JP2969252B2 - Binder composition for fabric - 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 for fabrics having excellent water-resistant adhesive strength and moisture-resistant adhesive strength.

[0002]

2. Description of the Related Art A composition containing a thermosetting resin (Japanese Patent Publication No. 6-49854) has been proposed as a binder composition for fabrics having excellent water-resistant adhesive strength and moisture-resistant adhesive strength. In this composition, it is disclosed that the strength is improved by using a thermosetting resin, but the gel content of the latex or the type of the thickener is not mentioned.

[0003]

By the way, in the binder composition for fabric, a resin latex synthesized using a non-reactive emulsifier is used as the latex, that is, the amount of the emulsifier in the aqueous phase exceeds 0.01 mmol / g. In general, latex is used, and a compound having high water solubility such as sodium polyacrylate is used as a thickener in order to increase the viscosity at the time of application. For this reason,
Water and moisture resistant adhesive strength becomes insufficient due to the effects of emulsifiers and thickeners. In order to improve this, it has been proposed to use a cationic thermosetting resin described in the above publication, but the stability is insufficient when the composition is exposed to high temperatures due to the use of the cationic resin. There is a problem that becomes.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to obtain a binder composition for fabrics having sufficient water-resistant adhesive strength and moisture-resistant adhesive strength without using a cationic thermosetting resin. The present inventors have found that the above problems can be improved by considering the amount of the emulsifier and the gel content of the aqueous phase of the latex, and arrived at the present invention.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on an aqueous binder that solves the above problems, and as a result, have reached the present invention. That is, the present invention contains a resin latex (A) in which the amount of an emulsifier in an aqueous phase is 0.01 mmol / g or less as a latex and the gel content is 60 to 95% by weight. B1) ~
(B5) A binder composition for a fabric, comprising a vinyl polymer (B) whose hydrophilicity and hydrophobicity reversibly change at a certain temperature selected from the group consisting of (B5). (B1): a polymer comprising a vinyl carboxylate (b) of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms, (B2): an N-alkyl or N-alkylene (meth)
(B3): a polymer composed of polyalkylene glycol monoalkyl ether mono (meth) acrylate or polyalkylene glycol monophenyl ether mono (meth) acrylate, (B3): a polyalkylene glycol monoalkyl ether mono ( (B4): polymer composed of polyalkylene glycol monoalkyl monovinyl ether, (B5): polymer composed of polyalkylene glycol monophenyl monovinyl ether Coalescing.

[0006] The amount of the emulsifier in the aqueous phase in the resin latex (A) in the present invention is 0.01 mmol (mmol).
/ G (resin) or less, preferably 0.002 mmol /
g. The amount of the emulsifier in the aqueous phase is 0.
When it exceeds 01 mmol / g, the water-resistant adhesiveness and the moisture-resistant adhesiveness to the fabric become insufficient. The amount of the emulsifier in the aqueous phase is represented by the weight of the resin component in the resin latex (A).

The amount of the emulsifier in the aqueous phase can be determined by analyzing and quantifying the aqueous phase obtained by removing the resin component from the resin latex by liquid chromatography or the like. As a method of removing the resin component from the resin latex, for example, a method of removing the resin component by coagulating and solidifying the resin component after freezing the resin latex, a method of removing the resin component by sedimentation and solidification by a centrifugal separator, an acid or an alkali. In addition, a method of removing and solidifying and removing the resin component may be used.

As a method for producing a resin latex having an emulsifier amount of 0.01 mmol / g or less in an aqueous phase, for example,
A method of emulsion polymerization of a monomer using an emulsifier having low solubility in water, a method of emulsion polymerization using an emulsifier having a radical polymerizable group, a method of emulsion polymerization using a water-soluble polymer as a protective colloid, an organic solvent After synthesizing a polymer obtained by (co) polymerizing an ion-forming monomer therein, neutralizing the obtained polymer with an acid or alkali, adding water, emulsifying the polymer, and removing the solvent.

Among these methods, an emulsion polymerization method is preferable in that a latex composed of a high molecular weight resin is obtained, and an emulsifier having a radical polymerizable group (SBR latex is preferable in that an SBR latex is easily obtained under ordinary conditions). Emulsion polymerization using a) is particularly preferred.

The emulsifier having low solubility in water includes HL
B value of 3 to 9, for example, amine or alkali metal salt of a fatty acid having 22 or more carbon atoms, ethylene oxide 1 to 6 of an aliphatic or aromatic alcohol having 15 or more carbon atoms
And a molar adduct.

An emulsifier (a) having a radical polymerizable group;
For example, the following may be mentioned. (1) Anionic (meth) acrylates, the following formula
And the like indicated by: CH₂= C (R³) CO₂(CH₂)_mSO₃M CH₂= C (R³) CO₂CH₂C (R⁴) (OCOR)⁵) CH₂SO₃M CH₂= C (R³) CO₂CH₂CH₂OCOArCO₂CH₂CH₂OSO₃ M CH₂= C (R³) CO₂(AO)_pSO₃M (where R³Is a hydrogen atom or a methyl group, and m is an integer of 1 to 4.
The number M is an alkali metal ion, ammonium ion or
Is an aminium ion, R⁴Is a hydrogen atom or a methyl group,
R⁵Is an alkyl group or alkenyl having 7 to 21 carbon atoms
Group, Ar is an aromatic or aliphatic ring, AO has 2 to 2 carbon atoms
An oxyalkylene group of 4, p is an integer of 2 to 30
You. (2) anionic allyl compounds represented by the following formula:
Etc .: CH₂= CHCH₂OCOCH (SO₃M) CH₂CO₂R⁵  CH₂= CHCH₂OCH₂CH (OH) CH₂OCOCH (SO₃M) CH₂ CO₂R⁵  (R⁶) (R⁷) Ar (CH₂CH = CH₂) O (AO)_qSO₃M (where M is an alkali metal ion or an ammonium ion
Or aminium ion, R⁵Is an alk having 7 to 21 carbon atoms
R or alkenyl, R⁶Is an alkyl having 4 to 18 carbon atoms
A kill group, an alkenyl group or an aralkyl group, R⁷Is a water cable
An atom or an alkyl or alkenyl group having 4 to 18 carbon atoms
Or an aralkyl group, Ar is an aromatic ring, AO has 2 carbon atoms
To 4 oxyalkylene groups, q represents an integer of 2 to 200
You. (3) anionic maleic esters represented by the following formula:
Things: R⁸OCOCH = CHCO₂CH₂CH (OH) CH₂SO₃M R⁹O (AO)_qCOCH = CHCO₂(CH₂)_rCH (R¹⁰) SO₃M R⁹(AO)_qOCOCH = CHCO₂M (where R⁸Is an alkyl group having 5 to 21 carbon atoms, alkenyl
Group or aralkyl group, M is an alkali metal ion,
Monium ion or aminium ion, R⁹And R
¹⁰Is an alkyl group having 1 to 21 carbon atoms, an alkenyl group or
Represents an aralkyl group, and AO represents an oxyalkylene having 2 to 4 carbon atoms.
And q represents an integer of 2 to 200, and r represents an integer of 0 to 3.
You. (4) anionic itaconic esters represented by the following formula:
Thing: CH₂= C (CH₂CO₂R ⁸ ) CO₂(CH₂)_mSO₃M CH₂= C (CH₂CO₂R⁸) CO₂CH₂CH (OH) CH₂SO₃M (where R⁸Is an alkyl group having 5 to 21 carbon atoms, alkenyl
M or an aralkyl group, m is an integer of 1-4, M is
Li metal ion, ammonium ion or aminium ion
Indicates ON. (5) Nonionic (meth) acrylates, the following formula
And the like indicated by: CH₂= C (R³) CO (AO)_qOR⁸  CH₂= C (R³) CO (PO)_q(EO)_sOH or CH₂= C (R³) CO (EO)_q(PO)_sOH (where R³Is a hydrogen atom or a methyl group, R⁸Is carbon number 5
To 21 alkyl groups, alkenyl groups or aralkyl
AO is an oxyalkylene group having 2 to 4 carbon atoms, q is 2
An integer of ~ 200, PO is an oxypropylene group, EO is
A xyethylene group, s represents an integer of 2 to 200. (6) Nonionic allyl compounds represented by the following formula:
Etc .: (R⁶) (R⁷) Ar (CH₂CH = CH₂) O (AO)_qH (where R⁶Is an alkyl group having 4 to 18 carbon atoms, alkenyl
Group or aralkyl group, R⁷Is a hydrogen atom or carbon number 4
To 18 alkyl groups, alkenyl groups or aralkyl
Group, Ar is an aromatic ring, AO is an oxyalkyl having 2 to 4 carbon atoms.
A kylene group and q represents an integer of 2 to 200. (7) Nonionic maleic esters represented by the following formula:
Things: R⁶(AO)_qOCOCH = CHCO₂(AO)_sR⁷  (Where R⁶Is an alkyl group having 4 to 18 carbon atoms, alkenyl
Group or aralkyl group, R⁷Is a hydrogen atom or carbon number 4
To 18 alkyl groups, alkenyl groups or aralkyl
Group, AO is an oxyalkylene group having 2 to 4 carbon atoms, q and
s shows the integer of 2-200. (8) Nonionic itaconic esters represented by the following formula:
Thing: CH₂= C [CH₂CO₂(AO)_qR⁶] CO₂(AO)_sR⁷ (Where R⁶Is an alkyl group having 4 to 18 carbon atoms, alkenyl
Group or aralkyl group, R⁷Is a hydrogen atom or carbon number 4
To 18 alkyl groups, alkenyl groups or aralkyl
Group, AO is an oxyalkylene group having 2 to 4 carbon atoms, q and
s shows the integer of 2-200. (9) Cationic (meth) acrylates, the following formula
Etc .: [CH₂= C (R³) COOCH₂CH (OH) CH₂N (R¹¹)₃] X (where R³Is a hydrogen atom or a methyl group, R¹¹Is the carbon number
4 to 21 alkyl groups, alkenyl groups or aralkyl
The group, X, represents a halogen atom. (10) Cationic allyl compounds represented by the following formula:
Etc .: [CH₂= CHCH₂CH (OH) CH₂N (CH₃) 2R¹¹] X [CH₂= CHCH₂N (CH₃)₂R¹¹] X (where R¹¹Is an alkyl group having 4 to 21 carbon atoms, alkenyl
And X represents a halogen atom. )

Among them, (1), (5) and (5) are preferred in that they have good copolymerizability with various monomers, especially with styrene.
(9) is preferred, and among (1), (meth) acrylates having an anionic group and a polyoxypropylene chain are particularly preferred.

The amount of (a) used when producing the resin latex is usually 0.1 to 20% by weight based on the resin content.

The resin constituting the resin latex (A) in the present invention is a (co) polymer of various monomers. The monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, glycidyl (meth) Acrylate, N, N-dibutyl (meth) acrylamide, cyclohexyl (meth) acrylamide, (meth) acrylonitrile, styrene, 1-methylstyrene, vinyl acetate, vinyl alcohol, butadiene, vinyl chloride, isoprene, chloroprene, hydroxyethyl (meth) ) Acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acryloyloxy polyglycerol, vinyl alcohol, Lyl alcohol, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-vinyl-2-pyrrolidone, vinylimidazole, N-methylol-ε-caprolactam, N-methylolmaleimide, N- Vinyl succinimide, p-aminostyrene, N-vinylcarbazole, 2-vinylpyridine, 2-cyanoethyl (meth) acrylate, (meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid,
(Meth) acrylic sulfonic acid, styrene sulfonic acid, vinylbenzoic acid, alkyl allyl sulfosuccinic acid, (meth) acryloyl polyoxyalkylene sulfate,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, vinylaniline, 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine (meth ) Acrylimide, 1,1,1-trimethylamine (meth) acrylimide, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, etc. Combinations .

As the resin latex (A), a latex of styrene-butadiene resin, styrene-acrylic resin, acrylic resin, vinyl acetate resin or ethylene-vinyl acetate resin is preferred.
Butadiene resin latex is preferred.

The resin content of the resin latex (A) is usually 2
0-75%, preferably 40-60%.

In the emulsion polymerization of the resin latex, known polymerization initiators and chain transfer agents are used. As the polymerization initiator, organic polymerization initiators [peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide,
Benzoyl peroxide, lauroyl peroxide, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), inorganic polymerization initiators, persulfates (sodium persulfate, ammonium persulfate,
Potassium persulfate, etc.) and the like. The amount of the polymerization initiator to be used is usually 0.01 to 5% by weight based on the resin component.

In the present invention, 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), terpinolene, terpinene, dipentene, alkyl mercaptan having 8 to 18 carbon atoms, alkylene dithiol having 8 to 18 carbon atoms, alkyl thioglycolate, dialkyl xanthogen disulfide, tetraalkyl thiuram disulfide, carbon tetrachloride, etc. No. 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 parts by weight based on 100 parts by weight of 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.). It may be contained during emulsion polymerization.

In the present invention, the resin latex has a gel content of usually 60 to 95% by weight, preferably 75 to 95% by weight.
90% by weight. If the gel content is less than 60% by weight, the adhesive strength, particularly the water-resistant adhesive strength and the moisture-resistant adhesive strength, will be insufficient. If the gel content exceeds 95% by weight, the film-forming properties of the latex will be poor, and the adhesive strength will be insufficient.

Here, the gel content in the present invention means:
About 1 g of resin latex (A) is poured into a glass mold,
A film having a thickness of about 0.3 mm after drying at room temperature was subjected to Soxhlet extraction with toluene, and the weight of the remaining solids (gel) was calculated using the resin latex (A) used.
It is expressed as a percentage based on the weight of the residue dried at 0 ° C.

The gel content can be adjusted by the monomer composition constituting the resin in (A) and the types and amounts of the polymerization initiator and the chain transfer agent used. In general, the amount of monomers having a plurality of radically polymerizable double bonds (butadiene, isoprene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, etc.) is small. Then, the gel content decreases, and the gel content decreases as the amounts of the polymerization initiator and the chain transfer agent increase. Further, when peroxides or persulfates are used as the polymerization initiator, the gel content increases, and even when a polyfunctional polymerization initiator and a chain transfer agent are used, the gel content increases.

In the resin latex (A) of the present invention, the resin component has a glass transition temperature of -50 to -20.
° C, especially −40 to −25 ° C., since the strength and flexibility of the obtained fabric are good. Here, the glass transition temperature means that latex is poured into a glass mold,
A film obtained by drying at 30 ° C. and 10 mmHg or less for 8 hours and storing in a desiccator to form a film having a thickness of about 0.3 mm was measured by a differential scanning calorimeter (DSC) under nitrogen at 20 ° C./min. It is. The glass transition temperature of the resin can be adjusted by the monomer composition of the resin.

The binder composition of the present invention contains, in addition to the resin latex (A), commonly used water-soluble thickeners [poly (meth) acrylic acid, polyvinyl alcohol, cellulose compounds, starches, etc.]. But a vinyl polymer (B) whose hydrophilicity and hydrophobicity reversibly change at a certain temperature selected from the group consisting of (B1) to (B5) as a thickener is contained. Is essential, so that the moisture-resistant adhesiveness can be particularly improved. The vinyl polymer (B) is a polymer (B1) composed of a vinyl carboxylic acid ester (b) of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms, N-alkyl or N-alkylene (meth) Polymer (B2) composed of acrylamide, polymer (B3) composed of polyalkylene glycol monoalkyl ether mono (meth) acrylate or polyalkylene glycol monophenyl ether mono (meth) acrylate, and polymer composed of polyalkylene glycol monoalkyl monovinyl ether The polymer (B5) is selected from the group consisting of the polymer (B5) composed of the union (B4) and the polyalkylene glycol monophenyl monovinyl ether, and among these, the polymer (B1) is preferable because of its high viscosity increasing effect.

The cyclic amine in the vinyl carboxylate (b) is not particularly limited as long as it has an active hydrogen for the addition of an alkylene oxide, and therefore has an amine nitrogen inside and outside the ring. Just do it. The active hydrogen group may be derived from an amino group, or may be derived from any group to which an alkylene oxide can be added, such as a hydroxyl group or a carboxyl group.

Examples of such a cyclic amine include, for example,
Non-aromatic heterocyclic amine [having an aziridine ring (aziridine, 2-methylaziridine, 2-
Those having a pyrrolidine ring (e.g., pyrrolidine, 2-methylpyrrolidine, 2-ethylpyrrolidine, 2-pyrrolidone, succinimide, 1,2-cyclohexanedicarboximide), and those having a piperidine ring (piperidine, 2- Methylpiperidine,
3,5-dimethylpiperidine, 2-ethylpiperidine,
4-piperidinopiperidine, 2-methyl-4-pyrrolidinopiperidine, ethylpicoliconate, etc., those having a piperazine ring (1-methylpiperazine, 1-methyl-3-ethylpiperazine, etc.), and a morpholine ring (Morpholine, 2-methylmorpholine, 3,
5-dimethylmorpholine, thiomorpholine, etc.),
Pyrolines (such as 3-pyrroline, 2,5-dimethyl-3-pyrroline, 2-phenyl-2-pyrroline), pyrazolines (such as pyrazoline), imidazoles (2-methylimidazole, 2-ethyl-4-methylimidazole) ,
2-phenylimidazole, pyrazoles (pyrazole, pyrazolecarboxylic acid, etc.), pyridones (α
-Pyridone, [gamma] -pyridone, etc.) and [epsilon] -caprolactam, pyridazinone, pyridalin, pyridoin, etc.]; aromatic heterocyclic amines [2-hydroxypyridine, 2-hydroxy-3,5-ditert-butylpyridine, 2-carboxyl] Pyridine, 4-pyridylcarbinol, 2-hydroxypyrimidine, pyrrole, 2-phenylpyrrole, etc.]; aromatic amines [aniline, 3-methylaniline, N-methylaniline, N-
Isopropylaniline and the like].

Among these cyclic amines, preferred are non-aromatic cyclic amines. Of these, those having a piperidine ring and those having a morpholine ring are most preferable, and those having a morpholine ring are most preferable.

The non-cyclic amine having 5 or more carbon atoms in (b) is not particularly limited as long as it is a non-cyclic amine having 5 or more carbon atoms having an active hydrogen for adding an alkylene oxide. For example, primary aliphatic acyclic amines having 5 or more carbon atoms (dimethylpropylamine, 2-ethylbutylamine, pentylamine, 2,2-dimethylbutylamine,
Hexylamine, cyclohexylamine, octylamine, 2-ethylhexylamine, isodecylamine, laurylamine, etc.), a secondary aliphatic acyclic amine having 5 or more carbon atoms [methylbutylamine, methylisobutylamine, methyl tert-butylamine, methyl Pentylamine, methylhexylamine, methyl (2-ethylhexyl) amine, methyloctylamine, methylnonylamine, methylisodecylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine,
Ethyl isobutylamine, ethyl tert-butylamine, ethylpentylamine, ethylhexylamine, ethyl (2-ethylhexyl) amine, ethyloctylamine, dipropylamine, diisopropylamine, propylbutylamine, propylisobutylamine, propyltertiarybutylamine, propylpentylamine ,
Propylhexylamine, propyl (2-ethylhexyl) amine, propyloctylamine, isopropylbutylamine, isopropylisobutylamine, isopropyltert-butylamine, isopropylpentylamine, isopropylhexylamine, isopropyl (2
-Ethylhexyl) amine, isopropyloctylamine, dibutylamine, diisobutylamine, ditertiarybutylamine, butylpentylamine, dipentylamine, dicyclohexylamine, etc.].

Preferred among the acyclic amines having 5 or more carbon atoms are primary aliphatic acyclic amines having 5 to 8 carbon atoms.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like. Preferred among these are ethylene oxide or propylene oxide, and combinations of both.

The number of moles of the alkylene oxide added is usually 1 to 50 mol, preferably 1 to 5 mol.

(B) is a cyclic amine or a compound having 5 carbon atoms.
An ester of the above alkylene oxide adduct of an acyclic amine with a vinyl carboxylic acid. The vinyl carboxylic acid does not need to have a vinyl group and a carboxyl group directly linked, and may be, for example, a radical polymerizable unsaturated fatty acid such as (meth) acrylic acid, (iso) crotonic acid, maleic acid, fumaric acid, and itaconic acid. Aromatic carboxylic acids; radically polymerizable aromatic carboxylic acids such as vinylbenzoic acid and 2-carboxy-4-isopropenyl-3-pyrrolidineacetic acid; and ester-forming derivatives (acid anhydrides or acid halides) thereof. .

Of these, (meth) acrylic acid, maleic acid, vinylbenzoic acid and ester-forming derivatives thereof are preferred, and (meth) acrylic acid and (meth) acrylic acid
Ester-forming derivatives of acrylic acid are particularly preferred.

The polymer (B1) may be a polymer of vinyl carboxylate (b) or a copolymer of (b) and another vinyl monomer (c). It is necessary to contain 50% by weight or more. Preferably,
The content is 70% by weight or more.

Other vinyl monomers (c) include:
(C-1) hydrophilic (excluding (b)), (c-2)
It may be of a lipophilic vinyl monomer.

As (c-1), nonionic compounds [hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acryloyloxy polyglycerol, vinyl alcohol, allyl Alcohol, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-vinyl-2-pyrrolidone, vinylimidazole, N-methylol-ε-caprolactam, N-
Methylol maleimide, N-vinyl succinimide, p
-Aminostyrene, N-vinylcarbazole, 2-vinylpyridine, 2-cyanoethyl (meth) acrylate, etc.]; anionic compound [(meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid , (Meth) acrylic sulfonic acid, styrene sulfonic acid, vinyl benzoic acid, alkyl allyl sulfosuccinic acid,
Acids such as (meth) acryloyl polyoxyalkylene sulfate and salts thereof]; cationic compounds [N,
N-dimethylaminoethyl (meth) acrylate, N,
N-dimethylaminopropyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, vinylaniline and acid salts thereof]; Compound having an amineimide group [1,1,1-trimethylamine (meth) acrylimide] , 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-
1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1,1-trimethylamine (meth) acrylimide, etc.].

As (c-2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, glycidyl (Meth) acrylate derivatives such as (meth) acrylate, N-alkyl (meth) acrylamide derivatives such as N, N-dibutyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, (meth) acrylonitrile, styrene,
Examples include 1-methylstyrene, vinyl acetate, butadiene, vinyl chloride, isoprene and the like.

The vinyl polymer (B1) can be obtained, for example, by the method described in JP-A-6-9848.

Examples of the polymer (B2) include (co) polymers of N-alkyl or N-alkylene (meth) acrylamide monomers and copolymers of the monomers with the other vinyl monomers (c). .

Specific examples of the N-alkyl or N-alkylene (meth) acrylamide monomer constituting the polymer (B2) include N-ethyl (meth) acrylamide,
N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, N- ( (Meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylhexahydroazene, (meth) acryloylmorpholine, N-tetrahydrofurfuryl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N
-Ethoxypropyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N- (2,2-dimethoxyethyl) -N-methyl (meth) acrylamide, N-1- Methyl-2-methoxyethyl (meth) acrylamide, N-1-methoxymethylpropyl (meth)
Acrylamide, N- (1,3-dioxolan-2-yl) -N-methyl (meth) acrylamide, N-8-acryloyl-1,4-dioxa-8-aza-spiro [4,5] decane, or N -Methoxyethyl-N-
n-Propyl (meth) acrylamide.

The polymer (B2) is described, for example, in JP-A-1-1-1.
It is obtained by the method described in JP-A-4276.

As the ω-alkoxypolyalkylene glycol mono (meth) acrylate or ω-phenoxypolyalkylene glycol mono (meth) acrylate constituting the polymer (B3), (meth) acrylic acid of ethylene oxide adduct of monohydric alcohol is used. Ester [ω-methoxy polyethylene glycol mono (meth) acrylate, ω-ethoxy polyethylene glycol mono (meth)
Acrylate, ω-propoxy polyethylene glycol mono (meth) acrylate, ω-butoxy polyethylene glycol mono (meth) acrylate, ω-cyclohexyl polyethylene glycol mono (meth) acrylate, ω-phenoxy polyethylene glycol mono (meth) acrylate, etc.], monovalent Ethylene oxide adduct of alcohol propylene oxide adduct [ω-methoxy (poly) oxypropylene polyoxyethylene mono (meth) acrylate etc.] Propylene oxide adduct of monohydric alcohol ethylene oxide adduct [ω-methoxypolyoxyethylene ( Poly) oxypropylene mono (meth) acrylate etc.] propylene oxide adduct of ethylene oxide adduct of propylene oxide adduct of monohydric alcohol [ω-methoxy (Poly) oxypropylene polyoxyethylene (poly) oxypropylene mono (meth) acrylate, etc.) or ethylene oxide adduct of propylene oxide adduct of monohydric alcohol ethylene oxide adduct [ω-methoxypolyoxyethylene (poly) oxypropylene Polyoxyethylene mono (meth) acrylate, etc.]. The polyoxyalkylene polymerization degree in the polyalkylene glycol mono (meth) acrylate is 2 to 50. Polymer (B3)
Examples thereof include (co) polymers of one or more of these mono (meth) acrylates and copolymers with comonomers. The same comonomer as the vinyl monomer (c) can be used.

The polymer (B3) is described, for example, in JP-A-6-2
It can be obtained by the method described in JP-A-3375.

The polyalkylene glycol monoalkyl monovinyl ether constituting the polymer (B4) includes
Vinyl ether obtained from ethylene oxide adduct of monohydric alcohol and vinyl chloride (polyethylene glycol monoethyl monovinyl ether, polyethylene glycol monopropyl monovinyl ether, polyethylene glycol monobutyl monovinyl ether, etc.) and propylene oxide / ethylene oxide adduct of monohydric alcohol Vinyl ether obtained from vinyl chloride [(poly)
Oxypropylene polyoxyethylene glycol monomethyl monovinyl ether] and (poly) oxyethylene (poly) oxypropylene polyoxyethylene glycol monomethyl monovinyl ether].
Examples of the polyalkylene glycol monophenyl monovinyl ether constituting the polymer (B5) include vinyl ethers (eg, polyethylene glycol monophenyl monovinyl ether) obtained from ethylene oxide adducts of phenols and vinyl chloride. The polyoxyalkylene polymerization degree in the polyalkylene glycol monovinyl ether is 2 to 50.

As the polymer (B4) or (B5),
One or more of these monovinyl ethers include (co) polymers and copolymers with comonomers. As the comonomer, the same as the above-mentioned vinyl monomer (c) can be used.

The polymer (B4) or (B5) is described, for example, in Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 30, page 2407 (1992).
Obtained by the method described in (1).

The weight average molecular weight of the vinyl polymer (B) is generally 1,000 to 5,000,000, preferably 1
000 to 2,000,000, particularly preferably 10
It is between 000 and 1,000,000.

In the fabric binder composition of the present invention, the ratio of (A) to (B) depends on the desired viscosity of the binder composition, but is usually 70% by weight.
９９99.99: 0.01 to 30, preferably 80 to 9
9.5: 0.05 to 20. The ratio of (B) is 0.0
If it is less than 1% by weight, the viscosity of the binder composition becomes too low.

The binder composition of the present invention may contain known fillers or additives as long as the effects of the present invention are not impaired. Examples of the filler include calcium carbonate, clay, talc, aluminum hydroxide and the like. Additives include vulcanizing agents, defoamers, pigment dispersants, thickeners, antistatic agents, preservatives, antifungal agents, film thickeners, wetting agents, pH adjusters, pH buffers, coloring agents And the like.

A method for producing a non-woven fabric using the binder composition of the present invention will be described. The binder obtained by adding various additives as needed to the composition of the present invention is applied to a web (obtained from fibers of wool, polyester, nylon, polypropylene, rayon, etc.) by a usual method (spray method, impregnation method, forming method). Method, printing method, etc.) and heating with a drying device (40-150
℃) dried to obtain a non-woven fabric.

A method for producing a carpet using the binder composition of the present invention will be described. First, a binder for a carpet backing is obtained by blending an additive such as a pigment dispersant, a filler, an antioxidant and an appropriate amount of dilution water into the resin latex (A) of the present invention, and then blending an aqueous solution of a thickener. . An ordinary stirring device can be used for the compounding. The obtained binder for carpet backing,
A fiber sheet (a sheet obtained from fibers of polyester, nylon, polypropylene, rayon, etc.) is applied by a usual method (spray method, forming method, printing method, etc.) and dried by heating (40 to 150 ° C.) with a drying device. , A carpet is obtained. Carpets include all types of carpets where latex is used as an adhesive, such as tufted carpets, hook drags, needle punch carpets, artificial turf, and the like.

[0052]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in the examples are parts by weight. Production Example 1 100 parts of 2-morpholinoethyl methacrylate (an ester of morpholine with one mole of ethylene oxide and methacrylic acid) and 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule. After freezing and deaeration, the system was sealed and polymerized at 50 ° C. for 8 hours to obtain a polymer 1.

Production Example 2 90 parts of 2- (2-morpholinoethoxy) ethyl methacrylate (2 mol adduct of morpholine with ethylene oxide, ester with methacrylic acid), 10 parts of methyl methacrylate and 2,2′-azobis (2,2) 0.1 part of 4-dimethylvaleronitrile) was added to the ampoule, frozen, degassed, sealed, and polymerized at 60 ° C. for 8 hours to obtain a polymer 2.

Production Example 3 80 parts of 2-morpholinopropyl methacrylate (ester of methacrylic acid with 1 mol of propylene oxide adduct of morpholine), 5 parts of styrene, 10 parts of methyl methacrylate, 5 parts of hydroxyethyl methacrylate and 2,2 ′ -Add 0.1 part of azobis (2,4-dimethylvaleronitrile) to the ampoule, freeze, deaerate and seal.
Polymerization was performed at 0 ° C. for 8 hours to obtain a polymer 3.

Production Example 4 80 parts of 2- (2-piperidinoethoxy) ethyl methacrylate, 10 parts of N, N-dibutylacrylamide, 10 parts of styrene and 2,2'-azobis (2,4-dimethylvaleronitrile) 0 0.5 part was added to an ampoule, frozen, degassed, sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer 4.

Production Example 5 An ampoule was added with 80 parts of an acrylate ester of a 4 mol ethylene oxide adduct of dimethylpropylamine, 20 parts of methyl methacrylate and 0.5 part of 2,2'-azobis (2,4-dimethylvaleronitrile). After freezing and degassing, the mixture was sealed and polymerized at 50 ° C. for 8 hours to obtain a polymer 5.

Production Example 6 In a pressurized reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas inlet tube, and a thermometer, methacryloyloxypolyoxypropylene (degree of polymerization =
9) Sulfuric acid ester Na salt 10 parts, water 97 parts, styrene 3
2 parts, methyl methacrylate 9 parts, methacrylic acid 4 parts,
1 part of sodium persulfate and lauryl mercaptan
After 2 parts were charged and the system was replaced with nitrogen gas under stirring, 50 parts of butadiene was press-fitted from a dropping cylinder, heated to 50 ° C., and reacted at the same temperature for 30 hours. The pH was adjusted to 8.5 with an aqueous sodium hydroxide solution, and unreacted monomers were stripped under reduced pressure to obtain SBR-based resin latex 1 (solid content: 47.9%, hereinafter referred to as SBR1). The amount of emulsifier in the aqueous phase of SBR1 is 0.0003 mmol
/ G (resin), the gel content was 82% by weight, and the glass transition temperature was -30 ° C.

Production Example 7 In the same manner as in Production Example 6, 22 parts of styrene, 4 parts of methyl methacrylate, 4 parts of methacrylic acid, and 5 parts of acrylonitrile
Part, butadiene 60 parts and methacryloyloxy polyoxypropylene (polymerization degree = 12) sulfuric acid ester Na salt sulfonate 10 parts are polymerized to obtain SBR resin latex 2 (solid content 48.3%, hereinafter referred to as SBR2). Was.
The amount of the emulsifier in the aqueous phase of SBR2 was 0.0005 mmol /
g (resin), the gel content was 85% by weight, and the glass transition temperature was -37 ° C.

Production Example 8 An SBR for comparison was prepared in the same manner as in Production Example 6 except that 10 parts of sodium alkyldiphenyl ether disulfonate [Eleminol MON-7 manufactured by Sanyo Chemical Industries, Ltd.] was used as an emulsifier.
Resin latex 3 (solid content 48.2%, hereinafter SBR3
). The amount of emulsifier in the aqueous phase of SBR3 is 0.1
mmol / g (resin), gel content 83% by weight, glass transition temperature -30 ° C.

Production Example 9 SBR resin latex 4 for comparison (solid content: 48.2) was prepared in the same manner as in Production Example 6 except that 3.5 parts of carbon tetrachloride was used instead of 0.2 part of lauryl mercaptan. %,
SBR4). The emulsifier amount of the aqueous phase of SBR4 was 0.0004 mmol / g (resin), the gel content was 40% by weight, and the glass transition temperature was -35 ° C.

Examples 1 to 5, Comparative Examples 1 to 3 95 parts of SBR1 obtained in Production Example 6 were mixed with 400 parts of heavy calcium carbonate, 0.5 part of potassium tetrapolyphosphate, and 0.5 part of a phenolic antioxidant. And polymer 1 obtained in Production Example 1
Was mixed with an appropriate amount of water to obtain a binder composition 1 of Example 1. Perform the same operation as above,
Binder composition 2 of Example 2 using SBR1 and polymer 2, Binder composition 3 of Example 3 using SBR2 and polymer 3, and Example 4 using SBR2 and polymer 4.
The binder composition 4 of Example 5 was obtained using the SBR1 and the polymer 5, respectively. Also,
Binder composition 6 of Comparative Example 1 was obtained using SBR3 and Polymer 1, and binder composition 7 of Comparative Example 2 was obtained using SBR4 and Polymer 1. In Example 1, 5 parts of a 40% aqueous solution of sodium polyacrylate was used instead of 5 parts of a 40% aqueous solution of the polymer 1 obtained in Production Example 1, and epichlorohydrin-modified diethylenetriamine adipate polycondensation resin 2 was used as a thermosetting resin. Then, the binder composition 8 of Comparative Example 3 was obtained.

The above binder composition was applied to a tufted carpet having a primary backing of polypropylene and a pile of nylon at a solid content of 900 g / m 2, respectively, and a secondary backing of jute was adhered thereto and dried at 125 ° C. for 15 minutes. To obtain a carpet sample. The adhesive strength (peeling strength) of the obtained carpet sample was determined according to JIS L-
1021. In addition, the high temperature stability of the binder composition was evaluated. Table 1 shows the results.

[0063]

[Table 1]

Normal strength: A value measured after a carpet sample was allowed to stand at 25 ° C. and 60% humidity for 24 hours. Water resistance strength: a value measured after immersing a carpet sample in water at 60 ° C. for 1 hour. Moisture resistance; Carpet sample is 24 hours at 50 ° C and 85% humidity
Measurement value after standing for a time. High-temperature stability: After leaving the binder composition to stand at 80 ° C. for 15 minutes in a sealed state, it is cooled to 25 ° C. and the state is observed. The fluidity was indicated by ○, and the gelled one was indicated by ×.

[0065]

The binder composition of the present invention has good stability when exposed to high temperatures and has excellent water- and moisture-resistant adhesive strength, and thus is useful for fabric production.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09J 201 / 00,125 / 10 C08F 2/24

Claims (4)

(57) [Claims] 1. The amount of an emulsifier in an aqueous phase as a latex is 0%.
01 mmol / g or less, and the gel content is 60 to 9
Contains 5% by weight of resin latex (A), and as a thickener, hydrophilicity and hydrophobicity reversibly change at a certain temperature selected from the group consisting of (B1) to (B5) below. A binder composition for fabric, comprising a vinyl polymer (B). (B1): a polymer comprising a vinyl carboxylate (b) of an alkylene oxide adduct of a cyclic amine or an acyclic amine having 5 or more carbon atoms, (B2): an N-alkyl or N-alkylene (meth)
(B3): a polymer composed of polyalkylene glycol monoalkyl ether mono (meth) acrylate or polyalkylene glycol monophenyl ether mono (meth) acrylate, (B4): a polyalkylene glycol monoalkyl monovinyl ether (B5): a polymer comprising polyalkylene glycol monophenyl monovinyl ether. 2. The composition according to claim 1, wherein (A) is a resin latex synthesized using an emulsifier (a) having a radical polymerizable group. 3. The composition according to claim 1, wherein (A) is a styrene-butadiene resin latex having a glass transition temperature of −50 to −20 ° C. 4. The composition according to claim 1, wherein the ratio of (A) to (B) is from 70 to 99.99: 0.01 to 30 based on weight.
4. The composition according to 2 or 3.