JPH0987972A - Composition for fiber processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a composition for carpet backing agent excellent in oil resistance and solvent resistance and having a good touch feeling by mixing of a specific copolymer latex and a soap free type polyurethane resin emulsion. SOLUTION: This composition comprises (A) a synthetic rubber latex prepared by copolymerizing 45-83wt.% of conjugated diene such as butadiene, 15-50wt.% of an unsaturated nitrile such as acrylonitrile and 2-10wt.% of an unsaturated carboxylic acid such as methacrylic acid in an aqueous medium and (B) a soap free type polyurethane emulsion where the weight ratio of (A)/(B) is 97/3-25/75 on the solid basis and in addition a filler such as clay is added to this composition for carpet backing. The polymerization of a conjugated diene, an unsaturated nitrile and an unsaturated carboxylic acid may be carried out in the presence of a soap free type polyurethane emulsion. Alternatively, a conjugated diene, an unsaturated nitrile and an unsaturated carboxylic acid may be copolymerized in an aqueous medium in the presence of a soap-free type polyurethane resin emulsion.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fiber processing composition, and more particularly to a fiber processing composition having improved oil resistance and solvent resistance, a method for producing the same, and a carpet using the same. It relates to a backing agent.

[0002]

2. Description of the Related Art Textile products such as carpets, mats, non-woven filters, non-woven nylon scrubbers, and synthetic leather base cloths are used in a wide range of fields and have become indispensable indispensable items.

As an adhesive for carpet backing,
Originally, natural rubber was used, but recently, adhesiveness,
Carboxy-modified styrene-butadiene latex, which is superior in basic properties such as elasticity, has become the mainstream.
As the binder for the non-woven fabric, acrylic resin or the above-mentioned carboxy-modified styrene-butadiene latex is used.

Textile products produced by using the above-mentioned carboxy-modified styrene-butadiene latex or acrylic resin have excellent basic properties such as water resistance, tear strength and peel strength, but for dry cleaning and degreasing of rolls. The solvent resistance and oil resistance required for the above are inferior, and they are swelled or easily dissolved in various organic solvents, lose their flexibility, and become hard, resulting in a problem in service life.

In order to solve this problem, an acrylonitrile-butadiene latex which is a synthetic rubber is used. This acrylonitrile-butadiene-based latex is excellent in oil resistance and solvent resistance while exhibiting rubber elasticity, and is also excellent in abrasion resistance and mechanical properties. Therefore, it is a backing agent for rental carpets and a non-woven fabric for roll degreasing that require cleaning resistance. It is used as a binder, etc.

However, in recent years, the use of organic solvents and the use of oils such as gasoline, benzine, kerosene, and turpentine under severe conditions have been increasing, and there is a strong demand for backing agents and binders having a long service life. However, the acrylonitrile-butadiene-based latex is not sufficiently durable to meet this demand.

[0007]

DISCLOSURE OF THE INVENTION The present invention further improves oil resistance and solvent resistance, particularly durability such as little swelling or dissolution into organic solvents such as acetone, MEK, and toluene. It is intended to provide the resin composition for fiber processing.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have identified a latex of a carboxyl group-containing unsaturated nitrile / conjugated diene copolymer and a polyurethane resin emulsion. By using a resin emulsion obtained by mixing or emulsion polymerization in a ratio as a backing agent or a binder, oil resistance,
It was discovered that a material having excellent solvent resistance was obtained, and the present invention was completed.

That is, the present invention is a fiber processing comprising a latex (A) of a copolymer of an unsaturated nitrile having a carboxyl group in the molecule and a conjugated diene, and a soap-free type polyurethane resin emulsion (B). The composition for use is preferably: TATEX (A), which is a copolymer of an unsaturated nitrile having a carboxyl group and a conjugated diene, and emulsion (B), which is a polyurethane resin, in a solid content weight ratio of 97 / Fiber processing composition containing 3 to 25/75 in proportion and filler (C)
The present invention provides a backing agent for carpet, which comprises Also provided is a method for producing a composition for fiber processing, which comprises emulsion-polymerizing a conjugated diene, an unsaturated nitrile and an unsaturated carboxylic acid in the presence of a soap-free type polyurethane resin emulsion in an aqueous medium. Is.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Latex (A), which is a copolymer of an unsaturated nitrile having a carboxyl group in the molecule and a conjugated diene, used in the present invention means an unsaturated nitrile, a conjugated diene and an unsaturated carboxylic acid. A synthetic rubber latex obtained by emulsion polymerization of these components as an ingredient in an aqueous medium.

Examples of the unsaturated nitrile include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable from the viewpoint of flexibility. The unsaturated nitrile component greatly affects oil resistance and rubber elasticity. The unsaturated nitrile component content is preferably in the range of about 15 to 50% by weight with respect to the entire constituent latex composition. If the unsaturated nitrile content is 50% by weight or more, the oil resistance and solvent resistance are very excellent, but the hardness becomes hard. Also, 15% by weight
If it is below, the desired solvent resistance cannot be obtained.

The conjugated diene component is not particularly limited, but an open-chain aliphatic conjugated diene having about 4 to 9 carbon atoms is preferable, and specific examples thereof include 1,3-butadiene and isoprene. Of these, 1,3-butadiene is preferably used in consideration of copolymerizability with other monomers and economic efficiency. The content of the conjugated diene is preferably about 45 to 83% by weight based on the composition of the constituent latex.

The acid component used to carboxylate the latex of the unsaturated nitrile / conjugated diene copolymer is an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, itaconic acid or fumaric acid, or itacone. Examples thereof include acids, maleic acid, and half esters such as fumaric acid. The amount of the acid component used is not particularly limited, but it is preferably about 2 to 10% by weight based on the whole unsaturated nitrile / conjugated diene copolymer latex composition.

The latex of the carboxylated unsaturated nitrile / conjugated diene copolymer further uses an ethylenically unsaturated monomer copolymerizable with the conjugated diene such as acrylic acid ester or methacrylic acid ester or a mixture thereof. You can also

Examples of the ethylenically unsaturated monomer copolymerizable with the conjugated diene include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
Propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate,
Acrylic alkyl esters and methacrylic acid acrylic esters such as pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, octyl acrylate, octyl methacrylate, octadecyl acrylate, octadecyl methacrylate, etc .; styrene, α Ethylenically unsaturated aromatic monomers such as methylstyrene, vinyltoluene, chlorostyrene, and 2,4-dibromostyrene; fumaric acid, itaconic acid, and unsaturated dicarboxylic acid monoalkyl esters,
For example, ethylenically unsaturated carboxylic acids such as monomethyl maleate, monoethyl fumarate, and mononormal butyl itaconate; vinyl esters such as vinyl acetate and vinyl propionate; vinylidene halides such as vinylidene chloride and vinylidene bromide; acrylic acid-2- Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as hydroxyethyl, 2-hydroxypropyl acrylate, and 2-hydroxyethyl methacrylate; glycidyl esters of ethylenically unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, and Examples thereof include radically polymerizable monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, and diacetone acrylamide. That.

These compounds are important compounds generally used for the purpose of imparting appropriate hardness to the latex film and improving adhesion, dispersibility, mechanical stability and freeze stability.

The minimum film-forming temperature (MFT) of latex is preferably 0 ° C. or lower in consideration of film-forming property.
It is not restricted to these conditions. As the emulsifier used in the production of the latex of the unsaturated nitrile / conjugated diene copolymer used in the present invention, those generally commercially available can be used. For example, aliphatic soap, rosin acid soap, alkyl sulfonate, alkyl sulfate, alkyl aromatic sulfate, peroxo sulfate, lauryl sulfate, dialkylaryl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate. , Polyoxyethylene alkylaryl sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester and the like.

This emulsifier is usually used in an amount of about 1 to 5 parts by weight. The molecular weight of the copolymer of the latex of the carboxylated unsaturated nitrile / conjugated diene copolymer obtained by this emulsion polymerization is not particularly limited, but is usually a high molecular weight product and is from 10,000 to several hundreds. Those having a molecular weight in the range of 10,000 are used.

The carboxylated unsaturated nitrile of the present invention
A crosslinking agent may be added to the latex of the conjugated diene copolymer. A crosslinking agent causes a crosslinking reaction, and various properties such as tensile strength and mechanical strength are increased. Examples of the cross-linking agent include zinc white and water-soluble melamine resin. Further, those obtained by copolymerizing styrene, acrylic acid esters, reactive monomers and the like can also be used as the crosslinking agent.

Next, a method for producing a latex of an unsaturated nitrile / conjugated diene copolymer used in the present invention will be described. That is, the above-mentioned unsaturated nitrile and conjugated diene and unsaturated carboxylic acid or its half ester, in a mixture containing an ethylenically unsaturated monomer copolymerizable as necessary, in the presence of an emulsifier, a free radical generating catalyst. It may be added and the polymerization may be carried out at 50 ° C to 80 ° C.

As the free radical generating catalyst, for example, KPS (K ₂ S ₂ O ₈ ), APS ((NH ₄ ) ₂ S ₂ O ₈ ),
Examples thereof include aqueous catalysts such as hydrogen peroxide, and oily catalysts such as t-butyl hydroperoxide and cumene hydroperoxide.

Additives usually used in radical polymerization, such as chain transfer agents, ethylenediaminetetraacetic acid, pH
Alkaline materials for conditioning can be used if desired.
The obtained carboxylated unsaturated nitrile / conjugated diene copolymer latex may be concentrated to a required solid content and used by a method such as stripping.

The soap-free type polyurethane resin emulsion used in the present invention can be obtained by the following method, and an emulsion of urethane prepolymer having a terminal isocyanate group can also be used.

That is, a neutralizing agent is added to an organic solvent solution or organic solvent dispersion of a hydrophilic group-containing polyurethane resin obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with polyisocyanate, if necessary. A method for obtaining an emulsion by mixing an aqueous solution containing, an active hydrogen-containing compound, and a hydrophilic group-containing compound with a hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyisocyanate with a neutralizing agent. A method for obtaining an emulsion by mixing with an aqueous solution containing water, or by previously adding a neutralizing agent to a prepolymer and then mixing with water to disperse in water, an active hydrogen-containing compound, and a hydrophilic group. A hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting a containing compound with a polyisocyanate, Agent and be mixed with an aqueous solution containing a polyamine, or a pre After adding a neutralizing agent to the prepolymer is mixed with an aqueous solution containing a polyamine method, etc. to obtain an emulsion.

The molecular weight of the polyurethane resin emulsion used in the present invention is not particularly limited, but it is preferable that it has a high molecular weight in consideration of the frictional properties and mechanical properties of the molded product.

Examples of the polyisocyanate used in the urethane resin emulsion of the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and 4,4'-diphenylmethane. Diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3, 3'-dichloro-4,
4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′dicyclohexyl Examples include methane diisocyanate.

As the other active hydrogen-containing compound capable of reacting with the isocyanate group used in the production of the polyurethane resin emulsion of the present invention, a high molecular compound and a low molecular compound are used.

The polymer compound of the active hydrogen-containing compound is a compound having an average molecular weight of 300 to 10,000, preferably 500 to 5,000, and having two or more active hydrogens in the molecule, for example, polyester. Examples thereof include polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols and polythioether polyols.

As the polyester polyol, for example, ethylene glycol, propylene glycol, 1,3-
Propanediol, 1,4-butanediol, 1,5-
Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, Tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol, bisphenol A,
Glycol components such as hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3 '
-Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
Naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) In addition to polyesters obtained by dehydration condensation reaction from acid components such as benzoic acid and ester-forming derivatives of these hydroxycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone and copolymers thereof Polymerized polyester can be used.

Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol. , Glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2 Oxide, Propylene Oxide Using One or Two or More Compounds Having At least Two Active Hydrogen Atoms such as 1,3-Propanetrithiol as an Initiator , Butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran,
Examples thereof include those obtained by addition-polymerizing one or more monomers such as cyclohexylene by a conventional method.

Examples of the polycarbonate polyol include compounds obtained by reacting glycols such as 1,4-butanediol, 1,6-hexanediol and diethylene glycol with diphenyl carbonate and phosgene.

The low molecular weight compound of the above active hydrogen-containing substance is a compound having a molecular weight of 300 or less and containing at least two or more active hydrogens. For example, a glycol component used as a raw material of polyester polyol; glycerin, Polyhydroxy compounds such as trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol; ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3 And amine compounds such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine 1,2-propanediamine, hydrazine, diethylenetriamine and triethylenetetramine. That.

The soap-free type polyurethane resin emulsion of the present invention is an emulsion of a polyurethane resin having a hydrophilic group in the molecule, and can be obtained by reacting a hydrophilic group-containing compound with the above active hydrogen-containing compound and polyisocyanate. .

The hydrophilic group-containing compound is an ionic compound having at least one active hydrogen in the molecule and containing a functional group such as a carboxylic acid salt, a sulfonic acid salt, a carboxylic acid group or a sulfonic acid group. Or a nonionic group containing at least one active hydrogen atom in the molecule and containing a group of ethylene oxide repeating units, a group of ethylene oxide repeating units and a group of other alkylene oxide repeating units. Compounds.

Specific examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine- Sulfonic acid-containing compounds such as 4,6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid, and their derivatives or polyester polyols obtained by copolymerizing these; 2,2-dimethylolpropionic acid and 2 Carboxylic acid-containing compounds such as 2-dimethylol butyric acid, 2,2-dimethylol valeric acid, dioxymaleic acid, 2,6-dioxybenzoic acid and 3,4-diaminobenzoic acid, and their derivatives or copolymerization thereof. Polyester polyol obtained; at least 3 repeating units of ethylene oxide % By weight or more, a molecular weight from 300 to 2 containing at least one or more active hydrogen in the polymer
10,000 polyoxyethylene glycols or polyoxyethylene-polyoxypropylene copolymer glycols, polyoxyethylene-polyoxybutylene copolymer glycols, polyoxyethylene-polyoxyalkylene copolymer glycols or monoalkyl ethers thereof, etc. And the polyester polyether polyols obtained by copolymerization, which may be used alone or in combination.

In producing the polyurethane resin emulsion used in the present invention, the content of the hydrophilic group bonded in the molecule is such that when the hydrophilic group is an ionic group such as a carboxyl group or a sulfonic acid group, At least 0.005 to 100 parts by weight of the obtained urethane resin solid content
It is preferable to have 0.2 equivalent.

When a nonionic compound is used, it is preferably at least 20 parts by weight, and more preferably 10 parts by weight or less, per 100 parts by weight of the solid content of the urethane resin finally obtained.

The polyurethane resin emulsion and the urethane prepolymer having a terminal polyisocyanate group according to the present invention are produced by a conventionally known method. That is, for example, it is produced by reacting the polyisocyanate with an active hydrogen-containing compound (including a hydrophilic group-containing compound) under the conditions of 20 to 120 ° C, preferably 30 to 100 ° C. In this case, the equivalent ratio of the isocyanate group and the active hydrogen group is 0.8: 1 to 1 in the case of polyurethane resin.
In the ratio of 1.2: 1, and 1.1: 1 to 3: 1 in the case of urethane prepolymer containing terminal polyisocyanate groups.
It is preferable to use it at a ratio of 1.2: 1 to 2: 1.

This reaction can be carried out without a solvent, but an organic solvent can be used for the purpose of controlling the reaction of the reaction system or reducing the viscosity. The organic solvent is not particularly limited, but examples thereof include aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; acetic acid esters such as ethyl acetate butyl acetate; dimethylformamide and N.
Amides such as methylpyrrolidone.

When such an organic solvent is distilled off from the finally obtained emulsion of polyurethane resin,
It is preferable to use one having a relatively low boiling point that can be easily removed by distillation. When it is unavoidable to use an organic solvent having a boiling point of 100 ° C. or higher, the amount used is preferably kept to the minimum necessary.

Examples of the hydrophilic group neutralizing agent that can be used in the production of the polyurethane resin emulsion used in the present invention include non-volatile bases such as sodium hydroxide and potassium hydroxide; trimethylamine, triethylamine, dimethylethanolamine and methyl. Diethanolamine,
Examples include tertiary amines such as triethanolamine and volatile bases such as ammonia.

The neutralizer may be added before, during, or after the polymerization of the hydrophilic group-containing unsaturated monomer, or during or after the urethanization reaction. Examples of the polyamine that can be used in the production of the polyurethane resin emulsion of the present invention include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, Isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexylethanol. Diamines such as amine, aminoethylpropanolamine, aminopropylpropanolamine and aminohexylpropanolamine; diethylenetriamine, dipropylenetriamine, trie Piperazines; polyamines such as Rentetoramin acid hydrazides and the like, are used these singly or in combination.

The aqueous polyurethane resin thus obtained may be used as it is, but it is also possible to use it by distilling off the organic solvent if necessary. The polyurethane resin emulsion thus obtained has a solid content of about 10-6.
It is a soap-free type resin emulsion having a hydrophilic group in a substantially solvent-free molecule of 0% by weight, preferably 15 to 50% by weight. Even if it is unavoidable that an organic solvent having a boiling point of 100 ° C. or higher must be used, it should be limited to 20% by weight per resin emulsion.

The present invention is characterized in that the solid content weight ratio of the latex of the carboxylated unsaturated nitrile / conjugated diene copolymer and the soap-free type polyurethane resin emulsion is 97/3 to 25/75. It is a composition. 55 / 45-2 from the point of oil resistance and solvent resistance
5/75 is preferred. If the ratio of the polyurethane resin emulsion is 3% by weight or less, the desired oil resistance and solvent resistance are not improved, and if it is 75% by weight or more, it is not preferable in terms of cost.

Either the latex of the carboxylated unsaturated nitrile / conjugated diene copolymer and the polyurethane resin emulsion are simply mixed, or the conjugated diene or the like is emulsion polymerized in the presence of the polyurethane resin (hereinafter referred to as seed polymerization). However, seed polymerization is preferred from the viewpoint of tensile strength.

A filler, a dispersant, an antiaging agent, a vulcanizing agent, etc. are blended and used in the fiber processing composition of the present invention depending on the use. If necessary, a vulcanization accelerating aid, a vulcanization accelerating agent, a heat sensitive agent, a thickener, a defoaming agent and the like are mixed and impregnated or applied to be used for fiber processing of carpets, nonwoven fabrics and the like.

Examples of the filler include heavy calcium carbonate, aluminum hydroxide, clay and the like. The role of the filler is to facilitate the volatilization of water in the compound, increase the nonvolatile content to improve the drying property, and reduce the cost of the compound.

Examples of the dispersant include sodium tripolyphosphate, sodium hexametaphosphate phosphate dispersants, anionic surfactants, low molecular weight sodium polyacrylate, and the like. As the antioxidant, a phenol-based antioxidant is generally used, but a sulfide-based antioxidant or the like may be used together.

Examples of the vulcanizing agent include sulfur, sulfur donors, organic peroxides, metal oxides, epoxy resins and melamine resins, but sulfur is preferred from the viewpoint of ease of use and cost. When sulfur is used, fine particles such as colloidal sulfur or precipitated sulfur are preferable, and they are added as a solution or an aqueous dispersion. The addition amount of a vulcanizing agent such as sulfur is required to be 0.01 to 2 parts by weight in terms of solid content based on 100 parts by weight of solid content of the resin emulsion composition.

The vulcanization accelerating aid is used for activating vulcanization, and examples thereof include zinc oxide, alkylammonium oleate, and diethanolamine. Zinc oxide is preferred from the viewpoint of ease of use in combination with sulfur. The vulcanization accelerating aid such as zinc oxide is required to be about 1 to 7 parts by weight in terms of solid content based on 100 parts by weight of solid content of the resin emulsion composition.

As the vulcanization accelerator, zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, zinc mercaptobenzothiazole zinc salt and the like are used. The thickener is used to adjust the viscosity of the resin emulsion composition blended liquid. As the thickener, a water-soluble polymer or an alkali-soluble acrylic emulsion is used, and for example, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, casein, sodium alginate, polyvinyl alcohol, polyethylene oxide, polyacrylate, etc. are used. . A viscous material that suits the application and processing machine is used properly.

When a non-soap-free type polyurethane resin emulsion containing an emulsifier is used, solvent resistance and oil resistance are inferior to those when a soap-free type polyurethane resin emulsion is used.

The basic raw material for the carpet backing compound of the present invention comprises the fiber processing composition of the present invention and a filler. The main thing that is manufactured with latex emulsion in carpet is tufted carpet,
Needle punch carpets and flocked carpets. Among them, it is useful to use for tufted and needle punch carpets, which require oil resistance and solvent resistance. The compounding composition differs depending on the type of backing.

Typical examples of blending for fiber processing will be described below. The composition for fiber processing is not limited to these examples. Formulation Example 1: For tufted carpet Solid part by weight Resin emulsion composition ¹⁾ 100 Dispersant 0.4 Zinc oxide 3.0 Anti-aging agent 0.3 Heavy calcium carbonate 250 Thickener ²⁾ Necessary amount consumption Foaming agent Required amount ¹⁾ Composition for fiber processing of the present invention ²⁾ Sodium polyacrylate Formulation example 2: For foam backing (gel foam) Solid content parts by weight Resin emulsion composition ¹⁾ 100 Potassium oleate 3 Sulfur 2 Zinc diethyldithiocarbamate dispersion liquid 1.5 Mercaptobenzothiazole zinc salt dispersion liquid 1 Anti-aging agent 1 Ammonia 0.5 Dispersing agent Appropriate amount filler (eg: clay) 75 Zinc oxide 5 Ammonium acetate 3 ^{1) For} textile processing of the present invention Composition Formulation Example 3: For foam backing (non-gel foam) Solid content parts by weight Resin emulsion composition ¹⁾ 100 Alky Rusulfufosuccinic acid 5 Sodium triphosphoric acid 0.5 Sulfur 2 Diethyldithiocarbamate zinc dispersion liquid 1.5 Mercaptobenzothiazole zinc salt dispersion liquid 1 Anti-aging agent 1 Dispersant proper amount Filler (for example: calcium carbonate) 150 Zinc oxide 3 Sodium lauryl sulfate 1 ¹⁾ Composition for fiber processing of the present invention The processed fiber product produced by using the composition of the present invention as described above has a texture and is excellent in oil resistance, solvent resistance, and good cleaning resistance. Furthermore, it has excellent wear resistance, dimensional stability, and mechanical strength.

Therefore, when performing dry cleaning, degreasing of rolls, etc., ketones such as acetone and MEK,
Organic solvents such as toluene, gasoline, benzine, kerosene,
It is useful as a backing agent or binder for fiber processing of carpets, non-woven fabrics, etc. when exposed to harsh conditions such as turpen.

Next, the present invention will be described in detail with reference to examples. In the examples, "parts" and "%" indicate parts by weight and% by weight, respectively.

[0057]

【Example】

Example 1 0.05 part of 100 parts of ion-exchanged water per 100 parts of monomer (butadiene, acrylonitrile, methacrylic acid).
Parts ethylenediaminetetraacetic acid (EDTA), 2.5 parts sodium alkylbenzene sulfonate, 0.35 parts t-dodecyl mercaptan, and 100 parts of the above monomer mixture (65% butadiene, 30% acrylonitrile, 5% methacrylic acid) in a reactor equipped with a stir mixer. The mixture was heated to 48 ° C., 0.25 parts of ammonium persulfate catalyst was injected, and emulsion polymerization was carried out.
The maximum polymerization temperature is 70 ° C, and the conversion rate from monomer to polymer is 9
When it reached 7% or more, the polymerization was stopped by cooling. After cooling to ambient temperature, the pH is further adjusted to 8.0 with ammonia.
It was adjusted to 9.0. Then, stripping was performed and the resin solid content was concentrated to 55%. Resin solid content 55
%, PH 8.4 carboxylated acrylonitrile.
A butadiene copolymer emulsion was obtained. Hydran HW-950 against 75 parts of resin solid content of this emulsion
(Soap-free anion type polyester urethane resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.
Resin solid content 30%, pH 6.9) 2 in terms of resin solid content
5 parts were added to obtain a resin emulsion composition.

Zinc oxide, sulfur and a vulcanization accelerator were added to this composition to prepare a vulcanized film, and the film was subjected to the following solvent resistance and oil resistance tests. Table 1 shows the results
It was shown to.

1) Solvent resistance and oil resistance test (a) Compounding (solid content ratio) Composition 100 parts Zinc oxide 3 Sulfur 0.5 Vulcanization accelerator 0.5 After mixing in the above mixing ratio, a compounding liquid Is adjusted to a viscosity of 1000 cps using a cellulosic thickener (trade name: Metrose SM-15). (B) Molding conditions The above-mentioned compounded solution is applied to a glass plate using a 1 mm applicator and dried at room temperature for 2 days. Then at 100 ℃ 20
After drying for 1 minute, it is further dried at 140 ° C. for 5 minutes. The vulcanized film is peeled from the glass plate and prepared into a size of 23 mm × 29 mm to prepare a test piece. (C) Solvent resistance and oil resistance test The area swelling ratio after immersing the test piece in acetone, MEK, toluene and kerosene liquid at room temperature for 1 hour was obtained.

Example 2 100 parts of ion-exchanged water per 100 parts of the monomer was added to 0.
05 parts of ethylenediaminetetraacetic acid (EDTA), 2.5
Parts of sodium alkylbenzene sulfonate, 0.35
Part of t-dodecyl mercaptan and mixed with 100
Parts of the monomer mixture (65% butadiene, 30% acrylonitrile, 5% methacrylic acid) and 33 parts of the hydrane HW-950 used in Example 1 in terms of resin solids and in a reactor equipped with a stir mixer. Mixed. The mixture was heated to 48 ° C., 0.25 parts of ammonium persulfate catalyst was injected, and emulsion polymerization was carried out. The maximum polymerization temperature was 70 ° C., and when the conversion rate from the monomer to the polymer reached 97% or more, the polymerization was stopped by cooling. After cooling to ambient temperature, the pH was further adjusted to 8.0-9.0 with ammonia. Then, stripping was performed and the resin solid content was concentrated to 55%. An emulsion composition of a carboxylated acrylonitrile butadiene / polyurethane polymer having a resin solid content of 55% and a pH of 8.3 was obtained. Using this emulsion composition, compounding and preparation were carried out in the same manner as in Example 1, and solvent resistance and oil resistance tests were conducted. The results are shown in Table 1.

A film was prepared based on the following test method and a tensile test was conducted. The results are shown in Table 2. (1) Molding Conditions The resin emulsion composition is poured into a 1 mm mold glass plate, dried at room temperature for 2 days, and then dried at 120 ° C. for 20 minutes.
The film is peeled from the glass plate and used as a test piece. (2) Measurement conditions (a) Specimen: JIS No. 3 dumbbell (b) Tensile speed: 500 mm / min Example 3 Carboxylated acrylonitrile obtained in Example 1
To 50 parts of resin solids of the latex of the butadiene copolymer, 50 parts of hydrane HW-950, which is the polyurethane resin emulsion used in Example 1, was added in terms of resin solids to obtain a resin emulsion composition. Using this composition, compounding and preparation were carried out in the same manner as in Example 1, and solvent resistance and oil resistance tests were conducted. The results are shown in Table 1.

Example 4 Carboxylated acrylonitrile obtained in Example 1
Hydran HW-920 (soap-free anion type polyester urethane resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc., resin solid content 49%, pH = 50 parts) relative to resin solid content 50 parts of latex of butadiene copolymer
6.7) was added in an amount of 50 parts in terms of resin solid content to obtain a resin emulsion composition. Using this composition, Example 1
In the same manner as above, a mixture was prepared, and solvent resistance and oil resistance tests were conducted. The results are shown in Table 1.

Example 5 Carboxylated acrylonitrile obtained in Example 1
Hydran AP-60LM (soap-free anion type polyester urethane resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc., resin solid content 42%, pH to 50 parts resin solid content of latex of butadiene copolymer)
6.7) was added in an amount of 50 parts in terms of resin solid content to obtain a resin emulsion composition. Using this composition, Example 1
The solvent resistance and oil resistance tests were carried out in the same manner as in (1) above, and the results are shown in Table 1.

Example 6 140 parts of ion-exchanged water per 100 parts of the monomer were added in an amount of 0.
03 parts of ethylenediaminetetraacetic acid (EDTA), 2.9
1 part of polyoxyethylene sulfate sodium salt, 0.5 part of t-dodecyl mercaptan, and 100 parts of the above monomer mixture (50% butadiene, 40% acrylonitrile, 5% methacrylonitrile, 5% methacrylic acid). And in a reactor equipped with a stir mixer. Mix 4
The temperature is raised to 8 ° C., 0.1 part of potassium persulfate catalyst is injected, and emulsion polymerization is carried out. The maximum polymerization temperature was 70 ° C., and when the conversion rate from the monomer to the polymer reached 96% or more, the polymerization was stopped by cooling. After cooling to ambient temperature, pH with ammonia
Was further adjusted to 8.5 to 9.0. Then, stripping was performed and the resin solid content was concentrated to 41%. A carboxylated acrylonitrile-butadiene copolymer emulsion having a resin solid content of 41% and a pH of 8.9 was obtained.
Polyurethane resin emulsion used in Example 4, Hydran HW for 75 parts of resin solid content of this emulsion
25 parts of -920 in terms of resin solid content was added to obtain a resin emulsion composition. Using this composition, Example 1
In the same manner as above, a mixture was prepared, and solvent resistance and oil resistance tests were conducted. The results are shown in Table 1.

Comparative Example 1 Carboxylated acrylonitrile obtained in Example 1
Example 1 using a latex of butadiene copolymer
In the same manner as in (1) and (2), a solvent resistance test was conducted and the results are shown in Table 1.

Comparative Example 2 Carboxylated acrylonitrile obtained in Example 1
Bondic 1612 NSC (polyether urethane resin emulsion with emulsifier, Dainippon Ink and Chemicals, Inc., resin solid content 50%, pH 8.8) is used as resin solid for 75 parts of resin solid content of latex of butadiene copolymer. 25 parts in terms of minutes were added to obtain a resin emulsion composition. Using this resin emulsion composition, compounding and preparation were carried out in the same manner as in Example 1, and solvent resistance and oil resistance tests were conducted. The results are shown in Table 1.

[0067]

[Table 1] The numbers in the table indicate the area expansion rate (%).

[0068]

[Table 2] The numbers in the table indicate the maximum point stress (Kg / cm ² ).

From Table 2, from the viewpoint of tensile strength, Example 2
It turns out that the case is better.

[0070]

EFFECTS OF THE INVENTION A processed fiber product produced by using the composition for processing a fiber according to the present invention is superior in texture and oil resistance and solvent resistance to a processed product produced by using a conventional polymer. Good washing resistance, cleaning resistance, abrasion resistance, dimensional stability and mechanical strength.

Therefore, when an organic solvent is handled and dry cleaning is performed, particularly, ketones such as acetone and MEK, organic solvents such as toluene, gasoline, benzine,
It is useful as a backing agent or binder for fiber processing of carpets, non-woven fabrics and the like when used under severe conditions of oils such as kerosene and turpentine.

Claims (5)

[Claims] 1. A latex (A) of a copolymer of an unsaturated nitrile having a carboxyl group in the molecule and a conjugated diene.
And a soap-free type polyurethane resin emulsion (B). 2. A copolymer latex (A) and a soap-free type polyurethane resin emulsion (B),
The composition according to claim 1, which has a solid content weight ratio of 97/3 to 25/75. 3. A copolymer latex (A) is obtained by reacting 45 to 83% by weight of a conjugated diene, 15 to 50% by weight of an unsaturated nitrile and 2 to 10% by weight of an unsaturated carboxylic acid in an aqueous medium. The composition according to claim 1 or 2, which is characterized in that: 4. A method for producing a fiber processing composition, which comprises emulsion-polymerizing a conjugated diene, an unsaturated nitrile and a carboxylic acid in the presence of a soap-free type polyurethane resin emulsion in an aqueous medium. 5. A latex (A) of a copolymer of an unsaturated nitrile having a carboxyl group in the molecule and a conjugated diene.
And a soap-free type polyurethane resin emulsion (B) and a filler (C).