JP2001253996A - Heat reversible thickening binder composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat reversible thickening binder composition having a larger thickening effect at an elevated temperature than that of a conventional composition. SOLUTION: This heat reversible thickening binder composition consisting of (A) resin-based latex and (B) a heat reversible thickener where hydrophilicity and hydrophobicity reversibly change from one to the other at a fixed temperature as a border line features that the ingredient (A) is obtained by using a specific polymerizable emulsifier (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a binder composition, and more particularly, to a thermosensitive gelling binder composition suitable for use in a coating color of a coated paper or an adhesive, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the amount of an emulsifier in an aqueous 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-mentioned composition, if 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. And there is a problem that productivity is greatly impaired in production on an industrial level.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies and as a result, have found that the polymerizable emulsifier (C) represented by the general formula (1)
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), thereby allowing the resin latex (A) and the resin latex (A) The present inventors have found that a thermoreversible thickening binder composed of a reversible thickener has a very large thickening effect, and that a thermoreversible thickening binder composition having good stability against mechanical loads can be obtained, and has reached the present invention.

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

[0006]

Embedded image

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 a hydrocarbon group having an aromatic ring. m and n are m + n
Is an integer of 0 or 1 to 5 in which the average is 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, 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 a hydrocarbon-based aromatic ring and an aromatic ring containing a hetero atom. Examples of the hydrocarbon group 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, for example, an alkyl group, an alkenyl group, an aralkyl group, an alkyl-substituted aralkyl group, a styryl group, a polystyryl group and a fused benzyl group;
At least one (preferably 2 to 7) of m R ² and n R ³ is an aromatic ring-containing hydrocarbon group. Examples of the alkyl group include linear and branched hydrocarbon groups having 1 to 24 carbon atoms (eg, methyl group, ethyl group, n- and i-propyl group, neopentyl group, hexyl group, and octyl group). Examples of the straight-chain and branched hydrocarbon groups having 2 to 24 carbon atoms (octenyl group, nonenyl group, decenyl group, undecenel group, dodecenel group, etc.) and aralkyl groups include arylalkyl groups having 7 to 18 carbon atoms (benzyl group). , 2-phenylethyl group, 3-phenylpropyl group, etc.), polystyryl group, a group obtained by condensing or adding 2 to 8 styrene, and a condensed benzyl group includes a group obtained by condensing 2 to 8 benzyl chloride or the like. No. Of these, preferred are a styryl group, a poly (polymerization degree 2 to 6) styryl group, a benzyl group, a condensed (condensation degree 2 to 6) benzyl group, and a mixed group of these groups. Further, m and n are 0 or an integer of 1 to 5 where the average of m + n is 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; 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, a 2-propylidene group, a 1-propylidene group and a cyclohexylidene group, and examples of the arylalkylidene group include a phenylethylidene group. Preferred as 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; metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions and alkaline earth metal (magnesium, calcium, barium, etc.) ions; ammonium ions; mono- to tetraalkyl-substituted ammonium (carbon of alkyl group) Formulas 1 to 8, for example, tetramethyl,
Alkanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.) ion and the like. Preferred among these are alkali metal ions and ammonium ions. A is an alkylene group having 2 to 4 carbon atoms, examples of which include an ethylene group, a propylene group, and a butylene group, preferably an ethylene group or a propylene group, or a combination thereof. p and q are such that the average of p + q is 2 to 80, preferably 5 to 50, more preferably 15
1 or an integer of 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 polymerizable emulsifier has appropriate hydrophobicity or hydrophilicity, and 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 mono (meth) acrylate 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), polycyclic phenols (for example, styrenated phenol, benzylated phenol, etc .; in this case, the addition mole number of styrene or benzyl is 0.2 to 4 per phenol ring). With
A styrene or benzyl group may be directly added to the phenol ring, or a structure in which one or more styrene or benzyl groups are added to the styrene or benzyl group added to the phenol ring). Added, and bisphenols (for example, C-alkyl-substituted bisphenol, halogenated bisphenol, bisphenol F, bisphenol A, cyclohexylene bisphenol, bistrifluoromethylmethylenebisphenol (bisphenol AF), bisphenol S, bisphenol AD, etc.) or dihydroxydiphenyl; Phenols such as hydroxybenzophenone are styrenated or benzylated in the same manner as above, and alkylene oxide is added. It is below. In the case where the bis (polyoxyalkylene polycyclic phenyl ether) is a formaldehyde condensate, a trinuclear or higher condensate may be by-produced, and a monomethacrylated sulfate salt other than the general formula (1) may be used. Although produced, (C) also contains these by-products.

As an example of the manufacturing method (C), Japanese Patent Publication No.
As described in -62685, polycyclic phenol is condensed with formaldehyde, followed by addition reaction of 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.

The resin constituting the resin latex (A) in the present invention includes acrylic resin, styrene-acrylic resin, styrene-butadiene resin, butadiene-acrylic resin, butadiene-acrylonitrile resin, and vinyl acetate resin. , Ethylene-vinyl acetate resin,
Examples include vinyl polymers such as ethylene-propylene resins and polybutadiene resins.

The vinyl polymer is a (co) polymer of a radically polymerizable monomer. Examples of the radically 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, 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, 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.]; a 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, 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-
Halogen-containing monomers (vinyl chloride, vinylidene chloride, etc.); heterocyclic-containing monomers (N-vinyl-2-pyrrolidone, N-methylolmaleimide, N-vinylsuccinimide, etc.); unsaturated dibasic acids Dialkyl esters [dialkyl maleate (1-8 carbon atoms) ester, dialkyl itaconate (1-8 carbon atoms) ester, etc.]; silyl group-containing monomer [3-trimethoxysilylpropyl (meth) acrylate, etc.]; Anionic group-containing monomer [(meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, (meth) acrylsulfonic acid, styrenesulfonic acid, vinylbenzoic acid, alkyl (1 carbon atom) 10 to 10) allyl sulfosuccinic acid, (meth) acryloyl polyoxyalkylene (degree of polymerization 2-1)
5) Sulfuric acid esters and the like, and salts thereof (alkali metal salts such as sodium salt and amine salts such as triethanolamine)]; cationic group-containing monomers [N, N-dimethylaminoethyl (meth) acrylate, N 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
-Vinyl carbazole, 2-vinyl pyridine 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 of these.

Among these, alkyl (meth) acrylates, styrenes and diene monomers are preferred, and a combination of a diene monomer with an alkyl (meth) acrylate and / or styrene 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 not more than 0.01 mmol (mmol) / g (resin), the temperature-sensitive thickening is moderated. It is particularly preferable because the temperature range from the start of thickening to the gelation can be widened, while 0.002 mm
What is ol / g or less is more preferable. The amount of the emulsifier in the aqueous phase is a molar concentration based on the weight of the resin component in the resin latex (A).

The amount of the polymerizable emulsifier (C) to be used is generally 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 together 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 is 0.01 mmol / g (resin) or less. Known polymerizable emulsifiers include:
For example, anionic (meth) acrylic acid ester, anionic (meth) acrylamide, anionic allyl ester, and the like, specifically, JP-A-09-25454,
JP-A-09-111133, JP-A-08-259
No. 875, for example.

In producing the resin latex (A) by emulsion polymerization, a known polymerization initiator can be used. Examples of the polymerization initiator include organic polymerization initiators (peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, benzoyl peroxide, lauroyl peroxide, etc.), azo compounds (azobisisobutyrate). Onitrile, azobisisovaleronitrile, etc.), inorganic polymerization initiators [persulfates (sodium persulfate, ammonium persulfate, potassium persulfate, etc.), hydrogen peroxide, etc.]. Examples of the redox polymerization initiator include persulfate or / and peroxide as an oxidizing agent, and sodium pyrobisulfite, sodium sulfite, sodium hydrogen sulfate, ferrous sulfate, glucose, and sodium formaldehyde as a reducing agent. Sulfoxylate or / and L-ascorbic acid (salt) can be used in combination. 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 for the purpose of adjusting the molecular weight of the resin, the gel content of the resin, and the like. Examples of the chain transfer agent include α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene and the like), terpinolene, terpinene, dipentene, an alkyl mercaptan having 8 to 18 carbon atoms, and an alkylene having 8 to 18 carbon atoms. Examples include dithiol, alkyl thioglycolate, dialkylxanthogen disulfide, tetraalkylthiuram disulfide, chloroform, carbon tetrachloride and the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0 to 15% by weight, preferably 0 to 5% by weight, based on 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 buffer (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.
Usually, it is 0 to 5% by weight, preferably 0 to 3% by weight.

The weight average molecular weight of the resin of the resin latex (A) by 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 80C, preferably -50 to 50C. In addition, Tg is obtained by flowing a latex resin into a glass mold and drying it under reduced pressure at 30 ° C. for 8 hours. A film having a thickness of about 0.3 mm is obtained by differential scanning calorimetry (DSC).
Is a value measured under nitrogen at 20 ° C./min.

The gel content of the resin (A) is as follows:
Usually, it is 5 to 95% by weight, preferably 30 to 80% by weight. The gel content is the content of the toluene-insoluble component in the dried resin, and the resin latex (A) has a thickness of 1 mm.
And dried under reduced pressure at 30 ° C. overnight. After accurately weighing about 1 g of the obtained film, 400 m
This is a value calculated by the following equation after drying and dissolving in 1 l of toluene for 48 hours, filtering through a filter paper of known weight, drying under the above conditions, and precisely weighing. Gel content (%) = [weight of toluene-insoluble matter on filter paper / weight of film before dissolving in toluene] × 100

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

The solid content of (A) is usually 5-7.
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 a thermoreversible thickener (B) in which hydrophilicity and hydrophobicity reversibly change at the boundary of (a), (a) 1 to 40 moles of an adduct of an alkylene (2 to 4 carbon atoms) oxide of a cyclic amine ( (Co) polymers containing (meth) acrylic acid ester as an essential monomer [morpholinoethyl (meth) acrylate polymers and the like described in JP-A-6-9848, etc.]; Alkylene of cyclic amine (2-4 carbon atoms)
(C) polymer having a (meth) acrylic acid ester of an adduct of 1 to 40 moles of an oxide as an essential monomer [diisopropylaminoethyl (meth) acrylate polymer or the like];
(Co) polymer [N-isopropyl (meth) acrylamide polymer, N-methoxypropyl (meth) acrylamide containing (meth) acrylamide of monoalkylamine or alkoxyalkylamine having 3 to 6 carbon atoms as an essential monomer Polymers and the like described in JP-A-1-14276]; (d) (meth) acrylamide of dialkylamine, dialkoxyalkylamine or cyclic amine having a total of 2 to 8 carbon atoms as an essential monomer ( Co) polymer [N, N-diethyl (meth) acrylamide polymer,
N- (meth) acryloylpyrrolidine polymer etc.
No. 0-233184]; (e) a (co) polymer having a vinyl monomer having a polyiminoethylene group (polymerization degree: 2 to 50) as an essential monomer [tetraethyleneimine mono ( JP-A-9- (meth) acrylamide polymer
12778]]; (f) a (co) polymer having a (meth) acrylamide having a cyclic amino group or an alkylamino group having 5 or more carbon atoms in an alkyl group as an essential monomer [N-morpholino] Ethyl (meth) acrylamide polymer etc.]; (g) alkylene group having 2 to 2 carbon atoms
(Co) polymer having a polyoxyalkylene (polymerization degree of 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.];
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 (Li) alkylnaphthalene, 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.); Alkylene oxide adducts of formalin condensates (such as those described in JP-A-63-193901);
(U) Polymer comprising a monomer having an epoxy group and an alkylamino group having 5 or more carbon atoms in a cyclic amino group or an alkyl group (such as polymorpholinoethyl glycidyl ether described in JP-A-9-31340). (V) alkylene oxide-modified polyorganosiloxanes (such as those described in JP-A-6-256617); (v) cellulose-based thermoreversible thickeners (methylcellulose, hydroxymethylcellulose, etc.); (C1-6) ether polymers (vinyl methyl ether polymer etc.) and (f) vinyl acetate / vinyl alcohol copolymer etc. are mentioned.

Of these, (B) includes (A) to
The thermoreversible thickener (h) is preferred in that it provides high temperature-sensitive thickening, and vinyl monomers selected from (a) to (d) are particularly preferred. The weight-average molecular weight of the component (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) reversibly changes is usually 30 ° C or higher, preferably 40 to 95 ° C, and more preferably 60 to 80 ° C. The transition temperature is
The aqueous solution (B) of 1 mass% solid content was gradually heated (1 ° C /
Minutes) and measuring the temperature at which the aqueous solution begins to become cloudy.

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

In the thermoreversible thickening binder composition of the present invention, the ratio of (A) to (B) can be variously changed according to the required performance and the like. From the viewpoint of properties, (B) is 0.001 to 30 as a solid based on the total weight of (A) and (B).
%, Particularly preferably 0.005 to 20%.

The method for producing the thermoreversible thickening binder composition of the present invention includes the following methods (1) to (4). A resin latex (A) obtained using a polymerizable emulsifier (C) and a thermoreversible thickener (B) or an aqueous solution of the (B) are mixed at a temperature lower than the transition temperature of the (B). Method to obtain by mixing. 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 monomer constituting the resin latex (A) is emulsion-polymerized at a temperature lower than the transition temperature of (B) using the polymerizable emulsifier (C). How to get. In the above method, the temperature of the mixing or emulsion polymerization is (B)
The temperature 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), a monomer constituting (B) and a monomer constituting (A) are mixed, and the monomers are made into one liquid to carry out emulsion polymerization; And the monomer constituting (A) are separately prepared and emulsion-polymerized. In the manufacturing method of
The monomer constituting (B) is polymerized in an aqueous solution, and (B)
And then subjecting the monomer constituting (A) to emulsion polymerization in the same reaction vessel, and preliminarily subjecting (B) to aqueous solution polymerization in a separate reaction vessel in the presence of (B). To
Examples of the method include emulsion polymerization of a monomer constituting (A).

The composition of the present invention exhibits a thickening behavior in which the viscosity starts to increase at a certain temperature by heating, then rapidly increases, and finally reaches gelation at a certain temperature. Is thermoreversible. For example, the thickening start temperature of the composition of the present invention is usually 15 to 60 ° C, preferably 30 to 50 ° C. The difference between the thickening start temperature and the gelation temperature (temperature at which gelation occurs) is usually 5 to 50 ° C, preferably 10 to 40 ° C.
° C, more preferably 15 to 30 ° C. The thickening start temperature is determined by gradually heating (2 ° C./min) the viscosity of the composition of the present invention while measuring the viscosity with a viscometer (such as a B-type viscometer), and then the temperature at which the composition starts to thicken (temperature−temperature). The temperature at which the viscosity curve rises) is measured. The gelation temperature is a temperature at which the viscosity of the composition becomes 18,000 mPa · s or more.

The composition of the present invention may contain a known water-soluble polymer, if necessary. Specific examples include polyvinyl alcohol or modified products thereof (polyvinyl alcohol, partially saponified ethylene-vinyl acetate copolymer, partially acetalized polyvinyl alcohol, etc.), starch or modified products thereof (oxidized starch,
Phosphated starch, cationized starch, casein, soy protein, synthetic protein, mannangalactan derivative, carboxymethyl cellulose, etc.); polyacrylamides (acrylamide polymer, acrylamide-sodium (meth) acrylate copolymer, polyacrylamide) Mannich modified product], formalin resin (urea-formalin resin, melamine-formalin resin, etc.), polyethyleneimine, polyamidepolyamine-epichlorohydrin, soda salt of styrene-maleic acid copolymer, alkyl (meth) acrylate- (meth) ) Acrylic acid copolymer soda salt and the like. The content of the water-soluble polymer is 1 part by weight of the total solid content of (A) and (B),
Usually, it is 0 to 25 parts by weight, preferably 0.2 to 5 parts by weight.

The composition of the present invention may further contain, if necessary, known pigments such as various clays, kaolin, calcium carbonate, satin white, titanium oxide, aluminum hydroxide, barium sulfate, zinc oxide, calcium sulfate, talc, Plastic pigments (beads such as polystyrene, styrene / butadiene copolymer or styrene / acrylic copolymer)). The content of the pigment is usually 0 to 25 parts by weight, preferably 3 to 10 parts by weight, per 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.] 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 per 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.
Further, it can be used as a binder for nonwoven fabric, a binder for coated paper, and the like. In particular, it is necessary to use the broad temperature-sensitive thickening behavior of the composition to allow the resin component to penetrate into the base material to some extent during heating and drying, such as an adhesive (eg, a pressure-sensitive adhesive, an adhesive for paperwork). Agents, woodworking adhesives, etc.),
It can be particularly suitably used as a binder for a coating color for coated paper having a high pick strength, a coating agent (for example, a coating for woodworking, a coating for building materials, a printing ink, various primers, etc.), and the binder has a high surface area. It is sufficiently penetrated to the inside of the substrate while maintaining the concentration.

[0036]

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 (SBR1) 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, 4 parts of methacrylic acid, and a polymerization reactor were equipped with a stirrer, a dropping cylinder, a nitrogen gas inlet tube and a thermometer. Ammonium bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate as an emulsifier [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 in the general formula (1). 6, the average is 5, A is an ethylene group, M is ammonium, and p + q is 23.
-25, the average of which was 24] 5 parts, 1 part of sodium persulfate and 0.2 part of lauryl mercaptan were charged, and the system was purged with nitrogen gas under stirring, and then 37 parts of butadiene was injected from a dropping cylinder at 50 ° C. For 30 hours and further at 85 ° C. for 5 hours. Then, unreacted monomers are stripped under reduced pressure, and the pH is adjusted to 9.5 with an aqueous sodium hydroxide solution.
Thus, an SBR-based resin latex (hereinafter, referred to as “SBR1”) having a solid content of 47.9% and an emulsifier amount of 0.0008 mmol / g (resin) in an aqueous phase was obtained.

Production Example 2 (SBR2) Ammonium bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate as a polymerizable emulsifier [R ¹ is a methyl group, R ² and R ^{3 in the} general formula (1)]
Is a benzyl group, X is a methylene group, m + n is 4 to 6 and their average is 5, A is an ethylene group, M is ammonium, p + q
Is an SBR resin latex having a solid content of 47.9% and an aqueous phase emulsifier amount of 0.0010 mmol / g (resin) in the same manner as in Production Example 1 except that 5 to 20 parts and an average of 22 parts are used. (Hereinafter referred to as “SBR2”).

Production Example 3 (SBR3) Ammonium salt of bis (polyoxyalkylene polycyclic phenyl ether) methacrylate sulfate 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 to 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 and propylene groups having an average of 19 ethylene groups and an average of 4 propylene groups, M is ammonium, p +
q is 20 to 24, the average of which is 23] An SBR resin having a solid content of 47.9% and an emulsifier amount of 0.0003 mmol / g (resin) in an aqueous phase in the same manner as in Production Example 1 except that 5 parts is used. 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 charged into a glass ampoule and frozen. After deaeration, the system was 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 ampule.
After freezing and deaeration, the system 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'-
Add 1 part of azobis (2,4-dimethylvaleronitrile) to a glass ampoule, freeze, deaerate and seal,
Polymerization was carried out for an hour to obtain “thickener 3” (transition temperature = 56 ° C.).

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

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

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

Production Example 10 (Binder 4) A solid content of 47.9% and an emulsifier amount of aqueous phase of 0.0008 m in the same manner as in Production Example 9 except that thickener 2 was used in place of thickener 1.
A thermoreversible thickening binder composition (hereinafter referred to as "binder 4") having a mol / g (resin) and a gelling 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 a 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 7.9% and an emulsifier amount of 0.015 mmol / g (resin) in an aqueous phase was obtained.

[0048]

Embedded image

Here, Ar represents a phenyl group.

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

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

Examples "Examples 1 to 6" were prepared by mixing 20% aqueous solutions of "thickeners 1 to 3" with stirring at 25 ° C. at a mixing ratio shown in Table 1 with "SBR1 to 3". Was obtained. “Binders 1 to 4” were used as they were as the thermoreversible thickening binder compositions of “Examples 7 to 10”. Also, by mixing a 20% aqueous solution of the thickener 1 with “SBR4 to 6” at 25 ° C. with stirring at a mixing ratio shown in Table 2, the thermoreversible thickening binder composition of “Comparative Examples 1 to 3” was obtained. I got something.

[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 increase the viscosity (B-type viscometer,
Using an ST rotor, the unit was mPa · s; the same applies hereinafter). Table 3 shows the results.

[0056]

[Table 3]

As an index of the stability of the thermoreversible thickening binder compositions of Examples 1 to 10 and Comparative Examples 1 to 3 with respect to mechanical load, a load test using a maron tester was performed.
After applying a load of 1000 rpm for 10 minutes to a 100 g sample at a load of 10 kg, the sample was filtered through a 200 mesh SUS wire mesh, and the amount of aggregates remaining on the wire mesh was measured. Table 4 shows the results.

[0058]

[Table 4]

[0059]

The thermoreversible thickening binder composition of the present invention exhibits a larger thickening behavior than conventional compositions and has excellent stability against mechanical loads.
This is extremely useful when coating with an actual machine that often involves a mechanical load. Since such effects are exhibited, the composition of the present invention is extremely useful as a binder when it is desired to thicken the resin component while penetrating the resin component inside the base material to some extent during heating and drying, particularly in an adhesive or a coating agent. In addition, it is also useful when it is desired to obtain a bulky coating layer having high pick strength as a binder for coated paper.

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Claims (5)

[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 certain temperature (transition temperature) as a boundary. (A) a resin latex (A) obtained by using a polymerizable emulsifier (C) represented by the following general formula (1). Embedded image Here, 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
^At least one of ² and n R ³ is a hydrocarbon group having an aromatic ring. m and n are such that the average of m + n is 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
Is 1 or an integer of 2 to 40, the average of which is 2 to 80. 2. 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 fused benzyl group, wherein at least one of m R ² and n R ³ is The thermoreversible thickening binder composition according to claim 1, which is a valent hydrocarbon group. 3. The composition according to claim 1, wherein the amount of the polymerizable emulsifier (C) in the aqueous phase of (A) is a resin latex of 0.01 mmol / g (resin) or less. 4. A (co) polymer wherein (B) is a (meth) acrylic acid ester of an alkylene oxide adduct of a cyclic amine as an essential monomer, and an alkylene oxide adduct of a non-cyclic amine having 5 or more carbon atoms. A (co) polymer having a (meth) acrylic acid ester as an essential monomer, a (co) polymer having a (meth) acrylamide of a monoalkylamine or an alkoxyalkylamine as an essential monomer, and a dialkylamine, The composition according to any one of claims 1 to 3, wherein the composition is a thermoreversible thickener selected from the group consisting of (co) polymers containing (meth) acrylamide of a dialkoxyalkylamine or a cyclic amine as an essential monomer. . 5. The thermoreversible thickening binder composition according to claim 1, comprising at least one member selected from the group consisting of: A resin latex (A) obtained using a polymerizable emulsifier (C) and a thermoreversible thickener (B) or an aqueous solution of the (B) are mixed at a temperature lower than the transition temperature of the (B). The composition obtained by mixing with. 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 monomer constituting the resin latex (A) is emulsion-polymerized at a temperature lower than the transition temperature of (B) using the polymerizable emulsifier (C). A composition obtained by: