WO2010035955A2 - 황 및 가황 촉진제를 포함하지 않는 고무장갑용 라텍스 수지 조성물 및 그 조성물을 이용한 딥 성형물 제조방법 - Google Patents
황 및 가황 촉진제를 포함하지 않는 고무장갑용 라텍스 수지 조성물 및 그 조성물을 이용한 딥 성형물 제조방법 Download PDFInfo
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- WO2010035955A2 WO2010035955A2 PCT/KR2009/004444 KR2009004444W WO2010035955A2 WO 2010035955 A2 WO2010035955 A2 WO 2010035955A2 KR 2009004444 W KR2009004444 W KR 2009004444W WO 2010035955 A2 WO2010035955 A2 WO 2010035955A2
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- ethylenically unsaturated
- monomer
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- monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
- C08L13/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/30—Nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/045—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated conjugated hydrocarbons other than butadiene or isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
- C08J2321/02—Latex
Definitions
- the present invention relates to a latex resin composition for rubber gloves, and more particularly, by using a reactive compound containing two or more reactive groups, by providing a latex resin composition capable of manufacturing rubber gloves without containing sulfur and vulcanization accelerator By omitting the long stirring aging step in the manufacturing process to increase the productivity, it is possible to solve the problems caused by the side effects caused by the conventional sulfur and vulcanization accelerator.
- Rubber gloves are used in a wide range of fields such as household, food, electronics, and medical fields. Rubber gloves made by dip molding natural rubber latex have been used a lot, but the protein contained in natural rubber caused problems for some users because of allergic reactions such as pain or rash. As a result, sulfur and vulcanization accelerators are added to a synthetic rubber latex that does not cause an allergic reaction, for example, a carboxylic acid-modified nitrile copolymer latex such as acrylic acid-acrylonitrile-butadiene copolymer latex. Many gloves made by dip molding the blended latex composition have been used.
- Japanese Patent Laid-Open No. 2006-321955 a method for obtaining a dip molded product without using sulfur and a vulcanization accelerator is used to remove a long stirring aging process by using a latex composition for deep molding containing a conjugated diene rubber latex and an organic peroxide.
- a latex composition for deep molding containing a conjugated diene rubber latex and an organic peroxide.
- the organic peroxide solution is very harmful to the human body and is not safe because of the danger of fire and explosion when heat or impact is applied.
- U.S. Pat.No. 7,345,111 B2 uses a crosslinkable monomer in acrylic emulsion latex to make a glove which does not have a long stirring aging process and does not cause an allergic reaction by sulfur and vulcanization accelerators.
- an acrylic glove has the disadvantage of being too sensitive to temperature.
- the present invention has been made to solve the above problems, by using a crosslinkable reactive compound in the carboxylic acid-modified nitrile copolymer latex polymerization process to increase the productivity by eliminating the long stirring aging process during the glove manufacturing process It is an object of the present invention to provide a latex resin composition for rubber gloves, which does not cause an allergic reaction due to sulfur and a vulcanization accelerator, and which can give a molded article having high oil resistance and high mechanical strength and a soft touch.
- Another object of the present invention is to provide a method for producing a dip molding using the latex resin composition.
- the present invention is to solve the above problems, the conjugated diene monomer, ethylenically unsaturated nitrile monomer, ethylenically unsaturated acid monomer, and ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated nitrile monomer and ethylenically unsaturated acid monomer
- the latex resin composition for rubber gloves comprising a, it provides a latex resin composition for rubber gloves, characterized in that it further comprises a reactive compound containing two or more reactive groups.
- the molecular weight of the reactive compound is characterized in that 250 or more.
- the reactive group is characterized in that selected from the vinyl group, epoxy group and glycidyl group.
- the content of the component is 40 to 90% by weight conjugated diene monomer, 9 to 50% by weight ethylenically unsaturated nitrile monomer, 0.1 to 10% by weight ethylenically unsaturated acid monomer, and ethylenically unsaturated monomer copolymerizable with the monomer. 0.1 to 20% by weight, and 0.1 to 5% by weight of a reactive compound containing two or more reactive groups.
- the conjugated diene monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene or a mixture thereof It is done.
- the ethylenic unsaturated nitrile monomer is characterized in that acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloronitrile, ⁇ -cyano ethyl acrylonitrile or mixtures thereof.
- the ethylenically unsaturated acid monomer is characterized in that the ethylenically unsaturated carboxylic acid monomer, polycarboxylic acid anhydride, ethylenically unsaturated sulfonic acid monomer, ethylenically unsaturated polycarboxylic acid partial ester monomer or a mixture thereof.
- the ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated nitrile monomer and the ethylenically unsaturated acid monomer may be a vinyl aromatic monomer, a fluoroalkyl vinyl ether, an ethylenically unsaturated amide monomer, a vinyl pyridine, a vinyl nolvone, a nonconjugated diene monomer, Ethylenically unsaturated carboxylic acid ester monomers or mixtures thereof.
- the reactive compound containing two or more reactive groups may be selected from the group consisting of 3-alkoxy-2-hydroxypropyl acrylate having an alkoxy group composed of poly (tetramethylene ether) glycol diglycidyl ether, 12 carbon atoms and 13 carbon atoms. It is characterized in that the mixture, propylene glycol polybutylene glycol monoacrylate or a mixture thereof.
- the emulsion polymerization further comprises an emulsifier, a polymerization initiator, a molecular weight regulator or a mixture thereof.
- the present invention comprises the steps of (a) immersing the hand-shaped dip mold in the coagulant solution to attach a coagulant to the surface of the dip mold; (b) immersing the dip molding mold to which the coagulant is attached to the latex resin composition of any one of claims 1 to 9 to form a dip molding layer; And (c) heat treating the dip molding layer formed on the dip molding frame to crosslink the latex resin.
- the coagulant is barium chloride, calcium chloride, magnesium chloride, zinc chloride, aluminum chloride, barium nitrate, calcium nitrate, zinc nitrate, barium acetate, calcium acetate, zinc acetate, calcium sulfate, magnesium sulfate or aluminum sulfate It is characterized by.
- the present invention it is possible to provide a latex resin composition capable of producing rubber gloves without adding sulfur and vulcanization accelerator, and by using the latex resin composition while reducing the side effects caused by conventional sulfur and vulcanization accelerator It can provide rubber gloves with excellent physical properties.
- the present invention relates to a latex resin composition for rubber gloves comprising a conjugated diene monomer, an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, and an ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated nitrile monomer and ethylenically unsaturated acid monomer, It relates to a latex resin composition for rubber gloves, characterized in that it further comprises a reactive compound containing two or more reactive groups.
- the latex resin composition for rubber gloves of the present invention is 40 to 90% by weight conjugated diene monomer, 9 to 50% by weight ethylenically unsaturated nitrile monomer, 0.1 to 10% by weight ethylenically unsaturated acid monomer, other ethylenically unsaturated copolymerizable with such monomers 0.1 to 20% by weight of the monomer and 0.1 to 5% by weight of the reactive compound containing two or more reactive groups.
- conjugated diene monomers examples include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, and the like. , Alone or in combination of two or more thereof. Of these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is particularly preferably used.
- the amount of conjugated diene monomer used is 40 to 90% by weight, preferably 45 to 80% by weight of the monomer mixture. If the amount of conjugated diene monomer is too small, the latex resin molded part becomes hard and the wear feeling worsens. On the contrary, when too much, the oil resistance of a latex resin molded article will worsen and tensile strength will fall.
- the ethylenically unsaturated nitrile monomers include acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloronitrile, ⁇ -cyano ethyl acrylonitrile, and the like. These ethylenically unsaturated nitrile monomers may be used alone or in combination. It can use combining a species or more. Among them, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferably used.
- the amount of ethylenically unsaturated nitrile monomer used is 9 to 50% by weight, preferably 15 to 45% by weight of the monomer mixture. If the amount of the ethylenically unsaturated nitrile monomer is too small, the oil resistance of the latex resin molded article is deteriorated, the tensile strength is lowered, and if too much, the latex resin molded article is hardened and the wear feeling is bad.
- the ethylenically unsaturated acid monomers are ethylenically unsaturated monomers containing acidic groups such as carboxyl groups, sulfonic acid groups, and acid anhydride groups.
- acidic groups such as carboxyl groups, sulfonic acid groups, and acid anhydride groups.
- carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
- Polycarboxylic acid anhydrides such as maleic anhydride and citraconic anhydride
- Ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid
- ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate. It is preferable to use an ethylenic unsaturated carboxylic monomer among these, and methacrylic acid is especially preferable.
- Such ethylenically unsaturated acid monomers may be used in the form of alkali metal salts or ammonium salts.
- An ethylenic unsaturated acid monomer can be used individually or in combination of 2 or more types.
- the amount of ethylenically unsaturated acid monomer used is 0.1 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight of the monomer mixture. If the amount of the ethylenically unsaturated acid monomer is too small, the tensile strength of the latex resin molded article is lowered, and if it is too large, the latex resin molded article becomes hard and the wear feeling is poor.
- Vinyl aromatic monomers such as styrene, alkyl styrene, and vinyl naphthalene
- Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether
- Ethylenically unsaturated amide monomers Vinyl pyridine; Vinyl norbornene; Non-conjugated diene monomers such as dicyclopentadiene and 1,4-hexadiene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, difumaric acid Butyl, diethyl maleate, methoxy methyl (meth) acrylate, ethoxy ethyl (meth) acrylate, methoxy ethoxy ethyl (meth) acrylate, cyano methyl (meth) acrylate, 2-cyano ethyl (meth) acrylate, (Meth) acrylic acid 1-cyano
- ethylenically unsaturated monomers can be used individually or in combination of 2 or more types.
- the amount of ethylenically unsaturated monomer used is 0.1 to 20% by weight of the monomer mixture. If the amount of ethylenically unsaturated monomer is used too much, there is a poor balance between soft fit and tensile strength.
- the reactive compound containing two or more reactive groups is a relatively large molecular weight reactive compound having two or more reactive groups such as vinyl, epoxy and glycidyl groups, and it is possible to obtain a latex resin molded article without using sulfur and a vulcanization accelerator. Let's do it.
- reactive compounds include poly (tetramethylene ether) glycol diglycidyl ether (molecular weight about 860), 3-alkoxy-2-hydroxypropyl acrylate having an alkoxy group consisting of 12 carbon atoms and 13 carbon atoms A mixture (molecular weight about 330) and propylene glycol polybutylene glycol monoacrylate (molecular weight about 562); These compounds can be used individually or in combination of 2 or more types.
- poly (tetramethylene ether) glycol diglycidyl ether for example PTMG-DEP, a synthetic resin modulator of Yokaichi Chemical Co., Japan
- PTMG-DEP a synthetic resin modulator of Yokaichi Chemical Co., Japan
- Mixtures of 3-alkoxy-2-hydroxypropyl acrylates having an alkoxy group consisting of 12 carbon atoms and 13 carbon atoms can be used, for example TD-EXA, a synthetic resin regulator from Yokaichi.
- propylene glycol polybutylene glycol monoacrylate for example BLEMMER 10APB-500B, which is a synthetic resin regulator of NOF, can be used.
- the amount of the reactive compound is preferably used 0.1 to 5% by weight of the total latex resin composition, more preferably 0.5 to 3%. If the amount of the reactive compound is less than 0.1% by weight, the tensile strength of the dip molded article is lowered, and if it is greater than 5% by weight, the feel and fit are poor.
- the molecular weight of the reactive compound is used to be 250 or more, if the molecular weight is less than 250, the feel, fit and tensile strength of the dip molded product is inferior.
- the latex resin composition of the present invention can be prepared by emulsion polymerization of a mixture of the above monomers, and the emulsion polymerization method can be used a conventional emulsion polymerization method.
- the addition method of a monomer mixture is not specifically limited, The method of adding a monomer mixture to a polymerization reactor at once, the method of continuously adding a monomer mixture to a polymerization reactor, a part of monomer mixture is thrown into a polymerization reactor, and the remaining monomers are put into a polymerization reactor. You may use any of the methods of continuously supplying to a.
- polymerization temperature is not specifically limited, Usually, it is 10-90 degreeC, Preferably it is 25-75 degreeC.
- the emulsion polymerization may include materials commonly used, such as emulsifiers, polymerization initiators, molecular weight regulators.
- anionic surfactant a nonionic surfactant, cationic surfactant, an amphoteric surfactant, etc.
- anionic surfactants such as alkylbenzene sulfonates, aliphatic sulfonates, sulfuric acid ester salts of higher alcohols, ⁇ -olefin sulfonate salts, alkyl ether sulfuric acid ester salts and the like can be preferably used.
- the amount of the emulsifier to be used is preferably 0.3 to 10 parts by weight, more preferably 0.8 to 8 parts by weight based on 100 parts by weight of all monomers.
- a radical initiator can be used preferably.
- inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentanehydro peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutylate; And nitrogen compounds such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile and azobis is
- polymerization initiators may be used alone or in combination of two or more thereof.
- radical initiators inorganic or organic peroxides are preferably used, inorganic peroxides are more preferred, and persulfates may be particularly preferably used.
- the amount of the polymerization initiator to be used is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 1.5 parts by weight based on 100 parts by weight of all monomers.
- molecular weight regulator such as (alpha) -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; Sulfur-containing compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, diisopropylchianthogen disulfide, and the like.
- molecular weight modifiers may be used alone or in combination of two or more thereof.
- mercaptans are preferable, and t-dodecyl mercaptan can be used more preferably.
- usage-amount of a molecular weight modifier changes with the kind, Preferably it is 0.1-0.9 weight part, More preferably, it is 0.2-0.7 weight part with respect to 100 weight part of all monomers.
- pigments such as titanium oxide, fillers such as silica, thickeners, chelating agents, dispersants, pH adjusting agents, deoxygenating agents, particle size adjusting agents, antioxidants, oxygen scavenger Subsidiary materials, such as these, can be used.
- the unreacted monomer is removed and the solid content concentration or pH is adjusted to obtain the latex resin of the present invention.
- a conventional method can be used, and examples thereof include a direct dipping method, an anode adhesion dipping method, a Teague adhesion dipping method, and the like. Can be. Among them, an anode adhesion dipping method is preferable because of the advantage that a dip molded article having a uniform thickness can be easily obtained.
- coagulants include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetates such as barium acetate, calcium acetate and zinc acetate; Sulfates such as calcium sulfate, magnesium sulfate and aluminum sulfate. Of these, calcium chloride and calcium nitrate are preferred.
- the coagulant solution is a solution in which such coagulant is dissolved in water, alcohol or a mixture thereof.
- concentration of coagulant in the coagulant solution is usually 5 to 75% by weight, preferably 15 to 55% by weight.
- the dip molding machine to which a coagulant is stuck is immersed in the latex composition for dip molding made from the latex resin composition of the present invention, and then the dip molding machine is taken out to form a dip molding layer in the dip molding machine.
- the water component first evaporates and curing through crosslinking is performed.
- the dip molding layer crosslinked by heat treatment is peeled off from the dip mold to obtain a dip molding.
- a 5% potassium hydroxide solution and an appropriate amount of secondary distilled water were added to the latex to obtain a dip molding composition having a solid content concentration of 30% and pH 9.5.
- a coagulant solution was prepared by mixing 22 parts by weight calcium nitrate, 69.5 parts by weight methanol, 8 parts by weight calcium carbonate, and 0.5 parts by weight wetting agent (Teric 320 produced by Huntsman Corporation, Australia).
- the hand-shaped ceramic mold was immersed in this solution for 1 minute, taken out, and dried at 70 ° C. for 3 minutes to apply a coagulant to the hand-shaped mold.
- the mold to which the coagulant was applied was immersed in the dip molding composition for 1 minute, pulled up, dried at 70 ° C. for 1 minute, and leached for 3 minutes in water or hot water.
- the mold was dried at 70 ° C. for 3 minutes and crosslinked at 125 ° C. for 20 minutes.
- the cross-linked dip molding layer was peeled off from the hand-shaped mold to obtain a dip molding in the form of a glove.
- the physical properties of this dip molding are shown in Table 1.
- the physical property of the obtained dip molded product is evaluated by the following method.
- a dumbbell-shaped test piece was produced from the obtained dip molded product in accordance with ASTM D-412. Subsequently, the specimen was pulled at an elongation rate of 500 mm / min, and the stress at 300% elongation, the tensile strength at break and the elongation at break were measured.
- M100 (6) to M100 (0) is calculated as a percentage and this value is defined as the stress retention. If the stress retention is 50% or more, the fit is excellent.
- the glove condition of Table 1 is the result of comprehensive consideration of the basic properties of the glove, whether pinholes are formed, and stickiness.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Gloves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Moulding By Coating Moulds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Tensile Strength(MPa) | Elongation(%) | Modulus at 300% (MPa) | Tensile strength retention(%) | 장갑 상태 | |
실시예 1 | 21.7 | 669 | 3.60 | 60 | 양호 |
실시예 2 | 24.8 | 643 | 3.60 | 67 | 양호 |
실시예 3 | 19.3 | 685 | 4.96 | 62 | 양호 |
실시예 4 | 26.5 | 626 | 3.52 | 68 | 양호 |
비교예 1 | 5.6 | 730 | 2.39 | 40 | 나쁨 |
비교예 2 | 9.8 | 711 | 2.60 | 43 | 보통 |
Claims (12)
- 공액 디엔 단량체, 에틸렌성 불포화 니트릴 단량체, 에틸렌성 불포화산 단량체, 및 상기 에틸렌성 불포화 니트릴 단량체 및 에틸렌성 불포화산 단량체와 공중합 가능한 에틸렌성 불포화 단량체를 포함하는 고무장갑용 라텍스 수지 조성물에 있어서, 반응성기를 두개 이상 포함하는 반응성 화합물을 더 포함하는 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제 1 항에 있어서,상기 반응성 화합물의 분자량은 250이상인 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제 1 항에 있어서,상기 반응성기는 비닐기, 에폭시기 및 글리시딜기 중에서 선택되는 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제 1 항에 있어서,상기 구성성분의 함량은,공액 디엔 단량체 40 ~ 90중량%, 에틸렌성 불포화 니트릴 단량체 9 ~ 50중량%, 에틸렌성 불포화산 단량체 0.1 ~ 10중량%, 및 상기 단량체와 공중합 가능한 에틸렌성 불포화 단량체 0.1 ~ 20중량%, 및 반응성기를 두개 이상 포함하는 반응성 화합물 0.1 ~ 5중량% 인 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제1항에 있어서,상기 공액 디엔 단량체는 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 2-에틸-1,3-부타디엔, 1,3-펜타디엔, 이소프렌 또는 이들의 혼합물인 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제1항에 있어서,상기 에틸렌성 불포화 니트릴 단량체는 아크릴로니트릴, 메타크릴로니트릴, 후마로니트릴, α-클로로니트릴, α-시아노 에틸 아크릴로니트릴 또는 이들의 혼합물인 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제1항에 있어서,상기 에틸렌성 불포화산 단량체는 에틸렌성 불포화 카르본산 단량체, 폴리 카르본산 무수물, 에틸렌성 불포화 술폰산 단량체, 에틸렌성 불포화 폴리 카르본산 부분 에스테르(partial ester) 단량체 또는 이들의 혼합물인 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제1항에 있어서,상기 에틸렌성 불포화 니트릴 단량체 및 에틸렌성 불포화산 단량체와 공중합 가능한 에틸렌성 불포화 단량체로서는 비닐 방향족 단량체, 플로로알킬비닐 에테르, 에틸렌성 불포화 아미드 단량체, 비닐 피리딘, 비닐 놀보넨, 비공액 디엔 단량체, 에틸렌성 불포화 카르본산 에스테르 단량체 또는 이들의 혼합물인 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제1항에 있어서,상기 반응성기를 두개 이상 포함하는 반응성 화합물은 폴리(테트라메틸렌에테르) 글리콜 디글리시딜 에테르, 12개의 탄소 원자 및13개의 탄소 원자로 구성된 알콕시기를 가지는 3-알콕시-2-하이드록시프로필 아크릴레이트의 혼합물, 프로필렌 글리콜 폴리부티렌 글리콜 모노아크릴레이트 또는 이들의 혼합물인 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- 제 1항에 있어서,상기 단량체들의 유화중합시, 유화제, 중합 개시제, 분자량 조절제 또는 이들의 혼합물을 더 포함하여 유화중합하는 것을 특징으로 하는 고무장갑용 라텍스 수지 조성물.
- (a) 손 모양의 딥 성형틀을 응고제 용액에 담가 딥 성형틀의 표면에 응고제를 부착시키는 단계;(b) 상기 응고제가 부착된 딥 성형틀을 제1항 내지 제 10항 중 어느 한 항의 라텍스 수지 조성물에 침지하여 딥 성형층을 형성시키는 단계; 및(c) 상기 딥 성형틀에 형성된 딥 성형층을 가열 처리하여 라텍스 수지를 가교시키는 단계를 포함하는 딥 성형물을 제조하는 방법.
- 제11항에 있어서,상기 응고제는 바륨 클로라이드, 칼슘 클로라이드, 마그네슘 클로라이드, 징크 클로라이드, 알루미늄 클로라이드, 바륨 나이트레이트, 칼슘 나이트레이트, 징크 나이트레이트, 바륨 아세테이트, 칼슘 아세테이트, 징크 아세테이트, 칼슘 설페이트, 마그네슘 설페이트 또는 알루미늄 설페이트인 것을 특징으로 하는 딥 성형물을 제조하는 방법.
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US13/121,151 US8975351B2 (en) | 2008-09-26 | 2009-08-10 | Latex resin composition for rubber gloves without sulfur and vulcanization acceleator and method of manufacturing dip-formed article using the composition |
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CN103450398A (zh) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | 一种乳液聚合法制备快速硫化丁腈橡胶的方法 |
CN103450398B (zh) * | 2012-06-01 | 2015-08-12 | 中国石油天然气股份有限公司 | 一种乳液聚合法制备快速硫化丁腈橡胶的方法 |
WO2019192312A1 (zh) * | 2018-04-04 | 2019-10-10 | 汇鸿 (南通) 安全用品有限公司 | 一种浸胶手套浸胶后的表面处理方法 |
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Publication number | Publication date |
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US8975351B2 (en) | 2015-03-10 |
WO2010035955A3 (ko) | 2010-06-24 |
US20110229646A1 (en) | 2011-09-22 |
MY153076A (en) | 2014-12-31 |
KR101126583B1 (ko) | 2012-03-29 |
KR20100035191A (ko) | 2010-04-05 |
CN102159604A (zh) | 2011-08-17 |
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