compound. Is mentioned.

Examples of the cationic latex of the polyurethane urea resin include an addition polymer in which a polyamine component is used in combination with the polyol component. Examples of the polyamine component include an aromatic polyamine (such as diaminotoluene), an aliphatic or alicyclic polyamine (such as ethylenediamine and isophoronediamine), and an amino group-containing compound obtained by reacting a diisocyanate compound with water.

Among the cationic resin latexes (A) exemplified above, a vinyl polymer cationic resin latex is preferable, and a styrene-butadiene resin cationic resin latex is particularly preferable in terms of good adhesive strength. preferable.

The content of the cationic group in (A) is usually 0.01 to 100 meq per 100 g of the resin component in (A),
Preferably it is 0.5 to 50 meq. 0.01meq
If it is less than 100, the thermosensitive gelling property becomes insufficient, and if it exceeds 100 meq, the stability of the latex decreases. The resin concentration is usually 20 to 75% by weight, preferably 40 to 60% by weight.
% By weight. The particle size of the resin latex (A) is usually 10 to 500 nm, preferably 50 to 300 n.
m, and the pH is usually 3 to 12, preferably 6 to 10
It is. If the particle size exceeds 500nm or pH
Is less than 3 or more than 12, the thermosensitive gelling property cannot be sufficiently exhibited.

In the present invention, the thickening compound (B) whose hydrophilicity and hydrophobicity reversibly change at a certain temperature as a boundary and which contains an anionic group has a polyoxyethylene group and an anionic group. In addition to the compound (B1), a copolymer (B2) of an N-alkyl, N-alkylene or N-alkoxyalkyl (meth) acrylamide and a vinyl monomer having an anionic group, an ethylene oxide-modified polysiloxane having an anionic group And alkylene oxide adducts of alkylphenol formalin condensates having anionic groups, water-soluble celluloses having anionic groups, and polyvinyl methyl ether having anionic groups.

The compound (B1) having a polyoxyethylene group and an anionic group includes a vinyl monomer (b1) having a polyoxyethylene group and a vinyl monomer (b2) having an anionic group as constituent units. (B1-1), a polyester (B1-3) obtained by a reaction with an anionic derivative of a polyoxyethylene compound (B1-2), polyethylene glycol, a polyol having an anionic group, and a dibasic acid , Polyethylene glycol, a polyol having an anionic group and a polyurethane (B1-4) obtained by reaction with a diisocyanate compound, those containing a polyoxyethylene group usually at least 50% by weight, preferably at least 70% by weight. No.

The vinyl monomer having a polyoxyethylene group (b1) constituting the above (B1-1) includes polyethylene glycol mono (meth) acrylate,
Polyethylene glycol monomethyl ether mono (meth) acrylate, polyethylene glycol monobutyl ether mono (meth) acrylate, polyethylene glycol monophenyl ether mono (meth)
Examples include acrylic acid esters, ethylene oxide (2 to 50 mol) adducts of hydroxystyrene, and ethylene oxide (2 to 50 mol) adducts of allyl alcohol. The polymerization degree of ethylene oxide is usually 2 to 50 mol, preferably 3 to 25 mol.

The vinyl monomer (b2) having an anionic group constituting (B1-1) includes (meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinyl sulfonic acid, (meth) ) Acrylic sulfonic acid, styrene sulfonic acid, vinyl benzoic acid, alkyl allyl sulfosuccinic acid, (meth) acryloyl polyoxyalkylene sulfate, etc. and salts thereof (alkali metal salts, ammonium salts, amine salts, etc.).

(B1-1) is a copolymer of the vinyl monomers (b1) and (b2),
It may be a copolymer of 2) and another vinyl monomer (c).

Other vinyl monomers (c) include:
(C-1) hydrophilic [excluding (b1) and (b2)]
However, (c-2) it may be lipophilic.

As (c-1), nonionic compounds [hydroxyethyl (meth) acrylate, (meth) acryloyloxy polyglycerol, vinyl alcohol, allyl alcohol, (meth) acrylamide, N-
Methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-vinyl-2-pyrrolidone, N
-Methylol maleimide, N-vinyl succinimide,
2-cyanoethyl (meth) acrylate and the like]; anionic compound [(meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, (meth) acrylsulfonic acid, styrenesulfonic acid, vinylbenzoic acid Acid, alkylarylsulfosuccinic acid, (meth) acryloylpolyoxyalkylene sulfate, etc. and salts thereof; compounds having an amine imide group [1,
1,1-trimethylamine (meth) acrylimide,
1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-
2′-hydroxyethyl) amine (meth) acrylimide, 1,1,1-trimethylamine (meth) acrylimide and the like].

Examples of (c-2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, and glycidyl (meth). A) acrylate derivatives such as acrylates, N-alkyl (meth) acrylamide derivatives such as N, N-dibutyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, (meth) acrylonitrile, styrene, 1-methylstyrene, Examples include vinyl acetate, butadiene, vinyl chloride, isoprene and the like.

The vinyl polymer (B1-1) can be obtained, for example, by a method similar to the method described in JP-A-6-9848.

Examples of the anionic derivative (B1-2) of the polyoxyethylene compound include sulfates, phosphates and chloroacetates of ethylene oxide adducts of aromatic or aliphatic alcohols; alkylene glycols and aromatic or aliphatic alcohols Sulfate, phosphate or chloroacetate of a propylene oxide / ethylene oxide block adduct of the above, and salts thereof.

Polyester (B1-3) obtained by reaction with polyethylene glycol, polyol having anionic group and dibasic acid and polyurethane (B1) obtained by reaction with polyethylene glycol, polyol having anionic group and diisocyanate compound Examples of the polyol having an anionic group constituting -4) include ethylene glycol diester of phosphoric acid, an alkylene oxide adduct of hydroxybenzenesulfonic acid, dimethylolpropionic acid, and the like, and salts thereof.

N-alkyl, N-alkylene or N-
The N-alkyl, N-alkylene or N-alkoxyalkyl (meth) acrylamide constituting the copolymer (B2) of the alkoxyalkyl (meth) acrylamide and the vinyl monomer having an anionic group includes N-isopropyl (meth) ) Acrylamide, N- (meth) acryloylpiperidine, (meth) acryloylmorpholine, N
-Isopropoxypropyl (meth) acrylamide, N
-Ethoxyethyl (meth) acrylamide and the like.

The thickening compound (B), whose hydrophilicity and hydrophobicity reversibly change at a certain temperature and containing an anionic group, is heated and dried when used as a binder for coated paper. The compound (B1) having a polyoxyethylene group and an anionic group is preferable from the viewpoint of suppressing the transfer of the resin latex particles to the surface of the coating composition for paper coating and imparting high gloss and printability to the coating composition. Among the B1), a vinyl monomer having a polyoxyethylene group (b)
A copolymer (B1-1) containing 1) and a vinyl monomer (b2) having an anionic group as constituent units is preferred.

The molecular weight per anionic group (B) is usually at least 100, and preferably from 150 to 50,000 from the viewpoint that the thermosensitive gelling property is particularly excellent. If the molecular weight per anionic group is less than 100, the stability of the binder composition will decrease, and if it exceeds 50,000, the effect of imparting thermogelling properties will decrease.

The weight average molecular weight of (B) is usually 1,000
0-5,000,000, preferably 5,000-50
It is 0000.

In the binder composition of the present invention,
The weight ratio of (B) to the total of 100 parts by weight of the solid content of (A) and (B) is usually 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight. The ratio of (B) is 0.
When the amount is less than 01 parts by weight, the thermosensitive gelling property becomes insufficient, and 3
If the amount exceeds 0 parts by weight, the viscosity of the binder composition increases, and the workability deteriorates.

In the composition of the present invention containing (A) and (B), the equivalent ratio of the amount of the anionic group of (B) to the amount of the cationic group of (A) is usually 0.1. 001
-10, preferably 0.01-1.0, particularly preferably 0.05-0.5. The equivalent ratio of the amount of anionic group is 0.
When the content is less than 001% by weight, the coated paper obtained when used as a binder for coated paper has insufficient white paper gloss.

The compound (B) reversibly changes in hydrophilicity and hydrophobicity at a certain temperature as a boundary, and the temperature (transition temperature) at which the hydrophilicity changes to hydrophobicity is usually 15 to 10.
0 ° C, preferably 40 to 80 ° C. The transition temperature is determined by gradually heating a 1% aqueous solution of (B) and measuring the temperature at which the aqueous solution starts to become cloudy or gel.

The thermoreversible thickening binder composition of the present invention comprises a resin latex (A) and a compound (B) alone or a mixture obtained by diluting (B) with water, which is lower than the transition temperature of the compound (B). At normal temperature, mixing equipment (paddle type stirring blade, etc.)
And obtained by mixing.

The binder composition of the present invention may be used, if necessary, for the purpose of enhancing adhesion, for example, cationized starch, oxidized starch, casein, soy protein, synthetic protein, polyvinyl alcohol, maleic anhydride resin, Known water-soluble compounds such as carboxymethyl cellulose and hydroxyethyl cellulose can be contained.

If necessary, various clays, kaolin, calcium carbonate, satin white, titanium oxide, aluminum hydroxide, barium sulfate, zinc oxide, calcium sulfate, talc, plastic pigment (polystyrene, styrene / butadiene copolymer) Or styrene /
One or more known pigments such as beads such as acrylic copolymer).

Further, if necessary, a pigment dispersant [sodium poly (meth) acrylate, sodium pyrophosphate, sodium hexametaphosphate, etc.] and an antifoaming agent (mineral oil-based antifoaming agent, silicon-based antifoaming agent, etc.) , And other additives [lubricants, pH adjusters, preservatives, water-proofing agents, printability improvers, etc.].

The binder composition of the present invention can be used as a binder for coated paper, a binder for carpet backing, a binder for nonwoven fabric, a binder for paint, a binder for printing ink, an adhesive, a ceramic binder,
Examples include a binder for glass fiber. Among them, a binder for coated paper is preferable in that the characteristics of the thermosensitive gelling binder can be sufficiently exhibited.

[0043]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in the examples are parts by weight.

Production Example 1 9 parts of polyethylene glycol (degree of polymerization = 7) monomethyl ether monomethacrylate, 1 part of itaconic acid and 2,2
2'-azobis (2,4-dimethylvaleronitrile)
Add 0.01 part to the ampoule, freeze, deaerate and seal.
Polymerization was performed at 8 ° C. for 8 hours to obtain a polymer 1.

Production Example 2 8.5 parts of tetraethylene glycol monomethyl ether monomethacrylate, 1.5 parts of methacrylic acid and 2,2
2'-azobis (2,4-dimethylvaleronitrile)
Add 0.01 part to the ampoule, freeze, deaerate and seal.
Polymerization was performed at 8 ° C. for 8 hours to obtain a polymer 2.

Production Example 3 10 parts of tetraethylene glycol monomethyl ether monomethacrylate and 2,2'-azobis (2,4-
0.01 part of dimethylvaleronitrile) was added to the ampoule, frozen, degassed, sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer 3.

Production Example 4 A pressurized reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas inlet tube, and a thermometer has 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, 4 parts of methacrylic acid, and a radical polymerizable group. 5 parts of quaternary salt of acryloyloxypolypropylene (degree of polymerization = 12) dimethylaminoethyl ether with methyl chloride as an emulsifier, sodium persulfate 1
And 0.2 parts of lauryl mercaptan were charged, and the system was replaced with nitrogen gas under stirring. Then, 37 parts of butadiene was injected from a dropping cylinder and reacted at 50 ° C. for 30 hours and at 85 ° C. for 5 hours. The unreacted monomer is stripped under reduced pressure, and the pH is adjusted to 9.5 with an aqueous solution of sodium hydroxide, whereby the SBR resin latex 1 (solid content of 47.
9%, hereinafter referred to as SBR1).

Production Example 5 In the same manner as in Production Example 4, 50 parts of styrene, 4 parts of methyl methacrylate, 4 parts of methacrylic acid, and 5 parts of acrylonitrile
Parts, butadiene 32 parts and methacryloyloxypolyoxypropylene (degree of polymerization = 9) dimethylaminoethyl ether quaternary salt with dimethyl sulfate 5 parts, SBR resin latex 2 (solid content 48.3%, hereinafter referred to as SBR2) Obtained.

Examples 1 to 4, Comparative Example 1 100 parts of the SBR1 obtained in Production Example 4 was mixed with 3 parts of a 20% aqueous solution of the polymer 1 obtained in Production Example 1 with stirring. Thus, Composition 1 was obtained. Similarly,
The composition 2 of Example 2 was converted from SBR1 and polymer 2 to SBR.
2 and Polymer 1 to Composition 3 of Example 3, SBR2 and Polymer 2 to Composition 4 of Example 4, SBR1 and Polymer 3
From the composition 5 of Comparative Example 1.

The obtained compositions 1 to 5 were allowed to stand in a hot water bath at 80 ° C. for 15 minutes under sealed condition, and the viscosity at 80 ° C. was measured.
For 2 hours and the viscosity was measured. Table 1 shows the results.

[0051]

[Table 1]

Examples 5 to 8, Comparative Examples 2 and 3 25 parts of water, 0.3 part of dispersant [SN Dispersant 5040 manufactured by San Nopco Co., Ltd.], 0.1 part of sodium hydroxide
Part, antifoaming agent [San Nopco Co., Ltd. Nopco DF122]
0.1 part, 45 parts of clay and 5 parts of calcium carbonate are dispersed and mixed at 2,000 rpm for 30 minutes with a disper, and the resulting dispersion is pre-gelatinized phosphorylated starch (30% aqueous solution) 8.3.
Parts and 14.1 parts of Composition 1 were added and uniformly mixed to obtain Coating Color 1 of Example 5. The same operation as described above was repeated, except that the composition 2 was used in place of the composition 1 and the coating color 2 of Example 6 was used.
The coating color 3 of Example 7 using the composition 3, the coating color 4 of Example 8 using the composition 4, and the coating color 5 of Comparative Example 2 using the composition 5, respectively. Obtained. Further, a coating color 6 of Comparative Example 3 was obtained using SBR1 instead of the composition 1.

Each of the coating colors 1 to 6 was applied to a medium paper of 58 g / m ^{2 at} a dry coating amount of about 8 g / m ² by using a bar coater, and dried at 150 ° C. in a circulating drier. Dried for seconds and cut. After that, processing (temperature 6
0 ° C, nip pressure 90 kg / cm, paper passing twice)
6 were prepared, and various physical properties of each coated paper were measured. Table 2 shows the results.

[0054]

[Table 2]

Printing test: An offset ink was solid printed with an RI printing machine manufactured by Akira Seisakusho Co., Ltd. Gloss: 75 ° gloss was measured with a gloss meter manufactured by Tokyo Denshoku Co., Ltd.

[0054]

The binder composition of the present invention is a thermosensitive gelling binder composition which has a low viscosity at a low temperature but sharply thickens by heating to form a strong gel. Since the gelling properties are extremely good, high gloss and printability can be imparted, particularly when used as a coating color binder in the production of coated paper. Further, the binder composition of the present invention is useful as a coating agent or an impregnating agent for various fabrics, films or sheets. It is also useful as a binder for adhesives and paints.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C04B 26/04 C09D 11/10 C09D 11/10 201/02 201/02 D04H 1/58 D04H 1/58 D06M 15/693 D06M 15 / 21 D21H 1/28 Z 15/693 D06M 15/21 (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 1/00-101/14 D21H 19/44-19/62 C03C 25/00 -25/02 C04B 26/00-26/32 C09D 11/00-11/20 C09D 101/00-201/10 D04H 1/58-1 / 68,3 / 12,5 / 04 D06M 15/00-15 / 693

Claims (8)

(57) [Claims] Claims: 1. A cationic resin latex (A) comprising a thickening compound (B) having a hydrophilicity and a hydrophobicity reversibly changing at a certain temperature and containing an anionic group. A thermoreversible thickening binder composition. 2. The binder composition according to claim 1, wherein (A) is a resin latex obtained using a cationic emulsifier (a) having a radical polymerizable group. 3. The binder composition according to claim 1, wherein (A) is a styrene-butadiene resin latex emulsion-polymerized using (meth) acrylate having a cationic group and a polyoxypropylene chain as an emulsifier. Stuff. 4. The binder composition according to claim 1, wherein (B) is a thickening compound containing at least 50% by weight of a polyoxyethylene group and at least one anionic group. . 5. The method according to claim 1, wherein (B) is a copolymer of a vinyl monomer (b1) having a polyoxyethylene group and a vinyl monomer (b2) having an anionic group. A binder composition as described in the above. 6. The binder composition according to claim 1, wherein the molecular weight per anionic group (B) is from 150 to 50,000. 7. The method according to claim 1, wherein (B) is contained in an amount of 0.01 to 30 parts by weight (solid content) based on 100 parts by weight of the total solid content of (A) and (B). A binder composition as described in the above. 8. The binder composition according to claim 1, which is used as a binder for a coating color for producing coated paper.