WO2013077585A1 - 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품 - Google Patents
딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품 Download PDFInfo
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- WO2013077585A1 WO2013077585A1 PCT/KR2012/009540 KR2012009540W WO2013077585A1 WO 2013077585 A1 WO2013077585 A1 WO 2013077585A1 KR 2012009540 W KR2012009540 W KR 2012009540W WO 2013077585 A1 WO2013077585 A1 WO 2013077585A1
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- 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
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- 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
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- 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
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1386—Natural or synthetic rubber or rubber-like compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a carboxylic acid-modified nitrile-based copolymer latex for dip molding, a dip molding latex composition comprising the same, and a molded article prepared therefrom. More specifically, the glass transition temperature is -50 ° C to -15 ° C and the average.
- a carboxylic acid-modified nitrile copolymer latex having a particle diameter of 90 nm or more and a carboxylic acid-modified styrene copolymer latex having a glass transition temperature of 80 ° C. or more and having an average particle diameter of less than 90 nm a molded article having excellent tensile strength can be prepared by mixing and using the same.
- the present invention relates to a carboxylic acid-modified nitrile copolymer latex, a latex composition for deep molding including the same, and a molded article prepared therefrom.
- an object of the present invention is to provide a carboxylic acid-modified nitrile copolymer latex capable of producing a molded article having a higher tensile strength than the conventional gloves and excellent wear feeling.
- Another object of the present invention is to provide a latex composition for dip molding comprising the carboxylic acid-modified nitrile copolymer latex and molded articles prepared therefrom.
- the present invention is 85 to 97% by weight of a carboxylic acid-modified nitrile copolymer latex having a glass transition temperature of -50 °C to -15 °C and an average particle diameter of 90nm or more and the glass transition temperature of 80 °C or more and average
- a carboxylic acid-modified nitrile copolymer latex having a glass transition temperature of -50 °C to -15 °C and an average particle diameter of 90nm or more and the glass transition temperature of 80 °C or more and average
- Carbonic acid-modified nitrile-based copolymer latex of the present invention for achieving the above object is a carboxylic acid-modified nitrile copolymer having a glass transition temperature of -50 °C to -15 °C, the average particle diameter of 90nm or more and 200nm or less.
- Examples of preferred embodiments of the present invention include 85 to 97% by weight of a carboxylic acid-modified nitrile copolymer latex (hereinafter referred to as "latex A”) having a glass transition temperature of -50 ° C to -15 ° C and an average particle diameter of 90 nm to 200 nm. It is prepared by mixing 3 to 15% by weight of a carboxylic acid-modified styrenic copolymer latex (hereinafter referred to as "latex B”) having a glass transition temperature of 80 ° C to 105 ° C and an average particle diameter of 15 nm or more and less than 90 nm.
- latex A carboxylic acid-modified nitrile copolymer latex
- latex B carboxylic acid-modified styrenic copolymer latex
- the glass transition temperature of the latex A is less than -50 ° C, the tensile strength is significantly lowered.
- the latex A is higher than -15 ° C, cracks in the dip molded product are not preferable. If the average particle diameter is less than 90 nm, the viscosity of the latex is increased and the dip molded article is transparent, which is not preferable.
- the average particle diameter of the latex A exceeds 200 nm, the time is increased during manufacture of the latex and the productivity is lowered, and the tensile strength after the dip molded article is manufactured is not preferable.
- the glass transition temperature of the latex B is lower than 80 ° C.
- the tensile strength improvement of the dip molded article is lowered.
- the average particle diameter is 90 nm or more, the tensile strength improvement of a dip molded article falls, and a crack of a dip molded article is easy to produce.
- the average particle diameter of the latex B is less than 15 nm, it is difficult to manufacture by emulsion polymerization, and the amount of emulsifier is increased during manufacture, which is not preferable because the tensile strength and elongation of the dip molded product are lowered.
- the latex composition for dip molding of the present invention may include the latex A and latex B in a ratio of 97: 3 to 85:15, respectively.
- the latex A is more than 97% and the latex B is less than 3%, the tensile strength improvement is small, the latex A is less than 85% and the elongation is greater than 15%. It lowers and tensile strength falls, and it is unpreferable.
- a latex composition for dip molding comprising a carboxylic acid-modified nitrile copolymer latex for achieving another object of the present invention is a vulcanizing agent, ionic crosslinking agent, pigment, filler, thickener and and at least one additive selected from the group consisting of pH regulators.
- a dip molded article for achieving another object of the present invention is characterized by being obtained by dip molding the composition.
- latex is prepared by adding an emulsifier, a polymerization initiator, and a molecular weight regulator to each monomer constituting the latex A, and latex is prepared by adding an emulsifier, a polymerization initiator and a molecular weight regulator to each monomer constituting the latex B.
- a carboxylic acid nitrile-based latex After mixing to prepare a carboxylic acid nitrile-based latex, it is included in a dip molding latex composition to dip molding to produce a final product.
- latex A latex A
- latex B mixed carboxylic acid-modified nitrile copolymer latex and latex composition including the latex used to obtain the dip molded article of the present invention
- Latex A according to the present invention is prepared by emulsion polymerization by adding an emulsifier, a polymerization initiator, a molecular weight regulator and other additives to each monomer constituting the carboxylic acid-modified nitrile copolymer.
- the monomer constituting the carboxylic acid-modified nitrile copolymer is composed of a conjugated diene monomer, an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, and a copolymerizable unsaturated ethylenic monomer.
- the conjugated diene monomer is included 40 to 89% by weight, specifically 45 to 80% by weight, most specifically 50 to 78% by weight of the total monomer constituting the carboxylic acid-modified nitrile copolymer. If the conjugated diene monomer content is less than 40% by weight, the dip molded product becomes hard and the wear is poor. If the conjugated diene monomer content is more than 90% by weight, the oil resistance of the dip molded product is deteriorated and the tensile strength is lowered.
- the ethylenically unsaturated nitrile monomer is acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloronitrile and ⁇ -cyano ethyl acryl At least one selected from the group consisting of ronitrile, of which acrylonitrile and methacrylonitrile are preferred, and acrylonitrile is most preferably used.
- the ethylenically unsaturated nitrile monomer is contained in 10 to 50% by weight, specifically 15 to 45% by weight, most specifically 20 to 40% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer. If the content of the ethylenically unsaturated nitrile monomer is less than 10% by weight, the oil resistance of the dip molded product is poor, the tensile strength is lowered, and if it is more than 50% by weight, the dip molded product is hard and the wear feeling is poor.
- the ethylenically unsaturated acid monomer is an ethylenically unsaturated monomer containing at least one acidic group selected from the group consisting of carboxyl group, sulfonic acid group and acid anhydride group
- 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.
- methacrylic acid is particularly preferable
- the ethylenically unsaturated acid monomer is included in 0.1 to 10% by weight, specifically 0.5 to 9% by weight, more specifically 1 to 8% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer. If the content of the ethylenically unsaturated acid monomer is less than 0.1% by weight, the dip molded article is lowered in tensile strength. If the content of the ethylenically unsaturated acid monomer is more than 10% by weight, the dip molded article is hardened and wear is poor.
- the carboxylic acid-modified nitrile copolymer according to the present invention may optionally further include other ethylenically unsaturated monomers copolymerizable with the ethylenically unsaturated nitrile monomer and the ethylenically unsaturated acid monomer, specifically, styrene, alkyl styrene, And vinyl aromatic monomers selected from the group consisting of vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (Meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxy methyl (meth) acrylamide, and N-propoxy methyl (meth) acrylamide Ethylenically unsaturated amide monomers selected from the group consisting of; Non-conjugated diene monomers such as vinyl pyridine, vinyl norbornene,
- the amount of the ethylenically unsaturated nitrile monomer and other ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated acid monomer may be used within 20% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer, and more than 20% by weight. There is a poor balance between soft fit and tensile strength.
- the carboxylic acid-modified nitrile copolymer latex of the present invention can be prepared by emulsion polymerization by adding an emulsifier, a polymerization initiator, a molecular weight regulator, etc. to the monomers constituting the carboxylic acid-modified nitrile copolymer.
- anionic surfactant a nonionic surfactant, cationic surfactant, an amphoteric surfactant, etc.
- anionic surfactants selected from the group consisting of alkylbenzene sulfonates, aliphatic sulfonates, sulfuric acid ester salts of higher alcohols, ⁇ -olefin sulfonate salts, and alkyl ether sulfuric acid ester salts can be particularly preferably used.
- the amount of the emulsifier is 0.3 to 10 parts by weight, more specifically 0.8 to 8 parts by weight, most specifically 1.5 to 6 parts by weight based on 100 parts by weight of the monomer constituting the carboxylic acid-modified nitrile copolymer. Used.
- the amount of the emulsifier is less than 0.3 parts by weight, the stability during the polymerization is lowered, if it exceeds 10 parts by weight, there is a problem that the production of dip molded article is difficult to increase the foaming.
- a radical initiator can be used specifically ,.
- inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, 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; Azobis isobutyronitrile; Azobis-2,4-dimethylvaleronitrile; Azobiscyclohexane carbonitrile; And azobis iso butyric
- the amount of the polymerization initiator is less than 0.01 parts by weight, the polymerization rate is lowered, making it difficult to produce the final product. If it exceeds 2 parts by weight, the polymerization rate is too fast to control the polymerization.
- the activating agent may be selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate and sodium sulfite.
- molecular weight modifier such as (alpha) -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; And sulfur compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylquixanthogen disulfide.
- 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, Specifically, 0.1-2.0 weight part, More specifically, 0.2-1.5 weight part, most, with respect to 100 weight part of all monomers which comprise the said carboxylic acid modified nitrile copolymer. Specifically, it is 0.3-1.0 weight part.
- the amount of the molecular weight regulator is less than 0.1 part by weight, the physical properties of the dip molded article is significantly lowered, and if it exceeds 2 parts by weight, there is a problem that the polymerization stability is lowered.
- additives such as chelating agent, dispersing agent, pH adjusting agent, deoxygenating agent, particle size adjusting agent, anti-aging agent, oxygen scavenger and the like can be added.
- the method of adding the monomer mixture constituting the carboxylic acid-modified nitrile copolymer is not particularly limited, the method of introducing the monomer mixture into the polymerization reactor at once, the method of continuously introducing the monomer mixture into the polymerization reactor, and a part of the monomer mixture Any method of putting into a polymerization reactor and continuously supplying the remaining monomer to a polymerization reactor may be used.
- the polymerization temperature at the time of the said emulsion polymerization is not specifically limited, Usually, it is 10-90 degreeC, specifically, it is 25-75 degreeC.
- the conversion rate at the time of stopping a polymerization reaction is specifically 90% or more, More specifically, 93% or more.
- the carboxylic acid-modified nitrile copolymer latex can be obtained by removing the unreacted monomer and adjusting the solid content concentration and pH.
- the glass transition temperature can be adjusted according to the content of the conjugated diene monomer, and the average particle diameter can be adjusted according to the type or content of the emulsifier.
- the latex glass transition temperature was measured by differential scanning calorimetry, and the average particle diameter was measured by a laser scattering analyzer (Nicomp).
- Latex B according to the present invention is prepared by emulsion polymerization by adding an emulsifier, a polymerization initiator, a molecular weight regulator and other additives to each monomer constituting the carboxylic acid-modified styrene-based copolymer.
- the monomer constituting the carboxylic acid-modified styrene copolymer is an aromatic vinyl monomer; Ethylenically unsaturated nitrile monomers; Ethylenically unsaturated acid monomers; It consists of copolymerizable ethylenically unsaturated monomers.
- styrene As another monomer constituting the carboxylic acid-modified styrenic copolymer according to the present invention, for example, at least one selected from the group consisting of styrene and alphamethylstyrene, for example, of the aromatic vinyl monomer, styrene is most preferred. Used.
- the aromatic vinyl monomer is included in 80 to 99% by weight, specifically 82 to 98% by weight, most specifically 85 to 96% by weight of the total monomers constituting the carboxylic acid-modified styrene-based copolymer. If the aromatic vinyl monomer content is less than 80% by weight, the tensile strength during dip molding is lowered, and if it is more than 99% by weight, the polymerization stability is lowered.
- the ethylenically unsaturated nitrile monomer is acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloronitrile and ⁇ -cyano ethyl acryl At least one selected from the group consisting of ronitrile, of which acrylonitrile and methacrylonitrile are preferred, and acrylonitrile is most preferably used.
- the ethylenic unsaturated nitrile monomer is included in 1-20% by weight, specifically 2-18% by weight, most specifically 4-15% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer. If the ethylenic unsaturated nitrile monomer content is less than 1% by weight, the compatibility with the carboxylic acid nitrile copolymer is lowered, and if it is more than 20% by weight, the polymerization stability is lowered.
- the ethylenically unsaturated acid monomer is an ethylenically unsaturated monomer containing at least one acidic group selected from the group consisting of carboxyl groups, sulfonic acid groups, and acid anhydride groups.
- ethylenically unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid
- Polycarboxylic anhydrides such as maleic anhydride and citraconic anhydride
- Ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid
- One or more selected from the group consisting of ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxy propyl propyl may be used, but is not limited thereto.
- the ethylenically unsaturated acid monomer is included in 0.1 to 10% by weight, specifically 0.5 to 9% by weight, more specifically 1 to 8% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer. If the content of the ethylenically unsaturated acid monomer is less than 0.1% by weight, the polymerization stability is lowered. If the content of the ethylenically unsaturated acid monomer is more than 10% by weight, the dip molded product becomes hard and the wear feeling is poor.
- the carboxylic acid-modified styrenic copolymers according to the present invention may further comprise optionally ethylenically unsaturated nitrile monomers and other ethylenically unsaturated monomers copolymerizable with ethylenically unsaturated acid monomers.
- the amount of the ethylenically unsaturated nitrile monomer and other ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated acid monomer may be used within 5% by weight of the total monomers constituting the carboxylic acid-modified nitrile copolymer, and more than 5% by weight. There is a poor balance between soft fit and tensile strength.
- the carboxylic acid-modified nitrile copolymer latex of the present invention can be prepared by emulsion polymerization by adding an emulsifier, a polymerization initiator, a molecular weight regulator, etc. to the monomers constituting the carboxylic acid-modified nitrile copolymer.
- anionic surfactant a nonionic surfactant, cationic surfactant, an amphoteric surfactant, etc.
- anionic surfactants selected from the group consisting of alkylbenzene sulfonates, aliphatic sulfonates, sulfuric acid ester salts of higher alcohols, ⁇ -olefin sulfonate salts, and alkyl ether sulfuric acid ester salts can be particularly preferably used.
- the amount of the emulsifier is 0.3 to 30 parts by weight, more specifically 0.8 to 25 parts by weight, most specifically 1.5 to 20 parts by weight based on 100 parts by weight of the monomer constituting the carboxylic acid-modified nitrile copolymer. Used.
- the amount of the emulsifier is less than 0.3 parts by weight, the stability during the polymerization is lowered, if it exceeds 30 parts by weight there is a problem that the production of dip molded article is difficult to increase the foaming.
- a radical initiator can be used specifically ,.
- inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, 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; At least one selected from the group consisting of azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexane carbonitrile
- the amount of the polymerization initiator is less than 0.01 parts by weight, the polymerization rate is lowered, making it difficult to produce the final product. If it exceeds 2 parts by weight, the polymerization rate is too fast to control the polymerization.
- the activating agent may be selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate and sodium sulfite.
- molecular weight modifier such as (alpha) -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; And sulfur compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylquixanthogen disulfide.
- 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, Specifically, 0.1-2.0 weight part, More specifically, 0.2-1.5 weight part, most, with respect to 100 weight part of all monomers which comprise the said carboxylic acid modified nitrile copolymer. Specifically, it is 0.3-1.0 weight part.
- the amount of the molecular weight regulator is less than 0.1 part by weight, the physical properties of the dip molded article is significantly lowered, and if it exceeds 2 parts by weight, there is a problem that the polymerization stability is lowered.
- additives such as chelating agent, dispersing agent, pH adjusting agent, deoxygenating agent, particle size adjusting agent, anti-aging agent, oxygen scavenger and the like can be added.
- the method of adding the monomer mixture constituting the carboxylic acid-modified nitrile copolymer is not particularly limited, the method of introducing the monomer mixture into the polymerization reactor at once, the method of continuously introducing the monomer mixture into the polymerization reactor, and a part of the monomer mixture Any method of putting into a polymerization reactor and continuously supplying the remaining monomer to a polymerization reactor may be used.
- the polymerization temperature at the time of the said emulsion polymerization is not specifically limited, Usually, it is 10-95 degreeC, specifically, it is 25-95 degreeC.
- the conversion rate at the time of stopping the polymerization reaction is specifically 95% or more, and more specifically 98% or more.
- the carboxylic acid-modified nitrile copolymer latex can be obtained by removing the unreacted monomer and adjusting the solid content concentration and pH.
- the glass transition temperature can be adjusted according to the content of the conjugated diene monomer, and the average particle diameter can be adjusted according to the type or content of the emulsifier.
- the latex glass transition temperature was measured by differential scanning calorimetry, and the average particle diameter was measured by a laser scattering analyzer (Nicomp).
- a vulcanizing agent, an ionic crosslinking agent, a pigment, a filler, a thickener to the carboxylic acid-modified nitrile copolymer latex of the present invention prepared by mixing 85 to 97% by weight of latex A and 3 to 15% by weight of latex B obtained by the above method. And at least one additive selected from the group consisting of a pH adjusting agent, to prepare a latex composition for dip molding.
- a latex composition for dip molding is prepared including general additives used in dip molding compositions such as ionic crosslinkers, pigments such as titanium oxide, fillers such as silica, thickeners, and pH adjusting agents such as ammonia or alkali hydroxides.
- general additives used in dip molding compositions such as ionic crosslinkers, pigments such as titanium oxide, fillers such as silica, thickeners, and pH adjusting agents such as ammonia or alkali hydroxides.
- the carboxylic acid-modified nitrile copolymer latex in the composition is 80 to 99% by weight, specifically 85 to 98% by weight, most specifically 88 to 97% by weight of one of the dip molded article of the present invention Phosphorus gloves are preferred in terms of physical properties.
- Solid content concentration of the latex composition for dip molding of this invention is 10 to 40 weight% specifically, 15-35 weight% more specifically, 18-33 weight% most specifically.
- PH of the latex composition for dip molding of this invention is 8.0-12, More specifically, it is 9-11, Most specifically, it is 9.3-10.5.
- a conventional method can be used, and examples thereof include a direct dipping method, an anode adhesion dipping method, and a Teague adhesion dipping method.
- 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, aluminum chloride and the like; 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. The concentration of coagulant in the coagulant solution is usually 5 to 75% by weight, specifically 15 to 55% by weight.
- the dip molding mold 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 mold is taken out to form a dip molding layer on the dip molding mold.
- the water component evaporates first and curing through crosslinking is performed. Subsequently, the dip molding layer crosslinked by heat treatment is peeled off from the dip mold to obtain a dip molded product.
- 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 a stretching speed of 500 mm / min using a UTM (Universal Testing Machine), the tensile strength and elongation at break were measured, and the touch was measured by the stress when the elongation was 300%.
- UTM Universal Testing Machine
- the dip mold of the hand shape is immersed in the coagulant solution to attach the coagulant to the surface of the dip mold.
- 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; 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.
- the concentration of coagulant in the coagulant solution is usually 5 to 75% by weight, specifically 15 to 55% by weight, most specifically 18 to 40% by weight.
- the dip mold to which the coagulant is attached is immersed in the latex composition for dip molding made of the carboxylic acid-modified nitrile copolymer latex of the present invention, and the dip mold is taken out to form a dip mold layer in the dip mold.
- the dip molding layer formed on the dip mold is subjected to heat treatment to crosslink the carboxylic acid-modified nitrile copolymer latex.
- the water component first evaporates and vulcanization through crosslinking is performed.
- the dip molding layer crosslinked by heat treatment is peeled off from the dip mold to obtain a dip molded product.
- the process according to the invention can be used for any latex article which can be produced by technically known dip molding methods. Specifically, it can be applied to dip molded latex articles selected from health care products such as surgical gloves, inspection gloves, condoms, catheters or various kinds of industrial and household gloves.
- Agitator, thermometer, cooler, nitrogen inlet, 10L high pressure reactor equipped with a monomer, emulsifier, and polymerization initiator can be continuously added with nitrogen, and then acrylonitrile 25% by weight, 1,4-butadiene 70 2.5 weight part of sodium alkyl benzene sulfonates, 0.5 weight part of t-dodecyl mercaptans, and 140 weight part of ion-exchange water were added with respect to 100 weight part of monomer mixtures of 5 weight% of methacrylic acid, and it heated up to 40 degreeC.
- the glass transition temperature is -40 °C
- the average particle diameter is shown to 130nm
- the latex prepared by the above is called "latex-A”.
- a stirrer, a thermometer, a cooler, an inlet for nitrogen gas and a 10L high pressure reactor equipped with a monomer, an emulsifier, and a polymerization initiator were continuously replaced with nitrogen, followed by 82 wt% of styrene and 2 wt% of acrylonitrile.
- the glass transition temperature is 100 ° C. and the average particle diameter is 42 nm.
- the latex prepared by the above is called 'latex-B'.
- Latex was prepared by mixing Latex-A and Latex-B at 9: 1.
- a 3% 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 concentration of 25% and a pH of 10.0.
- a coagulant solution was prepared by mixing 22 parts by weight calcium nitrate, 69.5 parts by weight distilled water, 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 80 ° 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 80 ° C for 1 minute, and then immersed in water or hot water for 3 minutes.
- the mold was dried at 80 ° C. for 3 minutes and crosslinked at 130 ° C. for 20 minutes.
- the crosslinked dip molding layer was peeled off from the hand-shaped mold to obtain a dip molded article in the form of a glove.
- the physical properties of this dip molded article are shown in Table 1.
- Agitator, thermometer, cooler, nitrogen gas inlet and 10L high pressure reactor equipped with a monomer, emulsifier, and polymerization initiator can be continuously added with nitrogen, and then acrylonitrile 35% by weight, 1,4-butadiene 60 3 parts by weight of sodium alkyl benzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan and 140 parts by weight of ion-exchanged water were added to 100 parts by weight of the monomer mixture of 5% by weight and methacrylic acid, and the temperature was raised to 40 ° C.
- latex-C the latex prepared by the above is referred to as "latex-C”.
- a stirrer, a thermometer, a cooler, a nitrogen inlet and a 10L high pressure reactor equipped with a monomer, an emulsifier, and a polymerization initiator were continuously replaced with nitrogen, followed by 94 wt% of styrene and 2 wt% of acrylonitrile.
- %, 6 parts by weight of sodium alkyl benzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan and 300 parts by weight of ion-exchanged water were added to 100 parts by weight of the monomer mixture of 4% by weight acrylic acid, and the temperature was raised to 55 ° C.
- the glass transition temperature is 105 ° C. and the average particle diameter is 67 nm.
- the latex prepared by the above is called 'latex-D'.
- Latex was prepared by mixing Latex-C and Latex-D at 9: 1.
- Example 1 In the same manner as in Example 1, a dip molded article in the form of a glove was manufactured, and the physical properties thereof are shown in Table 1.
- Example 1 Except for mixing latex-A and latex-B in Example 1 was prepared in the same manner as in Example 1, except that the glove-shaped dip molded article was prepared, the physical properties are shown in Table 1.
- Example 1 Except for mixing the latex-A and latex-B in Example 1 was prepared in the same manner as in Example 1, the glove-shaped dip molded article was prepared, the physical properties are shown in Table 1.
- Example 1 Except for mixing the latex-A and latex-D in Example 1 in 9: 1, a dip molded article in the form of a glove was prepared in the same manner as in Example 1, the physical properties are shown in Table 1.
- Example 1 Except for mixing the latex-C and latex-B in Example 1 in 9: 1, a dip molded article in the form of a glove was prepared in the same manner as in Example 1, the physical properties are shown in Table 1.
- Example 1 Except that the latex-A alone in Example 1 was prepared in the same manner as in Example 1 glove-shaped dip molded article, the physical properties are shown in Table 1.
- Example 1 Except that the latex-C alone in Example 1 was prepared in the same manner as in Example 1 glove-shaped dip molded article, the physical properties are shown in Table 1.
- Example 1 8 Except for mixing the latex-A and latex-B in Example 1 8: 2 in the same manner as in Example 1 to prepare a dip-shaped molded article, the physical properties are shown in Table 1.
- Example 1 Except for mixing the latex-C and latex-D in Example 1 in 8: 2, a dip molded article in the form of a glove was prepared in the same manner as in Example 1, the physical properties are shown in Table 1.
- Agitator, thermometer, cooler, nitrogen inlet, 10L high pressure reactor equipped with a monomer, emulsifier, and polymerization initiator can be continuously added with nitrogen, and then acrylonitrile 35% by weight, 1,4-butadiene 60 5 parts by weight of sodium alkyl benzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan and 140 parts by weight of ion-exchanged water were added to 100 parts by weight of the monomer mixture of 5% by weight and methacrylic acid, and the temperature was raised to 40 ° C.
- the glass transition temperature is -21 ° C and the average particle diameter is 80 nm, and the latex prepared by the above is called "latex-E".
- a stirrer, a thermometer, a cooler, a nitrogen inlet and a 10L high pressure reactor equipped with a monomer, an emulsifier, and a polymerization initiator were continuously replaced with nitrogen, followed by 94 wt% of styrene and 2 wt% of acrylonitrile.
- %, 2 parts by weight of sodium alkyl benzene sulfonate, 0.5 parts by weight of t-dodecyl mercaptan and 300 parts by weight of ion-exchanged water were added to 100 parts by weight of the monomer mixture of 4% by weight of acrylic acid, and the temperature was raised to 55 ° C.
- the glass transition temperature is 105 ° C. and the average particle diameter is 99 nm.
- the latex prepared by the above is called 'latex-F'.
- Latex was prepared by mixing latex-E and latex-F at 9: 1.
- Example 1 In the same manner as in Example 1, a dip molded article in the form of a glove was manufactured, and the physical properties thereof are shown in Table 1.
- Example 1 9 Except for mixing the latex-C and latex-F in Example 1 9: 1 was prepared in the same manner as in Example 1 glove-shaped dip molded article, the physical properties are shown in Table 1.
- Example 1 Except for mixing the latex-E and latex-D 9: 1 in Example 1 was prepared in the same manner as in Example 1 glove-shaped dip molded article, the physical properties are shown in Table 1.
- the deep molded article made of carboxylic acid-modified nitrile-based latex mixed with carboxylic acid-modified styrene-based latex having a low glass transition temperature and a large average particle diameter has excellent tensile strength, elongation and stress properties. It can be seen.
- a carboxylic acid-modified nitrile copolymer latex having a glass transition temperature of -50 ° C to -15 ° C and an average particle diameter of 90 nm or more, and a carboxylic acid having a glass transition temperature of 80 ° C or more and an average particle diameter of less than 90 nm It is possible to manufacture molded articles having excellent tensile strength by mixing the modified styrene copolymer latex 3 to 15% by weight and then using the latex to prepare the latex.
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Abstract
Description
인장강도(MPa) | 신장률(%) | 300%에서의 응력(MPa) | |
실시예 1 | 34.8 | 622 | 4.8 |
실시예 2 | 32.9 | 630 | 4.7 |
실시예 3 | 30.2 | 652 | 4.0 |
실시예 4 | 34.5 | 600 | 5.0 |
실시예 5 | 33.5 | 614 | 4.8 |
실시예 6 | 35.0 | 624 | 4.6 |
비교예 1 | 23.8 | 682 | 3.1 |
비교예 2 | 27.9 | 659 | 3.7 |
실시예 7 | 28.9 | 564 | 6.5 |
실시예 8 | 27.0 | 528 | 6.2 |
비교예 3 | 25.0 | 538 | 5.6 |
비교예 4 | 26.5 | 570 | 4.2 |
비교예 5 | 24.0 | 538 | 5.8 |
Claims (18)
- 유리전이온도가 -50℃ 내지 -15℃이고, 평균입경이 90nm 이상 200nm 이하인 카르본산 변성 니트릴계 공중합체 라텍스; 및유리전이온도가 80℃ 이상이고 평균입경이 15nm 이상 90nm 미만인 카르본산 변성 스티렌계 공중합체 라텍스;를포함하여 이루어지는 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 1항에 있어서, 상기 유리전이온도가 -50℃ 내지 -15℃이고, 평균입경이 90nm 이상 200nm 이하인 카르본산 변성 니트릴계 공중합체 라텍스와 유리전이온도가 80℃ 이상이고 평균입경이 15nm 이상 90nm 미만인 카르본산 변성 스티렌계 공중합체 라텍스를 97:3 내지 85:15의 중량비로 포함하는 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 1항에 있어서, 상기 유리전이온도가 -50℃ 내지 -15℃이고, 평균입경이 90nm 이상 200nm 이하인 카르본산 변성 니트릴계 공중합체는 공액 디엔계 단량체 40 내지 89중량%, 에틸렌성 불포화 니트릴계 단량체 10 내지 50중량% 및 에틸렌성 불포화산 단량체 0.1 내지 10중량%를 포함하는 단량체 혼합물이 중합된 것임을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 3항에 있어서, 상기 공액 디엔계 단량체는 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 2-에틸-1,3-부타디엔, 1,3-펜타디엔 및 이소프렌으로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 3항에 있어서, 상기 에틸렌성 불포화 니트릴계 단량체는 아크릴로니트릴, 메타크릴로니트릴, 후마로니트릴, α-클로로니트릴 및 α-시아노 에틸 아크릴로니트릴로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 3항에 있어서, 상기 에틸렌성 불포화산 단량체는 아크릴산, 메타크릴산, 이타콘산, 말레이산, 푸마르산, 무수말레산, 무수 시트라콘산, 스티렌 술폰산, 푸마르산 모노부틸, 말레인산 모노부틸 및 말레인산 모노-2-히드록시 프로필로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 1항에 있어서, 상기 유리전이온도가 80℃ 이상이고 평균입경이 15nm 이상 90nm 미만인 카르본산 변성 스티렌계 공중합체는 방향족 비닐계 단량체 80 내지 99중량%, 에틸렌성 불포화 니트릴계 단량체 1 내지 20중량%, 에틸렌성 불포화산 단량체 0.1 내지 10중량%를 포함하는 단량체 혼합물이 중합된 것임을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 7항에 있어서, 상기 방향족 비닐계 단량체는 스티렌 및 알파메틸스티렌으로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 딥 성형용 카르본산 변성 스티렌계 공중합체 라텍스.
- 제 7항에 있어서, 상기 에틸렌성 불포화 니트릴계 단량체는 아크릴로니트릴, 메타크릴로니트릴, 후마로니트릴, α-클로로니트릴 및 α-시아노 에틸 아크릴로니트릴로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 7항에 있어서, 상기 에틸렌성 불포화 산 단량체는 아크릴산, 메타크릴산, 이타콘산, 말레이산, 푸마르산, 무수말레산, 무수 시트라콘산, 스티렌 술폰산, 푸마르산 모노부틸, 말레인산 모노부틸 및 말레인산 모노-2-히드록시 프로필로 이루어진 그룹으로부터 선택된 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 7항에 있어서, 상기 카르본산 변성 니트릴계 공중합체 라텍스는 상기 공중합체를 구성하는 단량체와 공중합 가능한 에틸렌성 불포화 단량체를 전체 공중합체 중 5중량% 이내로 더 포함함을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 11항에 있어서, 상기 공중합 가능한 에틸렌성 불포화 단량체는 비닐 방향족 단량체, 플로로알킬비닐 에테르, 에틸렌성 불포화 아미드 단량체, 비공액디엔 단량체, 및 에틸렌성 불포화 카르본산 에스테르 단량체로 이루어진 그룹으로부터 선택된 1종 이상임을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 1항에 있어서, 상기 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스는 카르본산 변성 니트릴계 공중합체를 구성하는 총 100중량부에 대하여 유화제 0.3 내지 30중량부, 중합개시제 0.01 내지 2중량부, 분자량 조절제 0.1 내지 2.0중량부를 포함하는 것을 특징으로 하는 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스.
- 제 1항 내지 제13항 중 어느 한 항에 따른 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스를 포함하는 딥 성형용 라텍스 조성물.
- 제 14항에 있어서, 상기 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스는 상기 조성물 중 80~99중량%로 포함됨을 특징으로 하는 딥 성형용 라텍스 조성물.
- 제 14항에 있어서, 상기 조성물은 안료, 가황촉매, 충진제, 증점제 및 pH 조절제로 이루어진 그룹으로부터 선택된 1종 이상의 첨가제를 포함함을 특징으로 하는 딥 성형용 라텍스 조성물.
- 제 14항 내지 제16항 중 어느 한 항에 따른 딥 성형용 라텍스 조성물을 딥 성형하여 얻어지는 딥 성형품.
- 제 17항에 있어서, 상기 딥 성형품은 검사장갑, 콘돔, 카테터, 산업용 장갑, 가정용 장갑 또는 건강 관리용품의 딥 성형 라텍스 물품인 것을 특징으로 하는 딥 성형품.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN201280048077.5A CN103930479B (zh) | 2011-11-22 | 2012-11-13 | 用于浸渍成型的羧酸改性腈共聚物胶乳、包含该胶乳的用于浸渍成型的胶乳组合物以及由其制备的成型制品 |
JP2014537008A JP5975583B2 (ja) | 2011-11-22 | 2012-11-13 | ディップ成形用カルボン酸変性ニトリル系共重合体ラテックス、これを含むディップ成形用ラテックス組成物及びこれから製造された成形品 |
US14/353,016 US9803070B2 (en) | 2011-11-22 | 2012-11-13 | Carboxylic acid modified-nitrile based copolymer latex for dip-forming, latex composition for dip-forming comprising the same, and product thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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KR10-2011-0122144 | 2011-11-22 | ||
KR1020110122144A KR101424856B1 (ko) | 2011-11-22 | 2011-11-22 | 딥 성형용 카르본산 변성 니트릴계 공중합체 라텍스, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품 |
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JP (1) | JP5975583B2 (ko) |
KR (1) | KR101424856B1 (ko) |
CN (1) | CN103930479B (ko) |
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- 2012-11-13 JP JP2014537008A patent/JP5975583B2/ja active Active
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- 2012-11-13 MY MYPI2014001460A patent/MY171931A/en unknown
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US10982075B2 (en) | 2016-06-01 | 2021-04-20 | Synthomer Sdn. Bhd. | Polymer latex for dip-molding applications |
Also Published As
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KR20130056505A (ko) | 2013-05-30 |
US9803070B2 (en) | 2017-10-31 |
US20140302265A1 (en) | 2014-10-09 |
CN103930479B (zh) | 2016-04-13 |
JP5975583B2 (ja) | 2016-08-23 |
JP2014530289A (ja) | 2014-11-17 |
KR101424856B1 (ko) | 2014-08-04 |
CN103930479A (zh) | 2014-07-16 |
MY171931A (en) | 2019-11-07 |
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