JPH0931132A - Self-thickening binder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a binder which has temp.-sensitive self-thickening properties and gives a heat-resistant coating film by subjecting a monomer which, when polymerized alone, gives a homopolymer having cloud point and another monomer to emulsion copolymn. to form a thermally reversible thickening dispersion of a water-insol. copolymer. SOLUTION: This binder comprises a water-base thermally reversible thickening dispersion of a water-insol. copolymer formed by the emulsion copolymn. in water of a monomer mixture comprising 1-40wt.% monomer which, when polymerizes alone, gives a homopolymer having cloud point (e.g. a vinylcarboxylic ester of an alkylene oxide adduct of an acylic amine or a 5C or higher acyclic amine) and 60-99wt.% other monomer (e.g. a conjugated diene or an arom. free-radical-polymerizable monomer). The binder, having a good water resistance, temp.-sensitive self-thickening properties, and temp.-sensitive gelling properties, gives a water-resistant film, and requiring no thickening agent to be compounded, the binder is useful in many applications.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a binder having a temperature-sensitive self-thickening property and giving a coating film excellent in water resistance.

[0002]

2. Description of the Related Art Recently, a temperature-sensitive gelling composition obtained by blending a resin latex having a chemical stability index of 24 or less with a polyvalent metal salt and an alkylene oxide adduct of an alkylphenol formalin condensate (JP-A-4-261453). )
Has been proposed. Further, the glass transition temperature obtained by emulsion polymerization using an ethylenically unsaturated surfactant is -30.
Temperature-sensitive gelling latex composition prepared by blending a resin latex at -50 ° C with a heat-sensitive gelling agent (JP-A-6-29900).
No. 0) has been proposed.

[0003]

However, the resin latex used in the above composition does not exhibit temperature-sensitive self-thickening,
Moreover, since a heat-sensitive gelling agent which is water-soluble at room temperature is added, there is a problem that the handling is complicated and the water resistance of the coating film is insufficient.

[0004]

Means for Solving the Problems The present inventor has diligently studied a polymer having a thickening property in a binder itself without using a thickening agent, and as a result, a homopolymer was found to have a monomer having a cloud point. The inventors have found that the polymer incorporates a self-thickening function by copolymerization and has reached the present invention.

That is, in the present invention, 1 to 40% by weight of a monomer (a) whose homopolymer has a cloud point and 60 to 9 other monomers.
A binder comprising a thermoreversible thickening aqueous dispersion (A) of 9% by weight of a water-insoluble copolymer.

Examples of the monomer (a) whose homopolymer has a cloud point include vinylcarboxylic acid ester (a1), N-alkyl, N of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms. -Alkylene or N-
Alkoxyalkyl (meth) acrylamide (a2),
Polyalkylene glycol monoalkyl ether mono (meth) acrylate (a3), polyalkylene glycol monophenyl ether mono (meth) acrylate (a4), polyethylene glycol monoalkyl mono (vinylphenyl) ether (a5), polyethyleneimine mono (meth) Examples thereof include acrylamide (a6). Of these, (a1) and (a2) are preferable in terms of sharp temperature-sensitive gelation property, and particularly (a1) and (a2) are preferable.
1) is preferred.

Specific examples of (a1) include morpholinoethyl (meth) acrylate, morpholinoethoxyethyl (meth) acrylate, morpholinopropyl (meth) acrylate, piperidinopropyl (meth) acrylate and piperidinoethoxyethyl (meth). ) Acrylate,
Examples thereof include N-methyl-N-butylaminoethyl (meth) acrylate and (meth) acrylic acid ester of a 4-mol ethylene oxide adduct of dimethylpropylamine.

Specific examples of (a2) include N-isopropyl (meth) acrylate and N, N-dimethyl (meth).
Acrylamide, N- (meth) acryloylpyrrolidine, N- (meth) acryloylhexahydroazene,
(Meth) acryloylmorpholine, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (butoxymethyl)
(Meth) acrylamide etc. are mentioned.

Specific examples of (a3) include tetraethylene glycol monomethyl ether mono (meth) acrylate, triethylene glycol monoethyl ether mono (meth) acrylate, pentaethylene glycol monopropyl ether mono (meth) acrylate, and tetraoxypropylene. -Pentaoxyethylene glycol monomethyl ether mono (meth) acrylate, tetraoxyethylene-pentaoxypropylene-tetraoxyethylene glycol monomethyl ether mono (meth) acrylate, and the like.

Specific examples of (a4) include tetraethylene glycol monophenyl ether mono (meth) acrylate, tetraoxypropylene-pentaoxyethylene glycol monophenyl ether mono (meth) acrylate, and tetraoxyethylene-pentaoxypropylene-tetra. Examples thereof include oxyethylene glycol monophenyl ether mono (meth) acrylate.

Specific examples of (a5) include tetraethylene glycol monomethyl mono (vinylphenyl) ether, pentaethylene glycol monoethyl mono (vinylphenyl) ether and pentaethylene glycol monophenyl mono (vinylphenyl) ether. .

Specific examples of (a6) include triethylenetetramine (meth) acrylamide and tetraethylenepentamine (meth) acrylamide.

The content of (a) in the water-insoluble copolymer is
It is usually 1 to 40% by weight, preferably 3 to 20% by weight. If it is less than 1% by weight, the temperature-sensitive gelation property becomes insufficient,
If it exceeds 40% by weight, the water resistance of the formed film is poor.

As the other monomer constituting the aqueous dispersion (A) together with (a), known ones can be used, and preferred are the conjugated diene monomer (b) and the aromatic radical polymerization. It is a polymerizable monomer (c).

Examples of the conjugated diene monomer (b) include butadiene, isoprene, chloroprene, and 2-methyl-1,3.
-Butadiene and the like. Of these, particularly preferred is butadiene.

(B) in the water-insoluble polymer of the present invention
The content of is preferably 20 to 60% by weight. 20
If it is less than 60% by weight, the adhesive strength when the resin latex is used as a binder such as fibers becomes insufficient, and if it exceeds 60% by weight, the durability of the formed film becomes poor.

Examples of the aromatic radically polymerizable monomer (c) include styrene, α-methylstyrene, vinyltoluene, p-methylstyrene and vinylnaphthalene. Of these, styrene is preferred.

The content of (c) in the water-insoluble polymer is preferably 10 to 75% by weight, more preferably 2
0 to 60% by weight. If it is less than 10% by weight, the strength of the resin latex-forming film becomes insufficient, and if it exceeds 75% by weight, the adhesive strength when the resin latex is used as a binder such as fibers becomes poor.

The monomer (d) other than (a) to (c) which may be used together with the monomers (a), (b) and (c) is a radically polymerizable unsaturated carboxylic acid [(meta ) Acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. and their anhydrides or half esters], (meth) acrylic acid esters [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methyl polyethylene glycol mono (meth)
Acrylate, butyl polyethylene glycol mono (meth) acrylate, phenyl polyethylene glycol mono (meth) acrylate, etc.], hydroxyl group-containing monomer [(meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (Meth) acrylic acid-3-hydroxypropyl, diethylene glycol mono (meth) acrylate, etc.], (meth) acrylamides [(meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, dimethylaminoethyl (meth ) Acrylamide etc.], vinyl cyanides [(meth) acrylonitrile etc.], crosslinkable monomers [divinylbenzene, ethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, Trimethylolpropane tetra (meth) acrylate, etc.] and the like. Of these,
Radical-polymerizable unsaturated carboxylic acids, (meth) acrylic acid esters and vinyl cyanides are preferred.

The content of (d) in the aqueous dispersion (A) is usually 50% by weight or less, but is 5 to 35% by weight from the viewpoint of suppressing the formation of aggregates during emulsion polymerization. It is preferable. On the other hand, if it exceeds 50% by weight, the adhesive strength is poor when the resin latex is used as a binder such as fiber.

The method for producing the aqueous dispersion (A) in the present invention includes emulsion polymerization of a monomer mixture containing (a) using an emulsifier (1), and the method described above in the presence of a water-soluble polymer. Method (2) of emulsion-polymerizing a monomer mixture, after copolymerizing the monomer mixture in an organic solvent to synthesize a polymer, the obtained polymer is optionally neutralized with an acid or an alkali, and then water. A method (3) of adding and emulsifying and removing the solvent can be mentioned. Of these,
The method of emulsion polymerization using an emulsifier having a radically polymerizable group in (1) is preferable because the formed film has good water resistance.

Examples of the emulsifier having a radically polymerizable group include (1) anionic (meth) acrylic acid esters [CH2 = C (R1) CO2 (CH2) mSO3M (in the formula, R1
Represents a hydrogen atom or a methyl group, m represents an integer of 1 to 24, and M represents an alkali metal ion, an ammonium ion or an aminium ion. ), CH2 = C (R1)
CO2CH2C (R2) (OCOR3) CH2SO3M or CH
2 = C (R1) CO2CH2C (R2) (CH2OCOR3) SO3M
(Wherein R1 and R2 are hydrogen atoms or methyl groups, R3 is alkyl or alkenyl groups having 7 to 21 carbon atoms, M is an alkali metal ion, ammonium ion or aminium ion), CH2 = C (R1) C
O2CH2CH2OCOAr (R4) CO2CH2CH2OSO3
M (wherein R 1 is a hydrogen atom or a methyl group, Ar is an aromatic ring, R 4 is a hydrogen atom or an alkyl group, an alkenyl group or an aralkyl group having 1 to 24 carbon atoms, M is an alkali metal ion, an ammonium ion or an aminium ion) CH2 = C (R1) CO (AO)
pOSO3M or CH2 = C (R1) CO (AO) pOCH2C
O2M (wherein R1 is a hydrogen atom or a methyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, p is an integer of 2 to 200, and M is an alkali metal ion, an ammonium ion or an aminium ion). Etc.],
(2) Anionic (meth) acrylamides [CH2 = C
CH2 = (R1) CONH (CH2) mSO3M (wherein R1 is a hydrogen atom or a methyl group, m is an integer of 1 to 24, M is an alkali metal ion, an ammonium ion or an aminium ion); C (R1) CONHC
H2C (R2) (OCOR3) CH2SO3M or CH2 = C
(R1) CONHCH2C (R2) (CH2OCOR3) SO3M
(Wherein R1 and R2 are hydrogen atoms or methyl groups, R3 is alkyl or alkenyl groups having 7 to 21 carbon atoms, M is an alkali metal ion, ammonium ion or aminium ion), CH2 = C (R1) C
ONHCH2CH2OCOAr (R4) CO2CH2CH2OS
O3M (wherein R1 is a hydrogen atom or a methyl group, Ar is an aromatic ring, R4 is a hydrogen atom or an alkyl group, an alkenyl group or an aralkyl group having 1 to 24 carbon atoms, M is an alkali metal ion, an ammonium ion or an aminium ion. CH2 = C (R1) CONHC
H2 (AO) pOSO3M or CH2 = C (R1) CONHC
H2 (AO) pOCH2CO2M (wherein R1 is a hydrogen atom or a methyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms,
p is an integer of 2 to 200, M is an alkali metal ion, ammonium ion or aminium ion. )], (3) anionic styrene derivatives [C
H2 = CHAr (CH2) rSO3M (where Ar is an aromatic ring,
r is an integer of 4 to 24, M is an alkali metal ion, an ammonium ion, or an aminium ion. ), CH2 = CHAr (AO) pSO3M or C
H2 = CHAr (AO) pOCH2CO2M (wherein Ar is an aromatic ring, p is an integer of 2 to 200, M is an alkali metal ion, an ammonium ion, or an aminium ion), etc.], (4 ) Nonionic (meth) acrylic acid esters [CH2 = C (R1) CO (EO) POR3
(In the formula, R1 is a hydrogen atom or a methyl group, EO is an oxyethylene group, p is an integer of 2-200, and R3 is a carbon number of 5-2.
1 represents an alkyl group, an alkenyl group or an aralkyl group. ), CH2 = C (R1) CO (PO) p (E
O) sOR4 or CH2 = C (R1) CO (EO) p (PO) sO
R4 (wherein R1 is a hydrogen atom or a methyl group, PO is an oxypropylene group, EO is an oxyethylene group, and p and s are 2
To 200, R4 represents a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group or an aralkyl group. )
And the like], (5) nonionic (meth) acrylic acid amides [CH2 = C (R1) CONHCH2 (EO) POR
3 (wherein R1 is a hydrogen atom or a methyl group, EO is an oxyethylene group, p is an integer of 2 to 200, and R3 is a carbon number of 5 to 2).
1 represents an alkyl group, an alkenyl group or an aralkyl group. ), CH2 = C (R1) CONHCH2
(PO) p (EO) sOR4 or CH2 = C (R1) CONHC
H2 (EO) p (PO) sOR4 (wherein R1 is a hydrogen atom or a methyl group, PO is an oxypropylene group, EO is an oxyethylene group, p and s are integers from 2 to 200, and R4 is a hydrogen atom or a carbon number of 1). To 21 of alkyl group, alkenyl group or aralkyl group), and (6) nonionic styrene derivatives [CH2 = CHAr (EO) PO].
R3 (where Ar is an aromatic ring, EO is an oxyethylene group,
p represents an integer of 2 to 200, and R3 represents an alkyl group, an alkenyl group or an aralkyl group having 5 to 21 carbon atoms. Etc.]], (7) Cationic (meth) acrylic acid esters {[CH2 = C (R1) CO2CH2CH (OH) CH
2N (R4) 3] X [wherein R1 is a hydrogen atom or a methyl group, R
4 is a hydrogen atom or an alkyl group having 4 to 21 carbon atoms, an alkenyl group or an aralkyl group, X is a halogen atom, NO
3, HSO4, CH3OSO2, (CH3O) 2PO2, CH3C
Indicates O2 or HCO3. ], Etc.}, [C
H2 = C (R1) CO (AO) pN (R4) 3] X [wherein R1 is a hydrogen atom or a methyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, p is an integer of 2 to 200, and R4 is A hydrogen atom or an alkyl group having 4 to 21 carbon atoms, an alkenyl group or an aralkyl group, X is a halogen atom, NO3, HSO4, CH
3OSO2, (CH3O) 2PO2, CH3CO2 or HCO3
Is shown. ], (8) Cationic (meth) acrylic acid amides {[CH2 = C (R1) CONHC
H2CH (OH) CH2N (R4) 3] X [wherein R1 is a hydrogen atom or a methyl group, R4 is a hydrogen atom or a carbon number of 4 to 21]
Alkyl group, alkenyl group or aralkyl group, X is a halogen atom, NO3, HSO4, CH3OSO2, (CH3
O) 2PO2, CH3CO2 or HCO3. ], [CH2 = C (R1) CONH (AO) pN (R
4) 3] X [wherein R 1 is a hydrogen atom or a methyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, p is an integer of 2 to 200, R 4 is a hydrogen atom or an alkyl group having 4 to 21 carbon atoms, Alkenyl group or aralkyl group, X is a halogen atom, NO3, HSO4, CH3OSO2, (CH3O) 2PO
2, CH3CO2 or HCO3. ], (9) Cationic styrene derivatives {[CH2 = CH
Ar (CH2) rN (R4) 3] X [wherein Ar is an aromatic ring, r is an integer of 4 to 24, R4 is a hydrogen atom or a carbon number of 1 to 21]
Alkyl group, alkenyl group or aralkyl group, X is a halogen atom, NO3, HSO4, CH3OSO2, (CH3
O) 2PO2, CH3CO2 or HCO3. ] [CH2 = CHAr (AO) pN (CH4) 3] X
[Wherein Ar is an aromatic ring, AO is an oxyalkylene group having 2 to 4 carbon atoms, p is an integer of 2 to 200, R4 is a hydrogen atom or an alkyl group, alkenyl group or aralkyl group having 1 to 21 carbon atoms, X Is a halogen atom, NO3, HSO4, C
H3OSO2, (CH3O) 2PO2, CH3CO2 or HC
Indicates O3. ] And the like} and the like.

Among them, the anionic (1) to (3) are preferable because they are less likely to be aggregated by the pigment dispersant [eg, sodium poly (meth) acrylate] used in ordinary paper coating paints. Is preferred. Among (1), (meth) acrylate having an anion group and a polyoxypropylene chain is particularly preferable.

The amount of the emulsifier used for producing the aqueous dispersion (A) is usually 0.1 to 20 relative to the resin content.
% By weight.

The resin content of the aqueous dispersion (A) is usually 20 to
It is 75%, preferably 40 to 60%. The polymer particle size in (A) is usually 10 to 500 n.
m, preferably 50-300 nm, pH of (A)
Is usually 3 to 12, preferably 6 to 10. When the particle size exceeds 500 nm or the pH is less than 3 or exceeds 12, the temperature-sensitive self-thickening cannot be sufficiently exerted.

In the production of the aqueous dispersion (A), a known polymerization initiator is used. Examples of the polymerization initiator include organic polymerization initiators [peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, benzoyl peroxide, lauroyl peroxide, etc.), azo compounds (azobisisobutyrate). Ronitrile, azobisisovaleronitrile, etc.)], inorganic polymerization initiators [persulfate (sodium persulfate, ammonium persulfate, potassium persulfate, etc.)
Etc.]. The amount of the polymerization initiator used is usually 0.01 to 5% by weight based on the monomer mixture.

In the production of the aqueous dispersion (A), 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, alkylenedithiol having 8 to 18 carbon atoms,
Examples thereof include alkyl thioglycolate, dialkylxanthogen disulfide, tetraalkylthiuram disulfide, carbon tetrachloride and the like. These are either alone or 2
More than one species can be used in combination. The amount of the chain transfer agent used is usually 0 to 15% by weight based on the monomer mixture.

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

The binder of the present invention contains, if necessary, cationized starch, oxidized starch, casein, soybean protein, synthetic protein, polyvinyl alcohol, maleic anhydride resin, carboxymethyl cellulose for the purpose of increasing the adhesive strength. , A known water-soluble compound such as hydroxyethyl cellulose can be contained.

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

Furthermore, if necessary, pigment dispersants [sodium poly (meth) acrylate, sodium pyrophosphate, sodium hexametaphosphate, etc.], defoaming agents (mineral oil-based defoaming agents, silicon-based defoaming agents, etc.) Other additives [lubricants, pH adjusters, preservatives, water resistance agents, printability improving agents, etc.] can also be included.

[0032]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples are parts by weight. Example 1 102 parts of water, 4 parts of morpholinoethyl methacrylate, 40 parts of styrene, and 9 parts of methyl methacrylate were placed in a pressure reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas introducing tube, and a thermometer.
Parts, methacrylic acid 4 parts, and acryloyloxypolyoxypropylene (polymerization degree = 12) sulfuric acid ester Na salt 2 parts, sodium persulfate 1 part and lauryl mercaptan 0.2 part as an emulsifier having a radically polymerizable group,
After replacing the inside of the system with nitrogen gas with stirring, 38 parts of butadiene was injected under pressure from a dropping cylinder, and the mixture was heated at 50 ° C for 30 hours and at 85 ° C for 5 hours.
Allowed to react for hours. By stripping unreacted monomer under reduced pressure and adjusting the pH to 9.5 with an aqueous sodium hydroxide solution, SBR dispersion 1 (solid content 47.9%)
I got

Example 2 In the same manner as in Example 1, 6 parts of morpholinoethoxyethyl methacrylate, 40 parts of styrene, 9 parts of methyl methacrylate, 4 parts of methacrylic acid, acryloyloxypolyoxypropylene (degree of polymerization = 12) sulfate ester Na salt Two
Parts and 36 parts of butadiene, SBR-based dispersion 2 (solid content 48.1%) was obtained.

Example 3 In the same manner as in Example 1, 7 parts of N, N-diisopropylaminoethoxyethyl acrylate, 45 parts of styrene, 4 parts of methyl methacrylate, 4 parts of methacrylic acid, 2 parts of acrylonitrile, 30 parts of butadiene and methacryloyloxy. Polyoxypropylene (degree of polymerization = 9) Sulfate ester N
An SBR dispersion 3 (solid content 48.3%) was obtained from 5 parts of the salt a and 42 parts of butadiene.

Example 4 In the same manner as in Example 1, 7 parts of N- (isopropyloxymethyl) acrylamide, 45 parts of styrene, 4 parts of methyl methacrylate, 4 parts of methacrylic acid, 2 parts of acrylonitrile, 30 parts of butadiene, and methacryloyloxypolyamide. SBR-based dispersion 4 (solid content 48.3%) was obtained from 5 parts of oxypropylene (degree of polymerization = 9) sulfuric acid ester Na salt and 42 parts of butadiene.

Comparative Example 1 In the same manner as in Example 1, 46 parts of styrene, 12 parts of methyl methacrylate, 4 parts of methacrylic acid, and acryloyloxypolyoxypropylene (polymerization degree = 12) sulfuric acid ester Na5 as an emulsifier having a radical polymerizable group. From the department
A dispersion 5 (solid content 48.3%) was obtained.

Comparative Example 2 Alkylene oxide adduct of alkylphenol formalin condensate as a temperature-sensitive thickening agent was added to 100 parts of Dispersion 5 obtained in Comparative Example 1 [Latemul NP-manufactured by Kao Corporation].
5150] 2 parts were added to obtain a thickening binder for comparison.

The temperature sensitivity was measured by measuring the viscosities of the dispersions 1 to 5 and the binder of Comparative Example 2 at 25 ° C. and after leaving them in a hot water bath at 80 ° C. for 15 minutes under a sealed stopper, respectively. The gelation property was evaluated. The results are shown in Table 1.

[0039]

[Table 1] ---------------------------------------------------- || Example | Comparative Example | │ │ 1 │ 2 │ 3 │ 4 │ 1 ｜ 2 │ ｜ −−−−−−−−−− + −−−−−−−−−−−−−−− + −−−−−−−− | ｜ Viscosity before heating (cP / 25 ℃) ｜ 150 ｜ 180 ｜ 250 ｜ 220 ｜ 170 ｜ 190 ｜ ｜ −−−−−−−−−− + −−− + −−− + −−− + −−−− ＋ －－－ ＋ －－－ ｜｜ Viscosity at 80 ℃ (cP / 80 ℃) ｜ ＞ 100,000 ｜ ＞ 100,000 ｜ ＞ 100,000 ｜ ＞ 100,000 ｜ 120 ｜ ＞ 100,000 ｜｜ −−−−−−−− −−− + −−− + −−− + −−− + −−− + −−− + −−− | ｜ Viscosity after cooling (cP / 25 ℃) ｜ 160 ｜ 180 ｜ 230 ｜ 240 ｜ 180 | > 100,000 | −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

Use Examples 1 to 6 The binders of Dispersions 1 to 5 and Comparative Example 2 were each uniformly applied to an asbestos slate plate at a rate of 150 g / m 2.
It was dried at 130 ° C. for 5 hours. Add this to 20 ° C water for 24
Water resistance was evaluated by observing abnormalities (swelling, whitening, etc.) of the coating before and after immersion for a period of time. Table 2 shows the results.

[0041]

[Table 2] ----------------------------------------------------- | | Example of use | | | | 1 | 2 | 3 | 4 | 5 | 6 | | | ------------ + --------------------- + --------- | Dispersion | Examples | Examples | Examples | Examples | Comparative Examples | Comparative Examples || or a binder | 1 | 2 | 3 | 4 | 1 | 2 || ------------- + --- + −−− + −−− + −−− + −− − + −−− | ｜ Abnormality of coating before immersion ｜ None ｜ None ｜ None ｜ None ｜ Swelling ｜ None ｜ ｜ −−−−−−−−− −− + −−− + −−− + −−− + −−− + − −− + −−− | | Abnormality of the film after immersion | None | | None | None | None | Blister | Whitening | −−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−

[0042]

The binder of the present invention has good water resistance and temperature-sensitive self-thickening property. Furthermore, since it has a temperature-sensitive gelling property, it can suppress binder migration during heating and drying and gives a film having excellent water resistance. Further, since it is not necessary to add a thickener, workability and handleability are good. In order to achieve such effects, as a binder used for a coating color for producing coated paper, and
It can be particularly preferably used as a binder used in a carpet backing binder composition for producing a carpet. It is also useful for applications such as binders for moisture-proof coatings, resins for water-resistant coatings, paints, and various adhesives.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 25/08 LEH C08L 25/08 LEH 33/00 LJG 33/00 LJG 35/00 LJG 35/00 LJG C09D 109 / 00 PGP C09D 109/00 PGP 125/00 PFB 125/00 PFB

Claims (3)

[Claims] 1. A monomer (a) whose homopolymer has a cloud point.
A binder comprising a thermoreversible thickening aqueous dispersion (A) of a water-insoluble copolymer of 1 to 40% by weight and another monomer of 60 to 99% by weight. 2. (A) is 1 to 40% by weight of a monomer (a) whose homopolymer has a cloud point with respect to a water-insoluble copolymer,
Consists of 20 to 60% by weight of conjugated diene monomer (b), 10 to 75% by weight of aromatic radical polymerizable monomer (c) and 0 to 50% by weight of other radical polymerizable monomer (d). The binder according to claim 1, which is an emulsion obtained by emulsion-copolymerizing a monomer in water. 3. The binder according to claim 1, wherein (A) is a dispersion obtained by emulsion polymerization using an emulsifier (e) having a radically polymerizable group.