WO2020054247A1 - Composition de latex et corps moulé en film - Google Patents

Composition de latex et corps moulé en film Download PDF

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WO2020054247A1
WO2020054247A1 PCT/JP2019/030373 JP2019030373W WO2020054247A1 WO 2020054247 A1 WO2020054247 A1 WO 2020054247A1 JP 2019030373 W JP2019030373 W JP 2019030373W WO 2020054247 A1 WO2020054247 A1 WO 2020054247A1
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Prior art keywords
latex
weight
latex composition
parts
synthetic polyisoprene
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Japanese (ja)
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実紗 林
小出村　順司
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Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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

Definitions

  • the present invention relates to a latex composition and a film molded product, and more particularly, to obtain a film molded product such as a dip molded product, which can shorten the ripening (pre-vulcanization) time and achieve high productivity.
  • the present invention relates to a latex composition capable of producing a film molded article such as a molded article, and a film molded article obtained by using such a latex composition.
  • a latex composition containing a latex of natural rubber is dip-molded to obtain a dip molded article used in contact with a human body such as a nipple, a balloon, a glove, a balloon, and a sack.
  • a human body such as a nipple, a balloon, a glove, a balloon, and a sack.
  • the latex of natural rubber contains a protein that causes a symptom of immediate allergy (Type I) in the human body, there is a case where there is a problem as a dip molded body that comes into direct contact with a living mucous membrane or an organ. Therefore, studies have been made to use a synthetic rubber latex instead of a natural rubber latex.
  • Patent Document 1 discloses a dip molding composition in which a latex of synthetic polyisoprene, which is a synthetic rubber, is mixed with zinc oxide, sulfur, and a vulcanization accelerator.
  • the technique of Patent Document 1 has a problem that aging (pre-vulcanization) requires a relatively long time to obtain a dip molded body having sufficient mechanical strength.
  • the problem that sulfurization takes a relatively long time was particularly noticeable in isoprene-containing polymers such as synthetic polyisoprene. Therefore, from the viewpoint of improvement in productivity, a latex composition capable of producing a dip molded product having sufficient mechanical strength even with a relatively short aging time has been demanded.
  • An object of the present invention is to provide a latex composition capable of producing a film formed body such as a formed body, and a film formed body obtained by using such a latex composition.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, a latex composition comprising a latex of a conjugated diene polymer, a vulcanizing agent, and a predetermined amount of a polyoxyalkylene surfactant. According to the present invention, the inventors have found that the above-mentioned problems can be solved, and have completed the present invention based on such findings.
  • a latex of a conjugated diene-based polymer, a vulcanizing agent, and a polyoxyalkylene-based surfactant are contained, and the polyoxyalkylene-based polymer is contained in 100 parts by weight of the conjugated diene-based polymer.
  • a latex composition having a surfactant content of 0.01 to 3 parts by weight is provided.
  • the polyoxyalkylene surfactant is a nonionic surfactant.
  • the nonionic surfactant is preferably a hydrocarbylated ether of polyoxyethylene.
  • the nonionic surfactant is preferably at least one selected from polyoxyalkylene glycol, polyoxyalkylene alkyl ether and polyoxyethylene distyrenated phenyl ether.
  • the nonionic surfactant is preferably at least one selected from polyoxyalkylene alkyl ethers and polyoxyethylene distyrenated phenyl ethers.
  • the latex composition of the present invention preferably further contains an activator.
  • the activator is preferably a metal oxide.
  • a film formed article comprising the latex composition of the present invention. Further, according to the present invention, there is provided a dip molded product obtained by dip molding the latex composition of the present invention.
  • the aging (pre-vulcanization) time can be shortened, and a film molding, such as a dip molding, can be manufactured with high productivity. It is possible to provide a latex composition and a film molded product obtained by using such a latex composition.
  • the latex composition of the present invention contains a latex of a conjugated diene polymer, a vulcanizing agent, and a polyoxyalkylene surfactant,
  • the content of the polyoxyalkylene-based surfactant is 0.01 to 3 parts by weight based on 100 parts by weight of the conjugated diene-based polymer.
  • the conjugated diene-based polymer constituting the latex of the conjugated diene-based polymer is not particularly limited, and examples thereof include synthetic polyisoprene, styrene-isoprene-styrene block copolymer (SIS), and natural rubber from which proteins have been removed. No. Among them, those containing isoprene units such as synthetic polyisoprene, SIS and natural rubber from which proteins have been removed are preferable, and synthetic polyisoprene is particularly preferable.
  • the conjugated diene-based polymer may be a carboxy-modified conjugated diene-based polymer obtained by modification with a monomer having a carboxyl group.
  • the synthetic polyisoprene may be a homopolymer of isoprene or a copolymer of isoprene and another ethylenically unsaturated monomer copolymerizable with isoprene. It may be polymerized.
  • the content of the isoprene unit in the synthetic polyisoprene is preferably 70% by weight or more based on all the monomer units, since a film molded body such as a dip molded body having flexibility and excellent tensile strength can be easily obtained.
  • the content is more preferably 90% by weight or more, further preferably 95% by weight or more, and particularly preferably 100% by weight (a homopolymer of isoprene).
  • ethylenically unsaturated monomers copolymerizable with isoprene include, for example, conjugated diene monomers other than isoprene such as butadiene, chloroprene and 1,3-pentadiene; acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ - Ethylenically unsaturated nitrile monomers such as chloroacrylonitrile; vinyl aromatic monomers such as styrene and alkylstyrene; methyl (meth) acrylate (meaning "methyl acrylate and / or methyl methacrylate” And ethyl (meth) acrylate), ethylenically unsaturated carboxylic acid ester monomers such as ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; Is mentioned.
  • Synthetic polyisoprene can be prepared by a conventionally known method, for example, using a Ziegler-based polymerization catalyst comprising trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium in an inert polymerization solvent.
  • a Ziegler-based polymerization catalyst comprising trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium in an inert polymerization solvent.
  • Isoprene and another copolymerizable ethylenically unsaturated monomer used as necessary can be obtained by solution polymerization.
  • the synthetic polyisoprene polymer solution obtained by the solution polymerization may be used as it is for the production of a synthetic polyisoprene latex, but after taking out a solid synthetic polyisoprene from the polymer solution, dissolving it in an organic solvent. Thus, it can be used for producing synthetic polyisoprene latex.
  • a polymer solution of synthetic polyisoprene is obtained by the above-described method, impurities such as a residue of a polymerization catalyst remaining in the polymer solution may be removed. Further, an antioxidant described below may be added to the solution during or after the polymerization.
  • commercially available solid synthetic polyisoprene can be used.
  • the isoprene units in the synthetic polyisoprene there are four types of cis-bond units, trans-bond units, 1,2-vinyl-bond units, and 3,4-vinyl-bond units, depending on the bonding state of isoprene.
  • the content ratio of the cis-bond unit in the isoprene unit contained in the synthetic polyisoprene is preferably at least 70% by weight based on all the isoprene units, It is more preferably at least 90% by weight, further preferably at least 95% by weight.
  • the weight average molecular weight of the synthetic polyisoprene is preferably 10,000 to 5,000,000, more preferably 500,000 to 5,000,000, and still more preferably, in terms of standard polystyrene by gel permeation chromatography analysis. Is from 800,000 to 3,000,000.
  • the weight average molecular weight of the synthetic polyisoprene falls within the above range, the tensile strength of a film molded product such as a dip molded product is improved, and the synthetic polyisoprene latex tends to be easily produced.
  • the polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the synthetic polyisoprene is preferably 50 to 85, more preferably 60 to 85, and even more preferably 70 to 85.
  • a solution or fine suspension of a synthetic polyisoprene dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of an anionic surfactant.
  • (2) a method for producing a synthetic polyisoprene latex by removing an organic solvent, if necessary, (2) using isoprene alone or a mixture of isoprene and an ethylenically unsaturated monomer copolymerizable therewith with anionic surfactant
  • Examples of the organic solvent used in the production method (1) include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane, and cyclohexene; pentane, hexane, and the like. Aliphatic hydrocarbon solvents such as heptane; halogenated hydrocarbon solvents such as methylene chloride, chloroform and ethylene dichloride; and the like. Of these, alicyclic hydrocarbon solvents are preferred, and cyclohexane is particularly preferred.
  • the amount of the organic solvent used is preferably 2,000 parts by weight or less, more preferably 20 to 1,500 parts by weight, and even more preferably 500 to 1500 parts by weight, based on 100 parts by weight of the synthetic polyisoprene.
  • anionic surfactant used in the production method (1) examples include fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, and sodium rosinate; dodecylbenzene sulfone Alkylbenzenesulfonates such as sodium silicate, potassium dodecylbenzenesulfonate, sodium decylbenzenesulfonate, potassium decylbenzenesulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate; sodium di (2-ethylhexyl) sulfosuccinate; Alkyl sulfosuccinates such as potassium (2-ethylhexyl) sulfosuccinate and sodium dioctyl sulfosuccinate; sodium lauryl sulfate, potassium lauryl sulfate, etc.
  • Alkyl sulfates such as sodium polyoxyethylene lauryl ether sulfate and potassium polyoxyethylene lauryl ether; monoalkyl phosphates such as sodium lauryl phosphate and potassium lauryl phosphate; No.
  • fatty acid salts, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates are preferred, and fatty acid salts and alkylbenzene sulfonates are particularly preferred.
  • a small amount of polymerization catalyst (particularly, aluminum and titanium) derived from synthetic polyisoprene can be more efficiently removed, and the generation of aggregates during the production of a latex composition is suppressed. It is preferable to use at least one selected from the group consisting of a sulfonate, an alkyl sulfosuccinate, an alkyl sulfate and a polyoxyethylene alkyl ether sulfate together with a fatty acid salt. It is particularly preferable to use the compound in combination with a fatty acid salt.
  • sodium rosinate and potassium rosinate are preferable as the fatty acid salt
  • sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate are preferable as the alkylbenzenesulfonate.
  • These surfactants may be used alone or in combination of two or more.
  • the obtained latex contains at least one selected from the group consisting of an alkylbenzene sulfonate, an alkyl sulfosuccinate, an alkyl sulfate, and a polyoxyethylene alkyl ether sulfate, and a fatty acid salt.
  • a surfactant other than the anionic surfactant may be used in combination, and such a surfactant other than the anionic surfactant may be ⁇ , ⁇ -non-ionic surfactant.
  • Copolymerizable surfactants such as a sulfoester of a saturated carboxylic acid, a sulfate ester of an ⁇ , ⁇ -unsaturated carboxylic acid, and a sulfoalkylaryl ether.
  • the amount of the anionic surfactant used in the production method (1) is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the synthetic polyisoprene. is there.
  • the total amount of these surfactants be within the above range. That is, for example, when a fatty acid salt is used in combination with at least one selected from an alkylbenzene sulfonate, an alkyl sulfosuccinate, an alkyl sulfate, and a polyoxyethylene alkyl ether sulfate, It is preferable that the total amount used is within the above range.
  • the amount of the anionic surfactant used is too small, a large amount of aggregates may be generated at the time of emulsification.On the other hand, if the amount is too large, foaming tends to occur, and a pinhole is formed in a film formed body such as a dip formed body. May occur.
  • an alkylbenzene sulfonate an alkyl sulfosuccinate, an alkyl sulfate and a polyoxyethylene alkyl ether sulfate as an anionic surfactant is used in combination with a fatty acid salt.
  • the ratio of these is defined as "fatty acid salt”: "at least one surfactant selected from alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate and polyoxyethylene alkyl ether sulfate.”
  • the weight ratio of the “total of the agents” is preferably in the range of 1: 1 to 10: 1, more preferably in the range of 1: 1 to 7: 1.
  • At least one surfactant selected from the group consisting of alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates is too large, the handling of synthetic polyisoprene may become excessive. There is a possibility that foaming may become intense, and this requires operations such as long-time standing and addition of an antifoaming agent, which may lead to deterioration of workability and cost increase.
  • the amount of water used in the production method (1) is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, and most preferably 100 parts by weight of the organic solvent solution of the synthetic polyisoprene. Is 50 to 100 parts by weight.
  • Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, and zeolite water, with soft water, ion-exchanged water and distilled water being preferred.
  • a device for emulsifying a solution or fine suspension of a synthetic polyisoprene dissolved or finely dispersed in an organic solvent in water in the presence of an anionic surfactant may be any device generally commercially available as an emulsifier or disperser. If it is not particularly limited, it can be used.
  • the method of adding the anionic surfactant to the solution or fine suspension of synthetic polyisoprene is not particularly limited, and may be previously added to either water or the solution or fine suspension of synthetic polyisoprene, or to both. It may be added, or may be added to the emulsion during the emulsification operation, and may be added all at once or in portions.
  • emulsifying apparatus examples include batch-type emulsifiers such as “Homogenizer” (trade name, manufactured by IKA), “Polytron” (trade name, manufactured by Kinematica), and “TK Auto Homo Mixer” (trade name, manufactured by Tokushu Kika Kogyo).
  • Homogenizer trade name, manufactured by IKA
  • Polytron trade name, manufactured by Kinematica
  • TK Auto Homo Mixer trade name, manufactured by Tokushu Kika Kogyo
  • the organic solvent from the emulsion obtained through the emulsification operation.
  • a method for removing the organic solvent from the emulsion a method capable of reducing the content of the organic solvent (preferably alicyclic hydrocarbon solvent) in the obtained synthetic polyisoprene latex to 500 ppm by weight or less is preferable, For example, methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be employed.
  • the total content of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent as the organic solvent in the obtained synthetic polyisoprene latex can be 500 ppm by weight or less.
  • the method is not particularly limited as long as it is such a method, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be employed.
  • vacuum concentration, atmospheric distillation, centrifugation may be subjected to concentration operation by a method such as membrane concentration, In particular, it is preferable to perform centrifugal separation from the viewpoint that the solid content concentration of the synthetic polyisoprene latex can be increased and the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
  • the centrifugation is carried out, for example, by using a continuous centrifuge, the centrifugal force, preferably 100 to 10,000 G, the solid content concentration of the synthetic polyisoprene latex before centrifugation, preferably 2 to 15% by weight,
  • the flow rate to be fed into the machine is preferably 500 to 1700 Kg / hr, and the back pressure (gauge pressure) of the centrifuge is preferably 0.03 to 1.6 MPa.
  • a synthetic polyisoprene latex can be obtained.
  • the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
  • the solid content concentration of the synthetic polyisoprene latex is preferably 30 to 70% by weight, more preferably 40 to 70% by weight. If the solid content concentration is too low, the solid content concentration of the latex composition will be low, so that the resulting film-formed body such as a dip-formed body will have a small thickness and will be easily broken. Conversely, if the solids content is too high, the viscosity of the synthetic polyisoprene latex will be high, and it may be difficult to transfer it in a pipe or agitate it in a mixing tank.
  • the volume average particle diameter of the synthetic polyisoprene latex is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, and still more preferably 0.5 to 2.0 ⁇ m.
  • the synthetic polyisoprene latex contains additives such as a pH adjuster, an antifoaming agent, a preservative, a cross-linking agent, a chelating agent, an oxygen scavenger, a dispersant, and an antioxidant which are usually blended in the latex field.
  • a pH adjuster examples include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; hydrogen carbonates of alkali metals such as sodium hydrogen carbonate; ammonia Organic amine compounds such as trimethylamine and triethanolamine; and the like, with preference given to alkali metal hydroxides or ammonia.
  • SIS styrene-isoprene-styrene block copolymer
  • SIS can be obtained by a conventionally known method, for example, by block copolymerizing isoprene and styrene in an inert polymerization solvent using an active organic metal such as n-butyllithium as an initiator. Then, the obtained SIS polymer solution may be used as it is for the production of SIS latex, but after removing solid SIS from the polymer solution, dissolving the solid SIS in an organic solvent, It can also be used for latex production.
  • the method for producing the SIS latex is not particularly limited, but a solution or fine suspension of SIS dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of a surfactant, and the organic solvent is removed as necessary.
  • a method of producing SIS latex is preferable.
  • impurities such as a residue of a polymerization catalyst remaining in the polymer solution after the synthesis may be removed.
  • an antioxidant described below may be added to the solution during or after the polymerization.
  • commercially available solid SIS can be used.
  • the organic solvent the same ones as in the case of the above-mentioned synthetic polyisoprene can be used, and an aromatic hydrocarbon solvent and an alicyclic hydrocarbon solvent are preferable, and cyclohexane and toluene are particularly preferable.
  • the amount of the organic solvent used is usually 50 to 2,000 parts by weight, preferably 80 to 1,000 parts by weight, more preferably 100 to 500 parts by weight, and still more preferably 150 to 300 parts by weight, per 100 parts by weight of SIS. Parts by weight.
  • the surfactant the same ones as in the case of the above-mentioned synthetic polyisoprene can be exemplified.
  • Anionic surfactants are preferable, and sodium rosinate and sodium dodecylbenzenesulfonate are particularly preferable.
  • the amount of the surfactant used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of SIS. If the amount is too small, the stability of the latex tends to be inferior. On the other hand, if it is too large, foaming tends to occur, which may cause problems during dip molding.
  • the amount of water used in the SIS latex production method described above is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, and most preferably 50 to 100 parts by weight of the SIS organic solvent solution. ⁇ 100.
  • Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, and zeolite water. Further, a polar solvent represented by an alcohol such as methanol may be used in combination with water.
  • the same method as in the case of the above-mentioned synthetic polyisoprene can be exemplified.
  • Examples of an apparatus for emulsifying an organic solvent solution or a fine suspension of SIS in water in the presence of a surfactant include those similar to the above-mentioned synthetic polyisoprene.
  • the method of adding the surfactant is not particularly limited, and may be added in advance to either or both of water or an organic solvent solution or a fine suspension of SIS, or during the emulsification operation. May be added to the emulsion, added all at once, or added in portions.
  • an SIS latex by removing an organic solvent from an emulsion obtained through an emulsification operation.
  • the method for removing the organic solvent from the emulsion is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be employed.
  • a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration in order to increase the solid content of the SIS latex.
  • the solid content of the SIS latex is preferably 30 to 70% by weight, more preferably 50 to 70% by weight. If the solid content is too low, the solid content of the latex composition will be low, so that when the film is formed into a film such as a dip, the film thickness becomes thin and the film is easily broken. Conversely, if the solids content is too high, the viscosity of the SIS latex will be high, making it difficult to transfer by piping or agitate in the mixing tank.
  • SIS latex is blended with additives such as a pH adjuster, an antifoaming agent, a preservative, a cross-linking agent, a chelating agent, an oxygen scavenger, a dispersant, and an antioxidant, which are usually compounded in the field of latex.
  • additives such as a pH adjuster, an antifoaming agent, a preservative, a cross-linking agent, a chelating agent, an oxygen scavenger, a dispersant, and an antioxidant, which are usually compounded in the field of latex.
  • pH adjuster include the same ones as in the case of the synthetic polyisoprene described above, and an alkali metal hydroxide or ammonia is preferable.
  • the content of the styrene unit in the styrene block in the SIS contained in the SIS latex thus obtained is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, based on all monomer units. , More preferably 100% by weight.
  • the content of the isoprene unit in the isoprene block in the SIS is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, and still more preferably 100% by weight, based on all monomer units.
  • the content ratio of the styrene unit to the isoprene unit in the SIS is usually from 1:99 to 90:10, preferably from 3:97 to 70:30, more preferably from 5:99 by weight ratio of “styrene unit: isoprene unit”. : 95 to 50:50, more preferably 10:90 to 30:70.
  • the weight average molecular weight of the SIS is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and further preferably 100,000 in terms of standard polystyrene by gel permeation chromatography analysis. ⁇ 300,000.
  • the weight average molecular weight of the SIS is in the above range, the balance between the tensile strength and the flexibility of the film-formed body such as the dip-formed body is improved, and the latex of the SIS tends to be easily produced.
  • the volume average particle diameter of the latex particles (SIS particles) in the SIS latex is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, and still more preferably 0.5 to 2.0 ⁇ m.
  • the volume average particle diameter of the latex particles is in the above range, the viscosity of the latex becomes appropriate and the handling becomes easy, and the formation of a film on the latex surface when the SIS latex is stored can be suppressed.
  • natural rubber from which proteins have been removed can also be used.
  • natural rubber used as a raw material of the natural rubber from which the protein has been removed natural rubber contained in the latex obtained from the natural rubber tree and natural rubber contained in the latex obtained by treating the latex can be used.
  • Natural rubber contained in field latex collected from a tree of natural rubber, and natural rubber contained in commercially available natural rubber latex obtained by treating field latex with ammonia or the like can be used.
  • the conjugated diene-based polymer used in the present invention may be a carboxy-modified carboxy-modified conjugated diene-based polymer.
  • the carboxy-modified conjugated diene-based polymer can be obtained by modifying the above-described conjugated diene-based polymer with a monomer having a carboxyl group.
  • the method for modifying the conjugated diene-based polymer with a monomer having a carboxyl group is not particularly limited.
  • the conjugated diene-based polymer is graft-polymerized with a monomer having a carboxyl group in an aqueous phase.
  • Method. The method of graft-polymerizing a monomer having a carboxyl group to the conjugated diene polymer in the aqueous phase is not particularly limited, and a conventionally known method may be used.
  • the conjugated diene polymer is reacted with the carboxyl group-containing monomer in the aqueous phase.
  • the organic peroxide is not particularly restricted but includes, for example, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t -Butyl peroxide, isobutyryl peroxide, benzoyl peroxide, and the like.
  • 1,1,3,3-tetramethylbutyl hydroperoxide is particularly preferable from the viewpoint of improving the mechanical strength of the obtained dip molded article.
  • One of these organic peroxides may be used alone, or two or more thereof may be used in combination.
  • the amount of the organic peroxide to be added is not particularly limited, but is preferably 0.01 to 3 parts by weight, more preferably 0 to 3 parts by weight, based on 100 parts by weight of the conjugated diene polymer contained in the latex of the conjugated diene polymer. 1 to 1 part by weight.
  • the organic peroxide can be used as a redox polymerization initiator in combination with a reducing agent.
  • a reducing agent include, but are not particularly limited to, compounds containing metal ions in a reduced state such as ferrous sulfate and cuprous naphthenate; sulfinates such as sodium hydroxymethanesulfinate; dimethylaniline; Amine compounds; and the like.
  • One of these reducing agents may be used alone, or two or more thereof may be used in combination.
  • the amount of the reducing agent is not particularly limited, but is preferably 0.01 to 1 part by weight based on 1 part by weight of the organic peroxide.
  • the method of adding the organic peroxide and the reducing agent is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be used, respectively.
  • the reaction temperature at the time of reacting the conjugated diene polymer with the monomer having a carboxyl group is not particularly limited, but is preferably 15 to 80 ° C, more preferably 30 to 50 ° C.
  • the reaction time for reacting the monomer having a carboxyl group with the conjugated diene polymer may be appropriately set according to the above reaction temperature, but is preferably 30 to 300 minutes, more preferably 60 to 120 minutes. is there.
  • the solid content concentration of the latex of the conjugated diene polymer when the monomer having a carboxyl group is reacted with the conjugated diene polymer is not particularly limited, but is preferably 5 to 60% by weight, more preferably 10 to 60% by weight. 40% by weight.
  • Examples of the monomer having a carboxyl group include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; and ethylenically unsaturated polyvalent monomers such as itaconic acid, maleic acid, fumaric acid, and butenetricarboxylic acid.
  • ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid
  • ethylenically unsaturated polyvalent monomers such as itaconic acid, maleic acid, fumaric acid, and butenetricarboxylic acid.
  • Carboxylic acid monomer Monoester monomer of ethylenically unsaturated polycarboxylic acid such as monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate; Polycarboxylic acid such as maleic anhydride and citraconic anhydride Acid anhydride; and the like, but since the effect of the carboxy modification becomes more remarkable, an ethylenically unsaturated monocarboxylic acid monomer is preferable, and acrylic acid and methacrylic acid are particularly preferable. In addition, these monomers may be used alone or in combination of two or more. Further, the carboxyl group includes those in the form of a salt with an alkali metal or ammonia.
  • the amount of the monomer having a carboxyl group to be used is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 40 parts by weight, based on 100 parts by weight of the conjugated diene polymer. Preferably it is 0.5 to 20 parts by weight.
  • the method for adding the monomer having a carboxyl group to the latex of the conjugated diene polymer is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be employed.
  • the rate of modification of the carboxy-modified conjugated diene polymer with a monomer having a carboxyl group may be appropriately controlled according to the intended use of the obtained latex composition, but is preferably 0.01 to 10% by weight, more preferably 0.01 to 10% by weight. Is 0.2 to 5% by weight, more preferably 0.3 to 3% by weight, particularly preferably 0.4 to 2% by weight.
  • the modification rate is represented by the following equation.
  • Modification rate (% by weight) (X / Y) ⁇ 100
  • X represents the weight of a unit of a monomer having a carboxyl group in the carboxy-modified conjugated diene-based polymer
  • Y represents the weight of the carboxy-modified conjugated diene-based polymer.
  • X is the carboxy-modified conjugated diene-based polymer, subjected to 1 H-NMR measurement, the method for calculating the results of the 1 H-NMR measurement or, determine the acid content by neutralization titration, is calculated from the amount of acid determined It can be determined by a method or the like.
  • the polymerization catalyst (graft polymerization catalyst) used for the graft polymerization is not particularly limited, and examples thereof include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; Organic peroxides such as peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, isobutyryl peroxide and benzoyl peroxide Oxides; azo compounds such as 2,2'-azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, methyl azobisisobutyrate; and the like, but film forming such as a dip molded product is obtained. It is said that the tensile strength of the body will be improved Terms, organic peroxides are preferred, 1,1,3,3-tetramethylbutyl
  • the above graft polymerization catalysts can be used alone or in combination of two or more.
  • the amount of the graft polymerization catalyst used depends on the type thereof, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the conjugated diene polymer.
  • the method for adding the graft polymerization catalyst is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be employed.
  • the latex of the conjugated diene-based polymer (including the carboxy-modified conjugated diene-based polymer) used in the present invention includes a pH adjuster, an antifoaming agent, a preservative, and a chelating agent which are usually blended in the field of latex. Further, additives such as an oxygen scavenger, a dispersant, and an antioxidant may be blended.
  • Examples of the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; hydrogen carbonates of alkali metals such as sodium hydrogen carbonate; ammonia Organic amine compounds such as trimethylamine and triethanolamine; and the like, with preference given to alkali metal hydroxides or ammonia.
  • the solid concentration of the latex of the conjugated diene polymer (including the carboxy-modified conjugated diene polymer) used in the present invention is preferably 30 to 70% by weight, more preferably 40 to 70% by weight.
  • the latex composition of the present invention contains a vulcanizing agent and a polyoxyalkylene surfactant in addition to the conjugated diene polymer latex described above.
  • a sulfur-based vulcanizing agent is suitably used.
  • the sulfur vulcanizing agent include sulfur such as powdered sulfur, sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, caprolactam disulfide (N , N'-dithio-bis (hexahydro-2H-azepinone-2)), phosphorus-containing polysulfides, polymeric polysulfides, and sulfur-containing compounds such as 2- (4'-morpholinodithio) benzothiazole.
  • sulfur can be preferably used.
  • the sulfur-based vulcanizing agents can be used alone or in combination of two or more.
  • the content of the vulcanizing agent in the latex composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the conjugated diene polymer. To 5 parts by weight, more preferably 0.5 to 3 parts by weight.
  • the polyoxyalkylene-based surfactant is not particularly limited as long as it has a polyoxyalkylene structure, and is a nonionic compound having a polyalkylene oxide chain, a nonionic surfactant, and a polyoxyalkylene surfactant.
  • Nonionic anionic surfactants which are anionic surfactants having an alkylene oxide chain, and the like. Among them, when obtaining a film molded body such as a dip molded body, the aging (pre-vulcanization) time Nonionic surfactants are preferred because of their great shortening effect.
  • the dispersibility of the vulcanizing agent in the latex composition can be increased by adding a polyoxyalkylene-based surfactant to the latex of the conjugated diene polymer together with the vulcanizing agent, This makes it possible to shorten the time required for aging (pre-vulcanization) when obtaining a film molded body such as a dip molded body, and as a result, it is possible to form a film molded body such as a dip molded body with high productivity. It enables the manufacture of the body.
  • nonionic surfactant examples include, but are not particularly limited to, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene (hardened) castor oil, And polyoxyethylene alkylamine.
  • polyoxyalkylene glycol examples include polyoxypropylene glycol ethylene oxide adducts such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene polyoxypropylene glycol.
  • polyoxyalkylene alkyl ether examples include, for example, a linear or branched ether to which 1 to 50 (preferably 1 to 10) propylene oxide and / or ethylene oxide are added.
  • linear or branched ethers to which 1 to 50 (preferably 1 to 10) propylene oxides are added and those to which 1 to 50 (preferably 1 to 10) ethylene oxides are added.
  • polyoxyalkylene alkylphenyl ether examples include compounds in which 1 to 50 (preferably 1 to 10) propylene oxide and / or ethylene oxide are added to an alkylphenol.
  • polyoxyethylene styrenated phenyl ether examples include ethylene oxide adducts of (mono, di, tri) styrenated phenols.
  • polyoxyethylene diphenylene which is an ethylene oxide adduct of distyrenated phenol, is mentioned.
  • Styrenated phenyl ethers are preferred.
  • Polyoxyethylene (hardened) castor oil includes castor oil or an ethylene oxide adduct of hardened castor oil.
  • nonionic surfactants having a polyoxyethylene structure are more preferable, and hydrocarbylated ethers of polyoxyethylene are more preferable, and polyoxyalkylene alkyl ethers and polyoxyethylene distyrene are preferable. Phenyl ether is more preferred, and polyoxyethylene distyrenated phenyl ether is particularly preferred.
  • the nonionic surfactant may be used alone or in combination of two or more.
  • nonionic anionic surfactant examples include a compound represented by the following general formula (1).
  • R 1 represents an alkyl group having 6 to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 25 carbon atoms
  • R 2 to R 5 is a group independently selected from the group consisting of hydrogen and a methyl group
  • M is an alkali metal atom or an ammonium ion
  • n is 3 to 40.
  • nonionic anionic surfactant examples include polyoxyethylene lauryl ether sulfate, polyoxyethylene cetyl ether sulfate, polyoxyethylene stearyl ether sulfate, and polyoxyethylene such as polyoxyethylene oleyl ether sulfate.
  • nonionic anionic surfactants nonionic anionic surfactants having a polyoxyethylene structure are preferred.
  • the nonionic anionic surfactant may be used alone or in combination of two or more.
  • the content of the polyoxyalkylene-based surfactant in the latex composition of the present invention is 0.01 to 3 parts by weight, preferably 0.01 to 0 parts by weight, per 100 parts by weight of the conjugated diene-based polymer.
  • the amount is 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight, and even more preferably 0.1 to 0.23 parts by weight. If the content of the polyoxyalkylene-based surfactant is too small, the effect of shortening the aging (pre-vulcanization) time cannot be obtained, while if it is too large, foaming occurs, and film forming such as dip forming can be performed favorably. You can not do it.
  • the latex composition of the present invention preferably further contains an activator.
  • the activator is not particularly limited as long as it has a function of activating vulcanization, and examples thereof include metal oxides.
  • the metal oxide also acts as a cross-linking agent for cross-linking the carboxyl group, thereby obtaining a film-formed body such as a dip-formed body. This is preferable because the tensile strength can be further increased.
  • the metal oxide examples include, but are not particularly limited to, zinc oxide, magnesium oxide, titanium oxide, calcium oxide, lead oxide, iron oxide, copper oxide, tin oxide, nickel oxide, chromium oxide, cobalt oxide, and aluminum oxide. No. Among these, zinc oxide is preferred from the viewpoint that the tensile strength of the obtained film molded body such as a dip molded body is further improved. These metal oxides may be used alone or in combination of two or more.
  • the content of the activator in the latex composition of the present invention is not particularly limited, but is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the conjugated diene polymer. To 10 parts by weight, more preferably 0.5 to 5 parts by weight.
  • the tensile strength of the obtained film molded body such as a dip molded body can be further improved.
  • the latex composition of the present invention preferably further contains a vulcanization accelerator.
  • a xanthogen compound is preferably used from the viewpoint that the resulting film-formed product such as a dip-formed product can suitably suppress the occurrence of the symptoms of delayed-type allergy (Type IV). .
  • the xanthogen compound is not particularly limited.
  • xanthogenic acid, xanthogenate, xanthogen disulfide (a compound in which two xanthogenic acids are bonded via a sulfur atom or the like), xanthogen polysulfide (three or more xanthogens) A compound in which an acid is bonded via a sulfur atom or the like).
  • Dibutylxanthogenates are more preferable, zinc diisopropylxanthate and zinc dibutylxanthate are more preferable, and zinc diisopropylxanthate is particularly preferable.
  • These xanthates may be used alone or in combination of two or more.
  • Xanthogen disulfide is a compound in which two xanthogenic acids are bonded via a sulfur atom or the like, and is not particularly limited. Examples thereof include xanthogen polysulfide, diisopropylxanthogen polysulfide, dibutylxanthogen polysulfide, and among them, diisopropylxanthogen disulfide and dibutylxanthogen disulfide are preferable.
  • Xanthogen polysulfide is a compound in which three or more xanthogenic acids are bonded via a sulfur atom or the like, and xanthogen trisulfide in which three xanthogenic acids are bonded via sulfur and four xanthogenic acids are bonded via sulfur. And xanthogen pentasulfide in which five xanthogenic acids are bonded via sulfur.
  • xanthogen compounds may be used alone or in combination of two or more.
  • a vulcanization accelerator other than the xanthogen compound may be used instead of the xanthogen compound or together with the xanthogen compound.
  • vulcanization accelerator other than such a xanthogen compound those usually used in film formation such as dip molding can be used, and examples thereof include diethyldithiocarbamic acid, dibutyldithiocarbamic acid, di-2-ethylhexyldithiocarbamic acid, and dicyclohexyldithiocarbamic acid.
  • Dithiocarbamic acids such as diphenyldithiocarbamic acid, dibenzyldithiocarbamic acid, and zinc salts thereof; 2-mercaptobenzothiazole, zinc 2-mercaptobenzothiazole, 2-mercaptothiazoline, dibenzothiazyl disulfide, 2- (2,4- Dinitrophenylthio) benzothiazole, 2- (N, N-diethylthio-carbamoylthio) benzothiazole, 2- (2,6-dimethyl-4-morpholinothio) benzothia Butyl, 2- (4'-morpholino dithio) benzothiazole, 4-morpholinyl-2-benzothiazyl disulfide, 1,3-bis (2-benzothiazyl mercaptomethyl) urea, etc., and zinc diethyldithiocarbamate , Zinc dibutyldithiocarbamate and zinc 2-mercaptobenzothiazole are
  • the content of the vulcanization accelerator in the latex composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the conjugated diene polymer. And more preferably 0.5 to 5 parts by weight.
  • the latex composition of the present invention further comprises a compounding agent such as an antioxidant; a dispersant; a reinforcing agent such as carbon black, silica, and talc; a filler such as calcium carbonate and clay; an ultraviolet absorber; It can be blended as needed.
  • a compounding agent such as an antioxidant
  • a dispersant such as carbon black, silica, and talc
  • a filler such as calcium carbonate and clay
  • an ultraviolet absorber an ultraviolet absorber
  • Antioxidants include 2,6-di-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl- ⁇ -dimethylamino-p-cresol, Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, styrenated phenol, 2,2′-methylene-bis (6- ⁇ -methyl-benzyl-p-cresol), 4, 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), alkylated bisphenol, butylated butyl p-cresol and dicyclopentadiene
  • the content of the antioxidant in the latex composition of the present invention is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the carboxy-modified conjugated diene-based polymer. Department.
  • the method for preparing the latex composition of the present invention is not particularly limited.
  • a vulcanizing agent, and a polyoxyalkylene-based surfactant, and, if necessary, a latex of the conjugated diene-based polymer described above are used.
  • a method of mixing various compounding agents a method of preparing an aqueous dispersion of components other than the latex of the conjugated diene polymer and then mixing the aqueous dispersion with the latex of the conjugated diene polymer may be employed.
  • an aqueous dispersion containing the vulcanization accelerator and a polyoxyalkylene-based surfactant is prepared in advance. However, it is preferable to mix them in the form of an aqueous dispersion.
  • the solid content of the latex composition of the present invention is preferably 10 to 60% by weight, more preferably 10 to 55% by weight.
  • the latex composition of the present invention comprises a latex of a conjugated diene-based polymer and a vulcanizing agent and a polyoxyalkylene-based surfactant, the ripening (pre-vulcanization) time is preferably reduced. Even when the time is shortened to 6 to 30 hours, more preferably 6 to 18 hours, a film formed body such as a dip formed body having sufficient mechanical properties can be obtained. ) Can be shortened and the production efficiency can be improved.
  • the temperature of the pre-vulcanization is not particularly limited, but is preferably 20 to 40 ° C.
  • the film molded article of the present invention is a film-shaped molded article comprising the latex composition of the present invention.
  • the film thickness of the film formed body of the present invention 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 article of the present invention is not particularly limited, but is preferably a dip molded article obtained by dip molding the latex composition of the present invention.
  • Dip molding is a method in which a mold is immersed in a latex composition, the composition is deposited on the surface of the mold, the mold is then lifted from the composition, and then the composition deposited on the surface of the mold is dried. is there.
  • the mold before dipping in the latex composition may be preheated. Before dipping the mold in the latex composition or after lifting the mold from the latex composition, a coagulant can be used as necessary.
  • the method of using the coagulant include a method of immersing the mold before dipping in the latex composition into a solution of the coagulant to adhere the coagulant to the mold (anode coagulation dipping method), and a method of depositing the latex composition.
  • anodic adhesion immersion method There is a method of immersing the formed mold in a coagulant solution (Tieg adhesion immersion method), but the anodic adhesion immersion method is preferable in that a dip molded article with less thickness unevenness can be obtained.
  • the coagulant 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 water-soluble polyvalent metal salts. Especially, a calcium salt is preferable and calcium nitrate is more preferable. These water-soluble polyvalent metal salts can be used alone or in combination of two or more.
  • the coagulant can be usually used as a solution of water, alcohol, or a mixture thereof, and is preferably used in the form of an aqueous solution.
  • This aqueous solution may further contain a water-soluble organic solvent such as methanol or ethanol or a nonionic surfactant.
  • the concentration of the coagulant varies depending on the type of the water-soluble polyvalent metal salt, but is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.
  • the mold After the mold has been pulled out of the latex composition, it is usually heated to dry the deposits formed on the mold. Drying conditions may be appropriately selected.
  • the obtained dip-formed layer is subjected to a heat treatment and vulcanized.
  • water-soluble impurities for example, excess emulsifier, coagulant, etc.
  • the operation of removing the water-soluble impurities may be performed after the heat treatment of the dip-formed layer, but is preferably performed before the heat treatment because water-soluble impurities can be more efficiently removed.
  • the vulcanization of the dip-formed layer is usually performed by performing a heat treatment at a temperature of 80 to 150 ° C., preferably for 10 to 130 minutes.
  • a heating method a method of external heating with infrared rays or heated air or internal heating with high frequency can be adopted. Of these, external heating with heated air is preferred.
  • the dip molding layer is detached from the dip molding die, whereby the dip molding is obtained as a film-like film molding.
  • a method of peeling off from the mold by hand or a method of peeling off by water pressure or compressed air pressure can be adopted.
  • a heat treatment may be further performed at a temperature of 60 to 120 ° C. for 10 to 120 minutes.
  • the film molded article of the present invention can be formed by a method (for example, a coating method or the like) capable of forming the above-described latex composition of the present invention into a film in addition to the above-described method of dip-forming the latex composition of the present invention. ) May be obtained by any method.
  • the film molded article of the present invention including the dip molded article of the present invention is obtained using the above-described latex composition of the present invention, the time required for aging (pre-vulcanization) is reduced. It is excellent in productivity and tear strength, and can be particularly suitably used, for example, as gloves.
  • the film formed body is a glove
  • inorganic particles such as talc and calcium carbonate or organic particles such as starch particles are gloved.
  • the glove may be sprayed on the surface, an elastomer layer containing fine particles may be formed on the glove surface, or the glove surface layer may be chlorinated.
  • the membrane molded article of the present invention including the dip molded article of the present invention may be a medical article such as a baby bottle nipple, a dropper, a tube, a water pillow, a balloon sack, a catheter, a condom, etc. And toys such as balls and the like; industrial products such as pressure molding bags and gas storage bags; and finger cots.
  • the above-described latex composition of the present invention can be used as an adhesive composition.
  • the content (solid content) of the latex composition of the present invention in the adhesive composition is preferably 5 to 60% by weight, more preferably 10 to 30% by weight.
  • the adhesive composition preferably contains an adhesive resin in addition to the latex composition of the present invention.
  • the adhesive resin is not particularly limited, but, for example, a resorcin-formaldehyde resin, a melamine resin, an epoxy resin and an isocyanate resin can be suitably used, and among these, a resorcin-formaldehyde resin is preferable.
  • a resorcin-formaldehyde resin known resins (for example, those disclosed in JP-A-55-142635) can be used.
  • the reaction ratio between resorcinol and formaldehyde is usually 1: 1 to 1: 5, preferably 1: 1 to 1: 3, in a molar ratio of "resorcinol: formaldehyde".
  • the adhesive composition may include a conventionally used 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or a similar compound.
  • a conventionally used 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or a similar compound.
  • Compounds, isocyanates, blocked isocyanates, ethylene urea, polyepoxides, modified polyvinyl chloride resins and the like can be contained.
  • the adhesive composition may contain a crosslinking aid.
  • a crosslinking aid By including a crosslinking aid, it is possible to improve the mechanical strength of the composite described below obtained using the adhesive composition.
  • the crosslinking assistant include quinone dioximes such as p-quinone dioxime; methacrylic esters such as lauryl methacrylate and methyl methacrylate; DAF (diallyl fumarate), DAP (diallyl phthalate), TAC (triallyl cyanurate), TAIC Allyl compounds such as (triallyl isocyanurate); maleimide compounds such as bismaleimide, phenylmaleimide and N, Nm-phenylenedimaleimide; sulfur;
  • the adhesive layer-forming substrate of the present invention is obtained by forming an adhesive layer formed using the latex composition or the adhesive composition of the present invention on the surface of the substrate.
  • the substrate is not particularly limited, but for example, a fiber substrate can be used.
  • the type of fiber constituting the fiber base is not particularly limited, and examples thereof include vinylon fiber, polyester fiber, nylon, polyamide fiber such as aramid (aromatic polyamide), glass fiber, cotton, rayon and the like. These can be appropriately selected according to the application.
  • the shape of the fiber base material is not particularly limited, and examples thereof include staples, filaments, cords, ropes, and woven fabrics (such as canvas), which can be appropriately selected depending on the use.
  • the adhesive layer-forming substrate can be used as a substrate-rubber composite by adhering to rubber via the adhesive layer.
  • the base-rubber composite is not particularly limited. For example, a rubber using a base cloth-like fiber base such as a cored rubber toothed belt or a canvas using a cord-like fiber base. A belt with teeth may be used.
  • the method for obtaining the substrate-rubber composite is not particularly limited.
  • a latex composition or an adhesive composition is adhered to a substrate by dipping or the like to obtain an adhesive layer-forming substrate,
  • a layer-forming base material is placed on rubber and heated and pressed. Pressing can be performed using a compression (press) molding machine, a metal roll, an injection molding machine, or the like.
  • the pressure for pressurization is preferably 0.5 to 20 MPa, more preferably 2 to 10 MPa.
  • the heating temperature is preferably from 130 to 300 ° C, more preferably from 150 to 250 ° C.
  • the heating and pressurizing treatment time is preferably 1 to 180 minutes, more preferably 5 to 120 minutes.
  • a mold for imparting a desired surface shape to the rubber of the target base material-rubber composite is preferably formed on the inner surface of the mold of the compressor used for pressurization or on the surface of the roll.
  • the substrate-rubber composite includes a substrate-rubber-substrate composite.
  • the substrate-rubber-substrate composite can be formed, for example, by combining a substrate (which may be a composite of two or more substrates) and a substrate-rubber composite. Specifically, a core wire as a base material, rubber and a base fabric as a base material are stacked (at this time, a latex composition or an adhesive composition is appropriately adhered to the core wire and the base fabric to form an adhesive layer forming base material.
  • the substrate-rubber-substrate composite can be obtained by applying pressure while heating.
  • the substrate-rubber composite obtained using the adhesive layer-forming substrate of the present invention has excellent mechanical strength, abrasion resistance and water resistance, and is therefore suitable for flat belts, V-belts, V-ribbed belts, It can be suitably used as a belt such as a round belt, a square belt, and a toothed belt. Further, the substrate-rubber composite obtained by using the adhesive layer-forming substrate of the present invention has excellent oil resistance and can be suitably used as a belt in oil. Further, the substrate-rubber composite obtained by using the adhesive layer-forming substrate of the present invention can be suitably used for hoses, tubes, diaphragms and the like.
  • Examples of the hose include a single-tube rubber hose, a multilayer rubber hose, a braided reinforcing hose, a cloth-wound reinforcing hose, and the like.
  • Examples of the diaphragm include a flat diaphragm and a rolling diaphragm.
  • the substrate-rubber composite obtained by using the adhesive layer-forming substrate of the present invention can be used as industrial products such as seals and rubber rolls in addition to the above-mentioned applications.
  • the seal include a moving part seal for rotating, swinging, and reciprocating movement, and a fixed part seal.
  • the moving part seal include an oil seal, a piston seal, a mechanical seal, a boot, a dust cover, a diaphragm, an accumulator, and the like.
  • Examples of the fixed part seal include an O-ring and various gaskets.
  • Examples of the rubber roll include rolls that are parts of OA equipment such as printing equipment and copying equipment; rolls for fiber processing such as drawing rolls for spinning and draft rolls for spinning; and rolls for iron making such as bridle rolls, snubber rolls, and steering rolls. No.
  • Modification rate (% by weight) (X / Y) ⁇ 100
  • X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified synthetic polyisoprene
  • Y represents the weight of the carboxy-modified synthetic polyisoprene
  • ⁇ Tear strength of dip molding> According to ASTM D624-00, the dip molded body was left in a constant temperature and humidity room at 23 ° C. and a relative humidity of 50% for 24 hours or more, then punched out with a dumbbell (trade name “Die C”, manufactured by Dumbbell Co.), and torn. A test piece for strength measurement was prepared. The test piece was pulled at a tensile speed of 500 mm / min with a Tensilon universal tester (trade name “RTG-1210”, manufactured by A & D), and the tear strength (unit: N / mm) was measured. The measurement of the tear strength of the dip molded body was performed on a dip molded body having an aging (pre-vulcanization) time of 6 hours and a dip molded body having an aging (pre-vulcanization) time of 48 hours.
  • a dumbbell trade name “Die C”, manufactured by Dumbbell Co.
  • the total feed flow rate of the cyclohexane solution (a) and the aqueous solution of the anionic surfactant (b) was 2,000 kg / hr, the temperature was 60 ° C., and the back pressure (gauge pressure) was 0.5 MPa.
  • the emulsion (c) is heated to 80 ° C. under reduced pressure of ⁇ 0.01 to ⁇ 0.09 MPa (gauge pressure), cyclohexane is distilled off, and an aqueous dispersion (d) of synthetic polyisoprene is removed. Obtained.
  • an antifoaming agent (trade name “SM5515”, manufactured by Dow Corning Toray Co., Ltd.) was continuously added while spraying so that the amount was 300 ppm by weight based on the synthetic polyisoprene in the emulsion (c). .
  • the emulsion (c) was adjusted to be 70% by volume or less of the volume of the tank, and three-stage inclined paddle blades were used as stirring blades, and the mixture was slowly stirred at 60 rpm. Was carried out.
  • the obtained aqueous dispersion of synthetic polyisoprene (d) was subjected to a continuous centrifugal separator (trade name “SRG510”, manufactured by Alfa Laval Co., Ltd.) to a concentration of 4,000 to 4,000. Centrifugation was performed at 5,000 G to obtain a latex of synthetic polyisoprene (A-1) as a light liquid.
  • the conditions for centrifugation were as follows: the solid content concentration of the aqueous dispersion (d) before centrifugation was 10% by weight, the flow rate during continuous centrifugation was 1300 kg / hr, and the back pressure (gauge pressure) of the centrifuge was 1. It was 5 MPa.
  • the resulting synthetic polyisoprene (A-1) latex had a solid content of 60% by weight.
  • ⁇ Production Example 2> (Production of latex of carboxy-modified synthetic polyisoprene (A-2)) To 100 parts of the synthetic polyisoprene in the latex of the synthetic polyisoprene (A-1) obtained in Production Example 1, 130 parts of distilled water was added for dilution. Then, in a latex of synthetic polyisoprene (A-1), a sodium salt of a ⁇ -naphthalenesulfonic acid formalin condensate as a dispersant (trade name “Demol T-45”, Kao Corporation) 0.8 parts) was diluted with 4 parts of distilled water to 100 parts of synthetic polyisoprene, and added over 5 minutes.
  • the synthetic polyisoprene (A-1) latex to which the dispersant was added was charged into a nitrogen-replaced reaction vessel equipped with a stirrer, and the temperature was raised to 30 ° C. while stirring.
  • 3 parts of methacrylic acid as a monomer having a carboxyl group and 16 parts of distilled water were mixed to prepare a methacrylic acid diluted solution.
  • This methacrylic acid diluted solution was added to the reaction vessel heated to 30 ° C. over 30 minutes.
  • the carboxy-modified synthetic polyisoprene (A-2) was concentrated by a centrifuge to obtain a light liquid having a solid content of 56%. Then, the modification rate of the obtained carboxy-modified synthetic polyisoprene (A-2) latex with a monomer having a carboxyl group was measured according to the above method, and the modification rate was 0.5% by weight.
  • Example 1 (Preparation of latex composition) While stirring the synthetic polyisoprene (A-1) latex obtained in Production Example 1, 100 parts of the synthetic polyisoprene in the synthetic polyisoprene (A-1) latex was added in terms of solid content. Was added so as to make 1 part, sodium dodecylbenzenesulfonate having a concentration of 10% by weight. While stirring the obtained mixture, 100 parts of the synthetic polyisoprene in the mixture was mixed with polyoxyethylene distyrenated phenyl ether (trade name “Emulgen A-60”) as a polyoxyalkylene-based surfactant. 0.15 parts (manufactured by Kao Corporation) was added and mixed.
  • polyoxyethylene distyrenated phenyl ether trade name “Emulgen A-60”
  • a latex composition was obtained by adding an aqueous dispersion of each compounding agent so as to be 3 parts, zinc dibutyldithiocarbamate 0.5 part, and mercaptobenzothiazole zinc salt 0.7 part. Then, the obtained latex composition is divided into two parts, one of which is aged (pre-vulcanization) for 6 hours in a constant temperature water bath adjusted to 25 ° C., and the other is a constant temperature water bath adjusted to 25 ° C. And aged for 48 hours (pre-vulcanization) to obtain a latex composition aged for 6 hours and a latex composition aged for 48 hours.
  • the hand mold coated with the coagulant was taken out of the oven and immersed in the aged latex composition obtained above for 6 hours for 10 seconds.
  • the hand mold was air-dried at room temperature for 10 minutes, and then immersed in warm water at 60 ° C. for 5 minutes to elute water-soluble impurities, thereby forming a dip-molded layer on the hand mold.
  • the dip-formed layer formed in the hand mold is vulcanized by heating it in an oven at a temperature of 130 ° C. for 30 minutes, then cooled to room temperature, sprayed with talc and peeled from the hand mold.
  • a glove-shaped dip molded product (aged for 6 hours) was obtained.
  • a glove-shaped dip molded product (48-hour aged product) was obtained in the same manner as above, except that the 48-hour aged latex composition was used instead of the 6-hour aged latex composition.
  • the tear strength was measured according to the said method using the obtained dip molded object (6 hours aged and 48 hours aged). Table 1 shows the results.
  • Example 2> (Preparation of xanthogen compound dispersion) 2 parts of zinc diisopropylxanthogenate as a xanthogen compound, 0.15 parts of polyoxyethylene distyrenated phenyl ether (trade name "Emulgen A-60", manufactured by Kao Corporation) as a polyoxyalkylene-based surfactant, and water 4 Xantogen compound dispersion was obtained by performing a crushing process by mixing .5 parts with a ball mill (trade name "Porcelain Ball Mill", manufactured by Nissin Kagaku Co., Ltd.). As a mixing condition using a ball mill, ceramic magnetic balls of ⁇ 15 mm and ⁇ 20 mm were used and rotated at 50 rpm for 72 hours or more.
  • a styrene-maleic acid mono-sec-butyl ester-maleic acid monomethyl ester polymer (trade name “Scriptset550”, manufactured by Hercules) is prepared, and sodium hydroxide is used to prepare 100% of carboxyl groups in the polymer.
  • a sodium salt aqueous solution (concentration: 10% by weight) was prepared.
  • this aqueous sodium salt solution was added to the latex of the carboxy-modified synthetic polyisoprene (A-2) obtained in Production Example 2 and the solid content was calculated based on 100 parts of the carboxy-modified synthetic polyisoprene (A-2) in the latex. Was added so as to be 0.8 parts to obtain a mixture.
  • each compounding agent was used so that 1.5 parts of zinc oxide and 1.5 parts of sulfur as an activator and 2 parts of an antioxidant (trade name “Wingstay @ L”, manufactured by Goodyear Corporation) as solids were calculated.
  • Weightstay @ L an antioxidant
  • the obtained latex composition is divided into two parts, one of which is aged (pre-vulcanization) for 6 hours in a constant temperature water bath adjusted to 25 ° C., and the other is a constant temperature water bath adjusted to 25 ° C.
  • aged for 48 hours pre-vulcanization
  • Example 3 As a polyoxyalkylene-based surfactant, polyoxyethylene lauryl ether (polyoxyethylene (6) lauryl ether, trade name "Emulgen 108", manufactured by Kao Corporation) is used instead of 0.15 part of polyoxyethylene distyrenated phenyl ether. 6) Aged latex composition, aged 48 hour latex composition, and a dip molded article (aged 6 hours and aged 48 hours) were prepared in the same manner as in Example 2 except that 0.15 part was used. Obtained and measured and evaluated similarly. Table 1 shows the results.
  • Example 4 As the polyoxyalkylene-based surfactant, instead of 0.15 parts of polyoxyethylene distyrenated phenyl ether, a polyoxyethylene alkyl ether (polyoxyethylene (9) alkyl (sec-C11-15) ether, trade name " Emulgen 709 "(manufactured by Kao Corporation) in the same manner as in Example 2 except that 0.15 part was used, and a 6-hour aged latex composition, a 48-hour aged latex composition, and a dip molded product (6-hour aged product) And aged for 48 hours) and measured and evaluated in the same manner. Table 1 shows the results.
  • Example 5 As a polyoxyalkylene surfactant, 0.15 parts of polyoxyethylene polyoxypropylene glycol (trade name “Emulgen PP-290”, manufactured by Kao Corporation) is used instead of 0.15 parts of polyoxyethylene distyrenated phenyl ether.
  • a 6-hour aged latex composition, a 48-hour aged latex composition, and a dip molded article (6-hour aged product and 48-hour aged product) were obtained in the same manner as in Example 2 except that Measurement and evaluation were performed. Table 1 shows the results.
  • ⁇ Comparative Example 1> Instead of 0.15 parts of polyoxyethylene distyrenated phenyl ether as a polyoxyalkylene surfactant, a sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate as an anionic surfactant (trade name “Demol T- 45 "(manufactured by Kao Corporation) in the same manner as in Example 2 except that 0.15 part was used, and a 6-hour aged latex composition, a 48-hour aged latex composition, and a dip molded product (a 6-hour aged product and (Aged for 48 hours) and measured and evaluated in the same manner. Table 1 shows the results.
  • the obtained dip molded article has a sufficient tear strength, so that the aging is performed for 6 hours. Even when shortened, it is possible to provide a dip molded body having sufficient mechanical strength, shorten the time required for aging (pre-vulcanization), and confirm that the product is excellent in productivity (Examples 1 to 5). ).

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
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Abstract

L'invention concerne une composition de latex contenant un latex d'un polymère de diène conjugué, un agent de vulcanisation et un tensioactif à base de polyoxyalkylène, la teneur en tensioactif à base de polyoxyalkylène étant de 0,01 à 3 parties en poids par rapport à 100 parties en poids du polymère de diène conjugué.
PCT/JP2019/030373 2018-09-14 2019-08-01 Composition de latex et corps moulé en film Ceased WO2020054247A1 (fr)

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JPWO2021132075A1 (fr) * 2019-12-27 2021-07-01
JPWO2022172696A1 (fr) * 2021-02-09 2022-08-18
JPWO2022181389A1 (fr) * 2021-02-25 2022-09-01
JP2022131081A (ja) * 2021-02-26 2022-09-07 日本ゼオン株式会社 ラテックス組成物およびディップ成形体
WO2023127858A1 (fr) 2021-12-27 2023-07-06 株式会社レゾナック Composition de latex de polychloroprène modifié par du soufre, procédé de production associé, objet en caoutchouc façonné et produit façonné par immersion
EP4108708A4 (fr) * 2020-02-20 2024-03-06 Zeon Corporation Procédé de fabrication de composition de latex

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JP7632306B2 (ja) 2019-12-27 2025-02-19 日本ゼオン株式会社 キサントゲン化合物分散体、共役ジエン系重合体ラテックス組成物、膜成形体、ディップ成形体、および接着剤組成物
EP4108708A4 (fr) * 2020-02-20 2024-03-06 Zeon Corporation Procédé de fabrication de composition de latex
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WO2023127858A1 (fr) 2021-12-27 2023-07-06 株式会社レゾナック Composition de latex de polychloroprène modifié par du soufre, procédé de production associé, objet en caoutchouc façonné et produit façonné par immersion

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