JP2000204199A - Binder composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a binder composition which has a low viscosity at a low temperature and can thermally increase the viscosity to form a strong gel by adding a water-soluble polymer to a combination of a temperature-sensitive gelling agent with a latex not forming an ion complex. SOLUTION: This binder composition comprises (A) a nonionic resin latex having an aqueous phase emulsifier content of <=0.01 mmol/g (resin), (B) a temperature-sensitive gelling agent, and (C) a water-soluble polymer. The component A is preferably a resin latex obtained by an emulsion polymerization using a nonionic emulsifier having a radically polymerizable group. The component B is preferably, for example, an anionic temperature-sensitive gelling agent comprising a copolymer consisting essentially of a polyoxyalkylenemonool mono(meth)acrylate, an anionic group-having vinylic monomer, etc. A component A:B solid content weight ratio is preferably 70:30 to 99.99:0.01, and a component (A+B):C solid content weight ratio is preferably 35:65 to 90:10.

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 thermosensitive gelling binder composition which gives a low-viscosity paint when used in a coating color for producing coated paper.

[0002]

2. Description of the Related Art Conventionally, a thermosensitive gelling agent such as an alkylene oxide adduct of an alkylphenol-formalin condensate is added to an anionic resin latex obtained by emulsion polymerization using an ethylenically unsaturated surfactant having an anionic group. A blended heat-sensitive gelling latex composition is known (JP-A-6-299000). Further, a binder composition comprising an anionic resin latex and a thermosensitive gelling agent containing a cationic group such as a morpholinoethyl methacrylate polymer has also been proposed (Japanese Patent Application Laid-Open No. Hei 9 (1998) -107).
-111133 gazette).

[0003]

However, Japanese Patent Application Laid-Open No.
Although the heat-sensitive gelling latex composition disclosed in JP-A-299000 is gelled by heating, once heated, the emulsion coagulates and gels, so it does not redisperse even when cooled, producing coated paper. However, there is a problem that it cannot be used for applications that may be temporarily heated in a coating process such as a coating color. Further, Japanese Patent Application Laid-Open No.
Since the binder composition disclosed in Japanese Patent No. 11133 is thermoreversible in gelation, it can be used for applications that may be temporarily heated in a coating process, and can be used in combination with a water-soluble polymer. It is described that the viscosity of the composition becomes too high, although high blank gloss and printability can be imparted, but due to the formation of the ion complex, especially when the amount of the water-soluble polymer used in combination is large. There were difficulties.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, the present inventors have also used the present invention for applications that may be temporarily heated in a coating process such as a coating color for manufacturing coated paper. As a result of intensive studies on a binder composition having a temperature-sensitive gelling property that can provide a low-viscosity coating material, the use of a water-soluble polymer in combination with a latex that does not form an ion complex and a temperature-sensitive gelling agent The inventors have found that the above problem can be solved, and have reached the present invention.

That is, according to the present invention, the amount of the emulsifier in the aqueous phase is 0.1.
A binder composition comprising a nonionic resin latex (A) of not more than 01 mmol / g (resin), a thermosensitive gelling agent (B) and a water-soluble polymer (C); and the binder composition It is a coating color for coated paper consisting of materials and pigments.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The resin constituting the nonionic resin latex (A) in the present invention is an acrylic resin, a styrene-acrylic resin, a styrene-butadiene resin, a butadiene-acrylic resin, a butadiene-acrylonitrile resin. Resin, vinyl acetate resin, ethylene-
Vinyl polymers such as vinyl acetate resins, ethylene-propylene resins, and polybutadiene resins are exemplified.

The vinyl polymer is a (co) polymer of a radical polymerizable monomer containing neither a cationic group nor an anionic group. Examples of the radical polymerizable monomer include (cyclo) alkyl (C 1 -C 1) ~ 22)
(Meth) acrylate [methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth)
Acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth)
Acrylate etc.]; aromatic ring-containing (meth) acrylate [benzyl (meth) acrylate etc.]; hydroxyl group-containing (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate Acrylate,
Glycerin mono (meth) acrylate, polyglycerin (polymerization degree 2 to 4) mono (meth) acrylate, etc.); (meth) acrylamide or a derivative thereof ((meth) acrylamide, N, N-dibutyl (meth) acrylamide, cyclohexyl (meth) ) Acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone acrylamide, etc.]; cyano group-containing monomers [(meth) acrylonitrile, 2-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) ) Acrylamide, etc.]; polyfunctional (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 2,2-bis (4-
Hydroxyethylphenyl) propanedi (meth) acrylate, etc.]; styrenes (styrene, α-methylstyrene, vinyltoluene, divinylbenzene, etc.); diene monomers (butadiene, isoprene, chloroprene, etc.);
Vinyl esters (vinyl acetate, vinyl propionate, etc.), epoxy group-containing monomers [glycidyl (meth) acrylate, allyl glycidyl ether, etc.]; monoolefins (ethylene, propylene, 1-butene, etc.), halogen-containing monomer (Vinyl chloride, vinylidene chloride, etc.), heterocyclic-containing monomers (N-vinyl-2-pyrrolidone, N-methylolmaleimide, N-vinylsuccinimide, etc.);
Unsaturated dibasic acid dialkyl esters [dialkyl maleate (carbon number 1 to 4) ester, itaconic acid dialkyl (carbon number 1 to 4) ester, etc.]; silyl group-containing monomer [3-trimethoxysilylpropyl (meta) Acrylate, etc.] and combinations of two or more of these. Among these, alkyl (meth) acrylates, styrenes and diene monomers are preferable, and a combination of a diene monomer with alkyl (meth) acrylate and / or styrenes is particularly preferable.

In the present invention, the amount of the emulsifier in the aqueous phase of the nonionic resin latex (A) must be not more than 0.01 mmol (mmol) / g (resin).
More preferably, it is not more than 02 mmol / g. When the amount of the emulsifier in the aqueous phase exceeds 0.01 mmol / g, the thermosensitive gelling property is inhibited.

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.

The amount of the emulsifier in the aqueous phase is 0.01 mmol / g
(Resin) As a method for producing the following nonionic resin latex (A), for example, a method in which a radically polymerizable monomer is emulsion-polymerized by a known method using an emulsifier having low solubility in water; A method of emulsion-polymerizing a radically polymerizable monomer by a known method using a nonionic emulsifier (a) having a compound; a method of emulsion-polymerizing a radically polymerizable monomer by a known method using a nonionic protective colloid; A method of synthesizing a polymer having a nonionic hydrophilic group (hydroxyl group, polyoxyethylene group, or the like) in a solvent by a known method, adding water, emulsifying the resultant, and removing the solvent after emulsification is used. Among these methods, the methods (1) and (2) are preferable in that the resin latex (A) can be easily obtained under ordinary conditions, and the method (2) is particularly preferable.

The nonionic emulsifier (a) having a radical polymerizable group includes, for example, (1) nonionic (meth) acrylic esters, those represented by the following formula: CH ₂ ＣC (R ¹ ) CO (AO) pOR ² (wherein 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, AO is an oxyalkylene group having 2 to 4 carbon atoms, (p represents an integer of 2 to 200); (2) Nonionic (meth) acrylic amides, such as those represented by the following formula: CH ₂ ＣC (R ¹ ) CONHR ³ (AO) pOR ² CH ₂ ^{= C (R 1) CON [} R 3 (AO) pOR 2] 2 ( wherein R ¹ is a hydrogen atom or a methyl group, R ³ is 1 to carbon atoms
4 alkylene groups, R ² is a hydrogen atom or a carbon atom
1 alkyl group, alkenyl group or aralkyl group, A
O is an oxyalkylene group having 2 to 4 carbon atoms, p is 2 to 20
Indicates an integer of 0. (3) Nonionic styrene derivatives, such as those represented by the following formula: CH ₂ ＣC (R ¹ ) Ar (AO) pOR ² (wherein R ¹ is a hydrogen atom or a methyl group, and Ar is an aromatic ring) , AO is an oxyalkylene group having 2 to 4 carbon atoms, p is 2
200 integers, R ² is 1 to 21 hydrogen atoms or carbon atoms
Represents an alkyl group, an alkenyl group or an aralkyl group. (4) Nonionic allyl compounds, such as those represented by the following formula: (R ² ) (R ⁴ ) Ar (CH ₂ CH ＝ CH ₂ ) (AO) pO
R ² CH ₂ ＣＨCHCH ₂ (AO) pOR ² (wherein R ² is a hydrogen atom or an alkyl group, alkenyl group or aralkyl group having 1 to 21 carbon atoms, R ⁴ is an alkyl group having 4 to 18 carbon atoms, alkenyl Or an aralkyl group, Ar is an aromatic ring, AO is an oxyalkylene group having 2 to 4 carbon atoms, and p is an integer of 2 to 200.); (5) Nonionic maleic esters represented by the following formula: R ² (AO) pOCOCH ＝ CHCO (AO) pOR ² (wherein R ² is a hydrogen atom or an alkyl, alkenyl, or aralkyl group having 1 to 21 carbon atoms, and AO is an oxy group having 2 to 4 carbon atoms) (6) nonionic itaconic esters, such as those represented by the following formula: CH ₂ ＣC [CH ₂ CO (AO) pOR ² ] CO (AO ) P
OR ² (wherein, R ² represents a hydrogen atom or an alkyl group, alkenyl group, or aralkyl group having 1 to 21 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and p represents an integer of 2 to 200.) And the like.

Among these, (1) nonionic (meth) acrylates, and (2) nonionic (meth) acrylic esters have high copolymerizability with radically polymerizable monomers and good polymerization stability. Meth) acrylamides and (3) nonionic styrene derivatives are preferred,
(1) and (3) are particularly preferred.

The emulsifier having the radical polymerizable group (a)
Is usually used in an amount of 0.1 to 20% by weight based on the resin component,
Preferably it is 1 to 10% by weight.

When the nonionic latex (A) is produced by emulsion polymerization, 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 (azobisiso Butyronitrile, azobisisovaleronitrile, etc.); inorganic polymerization initiators [persulfates (sodium persulfate, ammonium persulfate, potassium persulfate, etc.), hydrogen peroxide, etc.]. The amount of the polymerization initiator to be used is generally 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total amount of the monomer mixture.

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 (such as 2,4-diphenyl-4-methyl-1-pentene), terpinolene, terpinene, dipentene, an alkyl mercaptan having 8 to 18 carbon atoms, and an alkyl mercaptan having 8 to 18 carbon atoms. Examples thereof include alkylenedithiol, alkyl thioglycolate, dialkylxanthogen disulfide, tetraalkylthiuram disulfide, chloroform, and carbon tetrachloride. 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, preferably 0 to 5% by weight, based on the total amount of the monomer mixture.

Also, if necessary, reducing agents [sodium pyrobisulfite, sodium sulfite, sodium hydrogen sulfate, ferrous sulfate, glucose, sodium formaldehyde sulfoxylate, L-ascorbic acid (salt)], chelating agents (glycine, alanine) , Sodium ethylenediaminetetraacetate, etc.) and pH buffers (sodium tripolyphosphate, potassium tetrapolyphosphate, etc.). The amount of these additives to be used is generally 0 to 5% by weight, preferably 0 to 3% by weight, based on the total amount of the monomer mixture.

As the nonionic resin latex (A), an acrylic resin latex, a styrene-acrylic resin latex, a styrene-butadiene resin latex, and a butadiene-based latex are preferred because of their good adhesive strength.
Acrylic resin latex is preferable, and styrene-butadiene resin (styrene unit content: 20 to 60% by weight) latex is more preferable.

The resin concentration of the latex (A) is usually 20 to 75% by weight, preferably 40 to 60% by weight. The particle size of the resin latex (A) is usually 5
00 nm or less, preferably 50 to 300 nm, and p
H is usually 3 to 12, preferably 6 to 10. When the particle size exceeds 500 nm or when the pH is less than 3 or more than 12, thermogelling properties may not be sufficiently exhibited.

The thermosensitive gelling agent (B) according to the present invention is a compound having a transition temperature at which the aqueous liquid reversibly develops a thickening effect of the aqueous liquid upon heating, and comprises an anionic thermosensitive gelling agent (B).
1), a cationic thermosensitive gelling agent (B2) and a nonionic thermosensitive gelling agent (B3).

The anionic thermosensitive gelling agent includes:
(A) a monomer having a vinylalkyl (C1-6) ether (such as vinyl methyl ether) and an anionic group [(meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid , (Meth) acryl sulfonic acid, styrene sulfonic acid, vinyl benzoic acid, alkyl (C1-10) allyl sulfosuccinic acid, (meth) acryloyl polyoxyalkylene (degree of polymerization 2-1)
5) an acid such as a sulfate ester or a salt thereof (alkali metal salt, amine salt, etc.)] with (B) N-monosubstituted (meth) acrylamide [N-
Isopropyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, etc.] and the monomer having an anionic group as essential monomers;
A copolymer containing N, N-disubstituted (meth) acrylamide [N, N-diethyl (meth) acrylamide, N- (meth) acryloylpyrrolidine, etc.] and the above monomer having an anionic group as essential monomers. (D) polyoxyalkylene having 2 to 4 carbon atoms in the alkylene group (degree of polymerization: 3 to 4)
0) Mono (meth) acrylate of monool or diol [tetraethylene glycol monoethyl ether mono (meth) acrylate, pentaethylene glycol monobutyl ether mono (meth) acrylate, methoxytrioxypropylene tetraoxyethylene (meth)
Mono (meth) acrylate of acrylate, ethylene oxide 6 mol adduct of tetrapropylene glycol, etc.]
And (e) copolymers of polyoxyalkylenes having 2 to 4 carbon atoms in the alkylene group (degree of polymerization: 3 to 40) monools or diols. Monovinyl phenyl ether (tetraethylene glycol monomethyl ether monovinyl phenyl ether, pentaethylene glycol monoethyl ether monovinyl phenyl ether, methoxypentaoxypropylene tetraoxyethylene vinyl phenyl ether, monovinyl phenyl ether of ethylene oxide 8 mol adduct of tetrapropylene glycol, etc.) and In addition to copolymers containing the above-mentioned monomer having an anionic group as an essential monomer, etc., ethylene oxide-modified polysiloxane having anionic group, alkylphenol formal having anionic group Alkylene oxide adducts of condensates, water-soluble cellulose ethers or the like having an anionic group. Among these, (d) and (e) are preferable in that a lower-viscosity composition can be obtained when used in combination with the water-soluble polymer (C) described below.

The molecular weight per anionic group (B1) is usually 100 or more, preferably 150 to 50,000.
0. If the molecular weight per anionic group is less than 100, the thermosensitive gelling property may not be sufficiently exhibited.

As the cationic thermosensitive gelling agent (B2), (f) a (meth) acrylic acid ester of an alkylene oxide adduct of a cyclic amine containing an essential monomer (co)
Polymers [morpholinoethyl (meth) acrylate polymers and the like described in JP-A-6-9848, etc.];
(Co) polymer [diisopropylaminoethyl (meth) acrylate polymer or the like] containing (meth) acrylic acid ester of alkylene oxide adduct of acyclic amine having 5 or more carbon atoms as essential monomer; (T) polyimino (Co) polymers having a vinyl monomer having an ethylene group (degree of polymerization of 2 to 50) as an essential monomer [tetraethyleneimine mono (meth) acrylamide polymer and the like described in JP-A-9-12781 And the like); (i) a polymer comprising a monomer having an epoxy group and an alkylamino group having 5 or more carbon atoms of a cyclic amino group or an alkyl group (such as polymorpholinoethyl glycidyl ether described in JP-A-9-31340); And (nu) (meth) acrylamide having an alkylamino group having 5 or more carbon atoms of a (nu) cyclic amino group or an alkyl group as an essential monomer. That (co) polymer [N- morpholinoethyl (meth) acrylamide polymer and the like]; (Le)
Vinyl alkyl (C1-6) ether (vinyl methyl ether, vinyl isobutyl ether, etc.) and a monomer having a cationic group [N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl ( (Meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, vinylaniline, vinylimidazole, p-aminostyrene, N-vinylcarbazole, 2-vinylpyridine, etc., or salts thereof] as the essential monomer; (E) N-monosubstituted (meth) acrylia De [N- isopropyl (meth)
Acrylamide, N-methoxypropyl (meth) acrylamide, etc.] and a monomer having the above cationic group as essential monomers; (W) N, N-disubstituted (meth) acrylamide [N, N-diethyl (meth) acrylamide, N- (meth) acryloylpyrrolidine, etc.) and the above-mentioned monomer having a cationic group as essential monomers; (f) alkylene group having 2 to 4 carbon atoms Polyoxyalkylene (degree of polymerization 3 to 40) monool or diol mono (meth) acrylate [tetraethylene glycol monoethyl ether mono (meth) acrylate, pentaethylene glycol monobutyl ether mono (meth) acrylate, methoxytrioxypropylene tetra Oxyethylene (meth) acrylate, tetrapropylene glycol Mono (meth) acrylate of ethylene oxide 6 mol adduct) and the above-mentioned monomer having a cationic group as essential monomers; (yo) polyoxyalkylene having 2 to 4 carbon atoms of alkylene group (Polymerization degree: 3 to 40) Monovinyl phenyl ether of monool or diol (tetraethylene glycol monomethyl ether monovinyl phenyl ether, pentaethylene glycol monoethyl ether monovinyl phenyl ether, methoxypentaoxypropylene tetraoxyethylene vinyl phenyl ether, tetrapropylene glycol Monovinyl phenyl ether of ethylene oxide 8 mol adduct) and the above-mentioned monomer having a cationic group as essential monomers, and an ethylene oxide-modified polymer having a cationic group. Hexane, alkylene oxide adducts of alkylphenol formalin condensates having a cationic group include the water-soluble cellulose or the like having a cationic group. Of these, particularly preferred are (f) and (f) in that a lower viscosity composition is obtained when used in combination with the water-soluble polymer (C) described below.

The molecular weight of the cationic group (B2) is usually 100 or more, preferably 700 to 50,000.
0. If the molecular weight per cationic group is less than 100, the thermosensitive gelling property may not be sufficiently exhibited.

Examples of the nonionic thermosensitive gelling agent (B3) include alkylene oxide adducts of (ta) alkylnaphthalene formalin condensate (such as those described in JP-A-63-193901); Oxide-modified polyorganosiloxanes (such as those described in JP-A-6-256617); (so) cellulose-based temperature-sensitive gelling agents (methylcellulose, hydroxymethylcellulose, etc.); (tu) vinylalkyl (C1-6) Ether polymers (such as vinyl methyl ether polymers); (d) N-
(Co) polymers containing mono-substituted (meth) acrylamide as an essential monomer [N-isopropyl (meth) acrylamide polymer, N-methoxypropyl (meth) acrylamide polymer, etc. described in JP-A-1-14276. [N, N-diethyl (meth) acrylamide polymer, N- (meth) acryloylpyrrolidine polymer] (co) polymer having (N) N, N-disubstituted (meth) acrylamide as an essential monomer And the like described in JP-A-60-233184]; (la) an alkylene group having 2 to 4 carbon atoms
(Co) polymer having a polyoxyalkylene (degree of polymerization 3 to 40) monool or diol mono (meth) acrylate as an essential monomer [tetraethylene glycol monoethyl ether mono (meth) acrylate polymer, pentaethylene Glycol monobutyl ether mono (meth) acrylate polymer, methoxytrioxypropylene tetraoxyethylene (meth) acrylate polymer,
Mono (meth) acrylate polymer of ethylene oxide 6 mol adduct of tetrapropylene glycol etc.], (M)
A (co) polymer (tetraethylene glycol monomethyl ether monovinyl phenyl ether polymer) containing, as an essential monomer, a polyoxyalkylene having an alkylene group of 2 to 4 carbon atoms (degree of polymerization: 3 to 40) monool or diol monovinyl phenyl ether as an essential monomer Coalescent, pentaethylene glycol monoethyl ether monovinyl phenyl ether polymer, methoxypentaoxypropylene tetraoxyethylene vinyl phenyl ether polymer, monovinyl phenyl ether polymer of ethylene oxide 8 mol adduct of tetrapropylene glycol, etc.) and (u) vinyl acetate / Vinyl alcohol copolymer and the like. Among these, (la) and (mu) are preferable in that a composition having a lower viscosity can be obtained when used in combination with the water-soluble polymer (C) described below.

The anionic thermosensitive gelling agent (B1) or the cationic thermosensitive gelling agent (B2) may be used in an optional ratio together with the nonionic thermosensitive gelling agent (B3). it can.

The weight-average molecular weight of the thermosensitive gelling agent (B) is
Usually 1,000 to 5,000,000, preferably 2,
000 to 500,000. The transition temperature of (B) is usually 15 to 100 ° C, preferably 40 to 80 ° C.
It is. 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.

As the water-soluble polymer (C) in the present invention, those usually used for paper processing or fiber treatment, specifically, polyvinyl alcohol or a modified product thereof (polyvinyl alcohol, ethylene-vinyl acetate copolymer) Combined partial saponified product, polyvinyl alcohol partially acetalized product, etc.), starch or modified product thereof (oxidized starch, phosphate esterified starch, cationized starch, casein, soybean protein, synthetic protein, mannangalactan derivative, carboxymethyl cellulose, etc.) Polyacrylamides (acrylamide polymer, acrylamide-sodium (meth) acrylate copolymer, Mannich-modified polyacrylamide, etc.), formalin resin (urea-formalin resin, melamine-formalin resin, etc.), polyethyleneimine, Li amide polyamine - epichlorohydrin, styrene - sodium salt of maleic acid copolymer,
(Meth) acrylic acid alkyl ester- (meth) acrylic acid copolymer soda salt and the like. Among them, polyvinyl alcohol or a modified product thereof and starch or a modified product thereof are preferable from the viewpoint of providing good water retention.

The number average molecular weight of (C) is usually 2,000
~ 500,000, preferably 10,000-200,
000.

The weight ratio of the solid content of the nonionic resin latex (A) to the temperature-sensitive gelling agent (B) in the present invention is usually (50-99.999) :( 0.001-50), preferably (70). ９９99.99): (0.01 to 30). By setting the ratio of (B) within the above range, a coating paper having a low viscosity of the coating at normal temperature, good coating suitability, and gelling at the time of drying by heating to have a high white gloss and high printing suitability is obtained. A binder composition is obtained. Also,
The solid content weight ratio of [(A) + (B)] :( C) is usually (10-95) :( 90-5), preferably (35-9).
0): (65 to 10). By setting the ratio of (C) within the above range, it is possible to obtain a binder composition having low coating viscosity at room temperature and good water retention and good coating suitability.

The composition of the present invention comprising the resin latex (A), the temperature-sensitive gelling agent (B) and the water-soluble polymer (C) comprises (A) and (B) alone or (B) And (C) alone or (C) diluted with water at a temperature lower than the transition temperature of (B) by mixing with a usual mixing device (paddle-type stirring blade or the like). can get.

In the composition of the present invention, if necessary, known pigments [various clays, kaolin, calcium carbonate, satin white, titanium oxide, aluminum hydroxide, barium sulfate, zinc oxide, calcium sulfate, talc, plastic Pigment (beads such as polystyrene, styrene / butadiene copolymer or styrene / acrylic copolymer), etc.]. The pigment content is
It is usually 0 to 25 parts by weight, preferably 3 to 10 parts by weight, based on 1 part by weight of the total solid content of (A) + (B) + (C).

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 [lubricant, pH adjuster, preservative, waterproofing agent, printability improving agent, etc.]. The content of the additive is usually 0 to 2.5 parts by weight, preferably 0.001 part by weight based on 1 part by weight of the total solid content of (A) + (B) + (C).
5 to 0.5 parts by weight.

The binder composition of the present invention has a characteristic that it has a low viscosity at room temperature, a temperature-sensitive gelling property upon heating and drying to increase the viscosity, and returns to the original low viscosity when cooled. It is particularly useful as a binder for paper coating colors. Further, it can be suitably used as a carpet backing binder, a binder for nonwoven fabric, a binder for various paints, a binder for printing ink, an adhesive, a ceramic binder, and a binder for glass fiber.

An example of the formulation of a coating color for coated paper using the binder composition of the present invention is as follows (parts by solids). (Normal) (preferably) resin latex (A) 2 to 50 to 25 thermosensitive gelling agent (B) 0.0001 to 50 0.0005 to 11 water-soluble polymer (C) 2 to 50 5 to 25 pigment 100 100 Pigment dispersant 0-10 0.05-5 Other additives 0-10 0.05-5 Further, the solid content concentration of the coating color for coated paper is usually 10-10.
It is 80% by weight, preferably 30 to 65% by weight.

Next, a method for producing a coating color for coated paper using the binder composition of the present invention will be described.
First, a pigment is dispersed in water using a dispersing device in the presence of a pigment dispersant, an antifoaming agent, etc., to obtain a pigment slurry. Next, a coating color is obtained by blending the binder composition of the present invention and the other additives described above. Examples of the dispersing device include a high-speed mixer, a Keddy mill, a speed mill, a sigma blade kneader, a more house mill, and a lead kneader.

The coated paper is obtained by applying a coating color for coated paper to a base paper for coating using a coating machine, heating and drying and, if necessary, smoothing. The coating amount of the coating color is usually 1 to 50 g / m ² as a weight after drying is preferably 5 to 25 g / m ^2.

The base paper for coating is not particularly limited, and acidic or neutral, high-quality paper, medium-quality paper or lower-grade paper (with a basis weight of 35 to 400 g / m ²⁾ is used as it is or after being calendered. You. If necessary, a modified starch aqueous solution, a general coating color or a coating color obtained by using the binder composition of the present invention may be dried in an amount of 0.1 to 50 g / m ^{2 as a} preliminary coating. The coated paper may be used as a base paper for coating, and if necessary, the pre-coated paper which has been subjected to a smoothing treatment may be used as the base paper for coating.

The coating is performed in one or two or more layers by a coating machine. Coating machines include roll coaters (size presses, gate roll coaters, etc.), double-sided simultaneous coating type coaters (build blade coaters, twin blade coaters, etc.), various blade coaters (bench type coaters, helicopters, etc.), air knife coaters , A rod coater, a brush coater, a curtain coater, a chaplex coater, a bar coater, a gravure coater and the like.

The paper coated with the coating color is dried by a drier and then subjected to a smoothing treatment as required. Examples of the dryer include an infrared dryer, a drum dryer, an air cap dryer, an air foil dryer, an air conditioner bear dryer, and a combination thereof. The drying temperature varies depending on the type of dryer, but the temperature inside the dryer is usually 50 to 300 ° C.

The smoothing process is performed using a normal calendar (super calendar, gloss calendar, soft calendar,
(A machine calendar or the like) on-machine or off-machine, and can also be performed by a so-called cast finish such as a wet casting method using a cast drum, a re-wet casting method or a gelling casting method. The processing pressure and temperature are not particularly limited, and the nip pressure is usually 20 to 500 kg / cm, and the temperature is usually room temperature to 300 ° C. The number of pressure nips is usually 1
~ 15. In addition, a water application device using a roll, an electrostatic humidifier, a steam humidifier, or the like may be disposed together with the calendar for humidity control and humidification of the processed paper after finishing.

[0041]

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 examples, parts are parts by weight and% is% by weight.

Production Example 1 8.5 parts of tetraethylene glycol monoethyl ether monoacrylate, 1.5 parts of methacrylic acid,
2'-azobis (2,4-dimethylvaleronitrile)
Add 0.01 part to the ampoule, freeze, deaerate and seal.
At 8 ° C. for 8 hours to form an anionic thermosensitive gelling agent (B
1-1) was obtained. The number average molecular weight (GP) of (B1-1)
C, the same hereinafter) was about 250,000, and the transition temperature (1% aqueous solution, hereinafter the same) was 55 ° C.

Production Example 2 9 parts of tetraethylene glycol monoethyl ether monomethacrylate, 1 part of dimethylaminoethyl methacrylate and 0.01 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were added to an ampoule and frozen. After deaeration, the system was sealed and polymerized at 50 ° C. for 8 hours to obtain a cationic thermosensitive gelling agent (B2-1). The (B2-1) had a number average molecular weight of about 280,000 and a transition temperature of 48 ° C.

Production Example 3 9 parts of polyethylene glycol (degree of polymerization = 7) monobutyl ether monomethacrylate and 0.01 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule, which was frozen, degassed, and then sealed. Then, the mixture was polymerized at 50 ° C. for 8 hours to obtain a nonionic thermosensitive gelling agent (B3-1).
The (B3-1) had a number average molecular weight of about 200,000 and a transition temperature of 60 ° C.

Production Example 4 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, and 4 parts of hydroxyethyl acrylate were placed in a pressurized reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas inlet tube, and a thermometer.
Parts, an acrylic acid ester of ethylene oxide 14 mol adduct of nonylphenol as an emulsifier having a radical polymerizable group, 5 parts, 1 part of sodium persulfate and 0.2 part of lauryl mercaptan were charged, and the system was replaced with nitrogen gas under stirring. , 37 parts of butadiene was press-fitted from a drip cylinder,
The reaction was carried out at 50 ° C. for 30 hours and further at 85 ° C. for 10 hours. Subsequently, the unreacted monomer was stripped under reduced pressure, and the pH was adjusted to 9.5 with an aqueous sodium hydroxide solution to obtain a nonionic SBR resin latex (hereinafter referred to as SBR) having a solid content of 47.9%. The amount of emulsifier in the aqueous phase of this latex is 0.0004 mmol / g
(Resin).

Production Example 5 In the same manner as in Production Example 4, 50 parts of styrene, 4 parts of methyl methacrylate, 5 parts of acrylonitrile, 4 parts of acrylamide, 32 parts of butadiene and 5 parts of acrylic acid ester of ethylene oxide adduct of nonylphenol with 5 parts were solidified. A 48.3% nonionic SBR resin latex (hereinafter referred to as SBR) was obtained. The amount of the emulsifier in the aqueous phase of this latex is 0.0002 mmol / g (resin)
Met.

Production Example 6 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, 4 parts of methacrylic acid, and a radical polymerizable group were placed in a pressurized reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas inlet tube, and a thermometer. 5 parts of sodium salt of acryloyloxypolypropylene (degree of polymerization = 12), 1 part of sodium persulfate and 0.2 part of lauryl mercaptan were charged as an emulsifier having the same, and the system was replaced with nitrogen gas under stirring and then butadiene was added from a dropping cylinder. 37 parts were injected and reacted at 50 ° C. for 30 hours and further at 85 ° C. for 5 hours. Then, the unreacted monomer was stripped under reduced pressure, and the pH was adjusted to 9.5 with an aqueous sodium hydroxide solution.
% Anionic SBR resin latex (hereinafter referred to as SBR)
). The amount of the emulsifier in the aqueous phase of this latex was 0.0003 mmol / g (resin).

Examples 1 to 6 and Comparative Examples 1 and 2 Each component was blended according to the formulation shown in Table 1 to prepare binder compositions 1 to 6 of the present invention and binder compositions 7 to 8 for comparison.
Was prepared.

[0049]

[Table 1] PVA: 20% aqueous solution of polyvinyl alcohol [“PVA-117” manufactured by Kuraray Co., Ltd.] MS: 30% aqueous solution of pregelatinized phosphate esterified starch [“MS # 4 600” manufactured by Nippon Shokuhin Kako Co., Ltd.]

Examples 7 to 12, Comparative Examples 3 and 4 25 parts of water Dispersant [SN Dispersant 5040 manufactured by San Nopco Co., Ltd.] 0.3 part Sodium hydroxide 0.1 part Antifoaming agent [San Nopco (Kabu)] Manufactured by Nopco DF122] 0.1 part Binder composition (1 to 8) 20 parts Clay 45 parts Calcium carbonate 5 parts The above-mentioned binder composition is mixed with a mixture obtained by dispersing and mixing the above components with a disper (2,000 rpm) for 30 minutes. Coating colors 1 to 8 were prepared by adding 1 to 8 and mixing uniformly. The viscosity at 25 ° C. of each coating color was measured (using a B-type viscometer and ST rotor; the same applies hereinafter). Further, the composition was placed in a water bath at 80 ° C. for 30 minutes to measure the viscosity at 80 ° C. 80
After measuring the viscosity at ° C., it was placed in a water bath at 25 ° C. for 30 minutes to measure the viscosity after cooling. Table 2 shows the results.

[0051]

[Table 2]

Each of the coating colors 1 to 8 was applied to a medium paper of 58 g / m ² using a sheet-fed blade coater so that the dry coating amount was about 8 g / m ^2, and dried (coating speed). ; 30
m / min, dry air temperature; 150 ° C., drying time; 30
Seconds). Then treated with mini super calendar (temperature 6
Coated papers were prepared at 0 ° C., a nip pressure of 100 kg / cm, and paper passing twice), and the white paper gloss and printed gloss of each coated paper were measured. Table 3 shows the results.

[0053]

[Table 3]

Printing: Offset ink was solid-coated with an RI printing machine manufactured by Akira Seisakusho Co., Ltd. Gloss; 75 ° gloss of a blank or printed surface was measured with a gloss meter manufactured by Tokyo Denshoku Co., Ltd.

[0055]

The binder composition of the present invention is a thermoreversible thermosensitive gelling binder composition which has a low viscosity at a low temperature but rapidly thickens by heating to form a strong gel. When this is used for the production of coated paper, a paint color having better fluidity and excellent coatability than conventional ones is provided, and coated paper having high white gloss and printability can be obtained. Also,
Since it has low viscosity and excellent workability, it is also useful as an application agent for various fabrics, films or sheets, an impregnating agent, etc.
It is also useful as a binder for adhesives and paints.

Continued on the front page F-term (reference) 4J002 AB04X AC03W BB06W BB06X BB15W BC05W BC07W BC123 BE02X BE043 BE06X BF02W BG00W BG073 BG13X BG133 BH01X BH023 BJ00X BJ003 CC16X CC18X CH04X FA091CG04 BA041 MA14 PC10 4L055 AG11 AG12 AG27 AG47 AG48 AG63 AG64 AG71 AG72 AG74 AG97 AH02 AH36 AH37 AJ04 EA25 EA30 EA32 FA12 FA15 FA22

Claims (10)

[Claims] 1. The amount of an emulsifier in an aqueous phase is 0.01 mmol / g.
(Resin) A binder composition comprising the following nonionic resin latex (A), a temperature-sensitive gelling agent (B), and a water-soluble polymer (C). 2. The binder composition according to claim 1, wherein (A) is a resin latex obtained by emulsion polymerization using a nonionic emulsifier (a) having a radical polymerizable group. (B) a poly (oxyalkylene monool or diol mono (meth) acrylate and / or polyoxyalkylene monool or diol monovinylphenyl ether) and a vinyl monomer having an anionic group. 3. The binder composition according to claim 1, which is an anionic thermosensitive gelling agent comprising a copolymer (B1) as an essential monomer. 4. The binder composition according to claim 3, wherein the molecular weight per anionic group (B1) is from 150 to 50,000. 5. A method according to claim 1, wherein (B) is a mono (meth) acrylate of polyoxyalkylene monool or diol and / or a monovinyl phenyl ether of polyoxyalkylene monool or diol, and a vinyl monomer having a cationic group. 3. The binder composition according to claim 1, which is a cationic thermosensitive gelling agent comprising a copolymer (B2) as an essential monomer. 6. The binder composition according to claim 5, wherein the molecular weight per cationic group of (B2) is from 700 to 50,000. 7. A (co) polymer comprising (B) an essential monomer comprising a mono (meth) acrylate of a polyoxyalkylene monool or a diol and / or a monovinylphenyl ether of a polyoxyalkylene monool or a diol. 3. The binder composition according to claim 1, which is a nonionic thermosensitive gelling agent comprising B3). 8. The binder composition according to claim 1, wherein (C) is polyvinyl alcohol or a modified product thereof and / or starch or a modified product thereof. 9. The solid content weight ratio of (A) :( B) is (7)
0 to 99.99): (0.01 to 30), and the solid content weight ratio of [(A) + (B)] :( C) is (35 to 9).
90): (65 to 10), The binder composition according to any one of claims 1 to 8. 10. A coating color for coated paper comprising the binder composition according to claim 1 and a pigment.