WO2017146238A1 - Composition de latex et corps moulé en film - Google Patents

Composition de latex et corps moulé en film Download PDF

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Publication number
WO2017146238A1
WO2017146238A1 PCT/JP2017/007225 JP2017007225W WO2017146238A1 WO 2017146238 A1 WO2017146238 A1 WO 2017146238A1 JP 2017007225 W JP2017007225 W JP 2017007225W WO 2017146238 A1 WO2017146238 A1 WO 2017146238A1
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WIPO (PCT)
Prior art keywords
latex
carboxyl group
weight
latex composition
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2017/007225
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English (en)
Japanese (ja)
Inventor
直広 伊賀利
実紗 山本
昌 北川
慎二 加藤
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Zeon Corp
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Zeon Corp
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Publication date
Priority claimed from JP2016193443A external-priority patent/JP2017149928A/ja
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to EP17756672.6A priority Critical patent/EP3421532B1/fr
Priority to CN201780011194.7A priority patent/CN108602991B/zh
Priority to US16/078,554 priority patent/US11236218B2/en
Priority to MYPI2018001475A priority patent/MY194391A/en
Priority to KR1020187023980A priority patent/KR20180114064A/ko
Publication of WO2017146238A1 publication Critical patent/WO2017146238A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/04—Appliances for making gloves; Measuring devices for glove-making
    • 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
    • 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
    • C08K3/10—Metal compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • 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

Definitions

  • the present invention relates to a latex composition that can suppress the occurrence of delayed allergy (Type IV) in addition to immediate allergy (Type I), and has high tensile strength, large elongation, and a flexible texture.
  • the present invention relates to a latex composition capable of providing a film molded body such as a dip molded body, a method for producing such a latex composition, and a dip molded body and a film molded body obtained using such a latex composition.
  • a dip-molded product that is used in contact with a human body such as a nipple, a balloon, a glove, a balloon, and a sack is formed by dip-molding a latex composition containing a natural latex typified by a natural rubber latex.
  • natural rubber latex contains proteins that cause allergic symptoms in the human body, it contains proteins that cause immediate allergy (Type I) symptoms in the human body, so it is in direct contact with living mucous membranes or organs.
  • types I immediate allergy
  • Patent Document 1 includes zinc oxide, sulfur and a vulcanization accelerator in an emulsion containing a carboxylated nitrile butadiene random terpolymer of acrylonitrile, carboxylic acid, and butadiene and having a total solid content of 15 to 25% by weight. Is disclosed. However, the technique of Patent Document 1 can prevent the occurrence of immediate type allergy (Type I). On the other hand, when a dip-molded body is formed, the human body is caused by sulfur and a vulcanization accelerator contained in the dip-molded body. When touched, allergic symptoms of delayed type allergy (Type IV) may occur.
  • Type I immediate type allergy
  • Type IV allergic symptoms of delayed type allergy
  • Patent Document 2 contains 25 to 30% by weight of acrylonitrile residues, 62 to 71% by weight of butadiene residues, and 4 to 8% by weight of unsaturated carboxylic acid residues, contains zinc oxide, and is crosslinked. Latex compositions that do not contain sulfur as an agent and sulfur compounds as vulcanization accelerators are disclosed. According to the technique of Patent Document 2, since sulfur and sulfur compounds that are vulcanization accelerators are not included, not only immediate type allergy (Type I) but also delayed type allergy (Type IV) can be suppressed. However, the obtained dip-molded article had low elongation and was also inferior in texture and touch.
  • the present invention can suppress the occurrence of delayed type allergy (Type IV) in addition to immediate type allergy (Type I), and has a high tensile strength, large elongation, a flexible texture, etc.
  • An object of the present invention is to provide a latex composition capable of providing a film molded body, a method for producing such a latex composition, and a dip molded body and a film molded body obtained by using such a latex composition. To do.
  • the present inventors have obtained a latex obtained by blending a predetermined amount of a metal compound containing a trivalent or higher metal into a latex of a carboxyl group-containing conjugated diene rubber (A).
  • the present inventors have found that the above object can be achieved by a composition, and have completed the present invention.
  • a latex composition comprising a latex of a carboxyl group-containing conjugated diene rubber (A) and a metal compound (B) containing a trivalent or higher metal, the metal compound Is provided in a latex composition of 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing conjugated diene rubber (A).
  • the metal compound (B) is an aluminum compound.
  • the latex composition of the present invention further contains at least one alcoholic hydroxyl group-containing compound (C) selected from saccharide (c1), sugar alcohol (c2), hydroxy acid (c3) and hydroxy acid salt (c4). It is preferable to do.
  • the content of the metal compound (B) and the content of the alcoholic hydroxyl group-containing compound (C) are in a weight ratio of “metal compound (B): alcoholic hydroxyl group-containing compound (C)”. 1: 0.1 to 1:50.
  • the alcoholic hydroxyl group-containing compound (C) is at least one selected from sugar alcohol (c2) and hydroxy acid salt (c4).
  • the carboxyl group-containing conjugated diene rubber (A) comprises 56 to 78% by weight of a conjugated diene monomer unit, 20 to 40% by weight of an ethylenically unsaturated nitrile monomer unit, and an ethylenically unsaturated acid monomer.
  • the carboxyl group-containing conjugated diene rubber (A) is a conjugated diene monomer unit, an ethylenically unsaturated carboxylic acid monomer unit, an amide group-containing monomer unit, and an epoxy group-containing monomer. And at least one monomer unit selected from the units.
  • the monomer constituting at least one monomer unit selected from the amide group-containing monomer unit and the epoxy group-containing monomer unit is (meth) acrylamide.
  • the monomer constituting at least one monomer unit selected from the amide group-containing monomer unit and the epoxy group-containing monomer unit is an epoxy group-containing (meth) acrylate.
  • a method for producing a latex composition comprising a latex of a carboxyl group-containing conjugated diene rubber (A) and a metal compound (B) containing a trivalent or higher metal. And A monomer mixture containing at least a conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer is subjected to emulsion polymerization at 0 to 25 ° C., whereby the latex of the carboxyl group-containing conjugated diene rubber (A) is obtained. A first step to obtain; There is provided a method for producing a latex composition comprising a second step of blending the metal compound (B) with the latex of the carboxyl group-containing conjugated diene rubber (A).
  • a method for producing a latex composition comprising a latex of a carboxyl group-containing conjugated diene rubber (A) and a metal compound (B) containing a trivalent or higher metal.
  • a method for producing a latex composition comprising a second step of blending the metal compound (B) with the latex of the carboxyl group-containing conjugated diene rubber (A).
  • a saccharide (c1) in addition to the metal compound (B), a saccharide (c1), a sugar alcohol (to the latex of the carboxyl group-containing conjugated diene rubber (A) ( It is preferable to further blend at least one alcoholic hydroxyl group-containing compound (C) selected from c2), hydroxy acid (c3) and hydroxy acid salt (c4).
  • the manufacturing method of a dip molded object provided with the process of dip-molding the latex composition of the said invention or the latex composition obtained by the manufacturing method of the said invention is provided.
  • the film molded object which consists of a latex composition of the said invention is provided.
  • a dip-molded body that can suppress the occurrence of delayed allergy (Type IV) in addition to immediate allergy (Type I), and has high tensile strength, large elongation, and a soft texture. It is possible to provide a latex composition capable of providing a film molded body such as, a method for producing such a latex composition, and a dip molded body and a film molded body obtained using such a latex composition it can.
  • the latex composition of the present invention comprises a latex of carboxyl group-containing conjugated diene rubber (A) and a metal compound containing a trivalent or higher metal, and the content ratio of the metal compound is the carboxyl group-containing content.
  • the latex composition is 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the conjugated diene rubber (A).
  • Latex of carboxyl group-containing conjugated diene rubber (A) is a monomer comprising at least a conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer.
  • a latex of a copolymer obtained by copolymerizing a body mixture, and examples of the carboxyl group-containing conjugated diene rubber (A) include a carboxyl group-containing nitrile rubber (a1), a carboxyl group-containing styrene-butadiene rubber (a2), and At least one selected from carboxyl group-containing conjugated diene rubber (a3) is preferred.
  • the latex of the carboxyl group-containing nitrile rubber (a1) is a copolymer latex obtained by copolymerizing an ethylenically unsaturated nitrile monomer in addition to a conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer.
  • a latex of a copolymer obtained by copolymerizing other ethylenically unsaturated monomers copolymerizable with these used as necessary may be used.
  • conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. It is done. Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable.
  • These conjugated diene monomers can be used alone or in combination of two or more.
  • the content ratio of the conjugated diene monomer unit formed by the conjugated diene monomer in the carboxyl group-containing nitrile rubber (a1) is preferably 56 to 78% by weight, more preferably 56 to 73% by weight, More preferably, it is 56 to 70% by weight.
  • the ethylenically unsaturated carboxylic acid monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a carboxyl group.
  • a single amount of ethylenically unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid Body
  • ethylenically unsaturated polyvalent carboxylic acid monomer such as itaconic acid, maleic acid, fumaric acid
  • ethylenically unsaturated polyvalent carboxylic acid anhydride such as maleic anhydride, citraconic anhydride
  • monobutyl fumarate maleic acid
  • ethylenically unsaturated polyvalent carboxylic acid partial ester monomers such as monobutyl and mono-2-hydroxypropyl maleate.
  • ethylenically unsaturated monocarboxylic acid is preferable, and methacrylic acid is particularly preferable.
  • These ethylenically unsaturated carboxylic acid monomers can also be used as alkali metal salts or ammonium salts. Further, the ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more.
  • the content ratio of the ethylenically unsaturated carboxylic acid monomer unit formed by the ethylenically unsaturated carboxylic acid monomer in the carboxyl group-containing nitrile rubber (a1) is preferably 2 to 6.5% by weight.
  • the film molded product such as a dip molded product obtained is excellent in texture and stretched while having sufficient tensile strength. Can be big.
  • the ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a nitrile group.
  • acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethylacrylonitrile Etc acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable.
  • These ethylenically unsaturated nitrile monomers can be used alone or in combination of two or more.
  • the content ratio of the ethylenically unsaturated nitrile monomer unit formed by the ethylenically unsaturated nitrile monomer in the carboxyl group-containing nitrile rubber (a1) is preferably 20 to 40% by weight, more preferably It is 25 to 40% by weight, more preferably 30 to 40% by weight.
  • ethylenically unsaturated monomers copolymerizable with the conjugated diene monomer, ethylenically unsaturated carboxylic acid monomer and ethylenically unsaturated nitrile monomer are not particularly limited, and can be obtained.
  • an amide group-containing monomer and an epoxy group-containing monomer Preferable examples include at least one monomer selected from the group consisting of:
  • the amide group-containing monomer is not particularly limited as long as it has at least one amide group in one molecule.
  • (meth) acrylamide is preferable, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide is more preferable, and N-methylol (meth) acrylamide is particularly preferable.
  • These amide group-containing monomers can be used alone or in combination of two or more.
  • the content ratio of the amide group-containing monomer unit in the carboxyl group-containing nitrile rubber (a1) is preferably 0.1 to 5.0% by weight, more preferably 0.25 to 4.5% by weight, More preferably, it is 0.5 to 4.0% by weight.
  • the epoxy group-containing monomer is not particularly limited as long as it is a monomer having at least one epoxy group in one molecule.
  • an epoxy group-containing (meth) acrylate is preferable, and glycidyl (meth)
  • the content ratio of the epoxy group-containing monomer unit in the carboxyl group-containing nitrile rubber (a1) is preferably 0.1 to 4.0% by weight, more preferably 0.25 to 3.5% by weight, More preferably, it is 0.5 to 3.0% by weight.
  • the carboxyl group-containing nitrile rubber (a1) is a copolymerizable other ethylenically unsaturated monomer other than at least one monomer selected from amide group-containing monomers and epoxy group-containing monomers.
  • Such other copolymerizable ethylenically unsaturated monomers include, for example, vinyl aromatic monomers such as styrene, alkylstyrene and vinylnaphthalene; fluoro Fluoroalkyl vinyl ethers such as ethyl vinyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (meth) acrylate, (meth ) Tetrafluoropropyl acrylate, dibutyl maleate, dibutyl fumarate, diethyl maleate , Methoxymethyl (me
  • the content of other monomer units formed by other ethylenically unsaturated monomers is preferably 10% by weight or less, more preferably 5% by weight. Hereinafter, it is more preferably 3% by weight or less.
  • the latex of the carboxyl group-containing nitrile rubber (a1) used in the present invention is obtained by copolymerizing a monomer mixture containing the above-mentioned monomers, and a method of copolymerization by emulsion polymerization is preferred. The emulsion polymerization method will be described later.
  • the latex of carboxyl group-containing styrene-butadiene rubber (a2) used in the present invention is copolymerized with styrene in addition to 1,3-butadiene and an ethylenically unsaturated carboxylic acid monomer as a conjugated diene monomer.
  • the content ratio of butadiene units formed from 1,3-butadiene in the carboxyl group-containing styrene-butadiene rubber (a2) is preferably 56 to 78% by weight, more preferably 56 to 73% by weight, still more preferably. Is 56 to 70% by weight.
  • the ethylenically unsaturated carboxylic acid monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a carboxyl group.
  • the same as the latex of the carboxyl group-containing nitrile rubber (a1) described above Can be used.
  • the content of the ethylenically unsaturated carboxylic acid monomer unit formed by the ethylenically unsaturated carboxylic acid monomer in the carboxyl group-containing styrene-butadiene rubber (a2) is preferably 2 to 6.5% by weight.
  • the film molded product such as a dip molded product obtained is excellent in texture and stretched while having sufficient tensile strength. Can be big.
  • the content of styrene units formed by styrene is preferably 20 to 40% by weight, more preferably 25 to 40% by weight, and still more preferably 30 to 40%. % By weight.
  • 1,3-butadiene as the conjugated diene monomer ethylenically unsaturated carboxylic acid monomer and other ethylenically unsaturated monomers copolymerizable with styrene are not particularly limited, and can be obtained.
  • an amide group-containing monomer and an epoxy group-containing monomer Preferable examples include at least one monomer selected from the group consisting of:
  • the amide group-containing monomer is not particularly limited as long as it is a monomer having at least one amide group in one molecule.
  • the same amide group-containing nitrile rubber (a1) latex as described above is used. Can be used.
  • the content ratio of the amide group-containing monomer unit in the carboxyl group-containing styrene-butadiene rubber (a2) is preferably 0.1 to 5.0% by weight, more preferably 0.25 to 4.5% by weight. %, More preferably 0.5 to 4.0% by weight.
  • the epoxy group-containing monomer is not particularly limited as long as it is a monomer having at least one epoxy group in one molecule.
  • the epoxy group-containing monomer is the same as the latex of the carboxyl group-containing nitrile rubber (a1) described above. Can be used.
  • the content ratio of the epoxy group-containing monomer unit in the carboxyl group-containing styrene-butadiene rubber (a2) is preferably 0.1 to 4.0% by weight, more preferably 0.25 to 3.5% by weight. %, More preferably 0.5 to 3.0% by weight.
  • the carboxyl group-containing styrene-butadiene rubber (a2) is a copolymerizable other ethylenically unsaturated group other than at least one monomer selected from amide group-containing monomers and epoxy group-containing monomers.
  • the monomer may be copolymerized.
  • examples of such other copolymerizable ethylenically unsaturated monomers include those similar to the latex of the carboxyl group-containing nitrile rubber (a1) described above.
  • 1,3-butadiene such as isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene And conjugated diene monomers.
  • the content ratio of other monomer units formed by other ethylenically unsaturated monomers is preferably 10% by weight or less, more preferably 5%. % By weight or less, more preferably 3% by weight or less.
  • the latex of the carboxyl group-containing styrene-butadiene rubber (a2) used in the present invention can be obtained by copolymerizing a monomer mixture containing the above-mentioned monomers. preferable.
  • the emulsion polymerization method will be described later. *
  • the latex of carboxyl group-containing conjugated diene rubber (a3) used in the present invention is a copolymer latex obtained by copolymerizing a conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer. Further, it may be a latex of a copolymer obtained by copolymerizing another ethylenically unsaturated monomer copolymerizable with these, which is used as necessary.
  • the content ratio of the conjugated diene monomer unit formed by the conjugated diene monomer in the carboxyl group-containing conjugated diene rubber (a3) is preferably 80 to 98% by weight, more preferably 90 to 98% by weight, More preferably, it is 95 to 97.5% by weight.
  • the ethylenically unsaturated carboxylic acid monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a carboxyl group.
  • the same as the latex of the carboxyl group-containing nitrile rubber (a1) described above Can be used.
  • the content ratio of the ethylenically unsaturated carboxylic acid monomer unit formed by the ethylenically unsaturated carboxylic acid monomer is preferably 2 to 10% by weight, and more It is preferably 2 to 7.5% by weight, more preferably 2 to 6.5% by weight, even more preferably 2 to 6% by weight, particularly preferably 2 to 5% by weight, and most preferably 2.5 to 5%. % By weight.
  • the film molded product such as a dip molded product obtained is excellent in texture and stretched while having sufficient tensile strength. Can be big.
  • conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. Any one of these conjugated diene monomers may be used alone, or two or more may be used in combination.
  • ethylenically unsaturated monomers copolymerizable with the conjugated diene monomer and the ethylenically unsaturated carboxylic acid monomer are not particularly limited, but the obtained film molded body such as a dip molded body From the viewpoint that the tensile strength can be further increased and a high stress retention can be provided, at least one monomer selected from an amide group-containing monomer and an epoxy group-containing monomer is used. A body is mentioned suitably.
  • the amide group-containing monomer is not particularly limited as long as it is a monomer having at least one amide group in one molecule.
  • the same amide group-containing nitrile rubber (a1) latex as described above is used.
  • the content ratio of the amide group-containing monomer unit in the carboxyl group-containing conjugated diene rubber (a3) is preferably 0.1 to 5.0% by weight, more preferably 0.25 to 4.5% by weight, More preferably, it is 0.5 to 4.0% by weight.
  • the epoxy group-containing monomer is not particularly limited as long as it is a monomer having at least one epoxy group in one molecule.
  • the epoxy group-containing monomer is the same as the latex of the carboxyl group-containing nitrile rubber (a1) described above. Can be used.
  • the content ratio of the epoxy group-containing monomer unit in the carboxyl group-containing conjugated diene rubber (a3) is preferably 0.1 to 4.0% by weight, more preferably 0.25 to 3.5% by weight, More preferably, it is 0.5 to 3.0% by weight.
  • the carboxyl group-containing conjugated diene rubber (a3) is a copolymerizable other ethylenically unsaturated monomer other than at least one monomer selected from amide group-containing monomers and epoxy group-containing monomers.
  • Such other copolymerizable ethylenically unsaturated monomers may be, for example, those similar to the latex of the carboxyl group-containing nitrile rubber (a1) described above ( However, excluding styrene).
  • the content of other monomer units formed by other ethylenically unsaturated monomers is preferably 10% by weight or less, more preferably 5% by weight. Hereinafter, it is more preferably 3% by weight or less.
  • the latex of the carboxyl group-containing conjugated diene rubber (a3) used in the present invention is obtained by copolymerizing a monomer mixture containing the above-mentioned monomers, and a method of copolymerization by emulsion polymerization is preferred.
  • the emulsion polymerization method will be described later.
  • latex of the carboxyl group-containing conjugated diene rubber (A) (latex of carboxyl group-containing nitrile rubber (a1), latex of carboxyl group-containing styrene-butadiene rubber (a2), carboxyl group-containing conjugated diene rubber (a3)
  • the emulsion polymerization method for obtaining the latex will be described.
  • the latex of the carboxyl group-containing conjugated diene rubber (A) described above can be produced by emulsion polymerization of a monomer mixture containing the above-described monomer by a conventionally known emulsion polymerization method.
  • the polymerization temperature for carrying out the emulsion polymerization is not particularly limited, and may be selected, for example, in the range of 0 to 75 ° C., preferably in the range of 0 to 50 ° C. From the viewpoint of further increasing the tensile strength, it is preferable to control the temperature of the emulsion polymerization to 0 to 25 ° C., and to control the temperature of the emulsion polymerization to 0 to 25 ° C. to obtain a film molded body such as a dip molded body. The tensile strength can be further increased while the elongation is large and the texture is excellent.
  • the temperature of emulsion polymerization is preferably 0 to 75 ° C., more preferably 0 to 50 ° C., further preferably 0 to 25 ° C., even more preferably 5 to 20 ° C. 15 ° C. is particularly preferred.
  • a specific emulsion polymerization method is not particularly limited as long as the polymerization can be performed by controlling the polymerization temperature within the above range, and a monomer mixture containing the above-described monomers is used. And can be polymerized by a conventionally known method.
  • a single amount used for polymerization is preferably performed in the presence of 0.15 to 0.95 parts by weight of a chain transfer agent with respect to 100 parts by weight of the body mixture.
  • the amount of the chain transfer agent used is preferably 0.15 to 0.95 parts by weight, more preferably 0.20 to 0.70 parts by weight, more preferably 100 parts by weight of the monomer mixture used for the polymerization.
  • the amount is preferably 0.20 to 0.50 parts by weight.
  • the molecular weight of the carboxyl group-containing conjugated diene rubber (A) can be adjusted moderately, whereby the amount of carboxyl group-containing conjugated diene rubber (A) insoluble in methyl ethyl ketone and the degree of swelling with respect to methyl ethyl ketone are within a desired range. Thereby, the tensile strength, elongation, and stress at 500% elongation of a film molded body such as a dip molded body can be more highly balanced.
  • the methyl ethyl ketone insoluble content of the carboxyl group-containing conjugated diene rubber (A) can be preferably 50 to 90% by weight, more preferably 55 to 85% by weight.
  • the swelling degree of the carboxyl group-containing conjugated diene rubber (A) with respect to methyl ethyl ketone can be preferably 10 to 150 times, more preferably 10 to 100 times.
  • the methyl ethyl ketone insoluble content and the degree of swelling with respect to methyl ethyl ketone can be measured, for example, by the following method. That is, first, a film of carboxyl group-containing conjugated diene rubber (A) was obtained, and the weight (W1) of the dried film before being immersed in methyl ethyl ketone was measured, and the film before being immersed in an 80-mesh cage metal mesh In the put state, it is immersed in methyl ethyl ketone for 24 hours at room temperature. Then, the weight (W2) of the swelled film remaining in the cage wire net is measured, and then the film after the immersion is dried at 105 ° C.
  • A carboxyl group-containing conjugated diene rubber
  • the chain transfer agent used in the emulsion polymerization is not particularly limited as long as the molecular weight of the obtained carboxyl group-containing conjugated diene rubber (A) can be appropriately adjusted.
  • examples thereof include mercaptans such as mercaptan and t-dodecyl mercaptan, sulfides such as tetraethylthiuram sulfide and dibentamethylenethiuram hexasulfide, ⁇ -methylstyrene dimer, carbon tetrachloride and the like.
  • mercaptans are preferable, and t-dodecyl mercaptan is more preferable. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • polymerization auxiliary materials such as an emulsifier and a polymerization initiator can be used.
  • the method for adding these polymerization auxiliary materials is not particularly limited, and any method such as an initial batch addition method, a divided addition method, or a continuous addition method may be used.
  • Nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester; potassium dodecylbenzenesulfonate, dodecylbenzene
  • Anionic emulsifiers such as alkyl benzene sulfonates such as sodium sulfonate, higher alcohol sulfates and alkyl sulfosuccinates; Cationic emulsifiers such as alkyltrimethylammonium chloride, dialkylammonium chloride and benzylammonium chloride; ⁇ , ⁇ -unsaturated Such as sulfo ester of carboxylic acid, sulfate ester of ⁇ , ⁇ -unsaturated carboxylic acid, sulfoalkyl aryl ether, etc.
  • a polymerizable emulsifier can be mentioned.
  • anionic emulsifiers are preferable, alkylbenzene sulfonates are more preferable, and potassium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate are particularly preferable.
  • These emulsifiers can be used alone or in combination of two or more.
  • the amount of the emulsifier used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • the polymerization initiator is not particularly limited, and examples thereof include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, di- ⁇ - Organic peroxides such as cumyl peroxide, acetyl peroxide, isobutyryl peroxide, benzoyl peroxide; azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, methyl azobisisobutyrate; Can be mentionedThese polymerization initiators can be used alone or in combination of two or more. The amount of the poly
  • the peroxide initiator can be used as a redox polymerization initiator in combination with a reducing agent.
  • the reducing agent is not particularly limited, but is a compound containing a metal ion in a reduced state such as ferrous sulfate or cuprous naphthenate; a sulfonic acid compound such as sodium methanesulfonate; an amine compound such as dimethylaniline. And so on.
  • These reducing agents can be used alone or in combination of two or more.
  • the amount of the reducing agent used is preferably 3 to 1000 parts by weight with respect to 100 parts by weight of the peroxide.
  • the amount of water used for emulsion polymerization is preferably 80 to 600 parts by weight, particularly preferably 100 to 200 parts by weight, based on 100 parts by weight of all monomers used.
  • Examples of the monomer addition method include a method of adding monomers to be used in a reaction vessel all at once, a method of adding continuously or intermittently as the polymerization proceeds, and a part of the monomer is added. And a method in which the remaining monomer is continuously or intermittently added and polymerized, and any method may be employed.
  • the composition of the mixture may be constant or may be changed.
  • Each monomer may be added to the reaction vessel after previously mixing various monomers to be used, or may be added separately to the reaction vessel.
  • polymerization auxiliary materials such as a chelating agent, a dispersant, a pH adjuster, an oxygen scavenger, and a particle size adjuster can be used, and these are not particularly limited in type and amount used.
  • the polymerization time for carrying out the emulsion polymerization is not particularly limited, but is usually about 5 to 40 hours.
  • the monomer mixture is emulsion-polymerized, and when the predetermined polymerization conversion rate is reached, the polymerization reaction is stopped by cooling the polymerization system or adding a polymerization terminator.
  • the polymerization conversion rate when stopping the polymerization reaction is preferably 90% by weight or more, more preferably 93% by weight or more.
  • the polymerization terminator is not particularly limited.
  • hydroxylamine, hydroxyamine sulfate, diethylhydroxylamine, hydroxyaminesulfonic acid and its alkali metal salt sodium dimethyldithiocarbamate, hydroquinone derivative, catechol derivative, and hydroxydimethyl
  • aromatic hydroxydithiocarboxylic acids such as benzenethiocarboxylic acid, hydroxydiethylbenzenedithiocarboxylic acid, hydroxydibutylbenzenedithiocarboxylic acid, and alkali metal salts thereof.
  • the amount of the polymerization terminator used is preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • the unreacted monomer is removed, and the solid content concentration and pH are adjusted so that the latex of the carboxyl group-containing conjugated diene rubber (A) (the carboxyl group-containing nitrile described above) is obtained.
  • an anti-aging agent an antiseptic, an antibacterial agent, a dispersant, and the like may be appropriately added to the carboxyl group-containing conjugated diene rubber (A) latex used in the present invention, if necessary.
  • the number average particle diameter of the latex of the carboxyl group-containing conjugated diene rubber (A) used in the present invention is preferably 60 to 300 nm, more preferably 80 to 150 nm.
  • the particle diameter can be adjusted to a desired value by a method such as adjusting the amount of emulsifier and polymerization initiator used.
  • the latex composition of the present invention comprises a metal compound (B) containing a trivalent or higher metal in addition to the carboxyl group-containing conjugated diene rubber (A) latex described above.
  • the content ratio of the metal compound (B) containing a trivalent or higher metal to 100 parts by weight of the carboxyl group-containing conjugated diene rubber (A) is in the range of 0.1 to 1.5 parts by weight. .
  • the metal compound (B) containing a trivalent or higher metal acts as a crosslinking agent.
  • a metal compound (B) containing a trivalent or higher metal is used as a cross-linking agent instead of sulfur that is usually used as a cross-linking agent. Because it does not require a sulfur accelerator, in addition to immediate type allergy (Type I), it may cause delayed type allergy (Type IV) due to sulfur and sulfur-containing vulcanization accelerators. It can be effectively suppressed.
  • the above-mentioned specific amount of the metal compound (B) containing a trivalent or higher metal is contained in the latex of the carboxyl group-containing conjugated diene rubber (A), so that a dip-molded body or the like is obtained.
  • the obtained film molded body such as a dip molded body can be provided with a soft texture in addition to high tensile strength and high elongation.
  • a film molded body such as a dip molded body is used for a glove application, in addition to high tensile strength and large elongation, a feeling of use when a user wears this and works is important. Is. And when the present inventors examined such a usability
  • the metal compound (B) containing a trivalent or higher metal is not particularly limited as long as it is a compound containing a trivalent or higher metal, and examples thereof include an aluminum compound, a cobalt compound, a zirconium compound, and a titanium compound. Among these, an aluminum compound is preferable from the viewpoint that the carboxyl group-containing conjugated diene rubber (A) contained in the latex can be more favorably crosslinked.
  • the aluminum compound is not particularly limited.
  • these aluminum compounds can be used individually or in combination of 2 or more types. Among these, sodium aluminate is preferable from the viewpoint that the effects of the present invention can be made more remarkable.
  • the content ratio of the metal compound (B) containing a trivalent or higher valent metal in the latex composition of the present invention is 0.100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing conjugated diene rubber (A) contained in the latex. 1 to 1.5 parts by weight, preferably 0.1 to 1.25 parts by weight, more preferably 0.1 to 1 part by weight, still more preferably 0.1 to 0.8 parts by weight, Particularly preferred is 0.1 to 0.6 parts by weight. If the content ratio of the metal compound containing a trivalent or higher metal is too small, the crosslinking becomes insufficient, and the obtained film molded body such as a dip molded body is inferior in tensile strength. When a film molded body such as a dip molded body is obtained, the obtained film molded body such as a dip molded body has a small elongation and a poor texture.
  • the latex composition of the present invention includes a saccharide (c1), a sugar alcohol ( It is preferable to contain at least one alcoholic hydroxyl group-containing compound (C) selected from c2), hydroxy acid (c3) and hydroxy acid salt (c4).
  • the stability as a latex composition can be further improved, and when it is formed into a film molded body such as a dip molded body, the dip molded body obtained, etc.
  • the film molded body can be provided with a high stress retention.
  • an alcoholic hydroxyl group-containing compound (C) is blended with such a metal compound (B) containing a trivalent or higher metal.
  • a film molded body such as a dip molded body obtained by the action of the metal compound (B) containing a trivalent or higher metal and the alcoholic hydroxyl group-containing compound (C), In addition to having a high tensile strength, a high elongation, and a soft texture, it can also have a high stress retention.
  • the tensile strength is high and the elongation is large from the viewpoint of a feeling of use when this is worn and the work is performed.
  • M 100 such as (0)
  • the high stress retention represented by a percentage of stretch to stop to six minutes later stress M 100 (6)
  • the film composition such as a dip-molded body obtained with good stability as a latex composition has high tensile strength, large elongation, and stress at 500% elongation. In addition to being excellent in (texture), it can have a high stress retention.
  • the alcoholic hydroxyl group-containing compound (C) used in the present invention is at least one selected from saccharide (c1), sugar alcohol (c2), hydroxy acid (c3) and hydroxy acid salt (c4). From the viewpoint that the obtained film molded body such as a dip molded body can have a softer texture and a higher stress retention, sugar alcohol (c2) and hydroxy acid salt (c4) It is preferable to use at least one selected from When two or more alcoholic hydroxyl group-containing compounds (C) are used in combination, at least one selected from saccharide (c1) and sugar alcohol (c2), hydroxy acid (c3) and hydroxy acid salt It is preferable to use a combination of at least one selected from (c4), and it is more preferable to use a combination of sugar alcohol (c2) and hydroxy acid salt (c4).
  • the saccharide (c1) is not particularly limited as long as it is a monosaccharide or a polysaccharide in which two or more monosaccharides are bonded by a glycosidic bond.
  • the sugar alcohol (c2) is not particularly limited as long as it is a monosaccharide or polysaccharide sugar alcohol; for example, tritol such as glycerin; tetritol such as erythritol, D-threitol, L-threitol; D-arabinitol, Pentitols such as L-arabinitol, xylitol, ribitol, pentaerythritol; pentaerythritol; hexitols such as sorbitol, D-iditol, galactitol, D-glucitol, mannitol; heptitols such as boleitol, perseitol; D-erythro-D- Octitol such as galacto-octitol; and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, hexi
  • the hydroxy acid (c3) is not particularly limited as long as it is a carboxylic acid having a hydroxyl group.
  • glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, ⁇ -hydroxy Aliphatic acids such as butyric acid, malic acid, 3-methylmalic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinaleic acid, cerebronic acid, quinic acid, shikimic acid, serine Hydroxy acid; salicylic acid, creosote acid (homosalicylic acid, hydroxy (methyl) benzoic acid), vanillic acid, syringic acid, hydroxypropanoic acid, hydroxypentanoic acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxynona
  • aliphatic hydroxy acids are preferable, aliphatic ⁇ -hydroxy acids are more preferable, glycolic acid, lactic acid, tartronic acid, glyceric acid, malic acid, tartaric acid, and citric acid are more preferable, and glycolic acid is particularly preferable.
  • the hydroxy acid salt (c4) is not particularly limited as long as it is a salt of a hydroxy acid, and examples thereof include metal salts of hydroxy acid exemplified as specific examples of the hydroxy acid (c3), such as sodium and potassium. And alkali metal salts such as calcium and magnesium.
  • the hydroxy acid salt (c4) one kind may be used alone, or two or more kinds may be used in combination.
  • an alkali metal salt of hydroxy acid is preferable, and a sodium salt of hydroxy acid is preferable.
  • the hydroxy acid constituting the hydroxy acid salt (c4) is preferably an aliphatic hydroxy acid, more preferably an aliphatic ⁇ -hydroxy acid, glycolic acid, lactic acid, tartronic acid, glyceric acid, malic acid, tartaric acid, citric acid.
  • An acid is further preferred, and glycolic acid is particularly preferred. That is, sodium glycolate is particularly suitable as the hydroxy acid salt (c4).
  • the content of the alcoholic hydroxyl group-containing compound (C) in the latex composition of the present invention is “the metal compound (B) containing a trivalent or higher metal” relative to the metal compound (B) containing a trivalent or higher metal.
  • Alcoholic hydroxyl group-containing compound (C) preferably in an amount ranging from 1: 0.1 to 1:50, more preferably from 1: 0.2 to 1:45. The amount is more preferably in the range of 1: 0.3 to 1:30.
  • the content of the alcoholic hydroxyl group-containing compound (C) may be such that the content with respect to the metal compound (B) containing a trivalent or higher metal falls within the above range, but the carboxyl group contained in the latex
  • the content with respect to 100 parts by weight of the conjugated diene rubber (A) is preferably 0.03 to 15 parts by weight, and more preferably 0.05 to 10 parts by weight.
  • the latex composition of the present invention includes, for example, a metal compound (B) containing a trivalent or higher metal in a latex of a carboxyl group-containing conjugated diene rubber (A), and an alcoholic hydroxyl group-containing compound (if necessary) ( And C).
  • the metal compound (B) containing a trivalent or higher metal and the alcoholic hydroxyl group-containing compound (C) used as necessary can be favorably dispersed in the obtained latex composition.
  • the metal compound (B) containing a trivalent or higher metal and the alcoholic hydroxyl group-containing compound (C) used as necessary are dissolved in water or alcohol and added in the form of an aqueous solution or alcohol solution.
  • a stabilizer such as a chelating agent or a buffering agent in order to increase the stability of the solution when dissolved.
  • the latex composition of the present invention contains a latex of the carboxyl group-containing conjugated diene rubber (A) described above, a metal compound (B) containing a trivalent or higher metal, and an alcoholic hydroxyl group used as necessary.
  • a filler, a pH adjuster, a thickener, an anti-aging agent, a dispersant, a pigment, a filler, a softener and the like may be blended as desired.
  • the solid content concentration of the latex composition of the present invention is preferably 10 to 40% by weight, more preferably 15 to 35% by weight.
  • the pH of the latex composition of the present invention is preferably 7.5 to 12.0, more preferably 7.5 to 11.0, still more preferably 7.5 to 9.4, particularly preferably 7.5. ⁇ 9.2.
  • the dip molded body of the present invention can be obtained by dip molding the latex composition of the present invention described above.
  • a normal method may be employed, and examples thereof include a direct dipping method, an anode adhesion dipping method, and a teag adhesion dipping method.
  • the anode coagulation dipping method is preferable in that a dip-formed body having a uniform thickness is easily obtained.
  • a dip-molding mold is dipped in a coagulant solution to attach a coagulant to the mold surface, and then dipped in a latex composition to dip on the mold surface.
  • a molding layer is formed.
  • the coagulant examples include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride; nitrates such as barium nitrate, calcium nitrate, and zinc nitrate; acetic acid such as barium acetate, calcium acetate, and zinc acetate. Salts; sulfates such as calcium sulfate, magnesium sulfate, and aluminum sulfate; and the like. Of these, calcium chloride and calcium nitrate are preferred.
  • the coagulant is usually used as a solution of water, alcohol, or a mixture thereof.
  • the coagulant concentration is usually 5 to 50% by weight, preferably 10 to 35% by weight.
  • the obtained dip-molded layer is usually subjected to heat treatment to be crosslinked.
  • water-soluble impurities for example, excess emulsifier and coagulant
  • water-soluble impurities may be removed by immersing in water, preferably warm water of 30 to 70 ° C., for about 1 to 60 minutes.
  • the operation for removing the water-soluble impurities may be performed after the dip-molded layer is heat-treated, but it is preferably performed before the heat-treatment because the water-soluble impurities can be more efficiently removed.
  • the crosslinking of the dip-molded layer is usually performed by performing a heat treatment at a temperature of 80 to 150 ° C., preferably 10 to 130 minutes.
  • a heating method an external heating method using infrared rays or heated air or an internal heating method using high frequency can be employed. Of these, external heating with heated air is preferred.
  • the dip molded body is obtained as a film-shaped film molded body by detaching the crosslinked dip molded layer from the dip molding die.
  • the desorption method it is possible to adopt a method of peeling from the mold by hand, or peeling by water pressure or compressed air pressure. After the desorption, a heat treatment may be further performed at a temperature of 60 to 120 ° C. for 10 to 120 minutes.
  • the film thickness of the film molded body is preferably 0.03 to 0.50 mm, more preferably 0.05 to 0.40 mm, and particularly preferably 0.08 to 0.30 mm.
  • the film molded body of the present invention is a method that can form the latex composition of the present invention into a film (for example, a coating method, etc.). ) As long as it is obtained by any method.
  • the film molded body of the present invention including the dip molded body of the present invention is obtained using the above-described latex composition of the present invention, in addition to immediate allergy (Type I), delayed allergy (Type IV) ) Is also suppressed, and the tensile strength is high, the elongation is large, and a soft texture is provided. Therefore, it is suitable for glove use, particularly for surgical gloves.
  • the membrane molded body of the present invention including the dip molded body of the present invention is a medical product such as a baby bottle nipple, a dropper, a tube, a water pillow, a balloon sack, a catheter, and a condom in addition to gloves; a balloon, a doll, It can also be used for toys such as balls; industrial articles such as pressure forming bags and gas storage bags;
  • the stress retention rate was measured in Examples 2-1 to 2-9, 3-1 to 3-9, 4-1 to 4-8, and Comparative Examples 2-1 to 2-3, 4-1, 4 -2.
  • Production Example 1 Production of latex of carboxyl group-containing nitrile rubber (a1-1)
  • composition of the carboxyl group-containing nitrile rubber (a1-1) contained in the obtained latex is 34.0% by weight of acrylonitrile units, 62.5% by weight of 1,3-butadiene units, and 3.5% by weight of methacrylic acid units. Met.
  • Production Example 2 36 parts from 34 parts amount of the preparation acrylonitrile latex of the carboxyl group-containing nitrile rubber (a1-2), 61 parts of the usage 62.5 parts of 1,3-butadiene, the amount of methacrylic acid 3
  • a latex of carboxyl group-containing nitrile rubber (a1-2) having a solid content of 40% and a pH of 7.5 was obtained in the same manner as in Production Example 1, except that the amount was changed from 5 parts to 3 parts.
  • the composition of the carboxyl group-containing nitrile rubber (a1-2) contained in the obtained latex is 36.0% by weight of acrylonitrile units, 61.0% by weight of 1,3-butadiene units, and 3.0% by weight of methacrylic acid units. Met.
  • Production Example 3 Production of latex of carboxyl group-containing nitrile rubber (a1-3) The amount of acrylonitrile used was changed from 34 parts to 28.0 parts, and the amount of 1,3-butadiene used was changed from 62.5 parts to 68.5 parts. Except for the above, a latex of carboxyl group-containing nitrile rubber (a1-3) having a solid content of 40% and a pH of 7.5 was obtained in the same manner as in Production Example 1. The composition of the carboxyl group-containing nitrile rubber (a1-3) contained in the obtained latex was as follows: acrylonitrile unit 28.0% by weight, 1,3-butadiene unit 68.5% by weight, methacrylic acid unit 3.5% by weight. Met.
  • Production Example 4 Production of latex of carboxyl group-containing nitrile rubber (a1-4) The amount of acrylonitrile used was changed from 34 parts to 30.5 parts, the amount of 1,3-butadiene used was changed from 62.5 parts to 63.5 parts, The amount used was changed from 3.5 parts to 6 parts, respectively, and the pH after the unreacted monomer was distilled off under reduced pressure from the obtained copolymer latex was changed from 7.5 to 7.0.
  • a latex of carboxyl group-containing nitrile rubber (a1-4) having a solid content concentration of 40% and a pH of 7.0 was obtained in the same manner as in Production Example 1 except for the change.
  • composition of the carboxyl group-containing nitrile rubber (a1-4) contained in the obtained latex is 30.5% by weight of acrylonitrile units, 63.5% by weight of 1,3-butadiene units, and 6.0% by weight of methacrylic acid units. Met.
  • Production Example 5 Production of latex of carboxyl group-containing nitrile rubber (a1-5)
  • a pressure-resistant polymerization reaction vessel equipped with a stirrer
  • the temperature was maintained at 37 ° C.
  • Production Example 6 Production of latex of carboxyl group-containing styrene-butadiene rubber (a2-1) In a pressure-resistant vessel equipped with a stirrer, 50 parts of deionized water, 0.3 part of sodium dodecylbenzenesulfonate, 0.4 part of t-dodecyl mercaptan, 1, A monomer emulsion was obtained by charging 63 parts of 3-butadiene, 34 parts of styrene, and 3 parts of methacrylic acid.
  • composition of the obtained carboxyl group-containing styrene-butadiene rubber (a2-1) was 63% by weight of 1,3-butadiene units, 34% by weight of styrene units, and 3% by weight of methacrylic acid units.
  • Production Example 7 In a pressure-resistant polymerization reactor equipped with a latex stirrer of carboxyl group-containing butadiene rubber (a3-1), 97 parts of 1,3-butadiene, 3 parts of methacrylic acid, 0.8 part of t-dodecyl mercaptan as a chain transfer agent, deionized water 132 parts, sodium dodecylbenzenesulfonate 3 parts, ⁇ -naphthalenesulfonic acid formalin condensate 1 part, potassium persulfate 0.3 part, and ethylenediaminetetraacetate 0.005 part are charged, and the polymerization temperature is maintained at 37 ° C. Then, polymerization was started.
  • Production Example 8 Production of latex of carboxyl group-containing nitrile rubber (a1-6)
  • a pressure-resistant polymerization reaction vessel equipped with a stirrer 63 parts of 1,3-butadiene, 34 parts of acrylonitrile, 3 parts of methacrylic acid, t-dodecyl mercaptan as a chain transfer agent 25 parts, 132 parts of deionized water, 3 parts of sodium dodecylbenzenesulfonate, 1 part of sodium ⁇ -naphthalenesulfonate formalin condensate and 0.01 part of sodium hyposulfite were charged, and the polymerization reaction vessel temperature was maintained at 5 ° C.
  • the temperature of the reaction system was kept in the range of 5 to 10 ° C.
  • the unreacted monomer was distilled off from the copolymer latex under reduced pressure, and then the solid content concentration and pH were adjusted to obtain a carboxyl content having a solid content concentration of 40% by weight and pH 8.0.
  • a latex of group-containing nitrile rubber (a1-6) was obtained.
  • the carboxyl group-containing nitrile rubber (a1-6) contained in the obtained latex was measured for the amount of methyl ethyl ketone insoluble matter and the degree of swelling with respect to methyl ethyl ketone.
  • the composition of the obtained carboxyl group-containing nitrile rubber (a1-6) was 63% by weight of 1,3-butadiene units, 34% by weight of acrylonitrile units, and 3% by weight of methacrylic acid units.
  • Production Example 9 Production of latex of carboxyl group-containing styrene-butadiene rubber (a2-1)
  • a pressure-resistant polymerization reaction vessel equipped with a stirrer 63 parts of 1,3-butadiene, 34 parts of styrene, 3 parts of methacrylic acid, t-dodecyl mercaptan as a chain transfer agent 0.4 parts, 132 parts of deionized water, 1.5 parts of sodium dodecylbenzenesulfonate, 1 part of ⁇ -naphthalenesulfonic acid formalin condensate and 0.01 part of sodium hyposulfite were charged, and the temperature of the polymerization reaction vessel was 10. Held at 0C.
  • the carboxyl group-containing styrene-butadiene rubber (a2-2) contained in the obtained latex was measured for the insoluble content of methyl ethyl ketone and the degree of swelling with respect to methyl ethyl ketone.
  • the insoluble amount of methyl ethyl ketone was 70% by weight and the degree of swelling with respect to methyl ethyl ketone was 60%. It was twice.
  • the composition of the obtained carboxyl group-containing styrene-butadiene rubber (a2-2) was 63% by weight of 1,3-butadiene units, 34% by weight of styrene units, and 3% by weight of methacrylic acid units.
  • the carboxyl group-containing butadiene rubber (a3-2) contained in the obtained latex was measured for the insoluble content of methyl ethyl ketone and the degree of swelling with respect to methyl ethyl ketone.
  • the insoluble amount of methyl ethyl ketone was 65% by weight and the degree of swelling with respect to methyl ethyl ketone was 80 times. there were.
  • the composition of the resulting carboxyl group-containing butadiene rubber (a3-2) was 97% by weight of 1,3-butadiene units and 3% by weight of methacrylic acid units.
  • Production Example 11 Production of latex of carboxyl group-containing nitrile rubber (a1-7) Carboxyl group-containing nitrile rubber in the same manner as in Production Example 5, except that the amount of t-dodecyl mercaptan used as a chain transfer agent was changed to 0.50 parts. A latex (a1-7) was obtained. The carboxyl group-containing nitrile rubber (a1-7) contained in the obtained latex was measured for the insoluble content of methyl ethyl ketone and the degree of swelling with respect to methyl ethyl ketone.
  • the composition of the obtained carboxyl group-containing nitrile rubber (a1-7) was 63% by weight of 1,3-butadiene units, 34% by weight of acrylonitrile units, and 3% by weight of methacrylic acid units.
  • the composition of the obtained carboxyl group-containing nitrile rubber (a1-8) was 63% by weight of 1,3-butadiene units, 34% by weight of acrylonitrile units, and 3% by weight of methacrylic acid units.
  • Production Example 13 Production of latex of carboxyl group-containing nitrile rubber (a1-9)
  • a pressure-resistant polymerization reaction vessel equipped with a stirrer 62.5 parts of 1,3-butadiene, 34 parts of acrylonitrile, 3 parts of methacrylic acid, as an amide group-containing monomer N-methylolacrylamide 0.5 part, t-dodecyl mercaptan 0.25 part as chain transfer agent, deionized water 132 parts, sodium dodecylbenzenesulfonate 3 parts, sodium ⁇ -naphthalenesulfonate formalin condensate 1 part,
  • the polymerization reaction vessel temperature was maintained at 5 ° C.
  • a latex (a1-9) was obtained.
  • the composition of the obtained carboxy group-containing nitrile rubber (a1-9) was 62.5% by weight of 1,3-butadiene units, 34% by weight of acrylonitrile units, 3% by weight of methacrylic acid units, 0.5% of N-methylolacrylamide units. % By weight.
  • Production Example 14 Preparation of latex of carboxyl group-containing nitrile rubber (a1-10) Instead of N-methylolacrylamide as an amide group-containing monomer, except that 0.5 part of glycidyl methacrylate as an epoxy group-containing monomer was used In the same manner as in Production Example 13, a latex of carboxyl group-containing nitrile rubber (a1-10) was obtained.
  • the composition of the resulting carboxyl group-containing nitrile rubber (a1-10) was composed of 62.5% by weight of 1,3-butadiene units, 34% by weight of acrylonitrile units, 3% by weight of methacrylic acid units, and 0.5% by weight of glycidyl methacrylate units. Met.
  • Production Example 15 Manufacture of latex of carboxyl group-containing nitrile rubber (a1-11) The amount of 1,3-butadiene used was changed to 61 parts, and the amount of N-methylolacrylamide as an amide group-containing monomer was changed to 2.0 parts. Except for the above, a carboxyl group-containing nitrile rubber (a1-11) latex was obtained in the same manner as in Production Example 13. The composition of the obtained carboxyl group-containing nitrile rubber (a1-11) was composed of 61% by weight of 1,3-butadiene units, 34% by weight of acrylonitrile units, 3% by weight of methacrylic acid units, and 2.0% by weight of N-methylolacrylamide units. Met.
  • Production Example 16 61 parts of the amount of production of 1,3-butadiene latex of the carboxyl group-containing nitrile rubber (A1-12), except for changing each 2.0 parts usage glycidyl methacrylate as the epoxy group-containing monomer
  • a latex of carboxyl group-containing nitrile rubber (a1-12) was obtained.
  • the composition of the resulting carboxyl group-containing nitrile rubber (a1-12) was 61% by weight of 1,3-butadiene units, 34% by weight of acrylonitrile units, 3% by weight of methacrylic acid units, and 2.0% by weight of glycidyl methacrylate units. It was.
  • Production Example 17 Production of latex of carboxyl group-containing styrene-butadiene rubber (a2-3) In a pressure-resistant vessel equipped with a stirrer, 50 parts of deionized water, 0.3 part of sodium dodecylbenzenesulfonate, 0.4 t-dodecyl mercaptan as a chain transfer agent Parts, 1.3-butadiene 62.5 parts, styrene 34 parts, methacrylic acid 3 parts, and amide group-containing monomer N-methylolacrylamide 0.5 parts were obtained to obtain a monomer emulsion.
  • a2-3 carboxyl group-containing styrene-butadiene rubber
  • the resulting carboxyl group-containing styrene-butadiene rubber (a2-3) had a composition of 62.5% by weight of 1,3-butadiene units, 34% by weight of styrene units, 3% by weight of methacrylic acid units, 0 units of N-methylolacrylamide units. 0.5% by weight.
  • Production Example 18 Preparation of latex of carboxyl group-containing styrene-butadiene rubber (a2-4) Instead of N-methylolacrylamide as an amide group-containing monomer, 0.5 part of glycidyl methacrylate as an epoxy group-containing monomer was used. Except for the above, a carboxyl group-containing styrene-butadiene rubber (a2-4) latex was obtained in the same manner as in Production Example 17.
  • the resulting carboxyl group-containing styrene-butadiene rubber (a2-4) had a composition of 62.5% by weight of 1,3-butadiene units, 34% by weight of styrene units, 3% by weight of methacrylic acid units, 0.5% of glycidyl methacrylate units. % By weight.
  • Production Example 19 In a pressure-resistant polymerization reaction vessel equipped with a latex stirrer of carboxyl group-containing butadiene rubber (a3-3), 96.5 parts of 1.3-butadiene, 3 parts of methacrylic acid, and N-methylolacrylamide as an amide group-containing monomer were added.
  • sodium dimethyldithiocarbamate 0% as a polymerization terminator is used as a polymerization terminator.
  • the polymerization reaction was stopped by adding 1 part.
  • the unreacted monomer was distilled off from the copolymer latex under reduced pressure, and then the solid content concentration and pH were adjusted to obtain a carboxyl content having a solid content concentration of 40% by weight and pH 8.0.
  • a latex of group-containing butadiene rubber (a3-3) was obtained.
  • the composition of the obtained carboxyl group-containing butadiene rubber (a3-3) was 96.5% by weight of 1,3-butadiene units, 3% by weight of methacrylic acid units, and 0.5% by weight of N-methylolacrylamide units.
  • Production Example 20 Manufactured except that 0.5 part of glycidyl methacrylate as an epoxy group-containing monomer was used in place of N-methylolacrylamide as a latex amide group-containing monomer of carboxyl group-containing butadiene rubber (a3-4) In the same manner as in Example 19, a latex of carboxyl group-containing butadiene rubber (a3-4) was obtained.
  • the composition of the obtained carboxyl group-containing butadiene rubber (a3-4) was 96.5% by weight of 1,3-butadiene units, 3% by weight of methacrylic acid units, and 0.5% by weight of glycidyl methacrylate units.
  • Example 1-1 Preparation of Latex Composition
  • Deionized water was added to 250 parts of latex (100 parts in terms of carboxyl group-containing nitrile rubber (a1-1)) of carboxyl group-containing nitrile rubber (a1-1) obtained in Production Example 1.
  • the solid concentration was adjusted to 35% by weight, and then 0.4 part of a sodium aluminate aqueous solution was added in terms of sodium aluminate.
  • the latex composition was obtained by adjusting solid content concentration to 30 weight% by further adding deionized water. .
  • the obtained latex composition was subjected to an operation for removing aggregates and the like in the latex composition by filtration as necessary (Examples 1-2 to 1-5, Comparative Example 1 described later).
  • Examples 1-2 to 1-5, Comparative Example 1 described later the operation for removing aggregates and the like was performed in the same manner as necessary.
  • Example 1-2 Example 1-1, except that when preparing the latex composition, the amount of sodium aluminate aqueous solution added was changed to 0.2 parts in terms of sodium aluminate and the pH of the composition was adjusted to 8.5.
  • a latex composition and a dip-formed product (rubber glove) were produced in the same manner as described above and evaluated in the same manner. The results are shown in Table 1.
  • Example 1-3 In preparing the latex composition, instead of the latex of the carboxyl group-containing nitrile rubber (a1-1) obtained in Production Example 1, the carboxyl group-containing nitrile rubber (a1-2) obtained in Production Example 2 was used. While using latex (100 parts in terms of carboxyl group-containing nitrile rubber (a1-2)), the amount of sodium aluminate aqueous solution added was 0.3 parts in terms of sodium aluminate, and the pH of the composition was 8.5. A latex composition and a dip-molded body (rubber glove) were produced in the same manner as in Example 1-1 except that the above was adjusted, and evaluated in the same manner. The results are shown in Table 1.
  • Example 1-4 When preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-1) latex obtained in Production Example 1, the carboxyl group-containing nitrile rubber (a1-3) obtained in Production Example 3 was used. A latex composition and dip were prepared in the same manner as in Example 1-2 except that latex (100 parts in terms of carboxyl group-containing nitrile rubber (a1-3)) was used and the pH of the composition was adjusted to 8.3. A molded body (rubber glove) was produced and evaluated in the same manner. The results are shown in Table 1.
  • Example 1-5 When preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-1) latex obtained in Production Example 1, the carboxyl group-containing nitrile rubber (a1-4) obtained in Production Example 4 was used. Except that latex (100 parts in terms of carboxyl group-containing nitrile rubber (a1-4)) was used and the pH of the composition was adjusted to 7.5, the latex composition and A dip-molded body (rubber glove) was produced and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 1-1 A latex composition and a dip-molded body (rubber gloves) were prepared in the same manner as in Example 1-1 except that when preparing the latex composition, the aqueous sodium aluminate solution was not added and the pH was adjusted to 8.4. Were manufactured and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 1-2 In preparing the latex composition, 1 part of sulfur (crosslinking agent), 0.5 part of zinc dibutyldithiocarbamate (vulcanization accelerator), and 1.2 parts of zinc oxide were used in place of the sodium aluminate aqueous solution. A latex composition and a dip-formed product (rubber glove) were produced in the same manner as in Example 1-1 except that the pH was adjusted to 8.5, and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 1-3 A latex composition and a dip-formed product (rubber gloves) were prepared in the same manner as in Example 1-1 except that 1.5 parts of zinc oxide was used instead of the sodium aluminate aqueous solution when preparing the latex composition. Were manufactured and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 1-4 A latex composition and a dip-molded body (rubber) were prepared in the same manner as in Example 1-1 except that the amount of the sodium aluminate aqueous solution was changed to 2.0 parts in terms of sodium aluminate when preparing the latex composition. Gloves) were manufactured and evaluated in the same manner. The results are shown in Table 1.
  • Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 As shown in Table 1, latex containing carboxyl group-containing conjugated diene rubber (A) and a metal containing a trivalent or higher metal The content ratio of the metal compound (B) containing the compound (B) and containing a trivalent or higher metal is 0.1 to 1.5 with respect to 100 parts by weight of the carboxyl group-containing conjugated diene rubber (A).
  • the dip-molded body (rubber glove) obtained by using the latex composition in parts by weight has a large tensile strength and elongation and a soft texture (less stress at 500% elongation). Examples 1-1 to 1-5).
  • Example 2-1 250 parts latex of a carboxyl group-containing nitrile rubber obtained in Preparation Production Example 5 (a1-5) latex composition (carboxyl group-containing nitrile rubber (a1-5) 100 parts by equivalent), sodium aluminate 0.5 Part, 0.75 part of sorbitol and 0.75 part of sodium glycolate in water were added. And deionized water was added to this, and the latex composition was obtained by adjusting solid content concentration to 30 weight%.
  • a coagulant aqueous solution was prepared by mixing 30 parts of calcium nitrate, 0.05 part of polyethylene glycol octylphenyl ether, which is a nonionic emulsifier, and 70 parts of water.
  • a ceramic glove mold preliminarily heated to 70 ° C. is immersed in this aqueous coagulant solution for 5 seconds, pulled up, and dried at a temperature of 70 ° C. for 10 minutes to attach the coagulant to the glove mold. It was. Then, the glove mold with the coagulant attached is immersed in the latex composition obtained above for 10 seconds, pulled up, then immersed in warm water at 50 ° C.
  • Example 2-2 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-5) latex, 250 parts of the carboxyl group-containing styrene-butadiene rubber (a2-1) latex obtained in Production Example 6 (carboxyl A latex composition having a solid content concentration of 30% by weight and a dip-molded body (rubber gloves) except that a group-containing styrene-butadiene rubber (a2-1) 100 parts) was used. Were manufactured and evaluated in the same manner. The results are shown in Table 2.
  • Example 2-3 When preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-5) latex, 250 parts of the carboxyl group-containing butadiene rubber (a3-1) latex obtained in Production Example 7 (carboxyl group-containing) A latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber gloves) were produced in the same manner as in Example 2-1, except that 100 parts of butadiene rubber (a3-1) was used. Evaluation was performed in the same manner. The results are shown in Table 2.
  • Example 2-4 When preparing the latex composition, the solid content concentration was 30% by weight in the same manner as in Example 2-1, except that the blending amount of sorbitol was changed to 1.5 parts and sodium glycolate was not blended. A latex composition and a dip-molded body (rubber gloves) were produced and evaluated in the same manner. The results are shown in Table 2.
  • Example 2-5 When preparing the latex composition, the solid content concentration was 30% by weight in the same manner as in Example 2-1, except that the blending amount of sodium glycolate was changed to 1.5 parts and sorbitol was not blended. A latex composition and a dip-molded body (rubber gloves) were produced and evaluated in the same manner. The results are shown in Table 2.
  • Example 2-6 When preparing the latex composition, the amount of sodium aluminate was changed to 0.1 part, the amount of sorbitol was changed to 0.015 part, and the amount of sodium glycolate was changed to 0.015 part. In the same manner as in Example 2-1, a latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber glove) were produced and evaluated in the same manner. The results are shown in Table 2.
  • Example 2-7 When preparing the latex composition, the amount of sodium aluminate was changed to 0.1 part, the amount of sorbitol was changed to 0.5 part, and the amount of sodium glycolate was changed to 0.5 part, respectively.
  • a latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber glove) were produced and evaluated in the same manner. The results are shown in Table 2.
  • Example 2-8 When preparing the latex composition, the amount of sodium aluminate was changed to 1 part, the amount of sorbitol was changed to 0.15 parts, and the amount of sodium glycolate was changed to 0.15 parts, respectively.
  • a latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber glove) were produced and evaluated in the same manner. The results are shown in Table 2.
  • Example 2-9 Example 2 was prepared except that the amount of sodium aluminate was changed to 1 part, the amount of sorbitol was changed to 5 parts, and the amount of sodium glycolate was changed to 5 parts when preparing the latex composition.
  • a latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber gloves) were produced and evaluated in the same manner. The results are shown in Table 2.
  • Comparative Example 2-1 A latex composition and a dip-molded body having a solid content of 30% by weight were prepared in the same manner as in Example 2-1, except that sodium aluminate, sorbitol and sodium glycolate were not blended when preparing the latex composition. (Rubber gloves) were manufactured and evaluated in the same manner. The results are shown in Table 2.
  • Comparative Example 2-2 A latex composition and a dip-molded body having a solid content concentration of 30% by weight were prepared in the same manner as in Example 2-2, except that sodium aluminate, sorbitol and sodium glycolate were not blended when preparing the latex composition. (Rubber gloves) were manufactured and evaluated in the same manner. The results are shown in Table 2.
  • Comparative Example 2-3 A latex composition having a solid content concentration of 30% by weight and a dip-molded article were prepared in the same manner as in Example 2-3, except that sodium aluminate, sorbitol and sodium glycolate were not blended when preparing the latex composition. (Rubber gloves) were manufactured and evaluated in the same manner. The results are shown in Table 2.
  • a latex composition obtained by blending a carboxyl group-containing conjugated diene rubber (A) latex with an alcoholic hydroxyl group-containing compound (C) in addition to a metal compound (B) containing a trivalent or higher metal.
  • the dip-molded body (rubber glove) obtained by using such a latex composition is excellent in stability as a latex composition, has a large tensile strength and elongation, and has a soft texture (stress at 500% elongation). (Examples 2-1 to 2-9).
  • the resulting latex composition has a tensile strength when formed into a dip-molded body (rubber glove). As a result (Comparative Examples 2-1 to 2-3).
  • Example 3-1 250 parts latex of a carboxyl group-containing nitrile rubber obtained in Preparation Production Example 8 (a1-6) latex composition (carboxyl group-containing nitrile rubber (a1-6) 100 parts by equivalent), sodium aluminate 0.2 A mixed aqueous solution in which 0.4 part of sorbitol and 0.4 part of sodium glycolate were dissolved in water was added. And a deionized water and 5 weight% potassium hydroxide aqueous solution were added to this, and the latex composition was obtained by adjusting solid content concentration to 30 weight% and pH to 9.2.
  • a coagulant aqueous solution was prepared by mixing 30 parts of calcium nitrate, 0.05 part of polyethylene glycol octylphenyl ether, which is a nonionic emulsifier, and 70 parts of water.
  • a ceramic glove mold preliminarily heated to 70 ° C. is immersed in this aqueous coagulant solution for 5 seconds, pulled up, and dried at a temperature of 70 ° C. for 10 minutes to attach the coagulant to the glove mold. It was. Then, the glove mold with the coagulant attached is immersed in the latex composition obtained above for 10 seconds, pulled up, then immersed in warm water at 50 ° C.
  • Example 3-2 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-6) latex, 250 parts of the carboxyl group-containing styrene-butadiene rubber (a2-2) latex obtained in Production Example 9 (carboxyl A latex composition having a solid content concentration of 30% by weight and a dip-molded body (rubber glove) in the same manner as in Example 3-1, except that a group-containing styrene-butadiene rubber (a2-2) 100 parts) was used. Were manufactured and evaluated in the same manner. The results are shown in Table 3.
  • Example 3-3 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-6) latex, 250 parts of the carboxyl group-containing butadiene rubber (a3-2) latex obtained in Production Example 10 (carboxyl group-containing) Except that butadiene rubber (100 parts in terms of a3-2) was used, a latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber gloves) were produced in the same manner as in Example 3-1, Evaluation was performed in the same manner. The results are shown in Table 3.
  • Example 3-4 The amount of sodium aluminate is 0.2 to 0.5 parts, the amount of sorbitol is 0.4 to 0.75 parts, and the amount of sodium glycolate is 0.4 to 0.75 parts
  • a latex composition and a dip-molded body (rubber glove) having a solid content concentration of 30% by weight were produced in the same manner as in Example 3-1, except that each was changed. The results are shown in Table 3.
  • Example 3-5 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-6) latex, 250 parts of the carboxyl group-containing nitrile rubber (a1-5) latex obtained in Production Example 5 (carboxyl group-containing) A latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber gloves) were produced in the same manner as in Example 3-1, except that 100 parts of nitrile rubber (a1-5) was used. Evaluation was performed in the same manner. The results are shown in Table 3.
  • Example 3-6 When preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-6) latex, 250 parts of the carboxyl group-containing styrene-butadiene rubber (a2-1) latex obtained in Production Example 6 (carboxyl) A latex composition having a solid content concentration of 30% by weight and a dip-molded article (rubber gloves) except that a group-containing styrene-butadiene rubber (a2-1) 100 parts) was used. Were manufactured and evaluated in the same manner. The results are shown in Table 3.
  • Example 3-7 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-6) latex, 250 parts of the carboxyl group-containing butadiene rubber (a3-1) latex obtained in Production Example 7 (carboxyl group-containing) A latex composition having a solid content concentration of 30% by weight and a dip-molded body (rubber gloves) were produced in the same manner as in Example 3-1, except that 100 parts of butadiene rubber (a3-1) was used. Evaluation was performed in the same manner. The results are shown in Table 3.
  • Example 3-8 When preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-6) latex, 250 parts of the carboxyl group-containing nitrile rubber (a1-7) latex obtained in Production Example 11 (carboxyl group-containing) A latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber gloves) were produced in the same manner as in Example 3-1, except that 100 parts of nitrile rubber (a1-7) was used. Evaluation was performed in the same manner. The results are shown in Table 3.
  • Example 3-9 When preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-6) latex, 250 parts of the carboxyl group-containing nitrile rubber (a1-8) latex obtained in Production Example 12 (carboxyl group-containing) A latex composition having a solid content concentration of 30% by weight and a dip-formed product (rubber gloves) were produced in the same manner as in Example 3-1, except that 100 parts of nitrile rubber (a1-8) was used. Evaluation was performed in the same manner. The results are shown in Table 3.
  • the results shown in Table 3 indicate that by using the carboxyl group-containing conjugated diene rubber (A) obtained by emulsion polymerization at 0 to 25 ° C., the elongation is large and the soft texture (at 500% elongation) It is confirmed that the tensile strength can be further improved while keeping the stress of the Further, by comparing Examples 3-5, 3-8, and 3-9, the amount of chain transfer agent used was in the range of 0.15 to 0.95 parts by weight with respect to 100 parts by weight of the monomer mixture. It can be said that the tensile strength, the elongation, and the soft texture (the stress at the time of 500% elongation is small) can be appropriately adjusted within a suitable range.
  • Example 4-1 250 parts latex of a carboxyl group-containing nitrile rubber obtained in Preparation Production Example 13 (A1-9) latex composition (carboxyl group-containing nitrile rubber (A1-9) 100 parts by equivalent), sodium aluminate 0.2 A mixed aqueous solution in which 0.4 part of sorbitol and 0.4 part of sodium glycolate were dissolved in water was added. And the deionized water and 5% potassium hydroxide aqueous solution were added to this, and the latex composition was obtained by adjusting solid content concentration to 30 weight% and pH9.2.
  • Example 4-2 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-9) latex, 250 parts of the carboxyl group-containing nitrile rubber (a1-10) latex obtained in Production Example 14 (carboxyl group-containing) A latex composition and a dip-formed product (rubber glove) were produced in the same manner as in Example 4-1, except that 100 parts of nitrile rubber (a1-10) was used, and evaluated in the same manner. The results are shown in Table 4.
  • Example 4-3 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-9) latex, 250 parts of the carboxyl group-containing nitrile rubber (a1-11) latex obtained in Production Example 15 (carboxyl group-containing) A latex composition and a dip-molded body (rubber glove) were produced in the same manner as in Example 4-1, except that 100 parts of nitrile rubber (a1-11) was used, and evaluated in the same manner. The results are shown in Table 4.
  • Example 4-4 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-9) latex, 250 parts of the carboxyl group-containing nitrile rubber (a1-12) latex obtained in Production Example 16 (carboxyl group-containing) A latex composition and a dip-formed product (rubber glove) were produced in the same manner as in Example 4-1, except that 100 parts of nitrile rubber (a1-12) was used, and evaluated in the same manner. The results are shown in Table 4.
  • Example 4-5 When preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-9) latex, 250 parts of the carboxyl group-containing styrene-butadiene rubber (a2-3) latex obtained in Production Example 17 (carboxyl) A latex composition and a dip-molded body (rubber glove) were produced in the same manner as in Example 4-1, except that the group-containing styrene-butadiene rubber (100 parts in terms of a2-3) was used. went. The results are shown in Table 4.
  • Example 4-6 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-9) latex, 250 parts of the carboxyl group-containing styrene-butadiene rubber (a2-4) latex obtained in Production Example 18 (carboxyl) A latex composition and a dip-molded body (rubber glove) were produced in the same manner as in Example 4-1, except that the group-containing styrene-butadiene rubber (100 parts in terms of a2-4) was used. went. The results are shown in Table 4.
  • Example 4-7 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-9) latex, 250 parts of the carboxyl group-containing butadiene rubber (a3-3) latex obtained in Production Example 19 (carboxyl group-containing) A latex composition and a dip-molded body (rubber glove) were produced in the same manner as in Example 4-1, except that butadiene rubber (100 parts in terms of a3-3) was used, and evaluated in the same manner. The results are shown in Table 4.
  • Example 4-8 In preparing the latex composition, instead of the carboxyl group-containing nitrile rubber (a1-9) latex, 250 parts of the carboxyl group-containing butadiene rubber (a3-4) latex obtained in Production Example 20 (carboxyl group-containing) A latex composition and a dip-formed product (rubber gloves) were produced in the same manner as in Example 4-1, except that butadiene rubber (100 parts in terms of a3-4) was used, and evaluated in the same manner. The results are shown in Table 4.
  • Comparative Example 4-1 A latex composition and a dip-formed product (rubber gloves) were produced in the same manner as in Example 4-1, except that sodium aluminate, sorbitol and sodium glycolate were not blended when preparing the latex composition. Evaluation was performed in the same manner. The results are shown in Table 4.
  • Comparative Example 4-2 A latex composition and a dip-formed product (rubber gloves) were produced in the same manner as in Example 4-2, except that sodium aluminate, sorbitol and sodium glycolate were not blended when preparing the latex composition. Evaluation was performed in the same manner. The results are shown in Table 4.

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Abstract

L'invention concerne une composition de latex qui contient un latex d'un caoutchouc à base de diène conjugué contenant un groupe carboxyle (A) et un composé métallique contenant un métal trivalent ou supérieur, la teneur du composé métallique étant de 0,1 à 1,5 parties en poids pour 100 parties en poids du caoutchouc à base de diène conjugué contenant un groupe carboxyle (A).
PCT/JP2017/007225 2016-02-25 2017-02-24 Composition de latex et corps moulé en film Ceased WO2017146238A1 (fr)

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EP17756672.6A EP3421532B1 (fr) 2016-02-25 2017-02-24 Composition de latex et corps moulé en film
CN201780011194.7A CN108602991B (zh) 2016-02-25 2017-02-24 胶乳组合物及膜成型体
US16/078,554 US11236218B2 (en) 2016-09-30 2017-02-24 Latex composition and film molded body
MYPI2018001475A MY194391A (en) 2016-02-25 2017-02-24 Latex composition and film molded body
KR1020187023980A KR20180114064A (ko) 2016-02-25 2017-02-24 라텍스 조성물 및 막 성형체

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JP2016193430A JP6855734B2 (ja) 2016-02-25 2016-09-30 ラテックス組成物および膜成形体
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JP2016193434A JP6787008B2 (ja) 2016-02-25 2016-09-30 ラテックス組成物の製造方法
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JP2020049825A (ja) * 2018-09-27 2020-04-02 日本ゼオン株式会社 ディップ成形体の製造方法
WO2020066835A1 (fr) * 2018-09-26 2020-04-02 日本ゼオン株式会社 Méthode de fabrication de gants
CN111655780A (zh) * 2018-02-16 2020-09-11 日本瑞翁株式会社 胶乳组合物和膜成型体
JP2020164690A (ja) * 2019-03-29 2020-10-08 日本ゼオン株式会社 ディップ成形用ラテックス組成物
CN112912432A (zh) * 2019-09-27 2021-06-04 株式会社Lg化学 用于浸渍模塑的胶乳组合物、其制备方法和由其模塑的模塑制品
US11058162B2 (en) 2016-02-25 2021-07-13 Zeon Corporation Method for manufacturing glove
US11065788B2 (en) 2016-02-25 2021-07-20 Zeon Corporation Method for manufacturing gloves
JP2022093281A (ja) * 2020-12-11 2022-06-23 エルジー・ケム・リミテッド ディップ成形用ラテックス組成物由来の層を含むディップ成形品
WO2022168831A1 (fr) 2021-02-04 2022-08-11 ミドリ安全株式会社 Agent de réticulation d'aluminium pour moulage par immersion, composition de moulage par immersion, gants et procédé de production de gants
CN114981340A (zh) * 2020-12-11 2022-08-30 株式会社Lg化学 包括来自用于浸渍成型的胶乳组合物的层的浸渍成型制品
WO2025164576A1 (fr) * 2024-01-31 2025-08-07 デンカ株式会社 Polymère à base de chloroprène, latex polymère à base de chloroprène, composition de latex polymère à base de chloroprène, article moulé par immersion, composition de caoutchouc et article moulé

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07316211A (ja) * 1994-05-23 1995-12-05 Takeda Chem Ind Ltd 共重合体ラテックス組成物及びその製造方法
WO2000073367A1 (fr) * 1999-05-28 2000-12-07 Suzuki Latex Industry Co., Ltd. Produits de latex non collants
JP2005060577A (ja) * 2003-08-15 2005-03-10 Jsr Corp ラテックス組成物及びその製造方法、並びにこれを用いたアスファルト組成物及びカチオン性アスファルト乳剤
WO2007072900A1 (fr) * 2005-12-21 2007-06-28 Zeon Corporation Composition de caoutchouc reticulable et produit de caoutchouc reticule
JP2009520049A (ja) * 2005-12-16 2009-05-21 エクソンモービル・ケミカル・パテンツ・インク エラストマー組成物の加工助剤
JP2012188797A (ja) * 2011-02-25 2012-10-04 Nippon A&L Inc 紙塗工用共重合体ラテックス及び紙塗工用組成物
JP2015105281A (ja) * 2013-11-28 2015-06-08 日本ゼオン株式会社 ディップ成形用組成物およびディップ成形品
US20150232637A1 (en) * 2013-08-29 2015-08-20 Lg Chem, Ltd. Carboxylic acid-modified nitrile-based copolymer latex composition and dip molded article including the same
WO2016104057A1 (fr) * 2014-12-25 2016-06-30 日本ゼオン株式会社 Composition de latex pour moulage par immersion, et article moulé par immersion

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07316211A (ja) * 1994-05-23 1995-12-05 Takeda Chem Ind Ltd 共重合体ラテックス組成物及びその製造方法
WO2000073367A1 (fr) * 1999-05-28 2000-12-07 Suzuki Latex Industry Co., Ltd. Produits de latex non collants
JP2005060577A (ja) * 2003-08-15 2005-03-10 Jsr Corp ラテックス組成物及びその製造方法、並びにこれを用いたアスファルト組成物及びカチオン性アスファルト乳剤
JP2009520049A (ja) * 2005-12-16 2009-05-21 エクソンモービル・ケミカル・パテンツ・インク エラストマー組成物の加工助剤
WO2007072900A1 (fr) * 2005-12-21 2007-06-28 Zeon Corporation Composition de caoutchouc reticulable et produit de caoutchouc reticule
JP2012188797A (ja) * 2011-02-25 2012-10-04 Nippon A&L Inc 紙塗工用共重合体ラテックス及び紙塗工用組成物
US20150232637A1 (en) * 2013-08-29 2015-08-20 Lg Chem, Ltd. Carboxylic acid-modified nitrile-based copolymer latex composition and dip molded article including the same
JP2015105281A (ja) * 2013-11-28 2015-06-08 日本ゼオン株式会社 ディップ成形用組成物およびディップ成形品
WO2016104057A1 (fr) * 2014-12-25 2016-06-30 日本ゼオン株式会社 Composition de latex pour moulage par immersion, et article moulé par immersion

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11058162B2 (en) 2016-02-25 2021-07-13 Zeon Corporation Method for manufacturing glove
US11065788B2 (en) 2016-02-25 2021-07-20 Zeon Corporation Method for manufacturing gloves
CN111655780A (zh) * 2018-02-16 2020-09-11 日本瑞翁株式会社 胶乳组合物和膜成型体
WO2020066835A1 (fr) * 2018-09-26 2020-04-02 日本ゼオン株式会社 Méthode de fabrication de gants
JP7547204B2 (ja) 2018-09-26 2024-09-09 日本ゼオン株式会社 手袋の製造方法
JPWO2020066835A1 (ja) * 2018-09-26 2021-09-24 日本ゼオン株式会社 手袋の製造方法
JP7131255B2 (ja) 2018-09-27 2022-09-06 日本ゼオン株式会社 ディップ成形体の製造方法
JP2020049825A (ja) * 2018-09-27 2020-04-02 日本ゼオン株式会社 ディップ成形体の製造方法
JP2020164690A (ja) * 2019-03-29 2020-10-08 日本ゼオン株式会社 ディップ成形用ラテックス組成物
CN112912432B (zh) * 2019-09-27 2022-10-25 株式会社Lg化学 用于浸渍模塑的胶乳组合物、其制备方法和由其模塑的模塑制品
CN112912432A (zh) * 2019-09-27 2021-06-04 株式会社Lg化学 用于浸渍模塑的胶乳组合物、其制备方法和由其模塑的模塑制品
CN114981340A (zh) * 2020-12-11 2022-08-30 株式会社Lg化学 包括来自用于浸渍成型的胶乳组合物的层的浸渍成型制品
JP2022093281A (ja) * 2020-12-11 2022-06-23 エルジー・ケム・リミテッド ディップ成形用ラテックス組成物由来の層を含むディップ成形品
JP7348941B2 (ja) 2020-12-11 2023-09-21 エルジー・ケム・リミテッド ディップ成形用ラテックス組成物由来の層を含むディップ成形品
CN114981340B (zh) * 2020-12-11 2024-04-12 株式会社Lg化学 包括来自用于浸渍成型的胶乳组合物的层的浸渍成型制品
WO2022168831A1 (fr) 2021-02-04 2022-08-11 ミドリ安全株式会社 Agent de réticulation d'aluminium pour moulage par immersion, composition de moulage par immersion, gants et procédé de production de gants
WO2025164576A1 (fr) * 2024-01-31 2025-08-07 デンカ株式会社 Polymère à base de chloroprène, latex polymère à base de chloroprène, composition de latex polymère à base de chloroprène, article moulé par immersion, composition de caoutchouc et article moulé

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