Classifications

• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/04—Oxidation
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
  • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • C08F236/14—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 containing elements other than carbon and hydrogen
  • C08F236/16—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 containing elements other than carbon and hydrogen containing halogen
  • C08F236/18—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 containing elements other than carbon and hydrogen containing halogen containing chlorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2296—Oxides; Hydroxides of metals of zinc
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to a polymer latex composition containing an acrylonitrile-butadiene copolymer and a chloroprene copolymer, a dip molded product, and a method for producing a polymer latex composition.
• Chloroprene latex compositions containing chloroprene polymers are used in various fields such as dip molded products (dipped products), fiber treatment agents, paper processing agents, adhesives, adhesives, elastic asphalt (modified asphalt), elastic cement, etc. It's being used.
• chloroprene latex compositions are used as main raw materials for various gloves for industrial, examination, and surgical use.
• natural rubber was mainly used for gloves, but the demand for synthetic rubber gloves is increasing because of the problem of allergies caused by proteins contained in natural rubber.
• Acrylonitrile-butadiene latex compositions containing acrylonitrile-butadiene copolymers are most commonly used for examination gloves, and most of the polymers are carboxy-modified acrylonitrile-butadiene copolymer latex compositions copolymerized with methacrylic acid. It is a thing. Dip-molded articles obtained from this copolymer latex composition have excellent breaking strength and are resistant to tearing even with thin gloves. there were.
• plasticizers is adopted to give flexibility to gloves, but in order to develop excellent flexibility, it is necessary to add a large amount of plasticizers.
• a polymer having excellent flexibility for example, natural rubber, isoprene rubber, chloroprene rubber
• carboxy-modified acrylonitrile-butadiene copolymer can be considered.
• excellent flexibility and elongation at break cannot be obtained, and when added in a large amount, the breaking strength of the glove is greatly reduced.
• Patent Documents 1 and 2 Blends of acrylonitrile-butadiene copolymers and chloroprene polymers have been studied (Patent Documents 1 and 2 below), and gloves have also been studied (Patent Documents 3 and 4 below). It did not solve the problem of improvement.
• the present invention provides a polymer latex composition containing a carboxy-modified acrylonitrile-butadiene copolymer (A), a carboxy-modified chloroprene copolymer (B), and a metal oxide (C),
• a dip molded article obtained from the polymer latex composition described above comprising a carboxy-modified chloroprene copolymer (B) polymerization step and a mixing step, wherein the carboxy-modified chloroprene copolymer ( B) In the polymerization step, a raw material containing a 2-chloro-1,3-butadiene monomer (B-1) and a carboxy group-containing vinyl monomer (B-2), or a 2-chloro-1,3- Raw materials containing a butadiene monomer (B-1), a carboxyl group-containing vinyl monomer (B-2), and a 2,3-dichloro-1,3-butadiene monomer are mixed with at least pure water, chain A carboxy-modified chloroprene copolymer containing a carboxy-modified chloroprene copoly
• a polymer (B) latex is obtained, and in the mixing step, a carboxy-modified acrylonitrile-butadiene copolymer (A) latex containing a carboxy-modified acrylonitrile-butadiene copolymer (A) and the carboxy-modified chloroprene copolymer (B ) is mixed with a carboxy-modified chloroprene copolymer (B) latex containing ) to produce a polymer latex composition.
• a carboxy-modified chloroprene copolymer (B) comprises monomer units derived from a 2-chloro-1,3-butadiene monomer (B-1) and a carboxy group-containing vinyl monomer (B-2 ), and the monomer unit derived from the carboxy group-containing vinyl monomer (B-2) is 0.5 parts per 100 parts by mass of the carboxy-modified chloroprene copolymer (B). 5 to 5.0 parts by mass of the polymer latex composition according to [1].
• the carboxy group-containing vinyl monomer (B-2) is at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.
• [4] The polymer latex composition according to any one of [1] to [3], which contains sulfur, a vulcanization accelerator, and an antioxidant.
• the immersion-molded article after vulcanization obtained by vulcanizing the immersion-molded article containing the polymer latex composition at 120°C for 20 minutes has a breaking strength of 17 MPa or more, measured according to JISK6251, at break.
• [6] A dip molded article obtained from the polymer latex composition according to any one of [1] to [5].
• a modified chloroprene copolymer (B) latex is obtained, and in the mixing step, a carboxy-modified acrylonitrile-butadiene copolymer (A) latex containing a carboxy-modified acrylonitrile-butadiene copolymer (A) and the carboxy-modified chloroprene copolymer
• a method for producing a polymer latex composition comprising mixing a carboxy-modified chloroprene copolymer (B) latex containing coalescence (B).
• the polymer latex composition of the present invention it is possible to provide a dip-molded article that exhibits excellent flexibility and elongation at break, as well as high mechanical strength such as high breaking strength, and dipped products thereof.
• the polymer latex composition according to the present invention contains a carboxy-modified acrylonitrile-butadiene copolymer (A), a carboxy-modified chloroprene copolymer (B), and a metal oxide (C). Components that may be included in the polymer latex composition according to the present invention are described below.
• the carboxy-modified acrylonitrile-butadiene copolymer according to the present embodiment includes a monomer unit derived from an acrylonitrile monomer, a monomer unit derived from a butadiene monomer, and a monomer derived from a carboxy group-containing vinyl monomer. Includes body units.
• a carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention contains a monomer unit derived from a monomer other than an acrylonitrile monomer, a butadiene monomer and a carboxy group-containing vinyl monomer.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention includes a monomer unit derived from an acrylonitrile monomer, a monomer unit derived from a butadiene monomer, a carboxy group-containing vinyl monomer It can be composed of a terpolymer of monomer units derived from the body.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention has a monomer unit derived from an acrylonitrile monomer when the carboxy-modified acrylonitrile-butadiene copolymer is 100% by mass. % by mass.
• the content of monomer units derived from acrylonitrile monomers in the carboxy-modified acrylonitrile-butadiene copolymer is, for example, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40% by mass, and may be within a range between any two of the numerical values exemplified here.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention has a monomer unit derived from a butadiene monomer when the carboxy-modified acrylonitrile-butadiene copolymer is 100% by mass. % by mass.
• the content of monomer units derived from the butadiene monomer in the carboxy-modified acrylonitrile-butadiene copolymer is, for example, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75% by mass, and may be within a range between any two of the numerical values exemplified here.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention when the carboxy-modified acrylonitrile-butadiene copolymer is 100% by mass, a monomer unit derived from a carboxy group-containing vinyl monomer, It can be contained in an amount of 0.5 to 8% by mass.
• the content of monomer units derived from the carboxy group-containing vinyl monomer in the carboxy-modified acrylonitrile-butadiene copolymer is, for example, 0.5, 0.6, 0.7, 0.8, 0.9. , 1, 2, 3, 4, 5, 6, 7, 8% by weight, and may be within a range between any two of the numerical values exemplified herein.
• the copolymerization ratio of the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention is 25% to 40% by mass of acrylonitrile, 52% to 75% by mass of butadiene, and 0.5% of a carboxy group-containing vinyl monomer. % to 8% by mass, preferably 31% to 36% by mass of acrylonitrile, 59% to 69% by mass of butadiene, and 0.8% to 7% by mass of a carboxy group-containing vinyl monomer.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention includes, when the carboxy-modified acrylonitrile-butadiene copolymer is 100% by mass, a monomer unit derived from an acrylonitrile monomer, a butadiene monomer can contain a total of 90% by mass or more, preferably 95% by mass or more, and 98% by mass or more of the monomer units derived from the carboxyl group-containing vinyl monomer. more preferred.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention has a halogen content of less than 0.2% by mass when the carboxy-modified acrylonitrile-butadiene copolymer is 100% by mass. It is preferably less than 0.1% by mass.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention can also be halogen-free.
• a carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention includes monomer units derived from an acrylonitrile monomer, monomer units derived from a butadiene monomer, and a carboxy group-containing vinyl monomer. It can also be composed of derived monomeric units.
• the carboxy group-containing vinyl monomer can be at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid, and preferably contains methacrylic acid.
• the carboxy-modified acrylonitrile-butadiene copolymer according to one embodiment of the present invention can be dispersed in water, and the monomer is one or more selected from rosin acid and alkali metal salts. It can be a latex obtained by emulsion polymerization in the presence of an emulsifier.
• a latex containing a carboxy-modified acrylonitrile-butadiene copolymer contains a carboxy-modified acrylonitrile-butadiene copolymer as a main component, can contain a solvent such as water, and can contain other additives used during emulsion polymerization. can.
• the carboxy-modified acrylonitrile-butadiene copolymer latex contains one or more selected from rosin acid or an alkali metal salt with respect to 100% by mass of the carboxy-modified acrylonitrile-butadiene copolymer latex.
• the total solid content of the emulsifier and the carboxy-modified acrylonitrile-butadiene copolymer is preferably 40 to 50% by mass, more preferably 42 to 46% by mass.
• the carboxy-modified chloroprene copolymer according to the present embodiment is a copolymer containing monomer units derived from a chloroprene monomer and monomer units derived from a carboxy group-containing vinyl monomer.
• a carboxy-modified chloroprene copolymer according to one embodiment of the present invention is a copolymer of 2-chloro-1,3-butadiene (hereinafter also referred to as a chloroprene monomer) and a carboxy group-containing vinyl monomer.
• a copolymer of a chloroprene monomer, a carboxy group-containing vinyl monomer, and other monomers copolymerizable therewith and the other monomer is 1-chloro-1 ,3-butadiene, 2,3-dichloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, sulfur and the like, and as other monomers, two or more of these may be used in combination. .
• the carboxy-modified chloroprene copolymer contains monomer units derived from monomers other than the chloroprene monomer and the carboxy group-containing vinyl monomer
• the carboxy-modified chloroprene copolymer is a carboxy-modified chloroprene copolymer.
• the entire coalescence is taken as 100% by mass, it preferably contains 50% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more of monomer units derived from a chloroprene monomer. .
• the carboxy group-containing vinyl monomer can be at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid, and preferably contains methacrylic acid.
• the copolymerization amount of the carboxy group-containing vinyl monomer in the carboxy-modified chloroprene copolymer can be 0.5 to 5.0% by mass with respect to 100% by mass of the carboxy-modified chloroprene copolymer. 0 to 4.0% by mass is preferred.
• the content of monomer units derived from the carboxy group-containing vinyl monomer in the carboxy-modified chloroprene copolymer is, when the carboxy-modified chloroprene copolymer is 100% by mass, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0% by mass and within the range between any two of the numerical values illustrated here may be
• the content of monomer units derived from the chloroprene monomer in the carboxy-modified chloroprene copolymer can be 50 to 99.5% by mass when the carboxy-modified chloroprene copolymer is 100% by mass. Particularly preferably, it is 95.0 to 99.5% by mass.
• the content of monomer units derived from the chloroprene monomer is, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 95.5, 96, 96.5, 97, 97 .5, 98, 98.5, 99, 99.5% by weight, and may be within a range between any two of the numerical values exemplified herein.
• the carboxy-modified chloroprene copolymer (B) is a monomer derived from the chloroprene monomer (B-1) when the carboxy-modified chloroprene copolymer (B) is 100% by mass. It can contain 95.0 to 99.5% by mass of body units and 0.5 to 5.0% by mass of monomer units derived from the carboxy group-containing vinyl monomer (B-2).
• the content of monomer units other than the chloroprene monomer and the carboxy group-containing vinyl monomer in the carboxy-modified chloroprene copolymer is, for example, 0 or 5 when the carboxy-modified chloroprene copolymer is 100% by mass. , 10, 15, 20, 25, 30, 35, 40, 45, 50% by weight, and may be within a range between any two of the numerical values exemplified herein.
• the carboxy-modified chloroprene copolymer according to one embodiment of the present invention may contain no monomer units other than the chloroprene monomer and the carboxy group-containing vinyl monomer.
• the carboxy-modified chloroprene copolymer (B) is obtained by heating a carboxy-modified chloroprene copolymer (B) latex composition containing the carboxy-modified chloroprene copolymer (B) at 130° C. for 30 minutes. It is preferable that the breaking strength of the vulcanized dip-molded body after vulcanization obtained by vulcanization is 8 MPa or more and the breaking elongation is 600% or more, measured according to JIS K6251. The breaking strength is, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 MPa. may be within the range.
• the elongation at break is, for example, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100%, and may be within a range between any two of the numerical values exemplified herein. .
• the dip-molded article made of the carboxy-modified chloroprene copolymer (B) latex composition containing the carboxy-modified chloroprene copolymer (B) contains at least the carboxy-modified chloroprene copolymer (B) and the metal oxide (C). and can further include a vulcanizing agent.
• the above dip-molded article may further contain a vulcanization accelerator.
• the above dip-molded article may further contain an anti-aging agent.
• the method for producing the dip-molded article and the dip-molded article after vulcanization can be obtained according to the method of the examples. Also, the thickness can be set to 0.10 to 0.30 mm, for example.
• a polymer latex composition according to one embodiment of the present invention is a chloroprene-based polymer that contains monomer units derived from a chloroprene monomer and does not contain monomer units derived from a carboxy group-containing vinyl monomer.
• a polymer latex composition according to one embodiment of the present invention may also include a chloroprene polymer composed of chloroprene monomer units.
• the polymer latex composition according to one embodiment of the present invention contains more carboxy-modified chloroprene copolymer (B) than the chloroprene-based polymer that does not contain a monomer unit derived from a carboxy group-containing vinyl monomer. preferably included.
• the content of the chloroprene-based polymer containing no monomer units derived from a carboxy group-containing vinyl monomer, contained in the polymer latex composition is the carboxy-modified chloroprene copolymer contained in the polymer latex composition. It is preferably less than 50% by mass with respect to the total 100% by mass of (B) and the chloroprene-based polymer that does not contain a monomer unit derived from a carboxyl group-containing vinyl monomer. 10, 15, 20, 25, 30, 35, 40, 45, 50% by mass, and may be within a range between any two of the numerical values exemplified here.
• a method for producing a carboxy-modified chloroprene copolymer (B) comprises a 2-chloro-1,3-butadiene monomer (B-1) and a carboxy group-containing vinyl monomer (B- 2), or a 2-chloro-1,3-butadiene monomer (B-1), a carboxy group-containing vinyl monomer (B-2), and 2,3-dichloro-1,3 -
• a raw material containing a butadiene monomer is polymerized at a polymerization temperature of 5 to 55 ° C.
• a carboxy-modified chloroprene copolymer (B) polymerization step of obtaining a carboxy-modified chloroprene copolymer (B) latex containing a modified chloroprene copolymer (B) is included.
• a dispersant and/or a reducing agent can also be added in the polymerization step.
• raw material monomers can be polymerized by polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization.
• polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization.
• emulsion polymerization is preferable because of various advantages such as easy control, easy removal of the polymer from the polymerization-terminated liquid, and relatively high polymerization rate.
• Emulsion polymerization is a type of radical polymerization, in which raw material monomers are mixed with pH adjusters such as chain transfer agents, water, alkalis (e.g., metal hydroxides such as potassium hydroxide and sodium hydroxide), emulsifiers, and dispersants.
• pH adjusters such as chain transfer agents, water, alkalis (e.g., metal hydroxides such as potassium hydroxide and sodium hydroxide), emulsifiers, and dispersants.
• the mixture is put into a reaction vessel together with an agent, a reducing agent (eg, sodium hydrogen sulfite), a polymerization initiator, etc., and polymerized.
• chain transfer agent those used in normal emulsion polymerization of chloroprene can be used.
• chain transfer agents include long-chain alkylmercaptans such as n-dodecylmercaptan and tert-dodecylmercaptan; and dialkylxanthogen disulfides such as diisopropylxanthogen disulfide and diethylxanthogen disulfide. These chain transfer agents can be used singly or in combination of two or more.
• the amount of the chain transfer agent used is preferably 0.01 to 1 part by mass per 100 parts by mass of the monomer.
• emulsifiers include anionic emulsifiers and nonionic emulsifiers.
• anionic emulsifiers include fatty acid salts such as tallow fatty acid potassium, partially hydrogenated tallow fatty acid potassium, potassium oleate and sodium oleate; resinates; alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate;
• nonionic emulsifiers include polyethylene glycol ester emulsifiers and polyvinyl alcohol.
• anionic emulsifiers are preferred, and at least one selected from the group consisting of alkylbenzenesulfonates is more preferred.
• These emulsifiers can be used singly or in combination of two or more.
• the amount of emulsifier used is preferably 0.5 to 6.5 parts by weight per 100 parts by weight of the monomer.
• dispersant examples include sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate.
• a dispersing agent can be used individually by 1 type or in combination of 2 or more types.
• the amount of the dispersant used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the monomer. More preferably, an emulsifier and a dispersant are used in the polymerization step.
• pH adjusters examples include potassium hydroxide and sodium hydroxide. These pH adjusters may be used alone or in combination of two or more. Among the pH adjusters, potassium hydroxide and sodium hydroxide are preferably used because they are highly effective in increasing the pH value.
• the amount of the pH adjuster to be added can be 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the monomer.
• reducing agents examples include potassium pyrosulfite, potassium sulfite, potassium hydrogen sulfite, potassium phosphate, potassium hydrogen phosphate, and sodium hydrogen sulfite.
• the amount of the reducing agent added can be 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the monomer.
• polymerization initiator inorganic peroxides such as potassium persulfate, ammonium persulfate, sodium persulfate and hydrogen peroxide; organic peroxides such as benzoyl peroxide and the like can be used. These polymerization initiators can be used singly or in combination of two or more.
• the amount of the polymerization initiator used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer.
• the amount of water used for emulsion polymerization is preferably 50 to 300 parts by mass, more preferably 80 to 150 parts by mass, per 100 parts by mass of the monomer.
• the polymerization temperature is not particularly limited, but is preferably in the temperature range of 5 to 55° C., more preferably 10° C., from the viewpoint of easily maintaining the stability of the flexibility of the carboxy-modified chloroprene copolymer over time. ⁇ 50°C temperature range.
• the polymerization temperature is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55° C., and may be within a range between any two of the numerical values exemplified here. .
• the polymerization rate (polymerization conversion rate) of the raw material monomer is preferably 60% or higher, more preferably 70% or higher, and even more preferably 80% or higher.
• the upper limit can be, for example, 99% or less.
• the polymerization conversion is, for example, 60, 65, 70, 75, 80, 85, 90, 95, 99%, and may be within a range between any two of the values exemplified here. By setting the polymerization conversion rate within this range, the solid content of the carboxy-modified chloroprene copolymer and the polymerization time during production become appropriate, resulting in excellent productivity.
• the polymerization terminator added when the polymerization rate of the raw material monomer reaches the target polymerization rate and stops the polymerization includes, for example, thiodiphenylamine, 4-tert-butylcatechol, 2,2′-methylenebis(4- methyl-6-tert-butylphenol), diethylhydroxylamine and the like can be used.
• the concentration of solids is adjusted to the optimum range by a concentration operation.
• the solid content concentration is preferably in the range of 40 to 50% by mass.
• a latex containing the carboxy-modified chloroprene copolymer (B) can be obtained by the above production method.
• the latex containing the carboxy-modified chloroprene copolymer (B) according to one embodiment of the present invention may contain a free carboxyl group-containing vinyl monomer that is not bound to the carboxy-modified chloroprene copolymer (B). can.
• the content of the free carboxyl group-containing vinyl monomer can be 0.1 to 2.0% by mass with respect to 100% by mass of the carboxy-modified chloroprene copolymer (B).
• the content of the free carboxyl group-containing vinyl monomer can be evaluated by liquid chromatography.
• the carboxy-modified chloroprene copolymer in the polymer latex composition is 100% by mass
• the content of coalescence (B) is 10 to 50% by mass, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50% by mass. It may be within a range between two.
• the polymer latex composition according to the present invention comprises a carboxy-modified acrylonitrile-butadiene copolymer (A), a carboxy-modified chloroprene copolymer (B) and a metal oxide (C), and By setting the component ratio (A)/(B) of the modified acrylonitrile-butadiene copolymer (A) and the carboxy-modified chloroprene copolymer (B) to a specific range, excellent breaking strength and flexibility are achieved. Elongation at break can be expressed.
• the polymer latex composition according to the invention contains a metal oxide (C).
• a metal oxide (C) As described above, both the acrylonitrile-butadiene copolymer and the chloroprene copolymer contained in the polymer latex composition according to the present invention have monomer units derived from carboxy group-containing vinyl monomers. The carboxyl groups contained in each of these copolymers are ionically crosslinked by metal ions derived from metal oxides, thereby making it possible to obtain dip-molded articles having excellent breaking strength, flexibility, and elongation at break. Conceivable.
• metal oxides examples include zinc oxide, lead oxide, trilead tetraoxide, magnesium oxide, titanium oxide, and calcium oxide.
• the content of the metal oxide is such that the cross-linking between the carboxy-modified acrylonitrile-butadiene copolymer (A) and the carboxy-modified chloroprene copolymer (B) is more likely to progress sufficiently, and flexibility, elongation at break, strength at break, modulus From the viewpoint of easily obtaining a dip-molded article having excellent properties such as the above, it may be 0.5 to 10 parts by mass per 100 parts by mass of the solid content of the polymer latex composition.
• the solid content of the polymer latex composition refers to all components obtained by removing volatiles such as water from the polymer latex composition, and includes the carboxy-modified acrylonitrile-butadiene copolymer (A) and the carboxy-modified chloroprene copolymer. It contains coalescence (B) and non-volatile matter of various additives added during emulsion polymerization.
• the metal oxide content is, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10 parts by mass, any of the numerical values illustrated here It may be in a range between the two.
• a metal oxide can be used individually by 1 type or in combination of 2 or more types.
• the polymer latex composition according to one embodiment of the present invention may contain pH modifiers, freeze stabilizers, emulsifiers, viscosity modifiers, antioxidants, preservatives and the like.
• pH adjuster, emulsifier, etc. the pH adjuster, emulsifier, etc. used in producing the latex containing the carboxy-modified chloroprene copolymer (B) can be used.
• the polymer latex composition according to one embodiment of the present invention comprises vulcanizing agents, vulcanization accelerators, anti-aging agents (antioxidants such as ozone anti-aging agents), fillers, plasticizers, pigments, colorants, Additives such as wetting agents and antifoaming agents may be included.
• the polymer latex composition according to the present embodiment is a polymer containing a carboxy-modified acrylonitrile-butadiene copolymer (A), a carboxy-modified chloroprene copolymer (B), a metal oxide (C), and these additives. It can be a coalesced latex composition and can be a polymeric latex composition for dip molding.
• the polymer latex composition according to one embodiment of the present invention contains a vulcanizing agent, a vulcanization accelerator, an antioxidant, a filler, a plasticizer, a pigment, and a colorant before mixing these additives. , a wetting agent, and an antifoaming agent.
• vulcanizing agents include sulfur (molecular sulfur; for example, cyclic sulfur such as S8).
• the content of the vulcanizing agent is selected from the viewpoints that the crosslinking sufficiently progresses, the breaking strength of the dip-molded product, the modulus, etc. It may be 0.5 to 10 parts by weight per 100 parts by weight of the solid content of the composition.
• a vulcanizing agent can be used individually by 1 type or in combination of 2 or more types.
• vulcanization accelerators include thiuram-based, dithiocarbamate-based, thiourea-based, guanidine-based, xanthate-based, and thiazole-based vulcanization accelerators.
• a dithiocarbamate-based vulcanization accelerator can be used, and examples of the dithiocarbamate-based vulcanization accelerator include sodium dibutyldithiocarbamate, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, and zinc diethyldithiocarbamate.
• the vulcanization accelerator may be used in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the polymer latex composition from the viewpoint of obtaining appropriate strength.
• a vulcanization accelerator can be used individually by 1 type or in combination of 2 or more types.
• Anti-aging agents include ozone anti-aging agents, phenol anti-aging agents, and amine anti-aging agents.
• Amine anti-aging agents include octylated diphenylamine, p-(p-toluene-sulfonylamido)diphenylamine, 4,4′-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, N,N′-diphenyl-p-phenylamine, Examples include diphenylamine compounds such as diamine (DPPD) and N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD).
• DPPD diamine
• IPPD N-isopropyl-N'-phenyl-p-phenylenediamine
• antiozonants examples include N,N'-diphenyl-p-phenylenediamine (DPPD) and N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD).
• DPPD N,N'-diphenyl-p-phenylenediamine
• IPPD N-isopropyl-N'-phenyl-p-phenylenediamine
• a bindard phenol-based antioxidant can be used when the appearance (especially color tone) or sanitation is important, such as medical gloves.
• An example is a butylated reaction product of DCPD and p-cresol.
• the content of the anti-aging agent may be 0.1 to 5 parts by mass based on 100 parts by mass of the solid content of the polymer latex composition from the viewpoint of easily obtaining a sufficient anti-aging effect.
• the polymer latex composition according to one embodiment of the present invention conforms to JIS K6251 of a vulcanized dip-molded product obtained by vulcanizing an dip-molded product containing the polymer latex composition at 120°C for 20 minutes. It is preferable that the breaking strength measured according to the standard is 17 MPa or more. The breaking strength is, for example, 17, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40 MPa, and within the range between any two of the numerical values exemplified here. may
• the polymer latex composition according to one embodiment of the present invention conforms to JIS K6251 of a vulcanized dip-molded product obtained by vulcanizing an dip-molded product containing the polymer latex composition at 120°C for 20 minutes. It is preferred that the breaking elongation measured according to the standard is 550% or more. The elongation at break is, for example, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000%, and may be within a range between any two of the values exemplified here.
• the polymer latex composition according to one embodiment of the present invention conforms to JIS K6251 of a vulcanized dip-molded product obtained by vulcanizing an dip-molded product containing the polymer latex composition at 120°C for 20 minutes.
• the modulus at 100% elongation measured according to the standard is preferably 2.5 MPa or less.
• the modulus at 100% elongation is, for example, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 0, 2.1, 2.2, 2.3, 2.4, 2.5 MPa, and may be in the range between any two of the values exemplified herein.
• the polymer latex composition according to one embodiment of the present invention conforms to JIS K6251 of a vulcanized dip-molded product obtained by vulcanizing an dip-molded product containing the polymer latex composition at 120°C for 20 minutes.
• the 300% elongation modulus measured according to the standard is preferably 5.0 MPa or less.
• 300% elongation modulus is, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3 .6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8 , 4.9, 5.0 MPa, and may be in the range between any two of the values exemplified herein.
• the polymer latex composition according to one embodiment of the present invention is a vulcanized dip molded product obtained by vulcanizing an dip molded product containing the polymer latex composition at 120° C. for 20 minutes.
• the 500% elongation modulus measured according to the standard is preferably 15.0 MPa or less.
• the modulus at 500% elongation is, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 MPa, and within the range between any two of the numerical values exemplified here good too.
• the above dip-molded product contains at least the carboxy-modified acrylonitrile-butadiene copolymer (A), the carboxy-modified chloroprene copolymer (B) and the metal oxide (C), and can further contain a vulcanizing agent.
• the above dip-molded article may further contain a vulcanization accelerator.
• the above dip-molded article may further contain an anti-aging agent.
• the method for producing the above dip-molded article and the dip-molded article after vulcanization can be obtained by the methods of Examples. Also, the thickness can be 0.06 to 0.07 mm, for example.
• a method for producing a polymer latex composition according to an embodiment of the present invention can comprise a carboxy-modified chloroprene copolymer (B) polymerization step and a mixing step.
• a carboxy-modified chloroprene copolymer (B) polymerization step a raw material containing a 2-chloro-1,3-butadiene monomer (B-1) and a carboxy group-containing vinyl monomer (B-2), or Raw material containing 2-chloro-1,3-butadiene monomer (B-1), carboxy group-containing vinyl monomer (B-2), and 2,3-dichloro-1,3-butadiene monomer is polymerized at a polymerization temperature of 5 to 55° C.
• a carboxy-modified chloroprene copolymer (B ) containing a carboxy-modified chloroprene copolymer (B) latex can be obtained, and in the mixing step, a carboxy-modified acrylonitrile-butadiene copolymer (A) latex containing a carboxy-modified acrylonitrile-butadiene copolymer (A) and and a carboxy-modified chloroprene copolymer (B) latex containing the carboxy-modified chloroprene copolymer (B).
• the order of mixing in the mixing step is not particularly limited, but a polymer latex containing a carboxy-modified acrylonitrile-butadiene copolymer (A) and a polymer latex containing a carboxy-modified chloroprene copolymer (B) are mixed.
• a mixed solution containing the metal oxide (C) and components such as a vulcanizing agent and a vulcanization accelerator to be added as necessary is prepared in advance, and carboxy-modified acrylonitrile-butadiene is added to the mixed solution.
• a polymer latex containing the copolymer (A) and a polymer latex containing the carboxy-modified chloroprene copolymer (B) can also be added.
• a dip-molded article according to an embodiment of the present invention can be a dip-molded article of a polymer latex composition according to an embodiment of the present invention.
• a dip-molded article according to one embodiment of the present invention is a dip-molded article using the polymer latex composition according to one embodiment of the present invention. It can be obtained by molding.
• a dip-molded article according to an embodiment of the present invention is obtained by immersing a substrate in a coagulating liquid containing a polymer latex composition according to an embodiment of the present invention to form an dip-molded film on the substrate. be able to.
• the polymer latex composition according to the present embodiment is dip-molded.
• a molding method for producing the dip-molded article according to the present embodiment a known method can be used, and examples thereof include a simple dipping method, an adhesive dipping method, a thermal dipping method, an electrodeposition method, and the like.
• the adhesion dipping method can be used from the viewpoint of easy production and from the viewpoint of easily obtaining a dip molded article having a constant thickness.
• a mold coated with a flocculant is immersed in a polymer latex composition to coagulate the polymer latex composition. Water-soluble impurities are removed by leaching, followed by drying and vulcanization to form an immersion-molded film (rubber film), and then the immersion-molded film is released from the mold. Thereby, a film-like dip-molded article can be obtained.
• the thickness (eg, minimum thickness) of the dip-molded body may be 0.01-0.50 mm, 0.02-0.20 mm, or 0.04-0.10 mm.
• the thickness of the dip molded body is, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10 mm. Yes, and may be in a range between any two of the values exemplified here.
• the thickness of the dip-molded article can be adjusted by adjusting the time for which the mold is dipped in the polymer latex composition, the solid content concentration of the polymer latex composition, and the like. When it is desired to reduce the thickness of the dip-molded article, the dipping time may be shortened or the solid content concentration of the polymer latex composition may be lowered.
• a vulcanized product (immersion molded product after vulcanization) is obtained by vulcanizing a polymer latex composition according to an embodiment of the present invention and an unvulcanized dip molded product. Obtainable.
• a vulcanizate according to one embodiment of the present invention is a vulcanizate of the polymer latex composition according to one embodiment of the present invention and an unvulcanized dip-molded product, and It can be obtained by vulcanizing the combined latex composition and the unvulcanized dip-molded article.
• the vulcanizate according to this embodiment can be made into a film.
• the temperature for vulcanizing the polymer latex composition and the unvulcanized dip-molded article may be appropriately set according to the composition of the polymer latex composition, and is 100 to 220°C or 110 to 190°C. good.
• the vulcanization time for vulcanizing the polymer latex composition and the unvulcanized immersion molded article may be appropriately set depending on the composition of the rubber composition, the shape of the unvulcanized molded article, etc., and is 10 to 60 minutes. good.
• the dip-molded article and the vulcanizate according to one embodiment of the present invention have very high flexibility and sufficient breaking strength and breaking elongation as dip-molded articles.
• the dip molded body according to one embodiment of the present invention may be the vulcanizate molded body according to the present embodiment.
• a dip molded body according to an embodiment of the invention may be a glove, a balloon, a catheter or a boot. Examples of gloves include examination gloves, surgical gloves, household gloves, and the like.
• the dip-molded body according to one embodiment of the present invention has excellent breaking strength, is resistant to breaking even with thin gloves, and has improved flexibility and elongation at break. It can be suitably used as a glove for.
• Example 1 Carboxy-modified acrylonitrile-butadiene copolymer (A)> As the latex containing the carboxy-modified acrylonitrile-butadiene copolymer (A), an acrylonitrile-butadiene copolymer latex “LX550L” (Nippon Zeon Co., Ltd.) was used. As a result of H-NMR measurement, the composition was 33% by mass of acrylonitrile monomer-derived monomer units, 61% by mass of butadiene-derived monomer units, and 6% by mass of methacrylic acid-derived monomer units.
• Example 2 In Example 1, 97.5 parts by mass of 2-chloro-1,3-butadiene and 2.5 parts by mass of methacrylic acid were used as the monomers for preparing the latex containing the carboxy-modified chloroprene copolymer (B). A polymer latex was prepared in the same manner as in Example 1 except that H-NMR measurement revealed a polymer composition of 98.0% by mass of chloroprene-derived monomer units and 2.0% by mass of methacrylic acid-derived monomer units.
• Example 3 In Example 1, 94.0 parts by mass of 2-chloro-1,3-butadiene and 6.0 parts by mass of methacrylic acid were used as the monomers for preparing the latex containing the carboxy-modified chloroprene copolymer (B). A polymer latex was prepared in the same manner as in Example 1 except that 120 parts by mass of pure water and 1.87 parts by mass of sodium dodecylbenzenesulfonate were used. H-NMR measurement revealed a polymer composition of 95.0% by mass of chloroprene-derived monomer units and 5.0% by mass of methacrylic acid-derived monomer units.
• Example 6 In Example 1, 88.0 parts by mass of 2-chloro-1,3-butadiene, 2,3-dichloro-1, A latex composition was prepared in the same manner as in Example 1 except that 9.5 parts by mass of 3-butadiene and 2.5 parts by mass of methacrylic acid were used. H-NMR measurement revealed a polymer composition of 98.0% by mass of chloroprene-derived monomer units and 2.0% by mass of methacrylic acid-derived monomer units.
• Example 7 In Example 1, the monomers used in preparing the latex containing the carboxy-modified chloroprene copolymer (B) were 2-chloro-1,3-butadiene 97.5 parts by mass and maleic acid 2.5 parts by mass. A latex composition was prepared in the same manner as in Example 1, except that H-NMR measurement revealed a polymer composition of 98.0% by mass of chloroprene-derived monomer units and 2.0% by mass of maleic acid-derived monomer units.
• Example 1 In Example 1, instead of the latex containing the carboxy-modified chloroprene copolymer (B), a chloroprene polymer produced by the following method was used. 2-chloro-1,3-butadiene 100 parts by mass, n-dodecyl mercaptan 0.04 parts by mass, pure water 90 parts by mass, sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, trade name: G-15) 1.4 parts by mass, 0.16 parts by mass of sodium hydroxide, and 1.20 parts by mass of sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N).
• 2-chloro-1,3-butadiene 100 parts by mass, n-dodecyl mercaptan 0.04 parts by mass, pure water 90 parts by mass, sodium dodecylbenzenesulfonate (manufactured by Ka
• ⁇ Preparation of polymer latex composition> Using a ceramic ball mill, 1 part by mass of sulfur, 2 parts by mass of type 2 zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., trade name: type 2 zinc oxide), a vulcanization accelerator (zinc dibutyldithiocarbamate, Ouchi Shinko Kagaku company, trade name: Noccellar BZ) 2 parts by mass, anti-aging agent (phenol-based anti-aging agent, oligomer type hindered phenol (butylated reaction product of DCPD and p-cresol), manufactured by OMNOVA SOLUTIONS, trade name: Wingstay -L) 2 parts by mass, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 0.1 parts by mass, and 10.7 parts by mass of water at 20 ° C.
• type 2 zinc oxide manufactured by Sakai Chemical Industry Co., Ltd., trade name
• aqueous dispersion having a solid concentration of 40% was prepared by mixing.
• a 5% potassium hydroxide aqueous solution was added to adjust the pH to 10.
• Examples 1 to 7 and Comparative Examples 1 to 3 polymer latex solid content of 100 parts by mass and solid content of the aqueous dispersion of 7.1 mass.
• a polymer latex composition was prepared by mixing the parts and then adding water to adjust the total solids concentration to 13.5% by weight.
• Example 4 A polymer latex was prepared in the same manner as in Example 1. Using a ceramic ball mill, 1 part by mass of sulfur, 2 parts by mass of vulcanization accelerator, 2 parts by mass of anti-aging agent, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) By mixing 0.1 part by mass and 7.7 parts by mass of pure water at 20° C. for 16 hours, an aqueous dispersion having a solid concentration of 40% was prepared.
• a polymer latex composition was prepared by adjusting the concentration to 13.5% by weight.
• a coagulation liquid was obtained by mixing 72.7 parts by mass of water, 27.3 parts by mass of potassium nitrate tetrahydrate, and 0.05 parts by mass of a surfactant (manufactured by Kao Corporation, trade name: Emulgen 109P). .
• a ceramic cylinder material: ceramics, manufactured by Shinko Co., Ltd.
• a ceramic cylinder having an outer diameter of 50 mm was immersed in this coagulating liquid for 5 seconds, and then the cylinder was taken out. After drying at room temperature for 3 minutes, it was dried at 70° C. for 1 minute. The cylinder was then immersed in the latex composition described above for 23 seconds. Subsequently, after drying at 100° C.
• a film for evaluation (immersion molding, vulcanized film) was produced on the outer peripheral surface of the cylinder and the like. Evaluation was carried out by peeling the film for evaluation from the outer peripheral surface of the cylinder.
• ⁇ Evaluation method> (Copolymerization amount of monomer units derived from carboxy group-containing vinyl monomer in carboxy-modified chloroprene copolymer)
• the carboxy-modified chloroprene copolymer latex was frozen at ⁇ 60° C. for 24 hours and then vacuum-dried for 24 hours to obtain a carboxy-modified chloroprene copolymer film. This film was cut into 2 mm squares using scissors, immersed in an ethanol-toluene mixed solution and stirred for 1 hour.
• the modulus at 100%, 300% and 500% elongation, breaking strength and breaking elongation of the film for evaluation were measured according to JIS K 6251.
• the modulus at 300% elongation which is an index of flexibility, was 5.0 MPa or less
• the breaking elongation was 550% or more
• the breaking strength was 17.0 MPa or more, it was judged to be good.
• the carboxy-modified acrylonitrile-butadiene copolymer (A) and the carboxy-modified chloroprene copolymer (B) have a component ratio (A)/(B) of 90/10 to 50. /50, and when metal oxides are contained, the modulus at 300% elongation is low, the flexibility is excellent, the elongation at break is large, and the strength at break is high.
• Example 1 the latex containing the carboxy-modified chloroprene copolymer (B) obtained in Example 1 was the same as in Example 1 except that the latex containing the carboxy-modified acrylonitrile-butadiene copolymer (A) was not added.
• a polymer latex composition and an immersion-molded product were prepared, and vulcanized at 130° C. for 30 minutes. As a result of measurement, it was confirmed that the breaking strength was 8 MPa or more and the breaking elongation was 600% or more.

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