JP3464932B2 - 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 temperature-sensitive gelling binder composition suitable for coating colors of coated paper and adhesive applications.

[0002]

2. Description of the Related Art Conventionally, the amount of emulsifier in the water phase is 0.01 mmo.
A binder composition comprising a resin latex of 1 / g (resin) or less and a thermoreversible thickener is known (for example, JP-A-9-25454).

[0003]

However, although the above composition has a very sharp temperature-sensitizing viscosity and is useful for applications requiring such characteristics, it does not penetrate the substrate to some extent. However, there is a problem in that it cannot be used for applications where it is desired to dry.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the binder composition can be used by combining at least two thermoreversible thickeners having a difference in transition temperature of a certain value or more. On the contrary, they have found that a binder composition having a moderate temperature-sensitive viscosity increase can be obtained, and have reached the present invention.

That is, the present invention relates to a resin latex (A)
In a thermoreversible thickening binder composition comprising a thermoreversible thickener (B) whose hydrophilicity and hydrophobicity change reversibly at a constant temperature, the temperature (T1) at a constant temperature (T1) A thermoreversible thickener (B1) whose hydrophilicity and hydrophobicity change reversibly at the boundary, and a temperature (T2) higher than T1 by 5 ° C or more.
A thermoreversible thickener binder composition comprising a thermoreversible thickener (B2) whose hydrophilicity and hydrophobicity change reversibly at the boundary of.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the resin constituting the resin latex (A) in the present invention, acrylic resin, styrene-acrylic resin, styrene-butadiene resin,
Examples thereof include vinyl polymers such as butadiene-acrylic resin, butadiene-acrylonitrile resin, vinyl acetate resin, ethylene-vinyl acetate resin, ethylene-propylene resin, and polybutadiene resin.

The vinyl polymer is a (co) polymer of a radical-polymerizable monomer, and examples of the radical-polymerizable monomer include (cyclo) alkyl (having 1 to 1 carbon atoms).
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 and the like]; aromatic ring-containing (meth) acrylate [benzyl (meth) acrylate and the like]; hydroxyl group-containing (meth) acrylate [ 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, polyglycerin (polymerization degree 2 to 4) mono (meth)
Acrylate and the like]; (meth) acrylamide or its derivative [(meth) acrylamide, N, N-dibutyl (meth) acrylamide, cyclohexyl (meth) acrylamide, N-methyl (meth) acrylamide, N-
Methylol (meth) acrylamide, diacetone acrylamide, etc.]; cyano group-containing monomer [(meth) acrylonitrile, 2-cyanoethyl (meth) acrylate,
2-Cyanoethylacrylamide, etc.]; polyfunctional (meth)
Acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, 2,2
-Bis (4-hydroxyethylphenyl) propane di (meth) acrylate and the like]; styrenes (styrene, α
-Methylstyrene, vinyltoluene, divinylbenzene, etc.); diene-based monomers (butadiene, isoprene, chloroprene, etc.); vinyl esters (vinyl acetate, vinyl propionate, etc.); epoxy group-containing monomers [glycidyl (meth)] Acrylate, allyl glycidyl ether, etc.]; mono-olefins (ethylene, propylene, 1-
Butene, etc.); Halogen-containing monomer (vinyl chloride, vinylidene chloride, etc.); Heterocycle-containing monomer (N-vinyl-2-pyrrolidone, N-methylol maleimide, N-vinyl succinimide, etc.); Unsaturated dibasic acid Dialkyl esters [maleic acid dialkyl (C1-8) ester, itaconic acid dialkyl (C1-8) ester, etc.]; silyl group-containing monomers [3-trimethoxysilylpropyl (meth) acrylate, etc.]; Anionic group-containing monomer [(meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, (meth) acrylicsulfonic acid, styrenesulfonic acid, vinylbenzoic acid, alkyl (having 1 carbon atom) -10) allyl sulfosuccinic acid, (meth) acryloyl polyoxyalkylene (degree of polymerization 2-1
5) Sulfate, etc., and salts thereof (alkali metal salts such as sodium salt, amine salts such as triethanolamine)]; cationic group-containing monomer [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-dimethyl Aminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, vinylaniline, vinylimidazole, p-aminostyrene, N
-Vinylcarbazole, 2-vinylpyridine and the like, and salts thereof (inorganic acid salts such as hydrochloride and phosphate, formate,
Organic acid salts such as acetate)] and combinations of two or more thereof.

Among these, preferred are alkyl (meth) acrylates, styrenes and diene-based monomers, and the combination of diene-based monomers with alkyl (meth) acrylates and / or styrenes is particularly preferred.

When the amount of the emulsifier in the aqueous phase of the resin latex (A) in the present invention is 0.01 mmol (mmol) / g (resin) or less, the temperature-sensitive thickening is moderated while the thickening starts and gelation occurs. It is particularly preferable because the temperature range reaching the temperature can be widened, and it is more preferably 0.002 mmol / g or less. The amount of emulsifier in the aqueous phase is
It is the amount based on the weight of the resin component in the resin latex (A).

The amount of the emulsifier in the water phase is determined by analyzing the water phase obtained by removing the resin content from the resin latex by liquid chromatography or the like and quantifying it. Examples of the method for removing the resin component from the resin latex include, for example, a method in which the resin latex is frozen and then melted to coagulate and solidify and remove the resin component, a method in which the resin component is precipitated and solidified by a centrifuge to remove the acid or alkali. In addition, there may be mentioned a method of removing the resin component by sedimentation and solidification.

The amount of emulsifier in the aqueous phase is 0.01 mmol / g
(Resin) As a method for producing the following resin latex (A), for example, a method of emulsion-polymerizing a radical-polymerizable monomer by a known method using an emulsifier having a low solubility in water; an emulsifier having a radical-polymerizable group. A method of emulsion polymerizing a radically polymerizable monomer by a known method using (a); A method of emulsion polymerizing a radically polymerizable monomer by a known method using a protective colloid; a hydrophilic group (carboxyl group in an organic solvent). , A sulfonic acid group, an amino group, a dimethylamino group, a diethylamino group, a polyoxyethylene group, etc.) are synthesized by a known method, neutralized with an alkali or an acid if necessary, and water is added to remove the solvent after emulsification. And the like. Among these methods, the methods of and are preferable, and the method of is particularly preferable because the resin latex (A) can be easily obtained under ordinary conditions.

Examples of the emulsifier (a) having a radical polymerizable group include (1) anionic (meth) acrylic acid esters, those represented by the following formula: CH ₂ ═C (R ¹ ) CO _{2 (CH 2) mOSO 3 M CH} 2 = C (R 1) CO 2 CH 2 C (R 1) (OCOR 2) C
_{H 2 SO 3 M CH 2 =} C (R 1) CO 2 CH 2 CH 2 OCOArCO 2 CH
_{2 CH 2 OSO 3 M CH 2} = C (R 1) CO (AO) pOSO 3 M CH 2 = C (R 1) CO (AO) pOArCH 2 Ar (A
O) pOSO ₃ M (wherein R ¹ is a hydrogen atom or a methyl group, m is an integer of 1 to 4, M is an alkali metal ion, an ammonium ion or an aminium ion, R ² is an alkyl group having 4 to 21 carbon atoms, Alkenyl group or aralkyl group, Ar is an aromatic ring, AO is an oxyalkylene group having 2 to 4 carbon atoms, and p is 2
Indicates an integer of ˜200. ); (2) Anionic allylic compounds, represented by the following formula: CH ₂ ═CHCH ₂ OCOCH (SO ₃ M) CH ₂ CO ₂ R ² CH ₂ ═CHCH ₂ OCH ₂ CH (OH) CH ₂ OCOCH
(SO ₃ M) CH ₂ CO ₂ R ² (R ² ) (R ³ ) Ar (CH ₂ CH═CH ₂ ) (AO) pO
SO ₃ M (where M is an alkali metal ion, ammonium ion or aminium ion, R ² is an alkyl group, an alkenyl group or an aralkyl group having 4 to 21 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms) Group, alkenyl group or aralkyl group, Ar is an aromatic ring, AO is a carbon number of 2
The oxyalkylene group of 4 and p show the integer of 2-200. ); (3) Anionic maleic acid esters represented by the following formula: R ² OCOCH = CHCO ₂ CH ₂ CH (OH) CH ₂ SO
^{_{3 M R 3 (AO) pOCOCH}} = CHCO 2 (CH 2) nCH
(R ³ ) SO ₃ M R ³ (AO) pOCOCH═CHCO ₂ M (wherein R ² is an alkyl group, alkenyl group or aralkyl group having 4 to 21 carbon atoms, M is an alkali metal ion, R ³
Is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, an alkenyl group or an aralkyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, p is an integer of 2 to 200, n is an integer of 0 to 3, and M is an alkali. Indicates a metal ion, ammonium ion or aminium ion. ); (4) Anionic itaconic acid esters, those represented by the following formula: CH ₂ ═C (CH ₂ CO ₂ R ² ) CO ₂ (CH ₂ ) mOSO ₃ M CH ₂ ═C (CH ₂ CO ₂ R ² ) CO ₂ CH ₂ CH (OH) C
H ₂ OSO ₃ M (In the formula, R ² is an alkyl group, an alkenyl group or an aralkyl group having 4 to 21 carbon atoms, m is an integer of 1 to 4, and M is an alkali metal ion, an ammonium ion or an aminium ion.) (5) Cationic (meth) acrylic acid esters, those represented by the following formula: [CH ₂ = C (R ¹ ) COOCH ₂ CH (OH) CH ₂ N
_{^{(R 2) 3] X [}} CH 2 = C (R 1) CO (AO) pN (R 2) 3] X ( wherein R ¹ is a hydrogen atom or a methyl group, R ² is 4 carbon
21 alkyl, alkenyl or aralkyl groups,
X represents a halogen atom and p represents an integer of 2 to 200. ); (6) Cationic allyl compounds, those represented by the following formula, etc .: [CH ₂ ═CHCH ₂ CH (OH) CH ₂ N (R ² ) ₃ ] X [CH ₂ ═CHCH ₂ N (R ² ). ₃ ] X (in the formula, R ² represents an alkyl group, an alkenyl group or an aralkyl group having 4 to 21 carbon atoms, and X represents a halogen atom.) (7) Nonionic (meth) acrylic acid ester, represented by the following formula: Etc .: CH ₂ ═C (R ¹ ) CO (AO) pOR ³ (wherein R ¹ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom or an alkyl group, an alkenyl group or an aralkyl group having ^{1 to} 21 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, p is an integer of 2 to 200.); (8) Nonionic (meth) acrylic acid amides, those represented by the following formula: CH ₂ ═C ( R ¹ ) CONHR ⁴ (AO) pOR ³ CH ₂ ═C (R ¹ ) CON [R ⁴ (AO) pOR ³ ] ₂ (wherein R ¹ is a hydrogen atom or a methyl group, and R ⁴ is a carbon atom of 1 to 1).
4 alkylene group, R ³ is hydrogen atom or 1 to 2 carbon atoms
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. ); (9) Nonionic styrene derivatives represented by the following formula: CH ₂ ═C (R ¹ ) Ar (AO) pOR ³ (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, and p is 2
To an integer of 200, R ³ is a hydrogen atom or 1 to 21 carbon atoms
Is an alkyl group, an alkenyl group or an aralkyl group. ); (10) Nonionic allyl compounds, those represented by the following formula, etc .: (R ² ) (R ³ ) Ar (CH ₂ CH═CH ₂ ) (AO) pOR ³ (wherein R ² is a carbon number) 4 to 21 alkyl group, alkenyl group or aralkyl group, R ³ is a hydrogen atom or a C 1 to C 21 alkyl group, alkenyl group or aralkyl group, Ar is an aromatic ring, AO is a C ² to C 4 oxyalkylene. Group, p is an integer of 2 to 200.); (11) Nonionic maleic acid esters represented by the following formula: R ² (AO) pOCOCH = CHCO (AO) pOR ² (wherein R ² is an alkyl group, an alkenyl group, or an aralkyl group having 4 to 21 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and p is an integer of 2 to 200.) (12) Nonionic itaconic acid esters , Shown by the following formula Shall _{like: CH 2 = C [CH 2} CO (AO) pOR 2] CO (AO) p
OR ² (in the formula, R ² is an alkyl group, an alkenyl group or an aralkyl group having 4 to 21 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and p is an integer of 2 to 200); Can be mentioned.

Of these, (1), (5) and (7) are preferable in terms of high copolymerizability with a radically polymerizable monomer and good polymerization stability, and a more stable resin latex can be obtained. (1) is particularly preferable in that it is given.

Emulsifier (a) having the radically polymerizable group
The amount used is usually 0.1 to 20% by weight with respect to the resin content,
It is preferably 1 to 10% by weight.

In producing the resin latex (A) by emulsion polymerization, a known polymerization initiator is used. As the polymerization initiator, organic polymerization initiators [peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, benzoyl peroxide, lauroyl peroxide, etc.), azo compounds (azobisisobutyrate Ronitrile, azobisisovaleronitrile, etc.), an inorganic polymerization initiator [persulfate (sodium persulfate, ammonium persulfate, potassium persulfate, etc.), hydrogen peroxide, etc.] and the like. The amount of the polymerization initiator used is usually 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total amount of the monomer mixture.

A known chain transfer agent can be used for the purpose of adjusting the molecular weight of the resin, the gel content of the latex and the like. As the chain transfer agent, α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene, etc.), terpinolene, terpinene, dipentene, alkylmercaptan having 8 to 18 carbon atoms, 8 to 18 carbon atoms
Alkylenedithiol, alkyl thioglycolate,
Examples thereof include dialkylxanthogen disulfide, tetraalkylthiuram disulfide, chloroform and carbon tetrachloride. These may be used alone or in combination of two or more. The amount of chain transfer agent used is usually 0 to 15% by weight, preferably 0 to 15% by weight, based on the total amount of the monomer mixture.
It is 5% by weight.

If necessary, a reducing agent [sodium pyrobisulfite, sodium sulfite, sodium hydrogensulfate,
Ferrous sulfate, glucose, formaldehyde sodium sulfoxylate, L-ascorbic acid (salt)], chelating agent (glycine, alanine, sodium ethylenediaminetetraacetate, etc.), pH buffering agent (sodium tripolyphosphate, potassium tetrapolyphosphate, etc.) You may use together such additives. The amount of these additives used is usually 0 to 5% by weight, preferably 0 to 3% by weight, based on the total amount of the monomer mixture.
Is.

The weight average molecular weight of the resin of the resin latex (A) by the GPC method is usually 10,000 or more, preferably 100,000 to 1,000,000 or more.

The glass transition temperature (Tg) of (A) is usually -80 to 80 ° C, preferably -50 to 50 ° C.
The Tg was obtained by pouring a latex of a resin component into a glass mold and drying under reduced pressure at 30 ° C. for 8 hours to obtain a thickness of about 0.3.
It is a value measured under a condition of 20 ° C./min under nitrogen using a differential scanning calorimeter (DSC) for a film of mm.

The gel content in the resin (A) is
It is usually 5 to 95% by weight, preferably 30 to 80% by weight. The gel content is the content of toluene-insoluble matter in the dried resin, and the resin latex (A) has a thickness of 1 mm.
It was poured into a glass mold of No. 1 and dried under reduced pressure at 30 ° C. for one day. After precisely weighing about 1 g of the obtained film, 400 m
It is a value calculated by the following formula after being left to dissolve in 1 l of toluene for 48 hours and filtered through a filter paper of known weight, dried under the above-mentioned conditions, precisely weighed, and calculated. Gel content (%) = [weight of toluene insoluble matter on filter paper / weight of film before dissolution in toluene] × 100

The average particle size (arithmetic average; measured by the laser Doppler method) of the (A) is usually 50 to 500 nm, preferably 120 to 220 nm.

The solid content of (A) is usually 5 to 7.
It is 0% by weight, preferably 30 to 60% by weight, and the pH is usually 3 to 12, preferably 6 to 10.

In the present invention, as the thermoreversible thickener (B) whose hydrophilicity and hydrophobicity change reversibly at a certain temperature as a boundary, (a) an alkylene of a cyclic amine (having 2 to 4 carbon atoms) ) A (co) polymer having an (meth) acrylic acid ester of 1 to 40 mol of oxide as an essential monomer [morpholinoethyl (meth) acrylate polymer, etc.]
Those described in JP-A-9848]; (B) (meth) acrylic acid ester of an alkylene (C2-4) oxide 1-40 mol adduct of an acyclic amine having 5 or more carbon atoms as an essential monomer. (Co) polymer [diisopropylaminoethyl (meth) acrylate polymer, etc.]; (C) Monoalkylamine or alkoxyalkylamine (meth) acrylamide having a total of 3 to 6 carbon atoms is used as an essential monomer (co) ) Polymer [N-isopropyl (meth) acrylamide polymer, N-methoxypropyl (meth) acrylamide polymer, etc. described in JP-A-1-14276, etc.]; (d) Dialkyl having 2 to 8 carbon atoms in total. Amine, dialkoxyalkylamine or cyclic amine (meth)
(Co) polymer [N, which has acrylamide as an essential monomer]
N-diethyl (meth) acrylamide polymer, N- (meth) acryloylpyrrolidine polymer, etc.
Those described in Japanese Patent No. 3184]; (e) (Co) polymer [tetraethyleneimine mono (meth)] in which a vinyl monomer having a polyiminoethylene group (degree of polymerization of 2 to 50) is an essential monomer. Acrylamide polymer, etc.
No. 1, etc.]; (f) (co) polymer [N-morpholino] having (meth) acrylamide having a cyclic amino group or an alkylamino group having an alkyl group having 5 or more carbon atoms as an essential monomer. Ethyl (meth) acrylamide polymer and the like]; (to) alkylene group having 2 to 4 carbon atoms of polyoxyalkylene (polymerization degree 3 to 40) monool or diol mono (meth) acrylate as an essential monomer (Co) polymer [tetraethylene glycol monoethyl ether mono (meth) acrylate polymer, pentaethylene glycol monobutyl ether mono (meth) acrylate polymer, methoxytrioxypropylene tetraoxyethylene (meth) acrylate polymer, tetrapropylene glycol Mono (meth) acryloyl adduct of 6 mol of ethylene oxide Over preparative polymer and the like]; (h) the number of carbon atoms of the alkylene group is 2 to 4 of the polyoxyalkylene (polymerization degree 3
To 40) (co) polymer having monovinylphenyl ether of monool or diol as an essential monomer (tetraethylene glycol monomethyl ether monovinylphenyl ether polymer, pentaethylene glycol monoethyl ether monovinylphenyl ether polymer, methoxypentaoxy) Propylene tetraoxyethylene vinyl phenyl ether polymer, monovinyl phenyl ether polymer of 8 mole ethylene oxide adduct of tetrapropylene glycol, etc.) (Alkylene oxide adduct of (i) alkylnaphthalene formalin condensate (JP-A-63)
Those described in JP-A-193901); (N) A polymer comprising a monomer having an epoxy group and an alkylamino group having 5 or more carbon atoms such as a cyclic amino group or an alkyl group (polymorpholinoethyl glycidyl ether, etc.) 9-31
No. 340, etc.); (L) alkylene oxide-modified polyorganosiloxane (JP-A-6-2566).
No. 17, etc.); (e) Cellulose-based thermoreversible thickener (methyl cellulose, hydroxymethyl cellulose, etc.); (wa) Vinyl alkyl (C 1-6) ether polymer (vinyl methyl ether polymer) Etc.) and (f) vinyl acetate / vinyl alcohol copolymers and the like.

Of these, (B) is (a)-
The thermoreversible thickener (h) is preferable in that it gives a high temperature-sensitive thickening, and a vinyl monomer selected from (i) to (d) is particularly preferable. The weight average molecular weight of (B) by GPC is usually 1,000 to 5,000,000, preferably 2,000 to 500,000.

The (B) is a thermoreversible thickener (B1) whose hydrophilicity and hydrophobicity reversibly change at a constant temperature (T1) and a temperature (T2) different from T1. The thermoreversible thickener (B
2) and T1 <T2 and the difference is usually 5
It is necessary to be ℃ or more. Preferably 10 ° C to 5
0 ° C or higher, more preferably 20 ° C to 40 ° C
Is. If the difference between T1 and T2 is less than 5 ° C, the temperature-sensitive thickening becomes too sharp, and a broad temperature-sensitive thickening cannot be obtained.

Generally, in thermoreversible thickening, the higher the hydrophilicity, the higher the temperature at which the hydrophilicity and the hydrophobicity change reversibly,
The lower the hydrophilicity, the lower the temperature. Therefore, the (B
1) and (B2) are appropriately selected from those exemplified in (B) above so that the difference between T1 and T2 is within the above range.

The thermoreversible thickener (B1) or (B
The temperature (T1 or T2) at which the hydrophilicity and the hydrophobicity of 2) change reversibly is usually 15 to 100 ° C., preferably 30 to
It is 80 ° C. The temperature at which the hydrophilicity and the hydrophobicity reversibly change is gradually heated (for example, 2 ° C./min) to a 1 wt% aqueous solution of the thermoreversible thickener, and the aqueous solution becomes cloudy or gelled. It is determined by measuring the starting temperature.

The (B) may optionally contain other thermoreversible thickener (B3) in addition to (B1) and (B2). The difference between the temperature (T3) at which the hydrophilicity and hydrophobicity of (B3) reversibly changes and T1 or T2 may be 5 ° C. or more or less than 5 ° C.

The amount of (B1), (B2) and optionally (B3) in the (B) is usually 30 to 70% by weight for (B1), 30 to 70% by weight for (B2), and (B3). Is 0-4
0% by weight, preferably 35 to 50% by weight of (B1), 35 to 50% by weight of (B2), and 0 to 30 of (B3).
% By weight. The weight ratio of (B1) and (B2) is usually (2-8) :( 8-2), preferably (4-6):
(6 to 4).

In the thermoreversible thickening binder composition of the present invention, the solid content weight ratio of (A) and (B) is usually (A) :( B) = (70 to 99.999) :( 0.00
1-30), preferably (80-99.995):
(0.005 to 20). The amount of (B) is 0.001
When it is less than 30, the temperature-sensitive gelling property is not exhibited, and when it exceeds 30, the viscosity of the composition becomes too high.

The composition of the present invention is a resin latex (A).
And a thermoreversible thickener (B) alone or an aqueous solution of the (B) at a temperature lower than the temperature at which the hydrophilicity and the hydrophobicity of the (B) change, in an ordinary mixer (paddle-type stirrer). Etc.).

The composition of the present invention exhibits a broad thickening behavior in which the viscosity starts to increase at a constant temperature by heating and then gradually thickens to finally gelate at a constant temperature. The viscous behavior is thermoreversible. For example, the thickening initiation temperature of the composition of the present invention is usually 15 to 60 ° C., preferably 3
It is 0 to 50 ° C. The difference between the thickening start temperature and the gelling temperature is usually 5 to 50 ° C, preferably 10 to 40 ° C, more preferably 15 to 30 ° C. The thickening start temperature is the temperature at which the composition of the present invention starts to thicken gradually (2 ° C./min) while measuring the viscosity with a viscometer (B type viscometer, etc.) (temperature- It is determined by measuring the temperature at which the viscosity curve rises. The gelling temperature is the temperature when the viscosity of the composition exceeds 18,000 mPa · s.

If desired, the composition of the present invention may contain a known water-soluble polymer. Specific examples thereof include polyvinyl alcohol or a modified product thereof (polyvinyl alcohol, partially saponified ethylene-vinyl acetate copolymer, partially acetalized polyvinyl alcohol, etc.), starch or a modified product thereof (oxidized starch,
(Phosphoric acid esterified starch, cationized starch, casein, soybean protein, synthetic protein, mannangalactan derivative, carboxymethyl cellulose, etc.); polyacrylamides [acrylamide polymer, acrylamide- (meth) acrylic acid sodium copolymer, polyacrylamide Mannich modified product, etc.], formalin resin (urea-formalin resin, melamine-formalin resin, etc.), polyethyleneimine, polyamide polyamine-epichlorohydrin, soda salt of styrene-maleic acid copolymer, (meth) acrylic acid alkyl ester- (meth ) Examples include soda salts of acrylic acid copolymers. The content of the water-soluble polymer is 1 part by weight of the total solid content of (A) and (B),
It is usually 0 to 25 parts by weight, preferably 0.2 to 5 parts by weight.

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 of polystyrene, styrene / butadiene copolymer, styrene / acrylic copolymer, or the like)] can be included. The content of the pigment 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) and (B).

Further, if necessary, a pigment dispersant [sodium poly (meth) acrylate, sodium pyrophosphate, sodium hexametaphosphate, etc.], defoaming agent (mineral oil type defoaming agent, silicon type defoaming agent, etc.) Other additives such as lubricants, pH adjusters, preservatives, water resistance agents, printability improvers, etc. can also be included. The content of the additive is 1 part by weight of the total solid content of (A) and (B),
Usually 0 to 2.5 parts by weight, preferably 0.005 to 0.5
Parts by weight.

Specific applications of the thermoreversible thickening binder composition of the present invention include paints, inks, adhesives, printing pastes, cosmetics, resin mortars and cements.
It can also be used as a binder for non-woven fabric, a binder for coated paper, and the like. Above all, it is necessary to use the broad temperature-sensitive thickening behavior of the composition to allow the resin component to penetrate to the inside of the substrate to some extent during heating and drying, such as an adhesive (for example, pressure-sensitive adhesive, adhesive for paperworking). Agent, adhesive for woodworking, etc.),
It can be particularly suitably used as a binder for coating colors with high pick strength for coating paper, coating agents (for example, paints for woodwork, paints for building materials, printing inks, various primers, etc.). It is sufficiently permeated to the inside of the substrate while maintaining the concentration.

[0037]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the examples, parts are parts by weight, and% is% by weight.

Production Example 1 102 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 pressure reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas introducing tube and a thermometer. 5 parts by weight of acryloyloxy polypropylene (degree of polymerization = 12) sulfuric acid ester Na salt as an emulsifier having
Sodium persulfate 1 part and lauryl mercaptan 0.
After charging 2 parts of the mixture and replacing the inside of the system with nitrogen gas under stirring, 37 parts of butadiene was press-fitted from a dropping cylinder and reacted at 50 ° C. for 30 hours and at 85 ° C. for 5 hours. Then, unreacted monomer is stripped under reduced pressure, and the solid content is adjusted to 4 by adjusting the pH to 9.5 with an aqueous sodium hydroxide solution.
7.9%, amount of emulsifier in aqueous phase 0.0003 mmol / g
(Resin) SBR resin latex (hereinafter referred to as “SBR”) was obtained.

Production Example 2 100 parts of morpholinoethyl methacrylate and 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
A portion was added to an ampoule, freeze-deaerated, sealed, and polymerized at 50 ° C. for 8 hours to obtain “Polymer 1” (temperature at which hydrophilicity and hydrophobicity change = 34 ° C.).

Production Example 3 100 parts of N-acryloylpyrrolidine and 2,2'-
1 part of azobis (2,4-dimethylvaleronitrile) was added to an ampoule, freeze-deaerated, then sealed, and polymerized at 50 ° C. for 8 hours to give “polymer 2” (temperature at which hydrophilicity and hydrophobicity change = 56). C) was obtained.

Production Example 4 100 parts of N-isopropylacrylamide and 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
A part was added to an ampoule, freeze-deaerated, then sealed, and polymerized at 50 ° C. for 8 hours to obtain “Polymer 3” (temperature at which hydrophilicity and hydrophobicity change = 32 ° C.).

Production Example 5 N- (propylaminopropyl) acrylamide 100
Part and 2,2′-azobis (2,4-dimethylvaleronitrile) 1 part were added to an ampoule, freeze-deaerated and then sealed,
Polymerization was carried out at 50 ° C. for 8 hours to obtain a polymer 4 (temperature at which hydrophilicity and hydrophobicity change = 53 ° C.).

Example 1 To 100 parts of "SBR" obtained in Production Example 1, 1.5 parts of a 20% aqueous solution of "polymer 1" obtained in Production Example 2 and "polymer 2" obtained in Production Example 3 were added. "Composition 1" was obtained by mixing 1.5 parts of a 20% aqueous solution of the above with stirring at 25 ° C. The composition 1 was heated at a temperature gradient of 2 ° C. per minute to obtain a viscosity (B-type viscometer, ST rotor used, unit: mPa · s; the same applies hereinafter).
Was measured. Thickening start temperature is 32 ° C, gelation temperature is 56
It was ℃. Next, the thickened liquid was cooled with a temperature gradient of 2 ° C. per minute to measure the viscosity. The viscosity measurement results are shown in Table 1.

[0044]

[Table 1]

Example 2 In Example 1, instead of the 20% aqueous solution of “Polymer 1”, the same amount of 20% aqueous solution of “Polymer 3” obtained in Production Example 4 and 20% of “Polymer 2” were used. "Composition 2" was obtained in the same manner as in Example 1 except that the same amount of the 20% aqueous solution of "Polymer 4" obtained in Production Example 5 was used instead of the aqueous solution. The thickening start temperature, gelation temperature and viscosity of this product were measured in the same manner as in Example 1. The thickening start temperature was 31 ° C and the gelation temperature was 52 ° C. The viscosity measurement results are shown in Table 2.

[0046]

[Table 2]

Comparative Example 1 Instead of 1.5 parts of a 20% aqueous solution of "Polymer 1" and 1.5% of a 20% aqueous solution of "Polymer 2" in Example 1, Production Example 3 was used.
Comparative "composition 3" was obtained in the same manner as in Example 1 except that 3.0 parts of the 20% aqueous solution of "polymer 2" obtained in 1. was used.
About this, in the same manner as in Example 1, the thickening start temperature,
Gelation temperature and viscosity were measured. Thickening start temperature 52
The gelation temperature was 54 ° C. Table 3 shows the viscosity measurement results.
Shown in.

[0048]

[Table 3]

Comparative Example 2 Using the “SBR” obtained in Production Example 1 as it is, Example 1
The thickening start temperature, gelation temperature and viscosity were measured in the same manner as in. There was no thickening or gelation, and neither the thickening onset temperature nor the gelation temperature was observed. Table 4 shows the viscosity measurement results.
Shown in.

[0050]

[Table 4]

Examples 3 and 4 and Comparative Examples 3 and 4 Using a rubber roller on a JAS1 type lauan plywood having a thickness of 3 mm, each of the above-mentioned "composition 1" to "composition 3" and SBR is 100 g / solid basis. It is applied so that the coating amount is m ² , and a 0.2 mm thick semi-rigid polyvinyl chloride sheet is attached, dried at 40 ° C. for 60 minutes, and then at 80 ° C. for 100 minutes.
It was compressed at a pressure of kg / m ² for 5 hours to obtain vinyl chloride decorative board samples 1 to 4, respectively. 1 for each sample obtained
80 ° peel adhesive strength (25 ° C atmosphere, peel speed 200
mm / min, unit: kg / 25 mm) was measured. The results are shown in Table 5.

[0052]

[Table 5]

[0053]

Since the thermoreversible thickening binder composition of the present invention has a broadening thickening behavior as compared with the conventional compositions, it gradually thickens in a wide temperature range and reaches gelation. Because of the above effects, the composition of the present invention is extremely useful as a binder in the case where it is desired to increase the viscosity while allowing the resin component to penetrate to the inside of the substrate to some extent during heating and drying, especially in adhesives and coatings. It is also useful as a binder for coated paper when a bulky coating layer having high pick strength is desired.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C09D 5/00-201/10

Claims (7)

(57) [Claims] 1. A thermoreversible thickening binder composition comprising a resin latex (A) and a thermoreversible thickener (B) whose hydrophilicity and hydrophobicity reversibly change at a constant temperature as a boundary. B) Thermoreversible thickener (B1) whose hydrophilicity and hydrophobicity change reversibly at a constant temperature (T1) as a boundary
And a thermoreversible thickener (B) whose hydrophilicity and hydrophobicity reversibly change at a boundary of a temperature (T2) higher than T1 by 5 ° C or more (B
2) A thermoreversible thickening binder composition comprising: 2. In (A), the amount of emulsifier in the aqueous phase is 0.01 m.
The composition according to claim 1, which is a resin latex of not more than mol / g (resin). 3. The composition according to claim 1, wherein (A) is a resin latex obtained by emulsion polymerization using an emulsifier (a) having a radically polymerizable group. 4. (B) is a (co) polymer having a (meth) acrylic acid ester of an alkylene oxide adduct of a cyclic amine as an essential monomer, an alkylene oxide adduct of an acyclic amine having 5 or more carbon atoms. (Co) polymer having (meth) acrylic acid ester as an essential monomer, a (co) polymer having (meth) acrylamide of a monoalkylamine or alkoxyalkylamine as an essential monomer, and a dialkylamine, The composition according to any one of claims 1 to 3, which is a thermoreversible thickener selected from the group consisting of (co) polymers containing (meth) acrylamide of dialkoxyalkylamine or cyclic amine as an essential monomer. . 5. (B) is 30 to 70% by weight of (B1),
The composition according to any one of claims 1 to 4, which comprises 30 to 70% by weight of (B2) and 0 to 40% by weight of another thermoreversible thickener (B3). 6. The thickener according to claim 1, wherein the temperature difference between the thickening start temperature and the gelling temperature is 5 to 50 ° C. 7. The solid content weight ratio of (A) :( B) is (7)
0-99.99): (0.01-30).
The binder composition according to any one of to 6.