KR20140112351A - Carboxylic acid modified-nitrile based copolymer composition and dip-form article thereof - Google Patents

Abstract

The present invention relates to a carboxylic acid modified nitrile-based copolymer composition and a dip-molded product produced from the same. More specifically, the present invention provides a copolymer composition and a dip-molded product produced from the same, wherein the copolymer composition comprises: a carboxylic acid modified nitrile-based copolymer latex having a glass transition temperature of -60 to -10°C; and a carboxylic acid modified styrene-based copolymer latex having a glass transition temperature of 30 to 110°C. The present invention provides: a carboxylic acid modified nitrile-based copolymer composition which maintains its existing physical properties, has remarkably improved wearability and doping properties, and can produce a dip-molded product; and a dip-molded product produced from the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a carbonic acid-modified nitrile-based copolymer composition and a dip-formed product prepared from the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a carboxylic acid-modified nitrile-based copolymer composition and a dip-molded product, and more particularly to a carboxylic acid-modified nitrile-based copolymer composition capable of producing a deep-formed product or the like having remarkably improved wearability and doping property while maintaining existing properties, And a dip molded article produced therefrom.

Rubber gloves are used in a wide range of fields such as housework, food, electronics, and medical care. However, when the wearability and doping property of the glove is lowered at the time of work, the work efficiency of the worker is lowered. Most of the rubber gloves are manufactured by dipping process, and talcum powder, corn powder, etc. are treated on the surface in order to remove the adhesion of the glove surface and make it easy to wear in the post-process . However, since it uses powder, it is buried in the hands when worn, and contamination occurs when working in a clean room.

U.S. Patent No. 3,411,982 discloses a technique for improving the slip properties of rubber gloves by modifying the outer surface of rubber gloves by a halogenation process. In the halogenating step, the rubber gloves are immersed in a sodium hypochlorite solution containing 1 to 5% of chlorine for about 8 to 10 seconds, immediately transferred and washed, dried and immersed in a 12% hydrochloric acid solution for 8 to 10 seconds, Repeat several times against the inner surface of the rubber gloves. However, this chlorine treatment process has a problem that the process itself is troublesome and harmful chlorine components harm the health of the workers.

U.S. Patent Nos. 3,813,695, 3,326,742, 3,585,103, and British Patent 1,028,446 disclose a method of increasing the slip property by coating a hydrogel polymer solution on the outer and inner surfaces of surgical gloves. The hydrogel polymer solution is polyvinylpyrrolidone, polyhydroxyethyl methacrylate, polymethyl methacrylate, polyhydroxypropyl acrylate, or a copolymer thereof. However, the solution of the hydrogel polymer is costly, and the coating process is added, resulting in poor economical efficiency and troublesome problems.

The present invention provides a carboxylic acid-modified nitrile-based copolymer composition and a dip-formed article prepared therefrom, which are capable of producing a deep-formed product having greatly improved wearability and doping property while maintaining the existing properties .

In order to achieve the above object, the present invention relates to a process for producing a rubber composition, which comprises reacting a carboxylic acid modified nitrile-based copolymer latex (hereinafter referred to as "latex A") having a glass transition temperature of from -60 to -10 ° C. with a glass transition temperature (Hereinafter referred to as "latex B"). The present invention also provides a copolymer composition containing the carboxylic acid modified styrenic copolymer latex.

When the glass transition temperature of the latex A is less than -60 ° C, it does not improve wearability and doping even when mixed with latex B. When the glass transition temperature is higher than -10 ° C, the mechanical properties of the latex A are lower than those of existing products.

If the glass transition temperature of the latex B is lower than 30 ° C, the wearability and doping properties of the latex B deteriorate. If the glass transition temperature of the latex B is higher than 110 ° C, the mechanical properties of the latex B deteriorate.

In addition, the present disclosure provides a dip molded article produced from the copolymer composition.

The present disclosure also relates to a process for preparing a coagulant solution comprising: a) applying a coagulant solution to a mold and drying; b) applying a carboxylic acid-modified nitrile-based copolymer composition for dip molding to a mold to which a coagulant is applied to form a dip-formed layer; c) crosslinking said dip molding layer; And d) peeling the cross-linked dip-formed layer from the mold to obtain a dip-molded article.

The latex A comprises a conjugated diene monomer, an ethylenically unsaturated nitrile monomer and an ethylenic unsaturated acid monomer, and if necessary, other monomers copolymerizable with the monomers, an emulsifier, a polymerization initiator, a molecular weight regulator and other additives Is added and polymerized.

The conjugated diene-based monomer is at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene But are not limited thereto.

The ethylenically unsaturated nitrile monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile,? -Chloronitrile and? -Cyanoethyl acrylonitrile, but is not limited thereto Do not.

The ethylenic unsaturated acid monomer is at least one member selected from the group consisting of an ethylenically unsaturated carboxylic acid monomer, an ethylenic unsaturated sulfonic acid monomer and an ethylenic unsaturated acid anhydride monomer, more specifically, acrylic acid, methacrylic acid, itaconic acid, But are not limited to, at least one selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate.

Other monomers copolymerizable with these monomers, if necessary, include vinyl aromatic monomers selected from the group consisting of styrene, alkylstyrene, and vinylnaphthalene; Fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-propoxymethyl An ethylenically unsaturated amide monomer selected from the group consisting of: Non-conjugated diene monomers such as vinylpyridine, vinylnorbornene, dicyclopentadiene and 1,4-hexadiene; (Meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, di (meth) acrylate, di (meth) acrylate, Butyl methacrylate, diethyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl (meth) acrylate, (Meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, hydroxymethyl (meth) acrylate, An ethylenically unsaturated carboxylic acid ester monomer selected from the group consisting of (meth) acrylic acid hydroxypropyl, glycidyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; One or more of these may be used, but the present invention is not limited thereto.

As the emulsifier, at least one selected from the group consisting of alkylbenzenesulfonic acid salts, aliphatic sulfonic acid salts, sulfuric acid ester salts of alcohol,? -Olefin sulfonic acid salts and alkyl ether sulfuric acid ester salts may be used.

Examples of the polymerization initiator include sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p- menthol hydroperoxide, di- Cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutyrate, azobisisobutylo Nitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis iso-butyric acid methyl. However, the present invention is not limited thereto.

Examples of the molecular weight regulator include α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethylthiuram disulfide, But is not limited to, at least one selected from the group consisting of disulfide and diisopropylkantogen disulfide.

As the other additives, at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate and sodium sulfite may be used, but not limited thereto .

The latex B is obtained by adding a conjugated diene monomer, an aromatic vinyl monomer, an ethylenically unsaturated nitrile monomer and an ethylenically unsaturated acid monomer, and if necessary, other monomers copolymerizable with the monomers, emulsifiers, polymerization initiators, And other additives are added and polymerized.

Examples of the conjugated diene monomer include one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene But the present invention is not limited thereto.

As the aromatic vinyl monomer, at least one selected from the group consisting of styrene and alphamethylstyrene may be used, but the present invention is not limited thereto.

As the ethylenically unsaturated nitrile monomer, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile,? -Chloronitrile and? -Cyanoethyl acrylonitrile may be used. However, It does not.

The ethylenic unsaturated acid monomer is at least one member selected from the group consisting of an ethylenically unsaturated carboxylic acid monomer, an ethylenic unsaturated sulfonic acid monomer and an ethylenic unsaturated acid anhydride monomer, and more specifically, acrylic acid, methacrylic acid, itaconic acid, , But are not limited to, at least one selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate .

Other monomers copolymerizable with these monomers, if necessary, include vinyl aromatic monomers selected from the group consisting of alkyl styrene, and vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-propoxymethyl An ethylenically unsaturated amide monomer selected from the group consisting of: Non-conjugated diene monomers such as vinylpyridine, vinylnorbornene, dicyclopentadiene and 1,4-hexadiene; (Meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, di (meth) acrylate, di (meth) acrylate, Butyl methacrylate, diethyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl (meth) acrylate, (Meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, hydroxymethyl (meth) acrylate, An ethylenically unsaturated carboxylic acid ester monomer selected from the group consisting of (meth) acrylic acid hydroxypropyl, glycidyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; One or more of these may be used, but the present invention is not limited thereto.

As the emulsifier, at least one selected from the group consisting of alkylbenzenesulfonic acid salts, aliphatic sulfonic acid salts, sulfuric acid ester salts of alcohol,? -Olefin sulfonic acid salts and alkyl ether sulfuric acid ester salts may be used.

Examples of the polymerization initiator include sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p- menthol hydroperoxide, di- Cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutyrate, azobisisobutylo Nitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis iso-butyric acid methyl. However, the present invention is not limited thereto.

Examples of the molecular weight regulator include α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethylthiuram disulfide, But is not limited to, at least one selected from the group consisting of disulfide and diisopropylkantogen disulfide.

As the other additives, at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite may be used, but not limited thereto .

The carboxylic acid-modified nitrile-based copolymer composition may further include at least one member selected from the group consisting of a vulcanizing agent, an ionic crosslinking agent, a pigment, a filler, a thickener, and a pH adjuster.

As described above, according to the present invention, there is an effect of providing a carboxylic acid modified nitrile-based copolymer composition and a dip-formed article produced therefrom, which can produce a deep-formed product or the like having remarkably improved wearability and doping property while retaining existing physical properties .

In order to achieve the above object, the present invention provides a copolymer composition comprising two or more latexes different in glass transition temperature from those of the prior art.

In general, a molded article manufactured from a latex composition for deep molding containing a latex having a low glass transition temperature is produced by a latex composition for dip molding comprising a latex having a low stickiness on the surface and low wearability and doping property and having a high glass transition temperature Molded product has excellent wearability and doping property, but its mechanical properties are remarkably deteriorated and can not be used as a product for deep molding.

The present invention achieves the object of the present invention by providing a latex composition for deep molding which is specifically designed to include two or more latexes having different long and short glass transition temperatures as described above, but only the advantages thereof are exhibited.

Hereinafter, the carboxylic acid-modified nitrile-based copolymer composition of the present invention and the dip-molded article produced therefrom will be described in detail.

The latex A according to the present invention is a polymer having a glass transition temperature of -60 to -10 占 폚, -55 to -10 占 폚, -50 to -15 占 폚, -40 to -15 占 폚, or -37 to -15 占 폚, Within this range, there is an effect of excellent wearability and doping properties without deteriorating mechanical properties.

The latex A may have an average particle size of 100 to 160 nm, 110 to 150 nm, or 120 to 140 nm, for example. When applied to products such as films within this range, It has excellent effect.

The latex A according to the present invention may be contained in an amount of 76 to 98% by weight, 85 to 97% by weight or 85 to 90% by weight based on 100% by weight of the total of latexes A and B, It has an excellent effect on wearability and doping.

The latex B of the present invention has, for example, a glass transition temperature of 30 to 110 ° C, 35 to 105 ° C, or 40 to 100 ° C. Within this range, there is an effect of excellent wearability and doping property without deterioration of mechanical properties.

The latex B may have an average particle size of 160 to 260 nm, 170 to 250 nm, or 180 to 240 nm, for example. When applied to products such as a film within this range, the latex B has excellent both filling property, uniformity and strength .

The latex B is not the same as the average particle size of the latex A, for example.

The latex B of the present invention may be contained in an amount of 2 to 24% by weight, 3 to 15% by weight, or 3 to 15% by weight based on 100% by weight of the total of the latexes A and B, And it has an excellent effect of wearing property and doping property.

The copolymer composition according to the present invention may contain the latex A and the latex B (latex A: latex B) in a weight ratio of 98: 2 to 76:24 (based on solids), and as another example, 85: 15, or 89: 11 to 91: 9. Within this range, excellent effects such as wearability, doping property, and mechanical properties are obtained.

The latex A comprises a conjugated diene monomer, an ethylenically unsaturated nitrile monomer and an ethylenic unsaturated acid monomer, and if necessary, other monomers copolymerizable with the monomers, an emulsifier, a polymerization initiator, a molecular weight regulator and other additives And then polymerizing the resulting mixture.

The conjugated diene monomer, the ethylenically unsaturated nitrile monomer, the ethylenic unsaturated acid monomer, and other monomers copolymerizable with these monomers, emulsifiers, polymerization initiators, molecular weight modifiers, and other additives as needed are not particularly limited, Can be used, but specific examples will be described below.

Examples of the conjugated diene monomer include one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene Or more can be used.

As the ethylenically unsaturated nitrile monomer, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile,? -Chloronitrile and? -Cyanoethyl acrylonitrile may be used.

As the ethylenic unsaturated acid monomer, at least one selected from the group consisting of an ethylenic unsaturated carboxylic acid monomer, an ethylenic unsaturated sulfonic acid monomer and an ethylenic unsaturated acid anhydride monomer can be used, and specifically, acrylic acid, methacrylic acid, At least one selected from the group consisting of itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate can be used.

Other monomers copolymerizable with these monomers, if necessary, include vinyl aromatic monomers selected from the group consisting of styrene, alkylstyrene, and vinylnaphthalene; Fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-propoxymethyl An ethylenically unsaturated amide monomer selected from the group consisting of: Non-conjugated diene monomers such as vinylpyridine, vinylnorbornene, dicyclopentadiene and 1,4-hexadiene; (Meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, di (meth) acrylate, di (meth) acrylate, Butyl methacrylate, diethyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl (meth) acrylate, (Meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, hydroxymethyl (meth) acrylate, (Meth) acrylate is selected from the group consisting of ethylenically unsaturated carboxylic acid ester monomers selected from the group consisting of (meth) acrylic acid hydroxypropyl, glycidyl (meth) acrylate, and dimethylaminoethyl That can be used more than one species.

Examples of the emulsifier include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and more specifically, alkylbenzenesulfonates, aliphatic sulfonates, sulfuric acid ester salts of higher alcohols,? -Olefin sulfonic acid salts, Alkyl ether sulfuric acid ester salts, and the like.

As the polymerization initiator, a radical initiator is suitable. Examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthol hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutyrate; At least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl can be used.

Examples of the molecular weight regulator include mercaptans such as? -Methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; Containing sulfur compounds such as tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylkisantigen disulfide; and the like. At least one selected from the group consisting of sulfur-containing compounds such as tetraethyl thiuram disulfide,

The other additives may be selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite. One or more species can be used.

The latex B is obtained by adding a conjugated diene monomer, an aromatic vinyl monomer, an ethylenically unsaturated nitrile monomer and an ethylenically unsaturated acid monomer, and if necessary, other monomers copolymerizable with the monomers, emulsifiers, polymerization initiators, And other additives are added and polymerized.

Examples of the conjugated diene monomer include one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene But the present invention is not limited thereto.

As the aromatic vinyl monomer, at least one selected from the group consisting of styrene and alphamethylstyrene may be used, but the present invention is not limited thereto.

As the ethylenically unsaturated nitrile monomer, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile,? -Chloronitrile and? -Cyanoethyl acrylonitrile may be used. However, It does not.

As the ethylenic unsaturated acid monomer, at least one selected from the group consisting of an ethylenic unsaturated carboxylic acid monomer, an ethylenic unsaturated sulfonic acid monomer and an ethylenic unsaturated acid anhydride monomer can be used, and more specifically, acrylic acid, methacrylic acid At least one selected from the group consisting of maleic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate may be used. It is not limited.

Other monomers copolymerizable with these monomers, if necessary, include vinyl aromatic monomers selected from the group consisting of alkyl styrene, and vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; (Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-propoxymethyl An ethylenically unsaturated amide monomer selected from the group consisting of: Non-conjugated diene monomers such as vinylpyridine, vinylnorbornene, dicyclopentadiene and 1,4-hexadiene; (Meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, di (meth) acrylate, di (meth) acrylate, Butyl methacrylate, diethyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl (meth) acrylate, (Meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, hydroxymethyl (meth) acrylate, An ethylenically unsaturated carboxylic acid ester monomer selected from the group consisting of (meth) acrylic acid hydroxypropyl, glycidyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; But not limited to, at least one selected.

Examples of the emulsifier include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and more specifically, alkylbenzenesulfonates, aliphatic sulfonates, sulfuric acid ester salts of higher alcohols,? -Olefin sulfonic acid salts, Alkyl ether sulfuric acid ester salts, and the like.

As the polymerization initiator, a radical initiator is suitable. Examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthol hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutyrate; At least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl can be used.

Examples of the molecular weight regulator include mercaptans such as? -Methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; Containing sulfur compounds such as tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylkisantigen disulfide; and the like. At least one selected from the group consisting of sulfur-containing compounds such as tetraethyl thiuram disulfide,

The other additives may be selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite. One or more species can be used.

A specific example of the method for producing the latex 1 and the latex 2 is as follows.

1. Production method of latex A

40 to 90% by weight of a conjugated diene monomer, 9.9 to 50% by weight of an ethylenically unsaturated nitrile monomer, and 0.1 to 10% by weight of an ethylenically unsaturated acid monomer are added to a reaction vessel containing an aqueous solution and the total monomer 100 0.3 to 10 parts by weight of an emulsifier, 0.01 to 2 parts by weight of a polymerization initiator, and 0.1 to 2.0 parts by weight of a molecular weight modifier are added to the reaction mixture at a temperature ranging from 20 to 60 캜. When the conversion reaches 45 to 75% The polymerization is allowed to proceed at a temperature of up to 90 DEG C, and when the conversion reaches 84 to 99%, a base such as ammonium hydroxide is added to terminate the polymerization to produce latex A.

When the carboxylic acid-modified nitrile-based copolymer latex is prepared as described above, latex A having a glass transition temperature of -60 to -10 ° C can be prepared.

2. Manufacturing method of latex B

1 to 10% by weight of a conjugated diene monomer, 65 to 96% by weight of an aromatic vinyl monomer, 1 to 20% by weight of an ethylenically unsaturated acid monomer, 1 to 7% by weight of a vinyl cyanide monomer and 1 to 20 % ≪ / RTI > may be polymerized to produce latex B.

The latex B may be prepared in two steps or in multiple steps. Generally, the latex B may be prepared by preparing a seed latex and then coating it with one to three layers of shell. In the polymerization, other reaction conditions such as water, a polymerization initiator, an emulsifier, and an electrolyte can be polymerized by a conventional emulsion polymerization method.

On the other hand, the latex A and the latex B may include the latex A and the latex B in an amount of 80 to 99% by weight based on the solid content, and 85 to 98% by weight or 88 To 97% by weight (residual amount is additive, material and mixture thereof), and rubber gloves, which are a kind of dip-formed products finally produced within this range, are excellent in physical properties.

The copolymer composition may include one or more additives selected from the group consisting of a vulcanizing agent, a vulcanization accelerator, an ionic crosslinking agent, a pigment such as titanium oxide, a filler such as silica, a thickener, and a pH regulator such as ammonia or alkali hydroxide have.

In addition, it is of course possible to add a chelating agent, a dispersing agent, a deoxidizing agent, a particle size regulating agent, an anti-aging agent, and an oxygen scavenger at the time of polymerizing the latexes A and B, if necessary.

The solid content concentration of the copolymer composition excluding water is, for example, 10 to 40% by weight (moisture content 60 to 90%), and still another example is 15 to 35% by weight or 18 to 33% by weight.

For example, water may be added to adjust the solid concentration.

The pH of the copolymer composition is, for example, 8.0 to 12, and another example is 9 to 11, or 9.3 to 10.5.

The dip-molded article of the present invention is characterized in that it is obtained by dip-molding a copolymer composition comprising latex A and latex B as described above.

The dip molding method is not particularly limited and may be a method commonly used in the art. Specific examples thereof include a direct dipping method, an anode adhesion dipping method, and a Teague adhesion dipping method. Of these, it is preferable to use a deposition dipping method. In this case, a dip-shaped article having a uniform thickness can be easily obtained.

The method of manufacturing the dip-molded article of the present invention comprises the steps of: a) applying a coagulant solution to a mold and drying; b) applying a carboxylic acid-modified nitrile-based copolymer composition for dip molding to a mold to which a coagulant is applied to form a dip-formed layer; c) crosslinking said dip molding layer; And d) peeling the crosslinked dip molding layer from the mold to obtain a dip molded article.

The production method of the above dip-molded article will be described in detail as follows.

First, a hand shaped dip forming die is immersed in a coagulating agent solution, and a coagulant is attached to the surface of the dipping forming die.

Examples of coagulants include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, aluminum chloride, and the like; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetic acid salts such as barium acetate, calcium acetate and zinc acetate; Calcium sulfate, magnesium sulfate, and sulfate such as aluminum sulfate. Of these, calcium chloride and calcium nitrate are preferred.

The coagulant solution is a solution in which the above coagulant is dissolved in water, alcohol or a mixture thereof. The concentration of the coagulant in the coagulant solution may be, for example, 5 to 75% by weight, and still more preferably 15 to 55% by weight or 18 to 40% by weight.

Next, the dip forming mold to which the coagulant is attached is immersed in the carbonic acid modified nitrile-based copolymer latex composition for dip molding of the present invention, and the dip forming mold is taken out to form a dip molding layer in the dip forming mold. Subsequently, the dip molding layer formed in the dip forming mold is heat-treated to crosslink the carboxylic acid-modified nitrile-based copolymer latex. During the heat treatment, the water component first evaporates and vulcanization is carried out through crosslinking. Subsequently, the dip-formed layer crosslinked by the heat treatment is peeled off from the dip forming mold to obtain a dipped molded article.

The process according to the present disclosure can also be used for any latex article which can be produced by the technique of dip molding known in the art. Specifically, it can be applied to deep-formed latex articles selected from surgical gloves, examination gloves, condoms, catheters or various kinds of health care products such as industrial and household gloves.

Hereinafter, the present invention will be described in more detail with reference to the following Synthesis Examples and Examples, but the scope of the present invention is not limited to Synthesis Examples and Examples. The evaluation of the dip-molded article is carried out by the following method.

[Example]

Synthetic example  1 (latex A)

21 parts by weight of acrylonitrile, 74 parts by weight of 1,3-butadiene, 5 parts by weight of methacrylic acid, 0.6 parts by weight of tert-dodecyl mercaptan, 2.3 parts by weight of sodium dodecylbenzenesulfonate, And 0.3 parts by weight of potassium persulfate were charged, and the temperature was raised to 40 DEG C to initiate polymerization. When the conversion rate reached 65%, the temperature was elevated to 70 ° C to proceed the polymerization. When the conversion reached 94%, 0.3 part by weight of ammonium hydroxide was added to terminate the polymerization. Thereafter, the unreacted monomer was removed through a deodorization process, and ammonia water, an antioxidant and a defoamer were added to obtain a carboxylic acid modified nitrile copolymer latex having a solid concentration of 45.0% and a pH of 8.0.

The latex was found to have a Tg of -37 ° C as a result of DSC analysis (analytical instrument manufacturer: TA Corporation, product name: DSC Q10), and DLS (Dynamic Light Scattering) analysis (analytical instrument: PSS, product name: NICOMP 380DLS) Was 131 nm.

Synthetic example  2 (latex A)

12 parts by weight of acrylonitrile, 83 parts by weight of 1,3-butadiene, 5 parts by weight of methacrylic acid, 0.6 parts by weight of tert-dodecyl mercaptan, 2.3 parts by weight of sodium dodecylbenzenesulfonate, And 0.3 parts by weight of potassium persulfate were charged, and the temperature was raised to 40 DEG C to initiate polymerization. When the conversion rate reached 65%, the temperature was elevated to 70 ° C to proceed the polymerization. When the conversion reached 94%, 0.3 part by weight of ammonium hydroxide was added to terminate the polymerization. Thereafter, the unreacted monomer was removed through a deodorization process, and ammonia water, an antioxidant and a defoamer were added to obtain a carboxylic acid modified nitrile copolymer latex having a solid concentration of 45.0% and a pH of 8.0.

As a result of DSC analysis, the latex had a Tg of -47 ° C and an average particle size of 125 nm as a result of DLS analysis.

Synthetic example  3 (Latex A)

37 parts by weight of acrylonitrile, 58 parts by weight of 1,3-butadiene, 5 parts by weight of methacrylic acid, 0.6 part by weight of tert-dodecyl mercaptan, 2.3 parts by weight of sodium dodecylbenzenesulfonate, And 0.3 parts by weight of potassium persulfate were charged, and the temperature was raised to 40 DEG C to initiate polymerization. When the conversion rate reached 65%, the temperature was elevated to 70 ° C to proceed the polymerization. When the conversion reached 94%, 0.3 part by weight of ammonium hydroxide was added to terminate the polymerization. Thereafter, unreacted monomers were removed through a deodorization process, and ammonia water, an antioxidant and a defoamer were added to obtain a carboxylic acid modified nitrile copolymer latex having a solid concentration of 45.0% and a pH of 8.0.

The latex had a Tg of -15 ° C as a result of DSC analysis and an average particle diameter of 138 nm as a result of DLS analysis.

Synthetic example  4 (Latex A)

21 parts by weight of acrylonitrile, 74 parts by weight of 1,3-butadiene, 5 parts by weight of methacrylic acid, 0.6 parts by weight of tert-dodecyl mercaptan, 2.3 parts by weight of sodium dodecylbenzenesulfonate, And 0.6 parts by weight of potassium persulfate were charged, and the temperature was raised to 40 DEG C to initiate polymerization. When the conversion rate reached 65%, the temperature was elevated to 70 ° C to proceed the polymerization. When the conversion reached 92%, 0.3 part of ammonium hydroxide was added to terminate the polymerization. Thereafter, the unreacted monomer was removed through a deodorization process, and ammonia water, an antioxidant and a defoamer were added to obtain a carboxylic acid modified nitrile copolymer latex having a solid concentration of 45.0% and a pH of 8.0.

The latex had a Tg of -37 ° C as a result of DSC analysis, and an average particle size of 90 nm as a result of DLS analysis.

Synthetic example  5 (latex B)

Latex B was prepared in two steps as follows.

Step 1

34 parts by weight of 1,3-butadiene, 48 parts by weight of styrene, 10 parts by weight of methyl methacrylate, 3 parts by weight of acrylonitrile, 5 parts by weight of itaconic acid, 6 parts by weight of sodium dodecylbenzene sulfonate, 0.2 part by weight of dodecyl mercaptan, 0.4 part by weight of sodium bicarbonate and 420 parts by weight of ion-exchanged water, and the temperature was raised to 65 캜. 0.8 part by weight of potassium persulfate as a polymerization initiator was added thereto, followed by stirring for about 300 minutes to complete the polymerization of the seed. At this time, the average particle diameter of the obtained seed was 79 nm and the conversion was 97%.

Step 2

8 parts by weight of the seed latex obtained in the first step was heated to 80 DEG C, and then 3 parts by weight of 1,3-butadiene, 61 parts by weight of styrene, 18 parts by weight of methyl methacrylate, 5 parts by weight of acrylonitrile, 5 parts by weight of itaconic acid, 5 parts by weight of methacrylic acid, 3 parts by weight of acrylamide, 0.3 part by weight of sodium dodecylbenzenesulfonate, 0.1 part by weight of tert-dodecyl mercaptan, 0.4 part by weight of sodium bicarbonate, And 1.0 part by weight of potassium persulfate were continuously added for 360 minutes to polymerize.

After all of the above components were added, the temperature was raised to 90 ° C, and the reaction was further stirred for 180 minutes to complete the polymerization. The average particle size of the final latex B was 218 nm, the conversion rate was 99%, and the glass transition temperature was 88 占 폚.

Synthetic example  6 (latex B)

Latex B was prepared in two steps as follows.

Step 1

A seed was prepared in the same manner as in the first step of Synthesis Example 5.

Step 2

3 parts by weight of the seed latex obtained in the first step was heated to 80 DEG C and then 3 parts by weight of 1,3-butadiene, 61 parts by weight of styrene, 18 parts by weight of methyl methacrylate, 5 parts by weight of acrylonitrile, 5 parts by weight of itaconic acid, 5 parts by weight of methacrylic acid, 3 parts by weight of acrylamide, 0.3 part by weight of sodium dodecylbenzenesulfonate, 0.1 part by weight of tert-dodecyl mercaptan, 0.4 part by weight of sodium bicarbonate, And 1.0 part by weight of potassium persulfate were continuously added for 360 minutes to polymerize.

After all of the above components were added, the temperature was raised to 90 ° C, and the reaction was further stirred for 180 minutes to complete the polymerization. The average particle size of the final latex B was 293 nm, the conversion rate was 99%, and the glass transition temperature was 88 占 폚.

Synthetic example  7 (Latex A)

21 parts by weight of acrylonitrile, 74 parts by weight of 1,3-butadiene, 5 parts by weight of methacrylic acid, 0.6 parts by weight of tert-dodecylmercaptan, 1.8 parts by weight of sodium dodecylbenzene sulfonate, 0.5 parts by weight of sodium bicarbonate 0.5 , 140 parts by weight of water and 0.3 parts by weight of potassium persulfate were charged, and the temperature was raised to 40 DEG C to initiate polymerization. When the conversion rate reached 65%, the temperature was elevated to 70 ° C to proceed the polymerization. When the conversion reached 94%, 0.3 part by weight of ammonium hydroxide was added to terminate the polymerization. Thereafter, the unreacted monomer was removed through a deodorization process, and ammonia water, an antioxidant and a defoamer were added to obtain a carboxylic acid modified nitrile copolymer latex having a solid concentration of 45.0% and a pH of 8.0.

The latex showed a Tg of -37 ° C as a result of DSC analysis, and an average particle size of 180 nm as a result of DLS analysis.

Synthetic example  8 (latex B)

Latex B was prepared in two steps as follows.

Step 1

A seed was prepared in the same manner as in the first step of Synthesis Example 5.

Step 2

18 parts by weight of the seed latex obtained in the first step was heated to 80 DEG C and then 3 parts by weight of 1,3-butadiene, 61 parts by weight of styrene, 18 parts by weight of methyl methacrylate, 5 parts by weight of acrylonitrile, 5 parts by weight of itaconic acid, 5 parts by weight of methacrylic acid, 3 parts by weight of acrylamide, 0.3 part by weight of sodium dodecylbenzenesulfonate, 0.1 part by weight of tert-dodecyl mercaptan, 0.4 part by weight of sodium bicarbonate, And 1.0 part by weight of potassium persulfate were continuously added for 360 minutes to polymerize.

After all of the above components were added, the temperature was raised to 90 ° C, and the reaction was further stirred for 180 minutes to complete the polymerization. The average particle size of the final latex B was 142 nm, the conversion rate was 99%, and the glass transition temperature was 89 占 폚.

Example  One

The latexes prepared in Synthesis Example 1 and Synthesis Example 5 were mixed in a weight ratio (based on solid content, the same applies hereinafter) of Synthesis Example 1: Synthesis Example 5 = 97: 3. Thereafter, 5.73 parts by weight of a dispersion prepared by mixing 0.03 part by weight of potassium hydroxide, 0.7 part by weight of titanium oxide and 5 parts by weight of secondary distilled water was mixed with 333 parts by weight (solid content: 100 parts by weight) of the latex prepared by mixing, And distilled water was added thereto to prepare a carboxylic acid-modified nitrile-based copolymer composition for dip-molding having a solid content concentration of 30%.

Next, 22 parts by weight of calcium nitrate, 69.5 parts by weight of methanol, 8 parts by weight of calcium carbonate and 0.5 parts by weight of a wetting agent (Teric 320 produced by Huntsman Corporation, Australia) were mixed to prepare a coagulant solution. A hand-shaped ceramic mold was immersed in this solution for 1 minute and pulled out, followed by drying at 70 ° C for 3 minutes to apply the coagulant to the hand mold.

Then, the mold to which the coagulant was applied was immersed in the above-prepared carboxyl-modified nitrile-based copolymer composition for deep molding for 1 minute, dried at 70 ° C for 1 minute, leached in water or hot water for 3 minutes, ). The mold was again dried at 70 DEG C for 3 minutes and then crosslinked at 125 DEG C for 20 minutes. Then, the cross-linked dip-formed layer was peeled off from the hand-shaped mold to prepare a glove-shaped dip-molded article, and its physical properties are shown in Table 1 below.

Example  2

Except that the latexes prepared in Synthesis Example 1 and Synthesis Example 5 in Example 1 were mixed in a weight ratio of Synthesis Example 1: Synthesis Example 5 = 90: 10 in the same manner as in Example 1, , And their physical properties are shown in Table 1 below.

Example  3

Except that the latexes prepared in Synthesis Example 1 and Synthesis Example 5 in Example 1 were mixed in a weight ratio of Synthesis Example 1: Synthesis Example 5 = 85: 15 in the same manner as in Example 1, , And their physical properties are shown in Table 1 below.

Example  4

Except that latex prepared in Synthesis Example 2 and Synthesis Example 5 were mixed in a weight ratio of Synthesis Example 2: Synthesis Example 5 = 90: 10 in the following Example 1 to prepare a rubber glove-shaped dip product , And their physical properties are shown in Table 1 below.

Example  5

Except that the latexes prepared in Synthesis Example 3 and Synthesis Example 5 in Example 1 were mixed in a weight ratio of Synthesis Example 3: Synthesis Example 5 = 90: 10 in the same manner as in Example 1, , And their physical properties are shown in Table 1 below.

Comparative Example  One

A dip-shaped rubber glove was prepared in the same manner as in Example 1, except that the latex prepared in Synthesis Example 1 was used alone.

Comparative Example  2

Except that latex prepared in Synthesis Example 4 and Synthesis Example 5 in Example 1 were mixed in a weight ratio of Synthesis Example 4: Synthesis Example 5 = 90: 10 in the same manner as in Example 1, , And their physical properties are shown in Table 1 below.

Comparative Example  3

Except that the latexes prepared in Synthesis Example 1 and Synthesis Example 6 in Example 1 were mixed in a weight ratio of Synthesis Example 1: Synthesis Example 6 = 90: 10 in the same manner as in Example 1, , And their physical properties are shown in Table 1 below.

Comparative Example  4

Except that the latexes prepared in Synthesis Example 7 and Synthesis Example 8 in Example 1 were mixed in a weight ratio of Synthesis Example 7: Synthesis Example 8 = 90: 10, a rubber glove-shaped dip product was prepared , And their physical properties are shown in Table 1 below.

Comparative Example  5

Except that the latexes prepared in Synthesis Example 7 and Synthesis Example 5 in Example 1 were mixed in a weight ratio of Synthesis Example 7: Synthesis Example 5 = 90:10, a rubber glove-shaped dip product was prepared , And their physical properties are shown in Table 1 below.

Comparative Example  6

A dip-shaped rubber glove was prepared in the same manner as in Example 1, except that latexes prepared in Synthesis Example 1 and Synthesis Example 8 were mixed in a weight ratio of Synthesis Example 1: Synthesis Example 8 = 90:10 , And their physical properties are shown in Table 1 below.

[Test Example]

The physical properties of the respective molded articles prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Table 1 below.

* Particle size: The average particle size (NICOMP average particle diameter) was measured using an analyzer called NICOMP 380DLS manufactured by PSS.

* Glass transition temperature: Measured using DSC Q100 (TA Instruments).

* Modulus at 300% at tensile strength, elongation and elongation of 300%: A dumbbell-shaped specimen was prepared in accordance with ASTM D-412. Subsequently, the test piece was pulled at an elongation rate of 500 mm / min, and the stress at the elongation of 300%, the tensile strength at the elongation and the elongation at break were measured.

* Friction Coefficient Measurement: Friction coefficient was measured to evaluate wearability and doping. The coefficient of friction of the film surface and the coefficient of dynamic friction of the film surface were measured by a modified method of measuring the coefficient of friction by the spring scale specified in ASTM D 1894-78. A smooth wooden plate of 125cm * 26cm (3cm in thickness) was used as the support frame, and a spring scale and a reduction DC motor were attached to the support and pulled at a constant speed (about 160mm / min). The plastic plate to be slid in contact with the film-attached surface was a PMMA flat plate having a size of 30 cm * 15 cm (0.1 cm thickness). From the values of force acting on the spring balance, the friction coefficient was calculated using the following equation.

- Calculation of static friction coefficient

- Calculation of dynamic coefficient of friction

Where ms is the static friction coefficient

mK is the coefficient of dynamic friction

As is the read value at initial motion, g

Ak is the average reading value when motion is continued, g

B is the weight of the specimen, g

C is the weight of the sled, g.

division Tensile Strength (MPa) Elongation (%) Modulus at 300% elongation (MPa) Modulus at 500% elongation (MPa) Constant friction coefficient Coefficient of friction Example 1 38.5 550.0 7.3 26.9 0.8 0.7 Example 2 36.7 528.0 8.5 28.1 0.6 0.4 Example 3 35.5 517.0 8.8 29.8 0.4 0.3 Example 4 36.3 580.0 6.1 24.3 1.0 0.9 Example 5 35.8 515.0 9.0 31.4 0.3 0.2 Comparative Example 1 35.6 544.0 6.5 24.8 1.7 1.6 Comparative Example 2 30.0 430.0 10.3 Not measurable 1.5 1.4 Comparative Example 3 36.1 538.0 6.7 25.6 1.4 1.2 Comparative Example 4 28.7 525.0 6.2 23.5 1.2 1.1 Comparative Example 5 26.5 520.1 5.8 23.0 1.4 1.3 Comparative Example 6 32.3 530.3 6.7 25.3 1.5 1.4

As shown in Table 1, when the rubber composition of the present invention was in the range of Synthesis Example 1: Synthesis Example 1: Synthesis Example 5 = 98: 2 to 76: 24 as in Examples 1 to 5, rubber gloves having excellent mechanical properties, It was confirmed that a dip molded article was produced.

On the other hand, when the latex prepared in Synthesis Example 1 was used alone as in Comparative Example 1, it was confirmed that wearability and doping property were poor.

When the latex (Synthesis Example 4) having an average particle diameter of less than 100 nm was contained as in Comparative Example 2, it was confirmed that the physical properties of the glove were lowered and the effect of improving the wearability and doping was insufficient.

In addition, it was confirmed that when the latex having an average particle diameter exceeding 260 nm (Synthesis Example 6) was included as in Comparative Example 3, the effect of improving the wearability and doping was insufficient.

Further, when the latex (Synthesis Example 7) having a low Tg and the average particle size exceeding 160 nm as in Comparative Example 4 and the latex (Synthesis Example 8) having a high Tg and an average particle size of less than 160 nm were included, It was confirmed that the improvement effect of the doping property was insufficient.

When the average particle size of the latex (A) exceeds 160 nm or the average particle size of the latex (B) is less than 160 nm as in Comparative Examples 5 and 6, the physical properties of the glove are greatly deteriorated, .

For reference, it was confirmed that when the latex prepared in Synthesis Example 5 was used alone to produce a dip-molded article, the produced dip-molded article was too hard to measure the physical property to the extent that the film was broken.

Claims (15)

A carboxylic acid-modified nitrile-based copolymer latex (A) having a glass transition temperature of -60 to -10 DEG C and a carboxylic acid-modified styrenic copolymer latex (B) having a glass transition temperature of 30 to 110 DEG C,
Wherein the average particle size of the carboxylic acid-modified nitrile-based copolymer latex (A) is 100 to 160 nm and the average particle size of the carboxylic acid-modified styrene-based copolymer latex (B) is 160 to 260 nm
Copolymer composition. The method according to claim 1,
Wherein the carboxylic acid-modified nitrile-based copolymer and the carboxylic acid-modified styrene-based copolymer have a weight ratio (A: B) of 98: 2 to 76:24
Copolymer composition. The method according to claim 1,
The carboxylic acid-modified nitrile-based copolymer latex having a glass transition temperature of -60 to -10 占 폚 and the carboxylic acid modified styrenic copolymer latex having a glass transition temperature of 30 占 폚 to 110 占 폚, 99% by weight.
Copolymer composition. The method according to claim 1,
Wherein the carboxylic acid-modified nitrile-based copolymer latex comprises a conjugated diene-based monomer, an ethylenically unsaturated nitrile-based monomer, and an ethylenically unsaturated acid monomer
Copolymer composition. The method according to claim 1,
Wherein the carboxylic acid-modified styrene-based copolymer latex comprises a conjugated diene monomer, an aromatic vinyl monomer, an ethylenically unsaturated nitrile monomer and an ethylenic unsaturated acid monomer
Copolymer composition. The method according to claim 4 or 5,
The conjugated diene-based monomer is at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene Or more
Copolymer composition. The method according to claim 4 or 5,
Wherein the ethylenically unsaturated nitrile monomer is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile,? -Chloronitrile and? -Cyanoethyl acrylonitrile
Copolymer composition. The method according to claim 4 or 5,
Wherein the ethylenically unsaturated acid monomer is at least one member selected from the group consisting of an ethylenically unsaturated carboxylic acid monomer, an ethylenically unsaturated sulfonic acid monomer and an ethylenic unsaturated acid anhydride monomer
Copolymer composition. 9. The method of claim 8,
The ethylenic unsaturated acid monomer may be at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate And at least one selected from the group consisting of
Copolymer composition. 6. The method of claim 5,
Wherein the aromatic vinyl-based monomer is at least one selected from the group consisting of styrene and alkylstyrene
Copolymer composition. 11. The method of claim 10,
Wherein the alkyl styrene is alpha methyl styrene
Copolymer composition. 5. The method of claim 4,
(Meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylate, Acrylamide, N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, vinylpyridine, vinylnorbornene, dicyclopentadiene, 1,4-hexadiene, (Meth) acrylate, diethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (Meth) acrylate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl Cyano propyl, (meth Acrylate such as 2-ethyl-6-cyanooyl acrylate, 3-cyanopropyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (Meth) acrylate, and dimethylaminoethyl (meth) acrylate.
Copolymer composition. 6. The method of claim 5,
The carboxylic acid-modified styrenic copolymer latex may be at least one selected from the group consisting of vinyl naphthalene, fluoroethyl vinyl ether, (meth) acrylamide, N-methylol (meth) acrylamide, N- (Meth) acrylates such as methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, vinylpyridine, vinylnorbornene, dicyclopentadiene, (Meth) acrylate, dibutyl maleate, dibutyl maleate, diethyl maleate, di (meth) acrylate, methyl (meth) acrylate, (Meth) acrylate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, cyanomethyl (meth) acrylate, 2-cyanoethyl Meth) acrylate 2-ethyl-6-cy (Meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate and dimethylaminoethyl (Meth) acrylate, and at least one selected from the group consisting of
Copolymer composition. The method according to claim 1,
Wherein the copolymer composition further comprises at least one selected from the group consisting of a vulcanizing agent, an ionic crosslinking agent, a pigment, a filler, a thickener, and a pH adjuster
Copolymer composition. A process for preparing a copolymer composition according to any one of claims 1 to 5 or 10 to 14,
Deep molded products.