Classifications

• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
  • A41D19/00—Gloves
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
  • A41D19/00—Gloves
  • A41D19/015—Protective gloves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
  • C08L21/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/02—Copolymers with acrylonitrile
  • C08L9/04—Latex

Definitions

• the present invention relates to a laminate, and more particularly, to a laminate having excellent chemical permeation resistance and excellent wet grip and flexibility in a well-balanced manner.
• protective gloves are required to have excellent mechanical strength and durability, such as abrasion resistance, as well as excellent flexibility.
• protective gloves are often used in a state where they are wet with chemical solutions such as oil, they are also required to have excellent wet grip properties when the chemical solution is attached and resistance to chemical solution permeation.
• Patent Document 1 describes 50 to 80% by weight of 1,3-butadiene, 15 to 50% by weight of acrylonitrile, 0 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer, and ethylene copolymerizable therewith.
• a copolymer latex for dip molding is described which has a surface tension difference of 6 mN/m or more and a methyl ethyl ketone (MEK) insoluble content of 50% or more.
• MEK methyl ethyl ketone
• the present invention has been made in view of such circumstances, and an object of the present invention is to provide a laminate that has excellent resistance to permeation of chemical liquids and that has a good balance between wet grip properties and flexibility.
• the present inventors have found that the 100% tensile stress of the polymer layer is 1.1 MPa or less, and the surface roughness of the polymer layer is within a specific range. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.
• the 100% tensile stress of the polymer layer is 1.1 MPa or less, and the maximum height roughness Rz of the surface of the polymer layer is 135 to 350 ⁇ m, A laminate having an arithmetic mean roughness Ra of 20 to 72 ⁇ m is provided.
• the latex of the polymer is preferably a latex of the polymer (A) having a glass transition temperature of 10°C or less, and the latex composition has a glass transition temperature of 10°C. It is more preferred to further contain a latex of polymer (B) which is super.
• the polymer latex is preferably a nitrile group-containing conjugated diene polymer latex.
• the thickness of the polymer layer is preferably 0.05 to 1.0 mm.
• the substrate is preferably a fiber substrate.
• the laminate of the invention is preferably a glove.
• the laminate of the present invention is a laminate having a substrate and a polymer layer formed on the substrate, wherein the polymer layer is formed using a latex composition containing polymer latex. It is formed on the base material, the 100% tensile stress of the polymer layer is 1.1 MPa or less, the maximum height roughness Rz of the surface of the polymer layer is 135 to 350 ⁇ m, and arithmetic
• the laminate has an average roughness Ra of 20 to 72 ⁇ m.
• the base material used in the present invention is not particularly limited, but when the laminate of the present invention is used as a protective glove, a fiber base material can be preferably used. Natural fibers such as cotton, wool, hemp, and wool, and synthetic fibers such as polyester, polyurethane, acrylic, and nylon can be used as materials for the fibers constituting the fiber base material.
• the fibers constituting the fiber base material may be single fibers (one by one extracted from the above natural fibers or synthetic fibers), or may be twisted yarns composed of a plurality of single fibers. is preferably
• the fiber substrate may be a knitted or woven fabric of the fibers described above, or may be a non-woven fabric.
• the fiber base material may be sewn.
• the fiber base material is not particularly limited, for example, it is possible to use twisted monofilament yarns as fibers and to form a glove shape by weaving the twisted yarns.
• the average thickness of the fiber base material is preferably 50-3,000 ⁇ m, more preferably 100-2,000 ⁇ m.
• the polymer layer of the laminate of the present invention is formed on a substrate using a latex composition containing polymer latex.
• the polymer constituting the latex of the polymer used in the present invention is not particularly limited, but examples include nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), and synthetic polyisoprene rubber (IR). , polybutadiene rubber (BR), styrene-isoprene copolymer rubber, styrene-isoprene-styrene copolymer rubber and other conjugated diene polymers, polybutyl acrylate, butyl rubber (IIR), and the like.
• NBR nitrile rubber
• NR natural rubber
• SBR styrene-butadiene rubber
• IR synthetic polyisoprene rubber
• BR polybutadiene rubber
• styrene-isoprene copolymer rubber styrene-isoprene-styrene copolymer rubber and other conjugated diene polymers
• NBR nitrile rubber
• SBR styrene-butadiene rubber
• IR synthetic polyisoprene rubber
• polybutyl acrylate are more preferable.
• Conjugated diene polymers containing nitrile groups such as NBR (hereinafter referred to as "nitrile group-containing conjugated diene polymers” as appropriate) are more preferred.
• conjugated diene polymers may be conjugated diene polymers containing carboxyl groups (hereinafter referred to as "carboxyl group-containing conjugated diene polymers” as appropriate).
• the nitrile group-containing conjugated diene-based polymer is not particularly limited. A copolymer obtained by copolymerizing other ethylenically unsaturated acid monomers can be used.
• the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited, but an ethylenically unsaturated compound having a nitrile group and preferably having 3 to 18 carbon atoms can be used.
• Such ⁇ , ⁇ -ethylenically unsaturated nitrile monomers include, for example, acrylonitrile, methacrylonitrile, halogen-substituted acrylonitrile, etc. Among these, acrylonitrile is particularly preferred.
• These ⁇ , ⁇ -ethylenically unsaturated nitrile monomers may be used singly or in combination of two or more.
• the content ratio of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units in the nitrile group-containing conjugated diene polymer is preferably based on the total monomer units from the viewpoint of the flexibility and solvent resistance of the laminate. is 10 to 45% by weight, more preferably 15 to 40% by weight, still more preferably 20 to 40% by weight.
• conjugated diene monomer a conjugated diene monomer having 4 to 6 carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and chloroprene is preferable. , 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is particularly preferred.
• conjugated diene monomers may be used singly or in combination of two or more.
• the content of conjugated diene monomer units in the nitrile group-containing conjugated diene polymer is preferably 40 to 89.9% by weight, more preferably 40 to 89.9% by weight, based on the total monomer units, from the viewpoint of the flexibility of the laminate. is 50 to 84% by weight, more preferably 52 to 78% by weight, particularly preferably 55 to 75% by weight.
• the nitrile group-containing conjugated diene polymer can be copolymerized with a monomer forming an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a monomer forming a conjugated diene monomer unit. may be copolymerized with other ethylenically unsaturated acid monomers.
• Such other copolymerizable ethylenically unsaturated acid monomers are not particularly limited, but examples include vinyl aromatic monomers such as styrene, alkylstyrene, and vinylnaphthalene, monomers, monocarboxylic acid ester group-containing ethylenically unsaturated monomers, dicarboxylic acid diester group-containing ethylenically unsaturated monomers, sulfonic acid group-containing ethylenically unsaturated monomers, phosphoric acid group-containing ethylenically unsaturated monomers
• the nitrile group-containing conjugated diene polymer can be one containing a carboxyl group, and as a result, the resulting laminate has excellent mechanical properties.
• a carboxyl group-containing ethylenically unsaturated monomer is preferred from the viewpoint of being able to Polymers constituting the polymer latex include, for example, ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units, conjugated diene monomer units in nitrile group-containing conjugated diene polymers, and carboxyl group-containing ethylenically unsaturated It may be a polymer consisting of only monomers.
• the carboxyl group-containing ethylenically unsaturated monomer is not particularly limited, but ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; fumaric acid, maleic acid, itaconic acid, maleic anhydride, anhydride ethylenically unsaturated polycarboxylic acids such as itaconic acid and anhydrides thereof; partially esterified products of ethylenically unsaturated polycarboxylic acids such as methyl maleate and methyl itaconate; and the like.
• monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid
• partially esterified products of ethylenically unsaturated polycarboxylic acids such as
• the content ratio of the unit of the carboxyl group-containing ethylenically unsaturated monomer is the total monomer unit , preferably 0.1 to 15 wt%, more preferably 1 to 10 wt%, still more preferably 2 to 8 wt%.
• the monocarboxylic acid ester group-containing ethylenically unsaturated monomer is not particularly limited, but acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate; methyl methacrylate, ethyl methacrylate, methacrylic acid; methacrylic acid esters such as n-butyl; crotonic acid esters such as methyl crotonate; and the like. Among them, acrylic acid esters and methacrylic acid esters are preferred, and methyl acrylate and methyl methacrylate are more preferred.
• dicarboxylic acid diester group-containing ethylenically unsaturated monomer examples include, but are not limited to, maleic acid diesters such as dimethyl maleate; itaconic acid diesters such as methyl itaconate; and the like.
• the sulfonic acid group-containing ethylenically unsaturated monomer is not particularly limited, but vinylsulfonic acid, methylvinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, ethyl (meth)acrylic acid-2-sulfonate. , 2-acrylamido-2-hydroxypropanesulfonic acid and the like.
• phosphate group-containing ethylenically unsaturated monomer examples include, but are not limited to, propyl (meth)acrylate-3-chloro-2-phosphate, ethyl (meth)acrylate-2-phosphate, 3-allyloxy -2-hydroxypropane phosphate and the like.
• copolymerizable ethylenically unsaturated acid monomers may be used as alkali metal salts or ammonium salts, and may be used singly or in combination of two or more. good.
• carboxyl group-containing ethylenically unsaturated monomers are preferred, ethylenically unsaturated monocarboxylic acids are more preferred, and acrylic acid and methacrylic acid are preferred. More preferred, methacrylic acid is particularly preferred.
• the ratio is preferably 0.1 to 45% by weight with respect to the total monomer units, and more It is preferably 1 to 40% by weight, more preferably 2 to 38% by weight.
• the polymer latex used in the present invention can be obtained, for example, by emulsion polymerization of a monomer mixture containing the above monomers.
• auxiliary materials for polymerization such as emulsifiers, polymerization initiators, and molecular weight modifiers can be used.
• the emulsifier used for emulsion polymerization is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. preferable.
• anionic surfactant used in emulsion polymerization examples include a compound (a) having one anionic group and an aromatic ring, and a compound (b1) having two or more anionic groups and a benzene ring, which will be described later. ), a compound (b2) having one anionic group and no aromatic ring, and the like.
• a compound (a) having one anionic group and an aromatic ring and a compound (b1) having two or more anionic groups and a benzene ring, which will be described later.
• a compound (b2) having one anionic group and no aromatic ring and the like.
• the amount of emulsifier used in emulsion polymerization is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of all the monomers used.
• radical initiators include, but are not limited to, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl organic peroxides such as peroxides and t-butyl peroxyisobutyrate; azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl
• polymerization initiators may be used singly or in combination of two or more.
• the amount of polymerization initiator to be used is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, per 100 parts by weight of all the monomers used.
• molecular weight modifiers include, but are not limited to, ⁇ -methylstyrene dimer; mercaptans such as t-dodecylmercaptan, n-dodecylmercaptan and octylmercaptan; halogenated compounds such as carbon tetrachloride, methylene chloride and methylene bromide; hydrocarbons; sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropyl xanthogen disulfide; These molecular weight modifiers may be used singly or in combination of two or more.
• the amount of the molecular weight modifier used varies depending on its type, but is preferably 0.1 to 1.5 parts by weight, more preferably 0.2 to 1.0 parts by weight, based on 100 parts by weight of the total monomers used. Department.
• Emulsion polymerization is usually carried out in water.
• the amount of water used is preferably 80 to 500 parts by weight, more preferably 100 to 200 parts by weight, per 100 parts by weight of all the monomers used.
• secondary polymerization materials other than the above may be used as necessary.
• auxiliary materials for polymerization include chelating agents, dispersants, pH adjusters, oxygen scavengers, particle size adjusters, and the like, and the types and amounts used are not particularly limited.
• Methods of adding the monomers include, for example, a method of collectively adding the monomers used in the reaction vessel, a method of continuously or intermittently adding the monomers as the polymerization progresses, and a method of partially adding the monomers. reaction to a specific conversion rate, and then the remaining monomers are added continuously or intermittently for polymerization, and any method may be employed.
• the composition of the mixture can be constant or varied.
• each monomer may be added to the reaction vessel after previously mixing various monomers to be used, or may be added to the reaction vessel separately.
• the polymerization temperature during emulsion polymerization is not particularly limited, but is usually 0 to 95°C, preferably 5 to 70°C.
• the polymerization time is not particularly limited, but is usually about 5 to 40 hours.
• unreacted monomers may be removed and the solid content concentration and pH may be adjusted.
• the glass transition temperature of the polymer constituting the latex of the polymer used in the present invention is 10° C. or less, preferably ⁇ 55° C. to 5° C., from the viewpoint that the effect of the present invention becomes more pronounced. More preferably -45 to 0°C, particularly preferably -40 to -10°C.
• a method for adjusting the glass transition temperature of the polymer to the above range is not particularly limited, but includes, for example, a method for adjusting the content ratio of each monomer unit constituting the polymer to the above range.
• the volume average particle diameter of the polymer particles constituting the latex of the polymer used in the present invention is preferably 30 to 1000 nm, more preferably 50 to 500 nm, from the viewpoint that the effect of the present invention becomes more remarkable. More preferably, it is 70 to 200 nm.
• the volume-average particle size and median particle size of the polymer particles constituting the polymer latex can be measured using, for example, a light scattering and diffraction particle measuring device.
• the surface tension of the polymer latex at 25° C. is preferably 20 to 70 mN/m, more preferably 25 to 60 mN/m, still more preferably 30 to 50 mN/m, from the viewpoint that the effect of the present invention becomes more pronounced. is.
• the difference between the surface tension of the polymer latex at 25°C and the surface tension of the anionic surfactant at 25°C is preferably -10 to 15 mN/m, more than It is preferably -5 to 10 mN/m, more preferably 0 to 8 mN/m.
• the surface tension of the polymer latex at 25°C and the difference between the surface tension of the polymer latex at 25°C and the surface tension of the anionic surfactant at 25°C are described in Examples. method.
• the latex composition used in the present invention preferably contains an anionic surfactant in addition to the polymer latex.
• anionic surfactants include a compound (a) having one anionic group and an aromatic ring, a compound (b1) having two or more anionic groups and a benzene ring, and an anionic group. and a compound (b2) having no aromatic ring.
• the latex composition used in the present invention contains, as anionic surfactants, a compound (a) having one anionic group and an aromatic ring, and a compound (b1) having two or more anionic groups and a benzene ring. ) and/or a compound (b2) having one anionic group and no aromatic ring.
• the latex composition used in the present invention preferably contains a compound (a) having one anionic group and an aromatic ring.
• Compound (a) having one anionic group and having an aromatic ring hereinafter referred to as "compound (a)" as appropriate) is a compound having only one anionic group and having an aromatic ring is.
• Examples of the anionic group possessed by the compound (a) include a carboxylic acid group (--COOH), a carboxylic acid group (--COOX), a sulfonic acid group (--SO 3 H), a sulfonic acid group (--SO 3 X), and a sulfate ester.
• X is an atom or molecule that constitutes a cation.
• Examples of X include metal atoms such as lithium, sodium, potassium, calcium, magnesium and aluminum, ammonium and the like, with sodium, potassium and ammonium being preferred, and sodium being more preferred.
• the anionic group possessed by the compound (a) is preferably a sulfonate group or a sulfate ester group, more preferably a sulfonate group, and still more preferably a sodium sulfonate group (--SO 3 Na). That is, compound (a) is preferably a sulfonate or a sulfate, more preferably a sulfonate, and even more preferably a sodium sulfonate.
• the aromatic ring of the compound (a) is not particularly limited as long as it is a ring having aromaticity, but non-condensed aromatic rings such as benzene ring, condensed aromatic rings such as naphthalene ring, and the like can be mentioned.
• the compound (a) preferably has a non-condensed aromatic ring, and although the number of non-condensed aromatic rings in the compound (a) is not particularly limited, one is preferred.
• the non-condensed aromatic ring of the compound (a) is preferably a benzene ring, and although the number of benzene rings in the compound (a) is not particularly limited, one is preferred.
• the compound (a) preferably has an alkyl group.
• the alkyl group in compound (a) preferably has 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms.
• Examples of the compound (a) include sodium decylbenzenesulfonate, potassium decylbenzenesulfonate, sodium undecylbenzenesulfonate, potassium undecylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, and tridecylbenzenesulfonic acid.
• Alkylbenzenesulfonates such as sodium, potassium tridecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, and potassium tetradecylbenzenesulfonate can be mentioned.
• Acid salts are preferred, sodium alkylbenzenesulfonate is preferred, sodium dodecylbenzenesulfonate is preferred.
• Compound (a) may be used alone or in combination of two or more.
• the molecular weight of compound (a) is preferably from 100 to 600, more preferably from 200 to 500, even more preferably from 300 to 400, from the viewpoint that the effects of the present invention become more pronounced.
• the latex composition used in the present invention contains a compound (b1) having two or more anionic groups and a benzene ring and/or a compound (b2) having one anionic group and no aromatic ring. is preferred. That is, the latex composition used in the present invention preferably contains at least one of compound (b1) and compound (b2), and may contain both compound (b1) and compound (b2). The latex composition used in the present invention more preferably contains at least the compound (b1) from the viewpoint that the effects of the present invention become more pronounced.
• the number of anionic groups may be two or more, particularly although not limited, the number is preferably two.
• Examples of the anionic group possessed by the compound (b1) include a carboxylic acid group (--COOH), a carboxylic acid group (--COOX), a sulfonic acid group (--SO 3 H), a sulfonic acid group (--SO 3 X), and a sulfate ester.
• X is an atom or molecule that constitutes a cation.
• Examples of X include metal atoms such as lithium, sodium, potassium, calcium, magnesium and aluminum, ammonium and the like, with sodium, potassium and ammonium being preferred, and sodium being more preferred.
• the anionic group possessed by the compound (b1) is preferably a sulfonate group or a sulfate ester group, more preferably a sulfonate group, and still more preferably a sodium sulfonate group (--SO 3 Na). That is, compound (b1) is preferably a sulfonate or a sulfate ester salt, more preferably a sulfonate, and even more preferably a sodium sulfonate.
• the two or more anionic groups possessed by compound (b1) may be the same or different, but are preferably the same.
• the compound (b1) has a benzene ring.
• the number of benzene rings in the compound (b1) is not particularly limited, it is preferably two or more, more preferably two.
• Compound (b1) may have an aromatic ring other than the benzene ring.
• aromatic rings other than benzene rings include heteroatom-containing non-condensed aromatic rings and condensed aromatic rings such as naphthalene rings.
• the number of aromatic rings other than the benzene ring in the compound (b1) is preferably 2 or less, more preferably 1 or less, and still more preferably 0. That is, compound (b1) preferably does not have an aromatic ring other than a benzene ring.
• the compound (b1) preferably has an ether bond, and more preferably has a diphenyl ether structure.
• the compound (b1) preferably has an alkyl group.
• the alkyl group in compound (b1) preferably has 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms.
• Examples of the compound (b1) include alkyldiphenylether disulfonates such as disodium alkyldiphenyletherdisulfonate, dipotassium alkyldiphenyletherdisulfonate, and diammonium alkyldiphenyletherdisulfonate. Among them, the effect of the present invention becomes more remarkable. From this point of view, disodium alkyldiphenyl ether disulfonate is preferable, disodium alkyldiphenylether disulfonate having an alkyl group having 8 to 16 carbon atoms is more preferable, and disodium alkyldiphenylether disulfonate having an alkyl group having 10 to 14 carbon atoms is preferable. Sodium is more preferred. Compound (b1) may be used alone or in combination of two or more.
• the molecular weight of compound (b1) is preferably from 100 to 1000, more preferably from 200 to 850, even more preferably from 300 to 750, and particularly preferably from 400 to 650, from the viewpoint that the effects of the present invention become more pronounced.
• a compound (b2) having one anionic group and no aromatic ring (hereinafter referred to as "compound (b2)" as appropriate) has only one anionic group and an aromatic ring It is a compound that does not have
• Examples of the anionic group possessed by the compound (b2) include a carboxylic acid group (--COOH), a carboxylic acid group (--COOX), a sulfonic acid group (--SO 3 H), a sulfonic acid group (--SO 3 X), and a sulfate ester.
• X is an atom or molecule that constitutes a cation.
• Examples of X include metal atoms such as lithium, sodium, potassium, calcium, magnesium and aluminum, ammonium and the like, with sodium, potassium and ammonium being preferred, and sodium being more preferred.
• the anionic group possessed by the compound (b2) is preferably a sulfonate group or a sulfate group, more preferably a sulfate group, and even more preferably a sodium sulfate group (--OSO 3 Na). That is, the compound (b2) is preferably a sulfonate or a sulfate, more preferably a sulfate, and even more preferably a sodium sulfate.
• the compound (b2) preferably has an alkyl group.
• the number of carbon atoms in the alkyl group in compound (b2) is preferably 8-16, more preferably 10-14.
• Compound (b2) includes fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, sodium rosinate; di(2-ethylhexyl)sodium sulfosuccinate, di(2-ethylhexyl) ) Alkyl sulfosuccinates such as potassium sulfosuccinate and sodium dioctyl sulfosuccinate; sodium octyl sulfate, potassium octyl sulfate, sodium decyl sulfate, potassium decyl sulfate, sodium undecyl sulfate, potassium undecyl sulfate, sodium dodecyl sulfate (sodium lauryl sulfate), dodecyl Alkyl sulfate ester salts such as potassium sulfate (potassium lauryl s
• the molecular weight of compound (b2) is preferably from 100 to 600, more preferably from 200 to 450, even more preferably from 250 to 350, from the viewpoint that the effects of the present invention become more pronounced.
• the latex composition used in the present invention contains, as anionic surfactants, a compound (a) having one anionic group and an aromatic ring and a compound (b1) having two or more anionic groups and a benzene ring. ) and/or the compound (b2) having one anionic group and no aromatic ring, from the viewpoint that the effect of the present invention becomes more remarkable, the compound (a) is a sulfone acid salt or sulfate salt, and at least one of compound (b1) or compound (b2) is preferably sulfonate or sulfate salt.
• the content of the compound (a) is the polymer component contained in the latex composition from the viewpoint that the effect of the present invention becomes more pronounced.
• 100 parts by weight preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight, further preferably 0.8 to 2.4 parts by weight, 1.0 to 2 parts by weight 0 parts by weight is particularly preferred, and 1.2 to 1.5 parts by weight is most preferred.
• the content of the compound (b1) is the polymer component contained in the latex composition from the viewpoint that the effect of the present invention becomes more pronounced.
• 100 parts by weight preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 7.0 parts by weight, further preferably 1.0 to 5.0 parts by weight, 1.2 to 4 parts by weight .5 parts by weight is particularly preferred.
• the content of the compound (b2) is the polymer component contained in the latex composition from the viewpoint that the effect of the present invention becomes more pronounced.
• 100 parts by weight preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 7.0 parts by weight, further preferably 1.0 to 5.0 parts by weight, 1.2 to 4 parts by weight .5 parts by weight is particularly preferred.
• the total content of the compound (b1) and the compound (b2) is higher than the effect of the present invention.
• it is preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 7.0 parts by weight, with respect to 100 parts by weight of the polymer component contained in the latex composition. 0 to 5.0 parts by weight is more preferred, and 1.2 to 4.5 parts by weight is particularly preferred.
• the content of compound (a), compound (b1) and compound (b2) ) (weight of compound (a): total weight of compound (b1) and compound (b2)) is from 5:95 to It is preferably 95:5, more preferably 10:90 to 90:10, even more preferably 15:85 to 80:20, particularly preferably 20:80 to 70:30. .
• the latex composition used in the present invention preferably contains a latex of the polymer (A) having a glass transition temperature of 10°C or lower, and in addition to the latex of the polymer (A) having a glass transition temperature of 10°C or lower. Therefore, it is more preferable to further contain a latex of polymer (B) having a glass transition temperature of more than 10°C.
• Polymer (A) having a glass transition temperature of 10°C or lower (hereinafter referred to as “polymer (A) latex”) having a glass transition temperature of 10°C or lower ( A) (hereinafter referred to as “polymer (A)” as appropriate) is not particularly limited, but examples include nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), synthetic poly Examples include conjugated diene polymers such as isoprene rubber (IR), polybutadiene rubber (BR), styrene-isoprene copolymer rubber, styrene-isoprene-styrene copolymer rubber, polybutyl acrylate, butyl rubber (IIR), and the like.
• NBR nitrile rubber
• NR natural rubber
• SBR styrene-butadiene rubber
• synthetic poly Examples include conjugated diene polymers such as isoprene rubber (IR
• nitrile rubber NBR
• SBR styrene-butadiene rubber
• IR synthetic polyisoprene rubber
• polybutyl acrylate Preferred are nitrile group-containing conjugated diene polymers. These conjugated diene-based polymers may be carboxyl group-containing conjugated diene-based polymers.
• the polymer (A) having a glass transition temperature of 10° C. or lower those having a glass transition temperature of 10° C. or lower among those mentioned above as polymers constituting the latex of the polymer used in the present invention are suitable.
• the polymer (A) having a glass transition temperature of 10° C. or lower those mentioned above as the nitrile group-containing conjugated diene polymer capable of forming the latex of the polymer used in the present invention are suitable.
• the volume-average particle diameter of the polymer particles constituting the polymer (A) latex is preferably 30 to 1000 nm, more preferably 50 to 500 nm, and even more preferably 70 to 200 nm.
• the polymer (B) can be finely dispersed more favorably in the polymer (A) in the polymer layer of the laminate. As a result, the effects of the present invention become more pronounced, and the mechanical properties of the laminate can be enhanced.
• a polymer (B) (hereinafter referred to as “polymer (B)” as appropriate) is not particularly limited, but examples thereof include acrylic resins, PTFE resins, acrylonitrile-styrene (AS) resins, polyurethanes, vinyl chloride resins, and polystyrene resins. etc., and among these, acrylic resins are preferred. These polymers may be used individually by 1 type, and may be used in combination of 2 or more type.
• Acrylic resins include, for example, acrylic acid esters, methacrylic acid esters, acrylic acid, homopolymers of methacrylic acid, copolymers of acrylic acid esters and acrylic acid, copolymers of acrylic acid esters and methacrylic acid, methacrylic acid Copolymer of acid ester and acrylic acid, copolymer of methacrylic acid ester and methacrylic acid, copolymer of acrylic acid ester, methacrylic acid ester and acrylic acid, acrylic acid ester, methacrylic acid ester and methacrylic acid and copolymers of acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid.
• a homopolymer of acrylic acid ester, methacrylic acid ester, acrylic acid, or methacrylic acid and a homopolymer of methacrylic acid ester is used.
• the homopolymer of acrylic acid ester includes not only homopolymers of the same acrylic acid ester, but also copolymers of two or more acrylic acid esters (for example, ethyl acrylate and butyl acrylate).
• homopolymers of methacrylic acid esters include not only homopolymers of the same methacrylic acid esters, but also copolymers of two or more methacrylic acid esters.
• the total content of acrylic acid ester, methacrylic acid ester, acrylic acid, and methacrylic acid units in the acrylic resin is preferably 40 to 100% by weight, more preferably 70%, based on the total monomer units. ⁇ 100% by weight.
• Acrylic esters used to form acrylic resins include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec- Butyl, tert-butyl acrylate, n-pentyl acrylate, sec-pentyl acrylate, isopentyl acrylate, neopentyl acrylate, n-hexyl acrylate, isohexyl acrylate, neohexyl acrylate, sec-hexyl acrylate, and acrylic acid tert-hexyl and the like, among which methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate are preferred, and methyl acrylate is more preferred.
• Methacrylate esters used to form acrylic resins include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec- Butyl, tert-butyl methacrylate, n-pentyl methacrylate, sec-pentyl methacrylate, isopentyl methacrylate, neopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, neohexyl methacrylate, sec-hexyl methacrylate, and methacryl acid tert-hexyl and the like, among which methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate are preferred, and methyl methacrylate
• the acrylic resin may be obtained by copolymerizing an acrylic acid ester monomer, a methacrylic acid ester monomer, an acrylic acid monomer, or other monomers copolymerizable with a methacrylic acid monomer.
• copolymerizable monomers include ⁇ -olefin monomers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene; styrene, ⁇ -methylstyrene , aromatic monomers such as vinylpyridine; ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid; ⁇ , such as monomethyl maleate, monoethyl maleate and monoethyl itaconate, ⁇ -ethylenically unsaturated polycarboxylic acid monoesters; ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acids such as dimethyl maleate, di-n-butyl fumarate, dimethyl itaconate, and di-2-ethylhexyl itaconate Polyvalent esters; vinyl ester monomers such as vinyl acetate and vinyl propionate; ⁇ , ⁇ -
• the method for producing the acrylic resin latex as the polymer (B) is not particularly limited as long as it is a method capable of polymerizing the above monomers. A method by turbidity polymerization and the like can be mentioned.
• the polymer (B) is preferably obtained by using a persulfate such as sodium persulfate, potassium persulfate and ammonium persulfate as a polymerization initiator.
• a persulfate such as sodium persulfate, potassium persulfate and ammonium persulfate
• the polymer (B) can be made to have a sulfuric acid group at the polymer chain end as a residue of the polymerization initiator, whereby the latex of the polymer (B) can be chemically Better stability can be achieved.
• the weight average molecular weight (Mw) of the acrylic resin as the polymer (B) is not particularly limited, but is preferably 10,000 to 10,000,000, more preferably 10,000 to 5,000,000. be.
• the glass transition temperature of the polymer (B) is higher than 10°C, and from the viewpoint that the effects of the present invention become more pronounced, it is preferably 30°C or higher, more preferably 70°C or higher, and even more preferably It is 95° C. or higher, particularly preferably 105° C. or higher.
• the upper limit of the glass transition temperature of the polymer (B) is not particularly limited, it is preferably 200°C or lower, more preferably 150°C or lower.
• a method for adjusting the glass transition temperature of the polymer (B) to the above range is not particularly limited, but includes a method of adjusting the content ratio of each monomer unit constituting the polymer.
• the latex composition used in the present invention includes a latex of the polymer (A) having a glass transition temperature of 10°C or less and a polymer (A) having a glass transition temperature of more than 10°C. It is preferably a latex composition obtained by mixing the latex of coalescence (B) in a latex state.
• a latex composition obtained by mixing the latex of coalescence (B) in a latex state By mixing the latex of the polymer (A) and the latex of the polymer (B) in a latex state, dripping during molding can be suppressed when a laminate is obtained using such a latex composition. , the obtained laminate can be further excellent in wet grip properties.
• the particles of the polymer (A) and the particles of the polymer (B) are added to the latex composition.
• the particles can be uniformly finely dispersed.
• the polymer (B) can be co-precipitated in a state in which the polymer (B) is finely dispersed in the matrix of the polymer (A) in the resulting laminate. . Therefore, the action of the finely dispersed polymer (B) makes it possible to make the resulting laminate even more excellent in wet grip properties.
• the volume average particle diameter of the particles of the polymer (B) constituting the latex of the polymer (B) is It is preferably smaller than the volume-average particle size of the constituent polymer (A) particles.
• the volume average particle diameter of the particles of the polymer (B) constituting the latex of the polymer (B) is preferably 1 to 200 nm, more preferably 5 to 160 nm, even more preferably 5 to 120 nm, still more preferably 10 to 100 nm. 100 nm, particularly preferably 20 to 80 nm.
• the polymer (B) can be finely dispersed more favorably in the polymer (A) in the polymer layer of the laminate. As a result, the effects of the present invention become more pronounced, and the mechanical properties of the laminate can be enhanced.
• the content of the polymer (A) in the latex composition and the content of the polymer (B) is not particularly limited, but the content of the polymer (A) in 100% by weight of the polymer component contained in the latex composition is preferably 75 to 100% by weight, preferably 80 to 99% by weight. %, more preferably 85 to 95% by weight.
• the content of the polymer (B) is preferably 0 to 25% by weight, more preferably 1 to 20% by weight, based on 100% by weight of the polymer component contained in the latex composition. More preferably 5 to 15% by weight.
• the weight ratio of the polymer (A) to the polymer (B) in the latex composition (weight of the polymer (A):weight of the polymer (B)) has a more pronounced effect of the present invention. Therefore, it is preferably 75:25 to 100:0, more preferably 80:20 to 99:1, still more preferably 85:15 to 95:5.
• the latex composition used in the present invention preferably further contains a sulfur-based cross-linking agent in addition to the polymer latex and the anionic surfactant described above.
• the sulfur-based cross-linking agent is not particularly limited, but sulfur such as powdered sulfur, sulfur flowers, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothia Sulfur-containing compounds such as dil disulfide, caprolactam disulfide, phosphorus-containing polysulfide, and polymeric polysulfides; sulfur-donating compounds such as tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, and 2-(4′-morpholinodithio)benzothiazole; is mentioned.
• sulfur-based cross-linking agents may be used singly or in combination of two or more.
• the content of the sulfur-based cross-linking agent is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and still more preferably 0 parts by weight with respect to 100 parts by weight of the polymer component contained in the latex composition. .1 to 2 parts by weight.
• the latex composition used in the present invention preferably further contains a cross-linking accelerator (vulcanization accelerator) and zinc oxide in addition to the sulfur-based cross-linking agent.
• a cross-linking accelerator vulcanization accelerator
• zinc oxide in addition to the sulfur-based cross-linking agent.
• cross-linking accelerator examples include, but are not limited to, dithiocarbamines such as diethyldithiocarbamate, dibutyldithiocarbamate, di-2-ethylhexyldithiocarbamate, dicyclohexyldithiocarbamate, diphenyldithiocarbamate, and dibenzyldithiocarbamate.
• dithiocarbamines such as diethyldithiocarbamate, dibutyldithiocarbamate, di-2-ethylhexyldithiocarbamate, dicyclohexyldithiocarbamate, diphenyldithiocarbamate, and dibenzyldithiocarbamate.
• the content of the cross-linking accelerator is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polymer component contained in the latex composition.
• the content of zinc oxide is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer component contained in the latex composition.
• the latex composition used in the present invention may further contain a water-soluble polymer.
• water-soluble polymers examples include vinyl compounds such as polyvinyl alcohol and polyvinylpyrrolidone; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose and salts thereof; polycarboxylic acid compounds such as polyacrylic acid and sodium salts thereof. ; polyoxyethylene derivatives such as polyethylene glycol ether; and the like.
• cellulose derivatives and salts thereof are preferred, and carboxymethylcellulose and sodium salts thereof are more preferred.
• the content of the water-soluble polymer is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polymer component contained in the latex composition.
• the viscosity of a 4% by weight aqueous solution of the water-soluble polymer is not particularly limited, but is preferably 1 mPa s or more, more preferably 10 mPa s or more, preferably 20,000 mPa s or less, and 10,000 mPa s. The following are more preferred.
• the viscosity of a 1% by weight aqueous solution of the water-soluble polymer is not particularly limited, but is preferably 1 mPa s or more, more preferably 10 mPa s or more, preferably 20,000 mPa s or less, and 10,000 mPa s. The following are more preferred.
• the viscosity of the water-soluble polymer aqueous solution can be measured, for example, using a Brookfield viscometer under the conditions of 25° C. and 6 rpm.
• the water-soluble polymer is not particularly limited as long as it is soluble in water, and the solubility of the water-soluble polymer in water is not particularly limited, but is preferably 1 g or more, more preferably 1 g or more, with respect to 100 g of water at a temperature of 25 ° C. It is 7 g or more, particularly preferably 10 g or more.
• the upper limit of the water solubility of the water-soluble polymer is not particularly limited, but is usually 1,000,000 g or less.
• the weight average molecular weight (Mw) of the water-soluble polymer is not particularly limited, but is preferably 100 or more, more preferably 1,000 or more, preferably 5,000,000 or less, and more preferably 3,000,000 or less.
• the blending amount of the water-soluble polymer is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polymer component contained in the latex composition used in the present invention. , more preferably 0.15 to 4.5 parts by weight.
• the blending amount of the water-soluble polymer is within the above range, the resulting laminate has even better wet grip properties.
• the volume average particle size of the polymer particles in the latex composition used in the present invention is preferably 30 to 250 nm, more preferably 30 to 200 nm, still more preferably 50 to 180 nm.
• the obtained latex composition can be made excellent in storage stability, and the laminate can be improved by wet grip properties. It can be made even better.
• the volume average particle size of the polymer particles in the latex composition used in the present invention can be measured using, for example, a light scattering diffraction particle measuring device.
• the latex composition used in the present invention includes carbon black, silica, calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate, magnesium oxide, zinc (meth)acrylate, magnesium (meth)acrylate, titanium oxide, and the like. Fillers may be added.
• the amount of the filler compounded is preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymer component contained in the latex composition for dip molding of the present invention. More preferably 2 to 5 parts by weight. When the blending amount of the filler is within the above range, the resulting dip-molded article has even better wet grip properties.
• the latex composition used in the present invention may optionally contain additives other than the water-soluble salts and fillers, such as antioxidants, antioxidants, preservatives, antibacterial agents, wetting agents, and dispersing agents. , pigments, dyes, reinforcing agents, pH adjusters, and other additives may be added in predetermined amounts.
• additives other than the water-soluble salts and fillers such as antioxidants, antioxidants, preservatives, antibacterial agents, wetting agents, and dispersing agents.
• pigments, dyes, reinforcing agents, pH adjusters, and other additives may be added in predetermined amounts.
• the solid content concentration of the latex composition used in the present invention is preferably 20-65% by weight, more preferably 30-60% by weight, still more preferably 35-55% by weight.
• Methods for adjusting the solid content concentration of the latex composition used in the present invention within the range described above include, for example, a method of adjusting the solid content concentration of each component such as a polymer latex, and a concentration treatment or dilution treatment described later. method. Among these, the method of adjusting by concentration treatment is preferable from the viewpoint of productivity.
• the pH of the latex composition used in the present invention is preferably 5-13, more preferably 7-10, still more preferably 7.5-9.
• the method for producing the latex composition used in the present invention is not particularly limited as long as it can produce a latex composition containing polymer latex.
• a method for producing the latex composition used in the present invention a method of preparing two or more kinds of polymer latexes and mixing them in a latex state is preferable.
• a method for producing the latex composition used in the present invention a method for producing a latex composition containing an anionic surfactant in addition to a polymer latex is preferable. More preferred is a production method that yields a latex composition containing compound (a) and compounds (b1) and/or (b2) as anionic surfactants.
• two or more types of polymer latex are prepared and mixed in a latex state to obtain a polymer latex, a compound (a), and a compound Examples of methods by which latex compositions containing (b1) and/or (b2) are obtained.
• the latex composition used in the present invention includes, for example, a latex (A 1 -a) containing a first polymer (A 1 ) having a glass transition temperature of 10° C. or lower and a compound (a), and a latex (A 1 -a) having a glass transition temperature of A latex (A 2 -b) containing a second polymer (A 2 ) having a temperature of 10° C. or less and a compound (b1) and/or a compound (b2) is mixed in a latex state.
• a latex (A 1 ) containing a first polymer (A 1 ) having a glass transition temperature of 10° C. or lower and a compound (a)
• a latex (A 1 -a) having a glass transition temperature of A latex (A 2 -b) containing a second polymer (A 2 ) having a temperature of 10° C. or less and a compound (b1) and/or a compound (b2) is mixed in a latex state
• a method for producing the latex composition used in the present invention a method of mixing the latex (A 1 -a) and the latex (A 2 -b) in a latex state is preferable.
• the balance between flexibility and wet grip properties can be further improved while realizing permeability.
• aggregates of appropriate size are generated, and the surface of the resulting laminate is It is presumed that this is due to the formation of an appropriate concave-convex structure.
• the composition of polymer (A 1 ) and the composition of polymer (A 2 ) may be the same or different.
• the polymer (A 1 ) is a nitrile group-containing conjugated diene polymer
• the polymer (A 2 ) is a nitrile group-containing conjugated diene polymer having the same or different composition as the polymer (A 1 ).
• it may be a polymer other than the nitrile group-containing conjugated diene polymer (for example, polybutyl acrylate).
• the polymer (A 2 ) is a nitrile group-containing conjugated diene polymer
• the polymer (A 1 ) is a nitrile group-containing conjugated diene polymer having the same or different composition as the polymer (A 2 ).
• it may be a polymer other than the nitrile group-containing conjugated diene polymer (for example, polybutyl acrylate).
• the difference between the glass transition temperature of the polymer (A 1 ) and the glass transition temperature of the polymer (A 2 ) is preferably 30° C. or less, more preferably 20° C. or less, and 15° C. or less. It is more preferably 10°C or lower, particularly preferably 10°C or lower, and most preferably 5°C or lower.
• the latex composition used in the present invention includes, for example, a latex (Aa) containing a polymer (A) having a glass transition temperature of 10°C or less and a compound (a), and a latex (Aa) having a glass transition temperature of 10°C.
• a latex (Bb) containing a super polymer (B) and a compound (b1) and/or a compound (b2) may be obtained by a production method of mixing in a latex state.
• abbreviations such as “latex (Aa)” and “latex (Bb)” are used as appropriate.
• the latex composition used in the present invention is, for example, a latex (Ab) containing a polymer (A) having a glass transition temperature of 10° C. or lower and a compound (b1) and/or a compound (b2), Alternatively, a latex (Ba) containing a polymer (B) having a glass transition temperature of more than 10° C. and a compound (a) may be obtained by a production method of mixing in a latex state.
• the abbreviations “latex (Ab)” and “latex (Ba)” are used as appropriate.
• the compound (a) is contained in the latex containing the polymer and the compound (a) (latex (A 1 -a), latex (Aa), latex (Ba))
• the method of causing is not particularly limited, for example, a method of obtaining a latex containing a polymer and a compound (a) by performing polymerization in the presence of the compound (a), a method of preparing a latex containing a polymer, A method of adding the compound (a) can be mentioned. Among them, the method of polymerizing in the presence of the compound (a) is preferable.
• the latex containing the polymer and the compound (a) may further contain the compound (b1) and/or the compound (b2).
• the method for containing the compound (b1) and/or the compound (b2) is not particularly limited, and for example, the polymer is polymerized in the presence of the compound (b1) and/or the compound (b2). and a method of obtaining a latex containing compound (b1) and/or compound (b2), and a method of adding compound (b1) and/or compound (b2) after preparing a latex containing a polymer.
• the method of polymerizing in the presence of the compound (b1) and/or the compound (b2) is preferred.
• a latex containing a polymer and compound (b1) and/or compound (b2) (latex (A 2 -b), latex (Bb), latex (Ab))
• the method for containing the compound (b1) and/or the compound (b2) is not particularly limited. Examples include a method of obtaining a latex containing (b1) and/or compound (b2), and a method of adding compound (b1) and/or compound (b2) after preparing a latex containing a polymer. Among them, the method of polymerizing in the presence of the compound (b1) and/or the compound (b2) is preferred.
• the latex containing the polymer and compound (b1) and/or compound (b2) may further contain compound (a).
• the method of incorporating the compound (a) is not particularly limited, for example, a method of obtaining a latex containing the polymer and the compound (a) by performing polymerization in the presence of the compound (a), A method of adding the compound (a) after preparing a latex containing a polymer can be mentioned. Among them, the method of polymerizing in the presence of the compound (a) is preferable.
• latexes may be mixed in a latex state by appropriately combining the methods of mixing two types of latexes as described above.
• latex (A 1 -a), latex (A 2 -b), and latex (Ba) and/or latex (Bb) may be mixed in a latex state.
• the latex composition used in the present invention may be obtained through concentration treatment or dilution treatment.
• the latex composition used in the present invention is preferably obtained through concentration treatment.
• the concentration treatment method is not particularly limited, and examples thereof include vacuum distillation, normal pressure distillation, centrifugation, membrane concentration, and the like. Among these, the concentration method accompanied by heating is preferable, and the vacuum distillation accompanied by heating is more preferable. By adopting a concentration method involving heating, it is possible to reduce odor-causing bacteria or suppress the growth of odor-causing bacteria, and the laminate of the present invention is excellent in low odor. can be
• the heating temperature is preferably 50°C to 100°C.
• the pressure is preferably 20 kPa to 90 kPa.
• the concentration treatment may be applied to a mixture containing some of the components to be mixed in the latex composition, or may be applied to a mixture containing all of the components to be mixed in the latex composition.
• Each component to be blended as necessary may be added to the latex composition containing polymer latex obtained by the above production method.
• the polymer layer in the laminate of the present invention is formed from the latex composition containing the above polymer latex, and contains the polymer that constitutes the polymer latex. Further, when the latex composition contains two or more polymers, the polymer layer usually contains the two or more polymers, and the content ratio of each polymer in the polymer layer is , is usually equivalent to the content ratio of each polymer in the latex composition used.
• the 100% tensile stress of the polymer layer is 1.1 MPa or less, preferably 0.1 to 0.9 MPa, more preferably 0.2 to 0.75 MPa, and further It is preferably 0.3 to 0.7 MPa. If the 100% tensile stress of the polymer layer is too large, it becomes difficult to simultaneously achieve excellent wet grip properties, excellent chemical permeation resistance, and excellent flexibility of the laminate.
• the 100% tensile stress of the polymer layer can be controlled, for example, by adjusting the type of polymer latex used and the type and amount of surfactant used. When two or more polymer latexes are used, the 100% tensile stress of the polymer layer can be controlled by adjusting the type and ratio of each polymer latex. When two or more surfactants are used, the 100% tensile stress of the polymer layer can be controlled by adjusting the type and ratio of each surfactant.
• the 100% tensile stress of the polymer layer is measured by the following method.
• a latex for measurement is prepared which contains the latex of the polymer constituting the latex composition used in the present invention in the same proportion as the latex composition.
• a film molding is obtained by coating the prepared latex for measurement on a glass substrate and drying it.
• the 100% tensile stress of the obtained film molding is measured, and the obtained value is defined as the 100% tensile stress value of the polymer layer.
• the latex composition used in the present invention is made by adding additives such as a sulfur-based cross-linking agent, a cross-linking accelerator, zinc oxide, a water-soluble polymer, and a filler to the polymer latex, if necessary.
• additives such as a sulfur-based cross-linking agent, a cross-linking accelerator, zinc oxide, a water-soluble polymer, and a filler
• the maximum height roughness Rz of the surface of the polymer layer is 135 to 350 ⁇ m, preferably 155 to 320 ⁇ m, more preferably 180 to 310 ⁇ m, further preferably 230 to 300 ⁇ m. and particularly preferably 260 to 295 ⁇ m. Even if the maximum height roughness Rz of the surface of the polymer layer is too large or too small, the excellent wet grip property of the laminate, excellent chemical liquid permeation resistance, and excellent flexibility are all well-balanced. difficult to achieve.
• the surface arithmetic mean roughness Ra of the polymer layer is 20 to 72 ⁇ m, preferably 25 to 65 ⁇ m, more preferably 30 to 60 ⁇ m, further preferably 35 to 55 ⁇ m. If the arithmetic mean roughness Ra of the surface of the polymer layer is too large or too small, it becomes difficult to achieve a good balance among all of wet grip properties, chemical permeation resistance, and flexibility.
• the surface of the polymer layer has a load area ratio at 50% height of preferably 20 to 80%, more preferably 30 to 70%, and still more preferably 35 to 60%. and particularly preferably 40 to 52%.
• the 50% height is the average height of the maximum height (100% height) and the minimum height (0% height) in the measurement area
• the load area ratio at 50% height is the measurement It is the projected area ratio of the portion where the height is higher than 50% in the area.
• the maximum height roughness Rz, the arithmetic mean roughness Ra, and the load area ratio at 50% height of the surface of the polymer layer are, for example, the type of polymer latex used, It may be controlled by adjusting the type and amount of the surfactant to be used.
• the maximum height roughness Rz, the arithmetic mean roughness Ra, and The load area ratio at 50% height can be controlled.
• the maximum height roughness Rz of the surface of the polymer layer, the arithmetic average roughness Ra, and The load area ratio at 50% height can be controlled.
• the surface roughness of the polymer layer (maximum height roughness Rz, arithmetic mean roughness Ra, load area ratio at 50% height) is obtained using a laser microscope. It is obtained from the height data of the surface of the layer. Maximum height roughness Rz and arithmetic mean roughness Ra are obtained according to JIS B 0601:2013.
• the load area ratio at 50% height is obtained from the obtained height data, 50% height (average height of maximum height (100% height) and minimum height (0% height)) After calculating , it is obtained by calculating the projected area ratio of the portion whose height is higher than 50% in the measurement area. Specifically, it is determined by the method described in Examples.
• the thickness of the polymer layer formed on the substrate using the latex composition containing polymer latex is preferably 0.05 to 1.0 mm, more preferably 0.05 to 1.0 mm. 06 to 0.8 mm, more preferably 0.07 to 0.7 mm.
• the thickness of the laminate is preferably 0.1 to 10 mm, more preferably 0.4 to 2.0 mm. Yes, more preferably 0.5 to 1.1 mm.
• gloves made of only a polymer layer with no intervening base material are thin, so wet grip properties rarely pose a problem.
• a glove that is a laminate of a base material and a polymer layer made of a latex composition tends to be thick (thickness of the entire laminate of the base material and the polymer layer), resulting in poor wet grip.
• the laminate of the present invention excellent wet grip properties can be imparted to gloves.
• the laminate of the present invention comprises the substrate described above and a polymer layer formed on the substrate using a latex composition containing a polymer latex.
• the laminate of the present invention can be obtained, for example, by dip molding using a latex composition containing the base material and polymer latex described above.
• the formation of the polymer layer in the laminate of the present invention when using a latex composition for dip molding used for dip molding that contains two or more polymers, the formation
• the polymer layer to be formed contains the two or more types of polymers, and the content ratio of each polymer in the polymer layer to be formed is usually the ratio of each polymer in the dip molding latex composition used. Equivalent to the content ratio.
• the laminate of the present invention can be produced, for example, by immersing the substrate in the latex composition to form a polymer layer made of the latex composition on the substrate.
• the molding die for covering the substrate is not particularly limited, but various materials such as porcelain, glass, metal, and plastic can be used.
• the shape of the molding die may be a desired shape according to the shape of the final product.
• various glove molds such as a mold having a shape from the wrist to the fingertips can be used as the mold for covering the substrate. is preferred.
• the substrate before the substrate is immersed in the latex composition used in the present invention, it is preferable to immerse the substrate in the coagulant solution in advance so that the coagulant solution adheres to the substrate.
• the drying temperature at this time is not particularly limited and may be selected according to the solvent used, but is preferably 10 to 80°C, more preferably 15 to 70°C. Although the drying time is not particularly limited, it is preferably 600 to 1 second, more preferably 300 to 5 seconds.
• the substrate to which the coagulant solution has been adhered is immersed in the latex composition used in the present invention while being covered with a molding die having a desired shape, thereby coagulating the latex composition and forming a substrate.
• a polymer layer consisting of a latex composition On top is deposited a polymer layer consisting of a latex composition.
• the drying temperature at this time is not particularly limited, but is preferably 10 to 80°C, more preferably 15 to 80°C. Although the drying time is not particularly limited, it is preferably 120 minutes to 5 seconds, more preferably 60 minutes to 10 seconds.
• the latex composition may be previously aged (also referred to as pre-vulcanization).
• the temperature conditions for aging are not particularly limited, but are preferably 20 to 50°C.
• the time for aging is preferably 4 hours or more and 120 hours or less, more preferably 24 hours, from the viewpoint of preventing separation between the substrate and the polymer layer and improving the mechanical properties of the polymer layer. 72 hours or less.
• the heating temperature for cross-linking is preferably 60 to 160°C, more preferably 80 to 150°C. By setting the heating temperature within the above range, the time required for the cross-linking reaction can be shortened and the productivity of the laminate can be improved. It can improve the physical properties of the body.
• the heating time for cross-linking may be appropriately selected according to the heating temperature, but is usually 5 to 120 minutes.
• the polymer layer formed on the base material is immersed in hot water of 20 to 80° C. for about 0.5 to 60 minutes to obtain a polymer. It is preferable to remove water-soluble impurities (emulsifiers, water-soluble polymers, coagulants, etc.) from the layer.
• water-soluble impurities emulsifiers, water-soluble polymers, coagulants, etc.
• drying temperature and drying time at this time are not particularly limited, but may be the same as the drying temperature and drying time in the drying step after immersion in the latex composition described above.
• the laminate can be obtained by detaching (or demolding) from the molding die.
• detaching or demolding
• a heat treatment may be performed at a temperature of 60 to 120°C for 10 to 120 minutes.
• a surface treatment layer may be formed on the inner and/or outer surfaces of the laminate by chlorination treatment, coating treatment, or the like.
• a method for obtaining a laminate As a method for obtaining a laminate, a method of dip molding using a base material and a foamed latex composition can be considered.
• the arithmetic mean roughness Ra of the surface of the polymer layer of the laminate obtained tends to be too small, and as a result, the wet grip properties of the laminate obtained are inferior, and the flexibility is poor. It may deteriorate.
• a water-soluble metal salt is attached to the surface of the dip layer, and if necessary, drying and cross-linking are performed.
• a method of washing away the water-soluble metal salt adhered to the surface after carrying out the above is also conceivable.
• the maximum height roughness Rz and the arithmetic mean roughness Ra of the surface of the polymer layer of the laminate obtained tend to be too large, and the flexibility of the laminate obtained is inferior. , the resistance to chemical liquid permeation may be deteriorated.
• components derived from water-soluble metal salts for example, metal components
• these methods require a foaming step, a step of adhering a water-soluble metal salt, and a step of washing away the water-soluble metal salt, which may reduce the production efficiency of the laminate.
• the laminate of the present invention has excellent chemical liquid permeation resistance and excellent wet grip and flexibility in a well-balanced manner.
• it can be suitably used for gloves, especially for protective gloves.
• volume-average particle size of the polymer particles constituting the polymer latex was measured using a light scattering diffraction particle measuring device (manufactured by Coulter, trade name "LS-230").
• ⁇ Surface tension of polymer latex> A surface tension meter (DY-300, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the surface tension of the polymer latex. Measured values are expressed in units of mN/m. Measurements were performed at 25°C.
• ⁇ Difference between surface tension of polymer latex and surface tension of anionic surfactant> The surface tension of the polymer latex was measured by the method described above.
• a 5.0% by weight aqueous solution of the anionic surfactant (compound (a), compound (b1), compound (b2)) used in each production example was prepared, and a surface tensiometer (DY-300, Kyowa interface (manufactured by Kagaku Co., Ltd.) was used to measure the surface tension (the surface tension of the surfactant). Measurements were performed at 25°C.
• ⁇ Content of surfactant in latex composition for dip molding The content of the surfactant in the latex composition for dip molding was calculated from the amount of surfactant used in each production example, the polymerization conversion rate in each production example, and the compounding ratio in each example.
• Tensilon universal testing machine (trade name "RTG-1210", manufactured by Orientec) was used to measure the 100% tensile stress of the test piece at a tensile speed of 500 mm / min. 100% tensile stress (100% tensile stress of the polymer layer).
• the surface roughness of the polymer layer of the protective glove (maximum height roughness Rz, arithmetic mean roughness Ra, load area ratio at 50% height) is measured using a laser microscope (Keyence VK-X100) as follows. conditions were used to obtain height data for the surface of the polymer layer of the protective glove. Then, using analysis software ("surface roughness" measurement function of VK shape analysis application VK-H1XJ manufactured by Keyence Corporation), from the obtained height data, according to JIS B 0601: 2013, the maximum height roughness Rz and arithmetic mean roughness Ra were obtained.
• the oil permeation amount of protective gloves was measured by the following procedure. (1) A finger-shaped test piece was obtained by cutting out the index finger portion of the protective glove (laminate). (2) Put test oil IRM903 into an aluminum cup. (3) A filter paper (weight: W 1 ) was placed inside the test piece, and the inner surface of the portion of the test piece corresponding to the pad of the finger (the portion with an area of about 2 to 5 cm 2 ) was brought into close contact with the filter paper. .
• protective glove A A dip molded product (laminate) having a base material and a polymer layer, which was obtained without a step of foaming the polymer layer or a surface treatment step after molding the dip layer. It is.
• the protective glove A has excellent flexibility, but does not have wet grip properties at all.
• Protective glove B A dip molded article (laminate) having a base material and a polymer layer, obtained through a surface treatment step after molding the dip layer.
• the protective glove B has relatively high wet grip properties.
• ⁇ Production Example 1> (Production of latex of polybutyl acrylate (A-1)) Into a 5 MPa pressure vessel equipped with a stirrer, 100 parts of n-butyl acrylate as an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer and sodium alkyldiphenyl ether disulfonate (sodium dodecyldiphenyl ether disulfonate as a main component) were added as a compound (b1).
• the glass transition temperature (Tg) of polybutyl acrylate (A-1) contained in the resulting latex of polybutyl acrylate (A-1) was -50°C.
• Tg glass transition temperature
• ⁇ Production Example 2> (Production of latex of carboxyl group-containing nitrile rubber (A-2)) A polymerization reactor was charged with 67.5 parts of 1,3-butadiene as a conjugated diene monomer, 27 parts of acrylonitrile as an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, and methacryl as an ethylenically unsaturated monocarboxylic acid monomer.
• a latex of group-containing nitrile rubber (A-2) was obtained.
• the carboxyl group-containing nitrile rubber (A-2) contained in the obtained carboxyl group-containing nitrile rubber (A-2) latex had a glass transition temperature (Tg) of -24°C.
• Tg glass transition temperature
• the monomer composition of A-2) was almost the same as the charging ratio. Measurements were carried out in the same manner as in Production Example 1 using the carboxyl group-containing nitrile rubber (A-2) latex. Table 1 shows the results.
• ⁇ Production Example 3> (Production of Latex of Carboxyl Group-Containing Nitrile Rubber (A-3) Containing Methyl Methacrylate Units) 1,3-Butadiene was changed to 47.3 parts, acrylonitrile to 18.8 parts, methacrylic acid to 3.9 parts, and, together with these monomers, ⁇ , ⁇ -ethylenically unsaturated A carboxyl group containing a methyl methacrylate unit having a solid content concentration of 40% by weight and a pH of 8 was prepared in the same manner as in Production Example 2, except that 30 parts of methyl methacrylate was charged to the polymerization reactor as a monocarboxylic acid ester monomer.
• a latex containing nitrile rubber (A-3) was obtained.
• the glass transition temperature (Tg) of the carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units contained in the obtained latex of the carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units is The temperature was ⁇ 14° C., and the monomer composition of the carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units was substantially the same as the charging ratio. Measurements were performed in the same manner as in Production Example 1 using a latex of carboxyl group-containing nitrile rubber (A-3) containing methyl methacrylate units. Table 1 shows the results.
• carboxymethyl cellulose manufactured by Daicel Corporation, trade name "Daicel 2200", weight average molecular weight: 550,000
• a latex composition for dip molding having a solid concentration of 40% by weight was obtained.
• the content of the surfactant in the latex composition for dip molding was determined. Table 2 shows the results.
• a coagulant solution was prepared by dissolving 2.0% by weight of calcium nitrate as a coagulant in methanol.
• the latex composition for dip molding obtained above was aged (also referred to as prevulcanization) at a temperature of 30° C. for 48 hours.
• a ceramic glove mold covered with a glove-shaped fiber base material material: nylon, linear density: 300 denier, gauge number: 13 gauge, thickness: 0.8 mm
• the ceramic glove mold is immersed in the aged dip molding latex composition for 5 seconds, pulled out from the aged dip molding latex composition, and dried at a temperature of 25° C. for 20 minutes.
• a dip layer was formed on the fiber substrate.
• the ceramic glove mold with the dip layer formed thereon was subjected to heat treatment at a temperature of 110° C. for 30 minutes to crosslink the polymer in the dip layer, thereby forming a polymer layer.
• the fiber base material on which the polymer layer was formed was peeled off from the ceramic glove mold to obtain a protective glove (dip molding).
• the thickness of the polymer layer was 0.15 mm
• the thickness of the protective glove thickness of the protective glove (thickness of the entire laminate including the substrate and the polymer layer) was 1.0 mm.
• the 100% tensile stress of the polymer layer (100% tensile stress of the film molding) is 1.1 MPa or less
• the maximum height roughness Rz of the surface of the united layer is 135 to 350 ⁇ m
• the laminate having an arithmetic mean roughness Ra of 20 to 72 ⁇ m has excellent chemical liquid permeation resistance, and has a good balance between wet grip and flexibility. They were excellent (Examples 1 to 8).

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