JPH08269874A - Binder composition for fiber processing - Google Patents

Abstract

PURPOSE: To obtain a binder composition having excellent resistance to washing, resistance to dry cleaning and wear resistance and useful for flocking and pigment printing from an aqueous dispersion of a hydrolyzable silyl group-containing copolymer. CONSTITUTION: A water-soluble or a water-dispersible polymer having an amine imide group is formed from a copolymer comprising a polymerizable monomer having an amine imide group such as 1,1,1-trimethylamine methacrylimide and at least one kind of an ionic group or an ion-formable group-containing polymerizable monomer selected from among a carboxylic acid (salt) group-containing polymerizable monomer, a sulfonic acid (salt) group-containing polymerizable monomer and an amino group-containing polymerizable monomer, and a hydrolyzable silyl group-containing vinyl-based monomer as essential constituting units. A vinyl-based monomer having a hydrolyzable silyl group (a1) such as vinyl methyl dimethoxysilane is mixed with a vinyl-based monomer (a2) copolymerizable with the vinyl-based monomer having a hydrolyzable silyl group in an amount of the (a1) of 0.5-50wt.% to total weight of the (a1+a2) and the resultant mixture is subjected to emulsion polymerization in the presence of the polymer to obtain an aqueous dispersion of a resin having a glass transition point of from -20 deg.C to 20 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a binder for fiber processing. More specifically, it relates to a binder for fiber processing, which has excellent long-term storage stability and excellent durability such as washing resistance, dry cleaning resistance, and abrasion resistance.

[0002]

2. Description of the Related Art Conventionally, as a binder for fiber processing,
In order to impart durability such as washing resistance, dry cleaning resistance, and abrasion resistance, an aqueous dispersion of a polymer using N-methylol (meth) acrylamide as a reactive functional group-containing monomer is mainly used, Further, a curing agent such as an amino resin has been used in combination for further improving durability. However, although such a binder has durability, it has a problem in terms of influence on the human body because formalin is generated during heat curing. For the purpose of solving the problem of formalin generation, for example, in a low molecular weight emulsifier such as sodium dodecyl sulfate, a hydrolyzable silyl group-containing monomer, a polymerizable unsaturated carboxylic acid and an organic halogen monomer are used. A fiber processing binder comprising an aqueous resin dispersion obtained by emulsion polymerization of a monomer mixture as an essential monomer in the presence of an emulsifier is disclosed (Japanese Patent Publication No. 61-89373).

[0003]

However, since the above-mentioned binder uses a low-molecular-weight surfactant as an emulsifier, the long-term storage stability of the obtained fiber-processing binder is insufficient, and the initial value after long-term storage is low. There is a problem that an auxiliary cross-linking agent or the like must be added and used in order to exhibit the performance.

[0004]

The present inventors have found that long-term storage stability is extremely good, no formalin is generated during heat curing, and durability such as washing resistance, dry cleaning resistance, and abrasion resistance. The present invention has been achieved as a result of extensive studies to obtain an excellent fiber-processing binder. That is, the present invention relates to a vinyl-based monomer having a hydrolyzable silyl group (a
1) and other vinyl-based monomers (a
The monomer mixture (A) consisting of 2) is emulsion polymerized in the presence of a water-soluble or water-dispersible polymer (B) having an amine imide group, and has a glass transition temperature of -20 ° C to 20 ° C. A binder composition for fiber processing, which comprises an aqueous resin dispersion.

In the present invention, the hydrolyzable silyl group in the vinyl monomer (a1) having a hydrolyzable silyl group is a halogenosilyl group, an acyloxysilyl group,
Examples thereof include an amidosilyl group, an aminoxysilyl group, an alkenyloxysilyl group, an aminosilyl group, an oximesilyl group, an alkoxysilyl group and a thioalkoxysilyl group, and an alkoxysilyl group is preferable.

Specific examples of (a1) include vinylsilanes [vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.]; (meth) acryloxyalkylsilanes [ γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxy Propyltriethoxysilane, etc.] and the like described in JP-A-5-25354.

The above (a1) also includes an oligomer having at least one vinyl group and at least one hydrolyzable silyl group at the terminal or side chain. The oligomer has a polymer chain having a relatively low molecular weight such as a polyurethane chain, a polyamide chain, an epoxy resin chain and a polyester chain between the vinyl group and the hydrolyzable silyl group. Specifically, as described in JP-A-60-26022, a polyurethane-based oligomer having a vinyl group and an alkoxysilyl group [polycaprolactone triol (MW; 2,000;
0) terminal NCO compound (1 mol) by isophorone diisocyanate and 2-hydroxyethyl methacrylate (1
Mol) and γ-aminopropyltrimethoxysilane (2
Mol)); polyester-based oligomer [polycaprolactone diol (MW; 5,000) having one end (hydroxyl group) esterified with (meth) acrylic acid and another end (hydroxyl group) Hydrolyzable silyl group was added by reaction with isocyanate propyltriethoxysilane]; polyamide oligomer [obtained by reaction of polyamide resin having amino group with glycidyl methacrylate and epoxy silane coupling agent] Etc.]; Epoxy oligomers [such as those obtained by reacting an addition condensation product of bisphenol A and epichlorohydrin with a methacrylic acid ester having a secondary amino group and an amine group-containing silane coupling agent] and the like. To be These are used alone or as a mixture of two or more thereof. Of these, preferred are those having an alkoxysilyl group as a hydrolyzable silyl group, and (meth) acryloxyalkylsilanes and polyurethane oligomers having a vinyl group and an alkoxysilyl group are particularly preferred.

Other copolymerizable vinyl monomer (a2)
Is not particularly limited, but for example, (meth) acrylic acid alkyl ester [methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-
2-ethylhexyl, octyl (meth) acrylate,
Lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.]; hydroxyl group-containing monomer [(meth)]
2-Hydroxyethyl acrylate, 2-Hydroxypropyl (meth) acrylate, (Meth) acrylic acid-3
-Hydroxypropyl, diethylene glycol mono (meth) acrylate, etc.]; Aromatic vinyl monomers (styrene, vinyltoluene, etc.); Alkyl vinyl ethers (methyl vinyl ether, cyclohexyl vinyl ether, etc.); Vinyl esters (vinyl acetate, etc.); Nitrile groups Containing monomer [(meth) acrylonitrile, etc.]; Amide group containing monomer [(meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, etc.]; Epoxy group-containing vinyl-based monomer Polymer [Glycidyl (meth) acrylate, etc.]; Vinyl monomer having (poly) siloxane group {CH ₂ ═C (CH ₃ ).
_{COO (CH 2) 3 [Si} (CH 3) 2 O] n Si (CH 3)
₃ (in the formula, n = 1 to 130), etc .; a vinyl-based monomer having a perfluoroalkyl group having 3 to 30 carbon atoms ((meth) acrylic acid ester having a perfluoroalkyl group [CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCH = CH _2, etc.],
Maleic acid mono or diester having perfluoroalkyl group [C ₈ F ₁₇ (CH ₂ ) ₁₁ OCOCH = CHCOO
CH ₃ etc.], an olefin having a perfluoroalkyl group (C ₇ F ₁₅ CH ₂ CH═CH ₂ etc.), a vinyl ether or an allyl ether having a perfluoroalkyl group (C ₇ F ₁₅ CH ₂ OCH═CH ₂ etc.), Vinyl sulfone having perfluoroalkyl group (C ₈ F ₁₇ SO ₂ NHCH
₂ SO ₂ CH = CH ₂ etc.); polyvinyl monomer {divinyl monomer [divinylbenzene, diallyl phthalate,
1,6-hexanediol di (meth) acrylate,
(Poly) ethylene glycol di (meth) acrylate,
(Poly) propylene glycol di (meth) acrylate, triethanolamine di (meth) acrylate, bisphenol A di (meth) acrylate, etc.], trivinyl monomer [trivinylbenzene, trimethylolpropane tri (meth) acrylate, tri] Ethanolamine tri (meth) acrylate, etc.], tetravinyl monomer [pentaethriate tetra (meth) acrylate, etc.]
Etc .; Polymerizable oligomer having a vinyl group {Polyurethane, polyamide, epoxy resin, polyester or other oligomer having one or more polymerizable double bonds introduced therein [esterification product of polycaprolactone diol and (meth) acrylic acid] (For example, "Plaxel FM-1" manufactured by NOF CORPORATION), a prepolymer (1 mol) of a terminal hydroxyl group of polytetramethylene ether glycol and isophorone diisocyanate, and isocyanatoethyl acrylate (1).
Mol), a reaction product of a polyamide having an amino group and a (meth) acrylic acid ester, a reaction product of an epoxy resin and acrylic acid, (poly) caprolactone (meth)
Acrylate and the like] and the like. These are used as one kind or as a mixture of two or more kinds. Of these, particularly preferred are (meth) acrylic acid alkyl esters and aromatic vinyl monomers.

The proportion of (a1) constituting the copolymer (A) is usually 0. 0 based on the total weight of (a1) and (a2).
It is 5 to 50% by weight, preferably 3 to 40% by weight.
If the amount of (a1) is less than 0.5% by weight, the curability will be insufficient, resulting in poor washing resistance and dry cleaning resistance, and if it exceeds 50% by weight, the storage stability of the aqueous dispersion will decrease. . The weight average molecular weight of (A) is usually 10,000 to 2,000,000, preferably 100,000 to 1,000,000.

Aqueous polymer having amine imide group (B)
Examples thereof include one or more (co) polymers of a vinyl-based monomer (b1) containing an amine imide group, and a copolymer of the (b1) and a vinyl-based monomer having no amine imide group. The weight molecular weight of the (B) is usually 1,000.
To 100,000, preferably 3,000 to 5
It is 10,000. (B) can be produced by a known radical polymerization method.

Examples of the vinyl monomer (b1) having an amine imide group include 1,1,1-trimethylamine methacrylimide, 1,1-dimethyl-1-ethylamine methacrylimide and 1,1-dimethyl-1- ( 2-
Hydroxypropyl) amine methacrylimide, 1,1
-Dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine methacrylimide, 1,1-dimethyl-
1- (2'-hydroxy-3'-phenoxypropyl)
Examples thereof include amine methacrylimide and 1,1,1-trimethylamine acrylimide described in JP-A-5-25354. Of these, preferred are 1,1,1-trimethylamine methacrylimide and 1,1-dimethyl-1- (2-hydroxypropyl) amine methacrylimide.

As the vinyl-based monomer having no amine imide group, a vinyl-based monomer [N,
N-dimethylaminoethyl (meth) acrylate, N,
N-dimethylaminoethyl (meth) acrylamide and the like and salts thereof (organic acid salts, inorganic acid salts, etc.); vinyl monomers [(meth) acrylic acid, maleic acid, fumaric acid, etc. that impart anionic property] Itaconic acid, vinyl sulfonic acid,
(Meth) acrylic sulfonic acid and the like and salts thereof (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and the like)], and those exemplified as the above (a1) or (a2) can be used. Among these, preferred are (meth) acryloxyalkylsilanes among those exemplified in the paragraph (a1), (meth) acrylic acid alkyl esters among those exemplified in the paragraph (a2), hydroxyl group-containing polymerizable compounds. Monomers, vinyl-based monomers that impart cationicity and vinyl-based monomers that impart anionicity (carboxylic acid groups, sulfonic acid groups, etc.), and the (meth) acryloxyalkylsilanes and A combination of a (meth) acrylic acid alkyl ester, the hydroxyl group-containing polymerizable monomer and the vinyl monomer imparting the anionic property is particularly preferable in terms of durability. The amount of the vinyl monomer having no amine imide group is usually 0 to 50 parts by weight with respect to 1 part by weight of (b1).
Parts by weight, preferably 0-40 parts by weight. In the case of using a vinyl monomer that imparts cationicity or a vinyl monomer that imparts anionicity as the vinyl monomer having no amine imide group, it is more preferably 0.5 to 2
0 parts by weight. Further, when a vinyl-based monomer having a hydrolyzable silyl group is used as the vinyl-based monomer having no amineimide group, it is more preferably 0.1 to 1 part by weight.

(B1) When the amount of the vinyl-based monomer having no amineimide group used exceeds 1 part by weight, the stability of the aqueous dispersion, particularly the polymerization stability and the storage stability, deteriorates when the amount used exceeds 50 parts by weight. To do.

The ratio of (B) to the total of (A) and (B) is usually 0.5 to 50% by weight, preferably 2 to 30% by weight. If the amount of (B) is less than 0.5% by weight, the polymerization stability and storage stability of the aqueous dispersion may be reduced, and if it exceeds 50% by weight, durability such as dry cleaning resistance may be reduced.

The glass transition temperature (Tg) of the emulsion copolymer of the present invention is usually -20 ° C to 20 ° C, preferably -15 ° C to 15 ° C, more preferably -10 ° C to 1 ° C.
5 ° C. If the Tg is less than -20 ° C, the abrasion resistance will be reduced, or tack will remain and stains will easily occur. If the Tg is more than 20 ° C, the adhesive strength will be lowered and the texture will be deteriorated.

The binder composition for fiber processing of the present invention contains a non-radical polymerizable compound (C) having a hydrolyzable silyl group in order to further improve washing resistance, dry cleaning resistance and abrasion resistance. You may stay. The (C)
Is a hydrolyzable silyl group in the emulsion copolymer or (B) [when (B) also contains a hydrolyzable silyl group] in the process in which the binder composition for fiber processing of the present invention forms a dry film. Reacts with and improves the durability. When it is used as a binder for pigment printing, it may contain a silicone emulsion (D). (D) further improves the abrasion resistance of the binder composition.

Specific examples of the above (C) include silane monomers (methyltrimethoxysilane, methyltriethoxysilane, etc.); those having an epoxy group [2- (3 ',
4'-epoxycyclohexyl) ethyltrimethoxysilane, 3- (trimethoxysilyl) propylglycidyl ether, bis (2'3'-epoxypropyloxypropyl) dimethoxysilane, tris (2'3'-epoxypropyloxypropyl) methoxy Silane or the like]; those having a thiol group [3- (trimethoxysilyl) propanethiol, 3- (methyldimethoxysilyl) propanethiol, etc.]; those having an amino group [3-triethoxysilylpropylamine, N- (3 '-Trimethoxysilylpropyl) ethylenediamine, N- (3'-trimethoxysilylpropyl) urea, etc.]; those having a halogen (3-chloropropyltrimethoxysilane, etc.) and the like. Among these, those having a silane monomer and an epoxy group are particularly preferable.

The amount of (C) used is usually 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the copolymer.
10 to 10 parts by weight.

As a specific example of (D), a polysiloxane selected from the group consisting of organopolysiloxane, carboxyl group-containing organopolysiloxane, epoxy group-containing organopolysiloxane and amino group-containing organopolysiloxane is used as a suitable emulsifier, for example. Examples thereof include those obtained by emulsifying with a sulfate ester salt of a higher alcohol, an alkylbenzene sulfonate, a higher alcohol polyoxyalkylene adduct, an alkylphenol polyoxyalkylene adduct, a higher fatty acid sorbitan ester and the like. Of these, organopolysiloxane emulsions are preferred.

The amount of the (D) used (solid content) is usually 0.01 to 10 per 100 parts by weight of the solid content of the binder composition.
Parts by weight, preferably 0.1 to 5 parts by weight.

The method for producing the binder composition of the present invention is, for example, in the presence of the aqueous polymer (B) and the polymerization initiator, the monomer mixture (A) and, if necessary, (C), the (A) or 30 to 100 ° C. in an aqueous medium (water alone or a mixed solvent of water and a water-miscible solvent such as methanol or isopropanol, lower alcohols such as acetone, ketones such as acetone). Emulsion polymerization by a method; a part of (A) in the above aqueous medium is 30 to 10
Manufactured by a known emulsion polymerization method such as a method in which emulsion polymerization is first carried out at 0 ° C., and the remaining (A) [optionally containing (C)] and a polymerization initiator are added dropwise to carry out emulsion polymerization. it can. It is also possible to mix the aqueous dispersion of (C) and / or (D) after obtaining the aqueous dispersion.
From the viewpoint of storage stability of the resulting aqueous dispersion, the method of preliminarily containing (C) in the monomer mixture (A) and emulsion-polymerizing is particularly preferable.

In the present invention, a known emulsifier may be used together with (B) as long as the object of the present invention is not impaired. Examples of such emulsifiers include anionic emulsifiers (sodium dodecylbenzenesulfonate, sodium lauryl sulfate ester, sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkyl ether sulfate ester, etc.); nonionic emulsifiers (polyoxyethylene alkylphenyl ether, Polyoxyethylene alkyl ether, polypropylene glycol ethylene oxide adduct, etc.); cationic emulsifier (stearylbenzyldimethylammonium chloride,
Distearylbenzyldimethylammonium chloride and the like); polymerizable emulsifiers (sodium alkylallyl sulfosuccinate, sodium (meth) acryloyl polyoxyalkylene sulfate, etc.) and the like. These may be used in combination of two or more.

Production of aqueous polymer (B), or (B)
As the polymerization initiator used when emulsion-polymerizing the monomer mixture (A) in the presence of, known ones can be used. Examples of the polymerization initiator include persulfates (ammonium persulfate, sodium persulfate, potassium persulfate, etc.); peroxide compounds (benzoyl peroxide, lauryl peroxide, t-butyl hydroperoxide, hydrogen peroxide, etc.); azo Compounds << azobisisobutyronitrile, azobisisovaleronitrile, azobisamidinopropane-2 hydrochloride, azobiscyanovaleric acid, azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-
Hydroxyethyl] propionamide}, azobis [2
-Methyl-N- (hydroxyethyl) propionamide], etc. ;; redox initiator [combination of ammonium persulfate and a peroxide such as sodium bisulfite and a reducing (bis) sulfite, ammonium persulfate, dimethylaminoethanol, etc. Of a peroxide and an amine compound, a combination of hydrogen peroxide and a peroxide such as a divalent iron salt, and a reducing metal salt, and the like, and a combination of two or more thereof.

For the purpose of adjusting the molecular weight during the production of (B) or the emulsion polymerization of (A) in the presence of (B),
If necessary, known chain transfer agents (n-lauryl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, diphenyl ether, mercaptoethanol, γ
-Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.) may be used. In addition, for the purpose of controlling the viscosity of the aqueous dispersion of the present invention, a known electrolyte (sodium hydrogen carbonate, sodium tripolyphosphate, potassium chloride, etc.), a pH adjusting agent, during or after the production of the aqueous dispersion of the present invention (Ammonia, aqueous sodium hydroxide solution, etc.) may be used.

The particle size of the aqueous dispersion in the present invention is not particularly limited, but is usually 0.01 to 10 μm, preferably 0.05 to 1 μm.

In the binder composition of the present invention, after coating, the medium volatilizes at room temperature or by heating and drying, and the particles are fused to form a film, and the silyl groups in the polymer undergo a condensation reaction to crosslink. Produce a film. A curing catalyst may optionally be used to accelerate the formation of this crosslinked coating. Examples of the catalyst include organic titanate compounds [isopropyl triisostearoyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate, tetraisopropyl di (lauryl phosphite).
Titanate, etc.], organoaluminum compounds (acetoalkoxyaluminum diisopropinate, etc.), carboxylic acid tin compounds (tin dioctylate, dibutyltin dilaurate, dibutyltin malate, etc.), sulfur-containing organotin compounds (dibutyltin sulfide, etc.) , Dialkyl tin oxide (dibutyl tin oxide, dioctyl tin oxide, etc.), other carboxylic acid salts (sodium acetate, zinc caproate,
Lead octylate, cobalt naphthenate, etc.), acid phosphates (monomethyl acid phosphate, diethyl acid phosphate, monobutyl acid phosphate, etc.),
Carboxylic acid and its acid anhydride (adipic acid, maleic acid, citric acid, itaconic acid, succinic acid, phthalic acid, phthalic acid, trimellitic acid, maleic anhydride, phthalic anhydride, etc.), amine and its salt (triethylamine, Dibutylamine-2-hexoate, cyclic amidine and salts thereof, and quaternary ammonium salts (tetrabutylammonium hydroxide etc.) and the like. The amount of the catalyst used is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of (A) and (B).

The binder composition of the present invention can be used as it is as a binder for fiber processing,
If necessary, mix with other known resin emulsion (acrylic emulsion, urethane emulsion, epoxy emulsion, SBR latex, NBR latex, vinyl acetate emulsion, colloidal silica, etc.) and water-soluble resin (water-soluble acrylic resin, water-soluble alkyd resin, etc.) can do. Of these, urethane emulsions are particularly preferable in terms of durability. In addition to these, a known thickener, a cross-linking agent, a color paste (a pigment finely and uniformly dispersed in water), an antibacterial agent, an inorganic filler and the like can be optionally contained.

The binder composition of the present invention may be mixed with the above-mentioned other resin emulsion, color paste, various additives, and the like by mixing by ordinary stirring or various stirring devices (dispers, paint conditioners, ball mills, kneaders, The method of mixing using a sand grinder, a roll mill, a flat stone mill, etc. is mentioned.

The fiber material processed using the binder composition of the present invention can be selected according to various uses of fiber processing, and natural fibers such as cotton, hemp, wool and silk; rayon, acetate and the like. Semi-synthetic fiber; polyester,
Examples thereof include synthetic fibers such as polyamide, polyacrylonitrile, and polyolefin.

[0030]

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

Production Example 1 A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 511 parts of ion-exchanged water and 400 parts of isopropyl alcohol, and the system was purged with nitrogen gas while stirring. It was replaced and the temperature was raised to 85 ° C. At the same temperature,
1,1-dimethyl-1- (2-hydroxypropyl)
Amine methacrylimide (hereinafter referred to as AI) 28 parts, acrylic acid (hereinafter referred to as AA) 40 parts, methacrylic acid 40
Parts, 2-hydroxyethyl acrylate (hereinafter referred to as HEA) 28 parts, ethyl acrylate 40 parts, γ-methacryloxypropyltriethoxysilane 24 parts, dodecyl mercaptan 5.6 parts, azobisisovaleronitrile 4.2.
And 16 parts of methyl ethyl ketone were added dropwise over 3 hours, and the mixture was further reacted at the same temperature for 1 hour. The aqueous solution was cooled to 30 ° C., 58 parts of 28% ammonia water was added to adjust the pH to 8.5, and then the solution was further diluted with 595 parts of ion-exchanged water to prepare an aqueous solution of an amine imide group-containing aqueous polymer (solid content 11.0). %) Was obtained.

Production Example 2 881 parts of ion-exchanged water and 4.4 parts of sodium persulfate (hereinafter referred to as NAP) were charged in the same reaction vessel as in Production Example 1, and the inside of the system was replaced with nitrogen gas under stirring to 100 The temperature was raised to ° C. At the same temperature, AI 17 parts, AA 34 parts, HE
The mixture of 72 parts of A was added dropwise over 1 hour, and further reacted at the same temperature for 1 hour. Cool the aqueous solution to 30 ° C, 25%
Aqueous solution of polymer containing amine imide group (solid content 11.5%) by adjusting pH to 8.5 with aqueous ammonia.
I got

Example 1 206 parts of the aqueous polymer solution prepared in Preparation Example 1, 330 parts of deionized water and NAP2.5 were placed in the same reaction vessel as in Preparation Example 1.
Was charged, the system was replaced with nitrogen gas under stirring, and the temperature was changed to 85 ° C.
The temperature was raised to. At the same temperature, 20 parts of γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as MPS), 85 parts of methyl methacrylate (hereinafter referred to as MMA), 10 parts of n-butyl methacrylate (hereinafter referred to as BMA), and n-butyl acrylate. 202 parts (hereinafter referred to as BA) and γ-glycidoxypropyltrimethoxysilane (hereinafter referred to as EPSi
6 parts of the mixture was added dropwise over 2 hours and reacted at the same temperature for 1 hour. The aqueous dispersion is cooled to 30 ° C., 28
By adjusting the pH to 8.5 with% ammonia water,
Solid content 40.1%, viscosity 205 cP (B type viscometer, 60
An aqueous dispersion (rpm, 25 ° C.) was obtained. A glass transition temperature (hereinafter referred to as Tg) determined by differential scanning calorimetry using a film obtained by drying this aqueous dispersion at 105 ° C. for 45 minutes
Was 5 ° C. Various performance tests were conducted using this aqueous dispersion. The results are shown in Table 2.

Examples 2 to 5 and Comparative Examples 1 to 4 By the same method as in Example 1, aqueous dispersions of the respective copolymers were obtained from the raw materials shown in Table 1. Table 2 shows these Tg, results of various performance tests, and the like.

Example 6 The same performance test was conducted using the aqueous dispersion of Example 1 stored at 40 ° C. for 6 months. The results of this performance test are shown in Table 3.

Example 7 The same performance test was conducted using the aqueous dispersion of Example 3 stored at 40 ° C. for 6 months. The results of this performance test are shown in Table 3.

Comparative Example 6 The same performance test was conducted using the aqueous dispersion of Comparative Example 2 stored at 40 ° C. for 6 months. The results of this performance test are shown in Table 3.

[0038]

[Table 1]

ST: Styrene DBSNa: Sodium dodecyl sulfate nonyl: Polyoxyethylene nonylphenol (HLB = 1
Five)

1. Pigment printing performance test A binder composition was prepared according to the following formulation, and a cotton knit (width 30 cm x
80 pieces of cotton-like pattern (3 cm x 30 cm) on 40 cm)
Printing was performed using a mesh screen. The printed cloth is dried (80 ° C x 10 minutes) and further heat treated (135 ° C x 5).
After that, the friction fastness: JIS L-0849 Gakushin type, 200 g x 100
Time, dry and wet Washing resistance: JIS L-0844, A-4 method Dry cleaning resistance: JIS L-0860, Perkren method (adjustment of binder composition) Pigment paste 5 parts (SANDYE SUPER BLUE FBL-160, Sanyo) Aqueous dispersion 100 parts Silicone emulsion 3 parts Silicone emulsion 3 parts (Dimethylpolysiloxane 27 parts and nonylphenol ethylene oxide 20 parts with 3 parts of additives are mixed, and emulsion is obtained by adding 70 parts of water and emulsifying with a homogenizer) Agent 3 to 6 parts (Primal ASE-60, 3-fold dilution liquid made by Nippon Acrylic) Ammonia water was added in an appropriate amount to adjust the viscosity to about 15000 cP.

2. Adhesive performance test for flocking A binder half-cloth (width 2.
After coating with a doctor knife so that the coating amount would be 200 g / m ² on 5 cm × length 20 cm), nylon taffeta cloth (width 2.5 cm × length 20 cm) was attached. Then, after drying at 80 ° C. for 10 minutes and heat treatment at 130 ° C. for 10 minutes, the 180 ° peel strength was measured. Also, after the test piece was immersed in water for 1 hour, the moisture was lightly removed with a dry cloth and the 180-degree peel strength was similarly measured. (Preparation of Binder Composition) Aqueous dispersion 100 parts Thickener 1 to 3 parts (Primal ASE-60) Ammonia water An appropriate amount was mixed to adjust the viscosity to about 20,000 cP.

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

The binder composition of the present invention has the following features. (1) Long-term storage stability is extremely good. (2) It does not generate formalin during heat curing, and imparts excellent durability such as washing resistance, dry cleaning resistance, and abrasion resistance to the fiber. Since the binder composition of the present invention exhibits the above effects, it is extremely useful as a binder for fiber processing, especially for pigment printing and flock processing.

Claims (6)

[Claims] 1. A monomer mixture (A) comprising a vinyl-based monomer (a1) having a hydrolyzable silyl group and another vinyl-based monomer (a2) copolymerizable therewith, and an amine imide group Which is obtained by emulsion polymerization in the presence of a water-soluble or water-dispersible polymer (B) having a temperature of −20 ° C. to 20 ° C. and which has a glass transition temperature. Composition. 2. The amount of (a1) constituting (A) is (a1)
The composition according to claim 1, which is 0.5 to 50% by weight based on the total weight of 1) and (a2). 3. (B) is a polymerizable monomer (b1) having an amine imide group, a carboxylic acid (salt) group-containing polymerizable monomer, a sulfonic acid (salt) group-containing polymerizable monomer, The composition according to claim 1 or 2, which is a copolymer containing, as an essential constituent unit, at least one ionic group- or ion-forming group-containing monomer selected from amino group-containing polymerizable monomers. 4. The composition according to claim 3, wherein (B) is a copolymer further containing a vinyl monomer (a1) having a hydrolyzable silyl group as an essential constituent unit. 5. An adhesive for flocking, wherein:
4. The composition according to any one of 4 above. 6. A binder for pigment printing according to claim 1.
4. The composition according to any one of 4 above.