JP3464977B2 - 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 a coating color of coated paper and an adhesive application, and a method for producing the same.

[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, in the above composition, when the amount of the thermoreversible thickener (B) added is small, a sufficient thickening effect cannot be obtained, and the mechanical load of the composition is low. However, there is a problem that the productivity is greatly impaired in industrial level production.

[0004]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that the polymerizable emulsifier (C) represented by the general formula (1) is used.
Is used to improve the emulsion stability of the radical-polymerizable monomer constituting the resin latex (A), thereby optimizing the particle size of the resin latex (A). It was found that a thermoreversible thickening binder composed of a reversible thickener has a very large thickening effect, and a thermoreversible thickening binder composition having good stability against mechanical load can be obtained, and the present invention has been accomplished.

That is, the present invention relates to a resin latex (A)
In a thermoreversible thickener binder composition comprising a thermoreversible thickener (B) whose hydrophilicity and hydrophobicity reversibly change at the boundary of a constant temperature (transition temperature), (A) is represented by the following general formula: A thermoreversible binder composition comprising a resin latex (A) obtained by using the polymerizable emulsifier (C) represented by (1).

[0006]

[Chemical 2]

However, Ar is an aromatic ring, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are monovalent hydrocarbon groups, and at least one of m R ² and n R ³ is Is a hydrocarbon group having an aromatic ring. m and n are m + n
An integer of 0 or 1 to 5 having an average of 1 to 8, X is a covalent bond, an alkylene group, an alkylidene group, an arylalkylidene group, an oxygen atom, a sulfur atom, a sulfonyl group, a bistrifluoromethylmethylene group or a carbonyl group, M
Is a cation, A is an alkylene group having 2 to 4 carbon atoms, and p and q are 1 or 2 to 40 in which the average of p + q is 2 to 80.
Indicates an integer.

In the present invention, in the polymerizable emulsifier (C) represented by the general formula (1), the aromatic ring of Ar is
Examples include hydrocarbon-based aromatic rings and aromatic rings containing heteroatoms. Examples of the hydrocarbon system include a benzene ring and a naphthalene ring, and examples of the aromatic ring containing a hetero atom include a thiophene ring and a pyrrole ring. R ² and R ³ are monovalent hydrocarbon groups such as an alkyl group, an alkenyl group, an aralkyl group, an alkyl-substituted aralkyl group, a styryl group, a polystyryl group and a condensed benzyl group,
At least one (preferably 2 to 7) of m R ² and n R ³ is an aromatic ring-containing hydrocarbon group. As the alkyl group, linear and branched hydrocarbon groups having 1 to 24 carbon atoms (methyl group, ethyl group, n- and i-propyl group, neopentyl group, hexyl group, octyl group, etc.), alkenyl groups, As a straight-chain or branched hydrocarbon group having 2 to 24 carbon atoms (octenyl group, nonenyl group, decenyl group, undecenel group, dodecenel group, etc.) and an aralkyl group, an arylalkyl group having 7 to 18 carbon atoms (benzyl group) , 2-phenylethyl group, 3-phenylpropyl group, etc.), the polystyryl group is a group formed by condensing or adding 2 to 8 styrene, and the condensed benzyl group is a group formed by condensing 2 to 8 benzyl chloride. Can be mentioned. Among these, styryl group, poly (polymerization degree 2 to 6) styryl group, benzyl group, condensed (condensation degree 2 to 6) benzyl group and mixed groups of these groups are preferable. Further, m and n are 0 or an integer of 1 to 5 which makes the average of m + n 1 to 8, preferably 2 to 7. When a plurality of R ² and R ³ are present, they may be the same or different. The total number of aromatic rings (including Ar) in (C) is usually 3 to 16, preferably 4 to 12.
X is a covalent bond, an alkylene group, an alkylidene group, an arylalkylidene group, an oxygen atom, a sulfur atom, a sulfonyl group, a bistrifluoromethylmethylene group or a carbonyl group, and examples of the alkylene group include a methylene group, an ethylene group and a propylene group, Examples of the alkylidene group include an ethylidene group, 2-propylidene group, 1-propylidene group and cyclohexylidene group, and examples of the arylalkylidene group include a phenylethylidene group. Preferred among X are an alkylene group and an alkylidene group, and more preferred are a methylene group and a 2-propylidene group. M is a cation, a metal ion such as an alkali metal (sodium, potassium, lithium, etc.) ion, an alkaline earth metal (magnesium, calcium, barium, etc.) ion, an ammonium ion, a mono- to tetraalkyl-substituted ammonium (a carbon of an alkyl group) Number 1-8, for example tetramethyl,
(Eg, tetraethyl) ion; alkanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.) ion and the like. Of these, preferred are alkali metal ions and ammonium ions. A is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group and a butylene group, preferably an ethylene group or a propylene group, and a combination thereof. As for p and q, the average of p + q is 2 to 80, preferably 5 to 50, more preferably 15
Is an integer of 1 or 2 to 40.

When neither R ² nor R ³ is an aromatic ring-containing hydrocarbon group, the emulsion stability during radical polymerization is poor, and the particle size of the resulting resin latex (A) cannot be optimized. When the average of p + q is 5 to 50, the hydrophobicity or hydrophilicity of the polymerizable emulsifier is appropriate, the emulsion stability of the monomer during radical polymerization tends to be good, and the resulting resin latex (A) Easy to optimize particle size.

Specific examples of (C) include monomethacrylate sulfate salts of bis (polyoxyalkylene polycyclic phenyl ether) (the total number of aromatic rings in the polycyclic portion of polycyclic phenyl is usually 3 to 10). As the bis (polyoxyalkylene polycyclic phenyl ether), a polycyclic phenol (for example, styrenated phenol, benzylated phenol, etc., in which case the number of moles of styrene or benzyl added is 0.2 to 4 per phenol ring). Individual
The styrene or benzyl group may be directly added to the phenol ring, or the styrene or benzyl group added to the phenol ring may be further added with one or more styrene or benzyl groups). Added, and bisphenols (for example, C-alkyl-substituted bisphenol, halogenated bisphenol, bisphenol F, bisphenol A, cyclohexylene bisphenol, bistrifluoromethylmethylene bisphenol (bisphenol AF), bisphenol S, bisphenol AD, etc.) or dihydroxydiphenyl, Phenols such as hydroxybenzophenone, which are styrenated or benzylated in the same manner as above, with alkylene oxide added, etc. It is below. In addition, when bis (polyoxyalkylene polycyclic phenyl ether) is a formaldehyde condensate, a condensate of trinuclear or higher may be by-produced, and monomethacrylate sulfate ester salts other than the general formula (1) may be generated. Although produced, (C) also contains these by-products.

As an example of the manufacturing method of (C), Japanese Patent Publication No.
-62685, polycyclic phenols are condensed with formaldehyde, followed by addition reaction with alkylene oxide, followed by dehydration with (meth) acrylic acid,
After esterification, after sulfation with a known sulfating agent,
It can be manufactured by neutralizing as necessary.

As the resin constituting the resin latex (A) in the present invention, acrylic resin, styrene-acrylic resin, styrene-butadiene resin, butadiene-acrylic resin, butadiene-acrylonitrile resin, vinyl acetate resin , Ethylene-vinyl acetate resin,
Examples thereof include vinyl polymers such as 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 a combination of diene-based monomers with alkyl (meth) acrylates and / or styrenes is particularly preferred.

When the amount of the polymerizable emulsifier (C) 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. However, it is particularly preferable because the temperature range from the start of thickening to gelation can be widened.
It is more preferably ol / g or less. The amount of the emulsifier in the aqueous phase is the molar concentration with respect to the weight of the resin component in the resin latex (A).

The amount of the polymerizable emulsifier (C) used is usually 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the resin content of the resin latex (A). If necessary, other known polymerizable emulsifiers may be used in combination with the polymerizable emulsifier (C) as long as the effects of the present invention are not impaired. The amount of other known polymerizable emulsifiers used in combination is preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 20% by weight or less, based on the total amount of the polymerizable emulsifiers. . The total amount of the polymerizable emulsifier (C) and other known polymerizable emulsifiers in the aqueous phase of the resin latex (A) is such that the amount becomes 0.01 mmol / g (resin) or less. As a known polymerizable emulsifier,
For example, anionic (meth) acrylic acid ester, anionic (meth) acrylamide, anionic allyl ester, and the like, specifically, JP-A 09-25454,
JP 09-111133 A, JP 08-259 A
Examples thereof include those described in Japanese Patent No. 875.

When the resin latex (A) is produced by emulsion polymerization, a known polymerization initiator can be used. As the polymerization initiator, organic polymerization initiators [peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, parameteran 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. As the redox-type polymerization initiator, a persulfate or / and a peroxide as an oxidizing agent, and sodium pyrobisulfite, sodium sulfite, sodium hydrogensulfate, ferrous sulfate, glucose, sodium formaldehyde as a reducing agent. A combination of sulfoxylate and / or L-ascorbic acid (salt) can be used. 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.

Known chain transfer agents can be used for the purpose of adjusting the molecular weight of the resin, the gel content of the resin, 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, alkylene having 8 to 18 carbon atoms Examples thereof include dithiol, alkyl thioglycolate, dialkylxanthogen disulfide, tetraalkylthiuram disulfide, chloroform and carbon tetrachloride. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0 to 15% by weight, preferably 0 to 5 with respect to the total amount of the monomer mixture.
% By weight.

If necessary, additives such as a chelating agent (glycine, alanine, sodium ethylenediaminetetraacetate, etc.) and a pH buffering agent (sodium tripolyphosphate, potassium tetrapolyphosphate, etc.) may be used in combination.
The amount of these additives used is based on the total amount of the monomer mixture.
It is usually 0 to 5% by weight, preferably 0 to 3% by weight.

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

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

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 (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.

Constant temperature (transition temperature) in the present invention
As the thermoreversible thickener (B) whose hydrophilicity and hydrophobicity change reversibly at the boundary of (b), (i) an alkylene (C 2-4) oxide 1-40 mol adduct of cyclic amine ( (Co) polymer having meth) acrylic acid ester as an essential monomer [morpholinoethyl (meth) acrylate polymer, etc. described in JP-A-6-9848, etc.]; (B) non-carbon having 5 or more carbon atoms Cyclic amine alkylene (C2-4)
(Co) polymer [diisopropylaminoethyl (meth) acrylate polymer, etc.] containing (meth) acrylic acid ester of 1 to 40 mol of oxide as an essential monomer;
A (co) polymer having a (meth) acrylamide of a total alkyl number of 3 to 6 as a monoalkylamine or alkoxyalkylamine as an essential monomer [N-isopropyl (meth) acrylamide polymer, N-methoxypropyl (meth) acrylamide Polymers and the like described in JP-A-1-14276]; (d) (meth) acrylamide of dialkylamine, dialkoxyalkylamine or cyclic amine having a total carbon number of 2 to 8 is used as an essential monomer ( Co) polymer [N, N-diethyl (meth) acrylamide polymer,
N- (meth) acryloylpyrrolidine polymer, etc.
0-233184, etc.]; (e) (co) polymer [tetraethyleneimine mono ((polyethylenemino group having a polymerization degree of 2 to 50) vinyl monomer as an essential monomer (Meth) acrylamide polymer, etc.
No. 12781, etc.]; (f) (co) polymer [N-morpholino] having (meth) acrylamide having an alkylamino group having a cyclic amino group or an alkyl group having 5 or more carbon atoms as an essential monomer. Ethyl (meth) acrylamide polymer, etc.];
(Co) polymer having polyoxyalkylene (polymerization degree 3 to 40) monool or diol mono (meth) acrylate of 4 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 tetrapropylene glycol 6 mol adduct of ethylene oxide, etc.];
A (co) polymer (tetraethylene glycol monomethyl ether monovinyl phenyl ether polymer) in which a monovinyl phenyl ether of a polyoxyalkylene having an alkylene group having 2 to 4 carbon atoms (degree of polymerization 3 to 40) monool or diol is used as an essential monomer. Polymer, pentaethylene glycol monoethyl ether monovinyl phenyl ether polymer, methoxypentaoxypropylene tetraoxyethylene vinyl phenyl ether polymer, tetravinyl glycol 8 mol ethylene oxide adduct monovinyl phenyl ether polymer, etc.); Alkylene oxide adduct of formalin condensate (such as those described in JP-A-63-193901);
(N) 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) (L) alkylene oxide-modified polyorganosiloxane (such as those described in JP-A-6-256617); (e) Cellulose thermoreversible thickener (methyl cellulose, hydroxymethyl cellulose, etc.); (wa) Vinyl alkyl ( Examples include ether polymers having 1 to 6 carbon atoms (vinyl methyl ether polymers, etc.) and (f) vinyl acetate / vinyl alcohol copolymers.

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 constant temperature (transition temperature) at which the hydrophilicity and hydrophobicity of (B) change reversibly is usually 30 ° C. or higher, preferably 40 to 95 ° C., and more preferably 60 to 80 ° C. The transition temperature is
Slowly heat the aqueous solution of (B) having a solid content of 1% by mass (1 ° C /
Min) and the temperature at which the aqueous solution begins to turn cloudy is determined.

As the method for producing the thermoreversible thickener (B) of the present invention, conventionally known bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be mentioned. In the case of solution polymerization, solution polymerization using an aqueous solution or a water / hydrophilic organic solvent mixed solvent can be mentioned. As the hydrophilic organic solvent, lower alcohols having 1 to 4 carbon atoms (methanol, ethanol, isopropanol, etc.), ketones (Acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, etc.), glycols (ethylene glycol, propylene glycol, etc.)
And cellosolves (such as methyl cellosolve and ethyl cellosolve).

In the thermoreversible thickening binder composition of the present invention, the ratio of (A) and (B) can be variously changed according to the required performance, etc., but the viscosity of the composition and the temperature-sensitive gelation From the viewpoint of sex, 0.001 to 30 of (B) based on the total weight of (A) and (B) as a solid content
%, And particularly preferably 0.005 to 20%.

Examples of the method for producing the thermoreversible thickening binder composition of the present invention include the following methods (1) to (3). A mixer for mixing the resin latex (A) obtained by using the polymerizable emulsifier (C) and the thermoreversible thickener (B) or the aqueous solution of the (B) at a temperature lower than the transition temperature of the (B). How to get by mixing in. A vinyl polymerizable monomer constituting the thermoreversible thickener (B) and a monomer constituting the resin latex (A),
A method obtained by emulsion polymerization using a polymerizable emulsifier (C) at a temperature lower than the transition temperature of (B). In the presence of the thermoreversible thickener (B), the monomers constituting the resin latex (A) are emulsion polymerized at a temperature lower than the transition temperature of (B) using the polymerizable emulsifier (C). How to get it. In the above method, the temperature of mixing or emulsion polymerization is (B).
It is not particularly limited as long as it is lower than the transition temperature, but is preferably 10 ° C. to 70 ° C. lower than the transition temperature.

In the production method of (B), the monomer constituting (B) and the monomer constituting (A) are mixed to make the monomer into one liquid and emulsion polymerization is carried out, and (B) Examples thereof include a method of separately emulsion-polymerizing the monomer constituting (A) and the monomer constituting (A). In the manufacturing method of
A monomer constituting (B) is polymerized in an aqueous solution, and then (B)
And emulsion-polymerizing the monomer constituting (A) in the same reaction vessel, and (B) is previously polymerized in an aqueous solution, and the reaction is carried out in another reaction vessel in the presence of (B). To
Examples thereof include a method of emulsion-polymerizing the monomer constituting (A).

The composition of the present invention exhibits a thickening behavior in which it starts thickening by heating at a constant temperature and then rapidly thickens to finally gelate at a constant temperature. Is thermoreversible. For example, the thickening initiation temperature of the composition of the present invention is usually 15 to 60 ° C, preferably 30 to 50 ° C. Further, the difference between the thickening start temperature and the gelling temperature (temperature leading to gelation) is usually 5 to 50 ° C., preferably 10 to 40.
C., more preferably 15 to 30.degree. 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 a temperature at which the viscosity of the composition becomes 18,000 mPa · s or more.

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.], an antifoaming agent (mineral oil type antifoaming agent, silicone type antifoaming 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 mortar and cement.
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.

[0036]

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 (SBR1) 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, 4 parts of methacrylic acid were polymerized in a pressure reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas introducing tube and a thermometer. Bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfuric acid ester ammonium salt as a hydrophilic emulsifier [in the general formula (1), R ¹ is a methyl group, R ² and R ³ are styryl groups, X is a methylene group, and m + n is 2 to 2]. 6, the average of which is 5, A is an ethylene group, M is ammonium, and p + q is 23.
5 to 25 parts, the average of which is 24], 5 parts of sodium persulfate, and 0.2 part of lauryl mercaptan are charged, the system is replaced with nitrogen gas with stirring, and 37 parts of butadiene is press-fitted from a dropping cylinder at 50 ° C. For 30 hours and at 85 ° C. for 5 hours. Then, unreacted monomer is stripped under reduced pressure, and the pH is adjusted to 9.5 with an aqueous sodium hydroxide solution.
The SBR resin latex (hereinafter, referred to as “SBR1”) having a solid content of 47.9% and an emulsifier amount of the aqueous phase of 0.0008 mmol / g (resin) was obtained by adjusting the content of the SBR resin.

Production Example 2 (SBR2) Bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfuric acid ester ammonium salt as a polymerizable emulsifier [in the general formula (1), R ¹ is a methyl group, R ² and R ^3]
Is a benzyl group, X is a methylene group, m + n is 4 to 6 with an average of 5, A is an ethylene group, M is ammonium, p + q
Is 20 to 24 and the average is 22] The same procedure as in Production Example 1 except for using 5 parts, solid content 47.9%, aqueous phase emulsifier amount 0.0010 mmol / g (resin) SBR resin latex. (Hereinafter referred to as "SBR2").

Production Example 3 (SBR3) Bis (polyoxyalkylene polycyclic phenyl ether) methacrylated sulfuric acid ester ammonium salt as a polymerizable emulsifier [in the general formula (1), R ¹ is a methyl group, R ² and R ^2
3 is a styryl group and a benzyl group, the ratio of the styryl group and the benzyl group is 1/1 mol on average, X is a methylene group, m
+ N is 5 to 7 with an average of 6, A is a random copolymer of ethylene groups and propylene groups, with an average of 19 ethylene groups and an average of 4 propylene groups, M is ammonium, p +
q is 20 to 24 and its average is 23] SBR resin having a solid content of 47.9% and an aqueous phase emulsifier amount of 0.0003 mmol / g (resin) in the same manner as in Production Example 1 except that 5 parts were used. A latex (hereinafter referred to as "SBR3") was obtained.

Production Example 4 (Thickener 1) 95 parts of morpholinoethyl methacrylate, 5 parts of methacrylic acid and 0.1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were placed in a glass ampoule and frozen. The mixture was degassed, then sealed and polymerized at 50 ° C. for 8 hours to obtain “thickener 1” (transition temperature = 74 ° C.).

Production Example 5 (Thickener 2) 90 parts of morpholinoethyl methacrylate, 10 parts of methacrylic acid and 0.1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged into a glass ampoule,
After freeze-deaeration, the mixture was sealed and polymerized at 50 ° C. for 8 hours to obtain “thickener 2” (transition temperature = 65 ° C.).

Production Example 6 (Thickener 3) 100 parts of N-acryloylpyrrolidine and 2,2'-
1 part of azobis (2,4-dimethylvaleronitrile) was added to a glass ampoule, freeze-deaerated and hermetically sealed at 50 ° C for 8 hours.
Polymerization was carried out for a period of time to obtain “thickener 3” (transition temperature = 56 ° C.).

Production Example 7 (Binder 1) 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, 5 parts of methacrylic acid were placed in the same pressure reaction vessel as in Production Example 1.
Parts, morpholinoethyl methacrylate 0.4 parts, the same emulsifier 5 as used in Production Example 1 as the polymerizable emulsifier 5
Parts, cumene peroxide 0.01 part, iron sulfate (heptahydrate) 1.1 parts and lauryl mercaptan 0.2 part were charged, the system was replaced with nitrogen gas under stirring, and then 37 parts of butadiene from the dropping cylinder. Was pressed in and reacted at 10 ° C. for 15 hours. Then, the unreacted monomer is stripped under reduced pressure, and the pH is adjusted to 9.5 with an aqueous sodium hydroxide solution to obtain a solid content of 47.9% and an emulsifier amount of the aqueous phase of 0.0
A thermoreversible thickening binder composition (hereinafter referred to as “binder 1”) having a gelation temperature of 65 ° C. of 008 mmol / g (resin) was obtained.

Production Example 8 (Binder 2) A gel having an aqueous phase emulsifier content of 0.0008 mmol / g (resin) in the same manner as in Production Example 7 except that 0.4 part of acryloylpyrrolidine was used instead of morpholinoethyl methacrylate. A thermoreversible thickening binder composition (hereinafter referred to as "binder 2") having a temperature of 55 ° C was obtained.

Production Example 9 (Binder 3) 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, 5 parts of methacrylic acid were placed in the same pressure reaction vessel as in Production Example 1.
Part, 0.4 part of the thickener 1 produced in Production Example 4, the same emulsifier 5 as that used in Production Example 1 as the polymerizable emulsifier 5
Parts, cumene peroxide 0.01 part, iron sulfate (heptahydrate) 1.1 parts and lauryl mercaptan 0.2 part were charged, the system was replaced with nitrogen gas under stirring, and then 37 parts of butadiene from the dropping cylinder. Was pressed in and reacted at 10 ° C. for 15 hours. Then, the unreacted monomer is stripped under reduced pressure, and the pH is adjusted to 9.5 with an aqueous sodium hydroxide solution to obtain a solid content of 47.9% and an emulsifier amount of the aqueous phase of 0.0
A thermoreversible thickening binder composition (hereinafter referred to as “binder 3”) having a gelation temperature of 70 ° C. and 008 mmol / g (resin) was obtained.

Production Example 10 (Binder 4) In the same manner as in Production Example 9 except that Thickener 1 was changed to Thickener 2, the solid content was 47.9% and the amount of emulsifier in the aqueous phase was 0.0008 m.
A thermoreversible thickening binder composition (hereinafter referred to as “binder 4”) having a mol / g (resin) and a gelation temperature of 62 ° C. was obtained.

Comparative Production Example 1 (SBR4) A solid content of 4 was obtained in the same manner as in Production Example 1 except that 5 parts of the polymerizable emulsifier represented by the following formula (2) was used as the polymerizable emulsifier.
An SBR-based resin latex (hereinafter referred to as "SBR4") having a water phase emulsifier content of 7.9% and 0.015 mmol / g (resin) was obtained.

[0048]

[Chemical 3]

Here, Ar represents a phenyl group.

Comparative Production Example 2 (SBR5) A solid content of 47.9 was obtained in the same manner as in Production Example 1 except that 5 parts of sodium acryloyloxypolyoxypropylene (degree of polymerization = 12) sulfate ester was used as the polymerizable emulsifier.
%, An SBR-based resin latex (hereinafter referred to as “SBR5”) having an aqueous phase emulsifier content of 0.020 mmol / g (resin) was obtained.

Comparative Production Example 3 (SBR6) A solid content of 47.9 was obtained in the same manner as in Production Example 1 except that 5 parts of sodium acryloyloxypolyoxypropylene (degree of polymerization = 18) sulfate ester was used as the polymerizable emulsifier.
%, An SBR-based resin latex (hereinafter referred to as “SBR6”) having an aqueous phase emulsifier amount of 0.023 mmol / g (resin) was obtained.

In Examples "SBR1-3", 20% aqueous solutions of "thickeners 1-3" were blended at a blending ratio shown in Table 1 at 25 ° C under stirring to give "Examples 1-6". A thermoreversible thickening binder composition was obtained. Further, "Binders 1 to 4" were used as they were as the thermoreversible thickening binder composition of "Examples 7 to 10". Moreover, the thermoreversible thickening binder composition of "Comparative Examples 1 to 3" was prepared by blending "SBR4 to 6" with a 20% aqueous solution of the thickener 1 at a blending ratio shown in Table 2 at 25 ° C with stirring. I got a thing.

[0053]

[Table 1]

[0054]

[Table 2]

The compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were heated at a temperature gradient of 2 ° C./min to obtain a viscosity (B-type viscometer,
Using an ST rotor, the unit is mPa · s; the same applies hereinafter). The results are shown in Table 3.

[0056]

[Table 3]

A load test using a Maron tester was conducted as an index of the stability of the thermoreversible thickening binder compositions of Examples 1 to 10 and Comparative Examples 1 to 3 against mechanical load.
A load of 1000 rpm was applied to 100 g of the sample for 10 minutes under a load of 10 kg, and then the sample was filtered through a 200-mesh SUS wire netting to measure the amount of aggregates remaining on the wire netting. The results are shown in Table 4.

[0058]

[Table 4]

[0059]

EFFECTS OF THE INVENTION The thermoreversible thickening binder composition of the present invention exhibits greater thickening behavior than conventional compositions and is excellent in stability against mechanical load.
It is extremely useful for coating on actual machines, which are often subject to mechanical loads. From such an effect, the composition of the present invention is extremely useful as a binder, especially in an adhesive or a coating agent, when it is desired to increase the viscosity while allowing the resin component to penetrate to the inside of the substrate during heating and drying to some extent. It is also useful as a binder for coated paper when a bulky coating layer having high pick strength is desired.

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Claims (5)

(57) [Claims] 1. A thermoreversible thickener binder composition comprising a resin latex (A) and a thermoreversible thickener (B) which reversibly changes hydrophilicity and hydrophobicity at a boundary of a constant temperature (transition temperature). A thermoreversible thickening binder composition, wherein (A) is a resin latex (A) obtained by using a polymerizable emulsifier (C) represented by the following general formula (1). [Chemical 1] However, Ar is an aromatic ring, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are monovalent hydrocarbon groups, and m R
^At least one of ² and n R ³ is a hydrocarbon group having an aromatic ring. m and n have an average of m + n of 1 to
8, an integer of 0 or 1 to 5, X is a covalent bond, an alkylene group, an alkylidene group, an arylalkylidene group, an oxygen atom, a sulfur atom, a sulfonyl group, a bistrifluoromethylmethylene group or a carbonyl group, M is a cation,
A is an alkylene group having 2 to 4 carbon atoms, p and q are p + q
Represents an integer of 1 or 2 to 40 that the average of 2 to 80. 2. At least one of m R ² and n R ³ is an aromatic ring-containing 1 selected from the group consisting of an aralkyl group, an alkyl-substituted aralkyl group, a styryl group, a polystyryl group and a condensed benzyl group. The thermoreversible thickening binder composition according to claim 1, which is a valent hydrocarbon group. 3. The composition according to claim 1 or 2, which is a resin latex in which the amount of the polymerizable emulsifier (C) in the aqueous phase (A) is 0.01 mmol / g (resin) or less. 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. The thermoreversible thickening binder composition according to claim 1, comprising one or more selected from the group consisting of: A mixer for mixing the resin latex (A) obtained by using the polymerizable emulsifier (C) and the thermoreversible thickener (B) or the aqueous solution of the (B) at a temperature lower than the transition temperature of the (B). The composition obtained by mixing in. A vinyl polymerizable monomer constituting the thermoreversible thickener (B) and a monomer constituting the resin latex (A),
A composition obtained by emulsion polymerization using a polymerizable emulsifier (C) at a temperature lower than the transition temperature of (B). In the presence of the thermoreversible thickener (B), the monomers constituting the resin latex (A) are emulsion polymerized at a temperature lower than the transition temperature of (B) using the polymerizable emulsifier (C). The resulting composition.