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WO2018155113A1 - Procédé de production de latex de polyisoprène synthétique - Google Patents

Procédé de production de latex de polyisoprène synthétique Download PDF

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Publication number
WO2018155113A1
WO2018155113A1 PCT/JP2018/003209 JP2018003209W WO2018155113A1 WO 2018155113 A1 WO2018155113 A1 WO 2018155113A1 JP 2018003209 W JP2018003209 W JP 2018003209W WO 2018155113 A1 WO2018155113 A1 WO 2018155113A1
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Prior art keywords
synthetic polyisoprene
latex
solution
weight
producing
Prior art date
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Ceased
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PCT/JP2018/003209
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English (en)
Japanese (ja)
Inventor
吉隆 佐藤
小出村　順司
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Zeon Corp
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Zeon Corp
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Priority to JP2019501173A priority Critical patent/JPWO2018155113A1/ja
Publication of WO2018155113A1 publication Critical patent/WO2018155113A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/10—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to a method for producing a synthetic polyisoprene latex which is excellent in stability as a latex, excellent in tensile strength and elongation, and can provide a dip-molded body having a soft texture, and such production.
  • the present invention relates to a method for producing a latex composition using a synthetic polyisoprene latex obtained by the method, a method for producing a dip-molded product, and a method for producing an adhesive layer-forming substrate.
  • a latex composition containing latex of natural rubber is dip-molded to obtain a dip-molded body that is used in contact with a human body such as a nipple, a balloon, a glove, a balloon, and a sack.
  • natural rubber latex contains a protein that causes allergic symptoms in the human body, there are cases in which there is a problem as a dip-molded body that is in direct contact with a living mucosa or organ. Therefore, studies have been made on using synthetic rubber latex instead of natural rubber latex.
  • Patent Document 1 discloses a technique for obtaining a latex of synthetic polyisoprene by emulsifying and concentrating a solution in which synthetic polyisoprene is dissolved in cyclohexane.
  • the resultant synthetic polyisoprene latex is made into a latex composition by adding a crosslinking agent, and when stored for a long period of time, aggregates are likely to be generated in the latex composition.
  • the tensile strength of the dip-molded product obtained using the latex composition may be insufficient.
  • the present invention has been made in view of such a situation, and is a synthesis that is excellent in stability as a latex, excellent in tensile strength and elongation, and can provide a dip-molded body having a soft texture. It aims at providing the manufacturing method of polyisoprene latex.
  • the intensity ratio at two specific peaks measured by a Fourier transform infrared spectrophotometer as a synthetic polyisoprene is as follows.
  • the above-mentioned object can be achieved by obtaining a synthetic polyisoprene latex by emulsifying a synthetic polyisoprene solution obtained by dissolving the synthetic polyisoprene in an organic solvent using a composition controlled within a predetermined range.
  • the present invention has been completed.
  • the most strength when measured by FT-IR, for the most strength is large peak intensity I A in the range of 2,840 ⁇ 3,000 cm -1, of 1,000 ⁇ 1,200cm -1 the most strength is large peak intensity I B ratio in a range (I B / I a) is a synthetic polyisoprene is 0.4 or less, the synthetic polyisoprene solution prepared by dissolving in an organic solvent, a surfactant
  • a method for producing a synthetic polyisoprene latex comprising the step of obtaining a latex of the synthetic polyisoprene by emulsification in water in the presence.
  • the synthetic polyisoprene solution is solidified by solidifying a polymer solution obtained by solution polymerization of a monomer containing isoprene dissolved in an organic solvent. It is preferable that the product is obtained by re-dissolving the product in an organic solvent.
  • the synthetic polyisoprene solution is added with 0.001 to 0.3 parts by weight of an antioxidant to 100 parts by weight of the polymer component in the polymer solution. In this state, it is preferably obtained by performing the coagulation and the re-dissolution.
  • the synthetic polyisoprene solution is preferably obtained by solidifying a solution polymerized monomer containing isoprene dissolved in an organic solvent.
  • the synthetic polyisoprene solution is added with 0.001 to 0.3 parts by weight of an anti-aging agent with respect to 100 parts by weight of the synthetic polyisoprene in the synthetic polyisoprene solution. It is preferable that it is obtained by emulsifying.
  • solution polymerization is preferably performed in the presence of an organic alkali metal catalyst.
  • the manufacturing method of a latex composition provided with the process of adding a crosslinking agent to the synthetic polyisoprene latex obtained by said manufacturing method is provided. Furthermore, according to this invention, the manufacturing method of a dip molded object provided with the process of dip-molding the latex composition obtained by the said manufacturing method is provided. Furthermore, according to this invention, an adhesive layer forming base material provided with the process of forming in the base material surface the adhesive bond layer formed using the synthetic polyisoprene latex obtained by said manufacturing method is provided. .
  • a method for producing a synthetic polyisoprene latex that is excellent in stability as a latex, has excellent tensile strength and elongation, and can provide a dip-molded body having a soft texture, and such
  • the manufacturing method of the latex composition using the synthetic polyisoprene latex obtained by the various manufacturing methods, the manufacturing method of the dip-molded product, and the manufacturing method of the adhesive layer forming substrate can be provided.
  • Production method of the present invention when measured by FT-IR, for the most strength is large peak intensity I A in the range of 2,840 ⁇ 3,000 cm -1, the range of 1,000 ⁇ 1,200cm -1 the most ratio of the intensity is large peak intensity I B (I B / I a ) is a synthetic polyisoprene is 0.4 or less, the synthetic polyisoprene solution prepared by dissolving in an organic solvent in the presence of surfactants in Below, it is equipped with the process of obtaining the latex of synthetic polyisoprene by emulsifying in water.
  • the peak with the highest intensity in the range of 2,840 to 3,000 cm ⁇ 1 is the peak derived from the C—H stretching vibration in the synthetic polyisoprene.
  • the peak having the highest intensity in the range of 1,000 to 1,200 cm ⁇ 1 is estimated to be a peak derived from CO stretching vibration in the synthetic polyisoprene.
  • the peak intensity estimated to be derived from such CO stretching vibration peak intensity I B of the highest intensity in the range of 1,000 to 1,200 cm ⁇ 1
  • the smaller the ratio (I B / I A ) to the intensity of the peak estimated to be derived from C—H stretching vibration the intensity I A of the peak having the highest intensity in the range of 2,840 to 3,000 cm ⁇ 1
  • the degree of oxidation in the synthetic polyisoprene is small (the number of C—O bonds formed by the oxidation of the synthetic polyisoprene is small).
  • the synthetic polyisoprene constituting the synthetic polyisoprene latex the synthetic polyisoprene obtained by using the above-described peak intensity ratio (I B / I A ) controlled in the above range.
  • latex it is possible to suppress the generation of aggregates, and to suppress the generation of aggregates when stored for a long period of time with respect to a latex composition obtained by blending a synthetic polyisoprene latex with a crosslinking agent. While being able to improve, the tensile strength of the dip molded object manufactured using a latex composition can be improved notably.
  • the synthetic polyisoprene contained in the synthetic polyisoprene solution used in the present invention may be a homopolymer of isoprene or a copolymer of other ethylenically unsaturated monomers copolymerizable with isoprene. It may be.
  • the content of isoprene units in the synthetic polyisoprene is flexible, and it is easy to obtain a film molded body such as a dip molded body having excellent tensile strength. More preferred is 90% by weight or more, still more preferred is 95% by weight or more, and particularly preferred is 100% by weight (isoprene homopolymer).
  • Examples of other ethylenically unsaturated monomers copolymerizable with isoprene include 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”; The same applies to ethyl (meth) acrylate, etc.), ethylenically unsaturated carboxylic acid ester monomers such as ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; Is mentioned.
  • the content ratio of cis bond units in the isoprene units contained in the synthetic polyisoprene is preferably 70% by weight or more based on the total isoprene units. More preferably, it is 90 weight% or more, More preferably, it is 95 weight% or more.
  • 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 even more preferably, in terms of standard polystyrene by gel permeation chromatography analysis. Is 800,000 to 3,000,000.
  • the polymer Mooney viscosity (ML 1 + 4 , 100 ° C.) of the synthetic polyisoprene is preferably 50 to 80, more preferably 60 to 80, and still more preferably 70 to 80.
  • the synthetic polyisoprene contained in the synthetic polyisoprene solution used in the present invention has a density of 2,840 to 3,000 cm ⁇ 1 as measured by a Fourier transform infrared spectrophotometer (FT-IR).
  • FT-IR Fourier transform infrared spectrophotometer
  • the ratio of the highest intensity is large peak intensity I B in the range of 1,000 ⁇ 1,200cm -1 (I B / I a) is 0.4 or less Yes, preferably 0.2 or less, more preferably 0.1 or less.
  • the lower limit of the above-described intensity ratio (I B / I A ) is not particularly limited, but is generally about 0.005 or more.
  • the method for producing the synthetic polyisoprene solution containing the synthetic polyisoprene whose strength ratio (I B / I A ) is controlled within the above range is not particularly limited.
  • an organic solvent is used in the presence of a polymerization catalyst.
  • a method of obtaining a synthetic polyisoprene solution by re-dissolving a solid in an organic solvent can be mentioned.
  • the degree of thermal history during the production of a synthetic polyisoprene solution by reducing the degree of thermal history during the production of a synthetic polyisoprene solution, oxidation of the resulting synthetic polyisoprene is suppressed, and as a result, the synthetic polyisoprene is derived from CO stretching vibration. Then, the peak intensity (the intensity I B of the peak having the highest intensity in the range of 1,000 to 1,200 cm ⁇ 1 ) is reduced, and the intensity ratio (I B / I A ) is effectively reduced. Will be able to.
  • the drying condition is set to a lower temperature and a shorter time. Is preferred.
  • the above-mentioned strength ratio (depending on the type and amount of the polymerization catalyst used in solution polymerization of the monomer (isoprene and an ethylenically unsaturated monomer copolymerizable with isoprene that is used if necessary)) is also possible.
  • I B / I A can be controlled.
  • the polymerization catalyst is not particularly limited, and examples thereof include a Ziegler polymerization catalyst and an organic alkali metal catalyst.
  • the amount used in solution polymerization can be reduced, and as a result, the resulting synthetic polyisoprene is obtained.
  • the amount of the polymerization catalyst remaining in the catalyst can be reduced, the oxidation of the synthetic polyisoprene due to the action of the polymerization catalyst can be suppressed, and the above intensity ratio (I B / I A ) can be more effectively reduced.
  • an organic alkali metal catalyst is preferable.
  • the synthetic polyisoprene obtained can have a relatively low weight average molecular weight, and when the latex composition is formed by dip molding, the synthetic polyisoprene in the latex composition It is preferable to use a Ziegler-based polymerization catalyst from the viewpoint that it can act to bond the particles of isoprene and improve the film forming property.
  • the organic alkali metal catalyst is not particularly limited.
  • organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium; dilithiomethane, 1,4- Organic polyvalent lithium compounds such as dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-tris (lithiomethyl) benzene; organic sodium compounds such as sodium naphthalene; And organic power lithium compounds such as potassium naphthalene.
  • organic monolithium compound it is preferable to use an organic monolithium compound, and it is more preferable to use n-butyllithium.
  • These organic alkali metal catalysts can be used alone or in combination of two or more.
  • Examples of the method for adding the organic alkali metal catalyst include, for example, an organic alkali metal catalyst in a reaction vessel charged with a monomer (isoprene and an ethylenically unsaturated monomer copolymerizable with isoprene, if necessary). May be added as it is, or may be added in a state where the organic alkali metal catalyst is dissolved in an inert solvent such as hexane.
  • the Ziegler-based catalyst is not particularly limited, and a known catalyst can be used. For example, it is obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating with various electron donors and electron acceptors. Examples include a catalyst system in which a titanium trichloride composition and an organoaluminum compound are combined, and a supported catalyst system in which titanium tetrachloride and various electron donors are brought into contact with magnesium halide. Among these, titanium tetrachloride and organic A catalyst system using an aluminum compound is preferable, and a catalyst system using titanium tetrachloride and trialkylaluminum is particularly preferable.
  • the amount of the polymerization catalyst used is preferably 0.0070 to 0.085 parts by weight with respect to 100 parts by weight of the monomer used for polymerization, from the viewpoint that a synthetic polyisoprene solution can be produced with high productivity.
  • the amount is preferably 0.0076 to 0.056 parts by weight, and more preferably 0.0084 to 0.042 parts by weight.
  • organic solvent used for the solution polymerization examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane, and cyclohexene; and aliphatics such as pentane, hexane, and heptane. Hydrocarbon solvents; halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene dichloride; and the like. Of these, alicyclic hydrocarbon solvents are preferred, with cyclohexane being particularly preferred.
  • the amount of the organic solvent used is preferably 2,000 parts by weight or less, more preferably 20 to 1, based on 100 parts by weight of the polymer component (synthetic polyisoprene before solidification) obtained by solution polymerization. 500 parts by weight, more preferably 500 to 1500 parts by weight.
  • the polymerization temperature at the time of solution polymerization is preferably 40 to 80 ° C., more preferably 45 to 75 ° C. from the viewpoint that a synthetic polyisoprene solution can be produced with high productivity.
  • the polymer solution obtained by the solution polymerization described above is solidified by coagulation, and then the solid is redissolved in an organic solvent, so that a synthetic polyisoprene solution is obtained. Can be obtained.
  • impurities for example, unreacted monomers
  • the polymer solution can be appropriately removed by coagulating and re-dissolving the polymer solution.
  • the method of coagulating the polymer solution is not particularly limited.
  • a polar solvent typified by alcohol such as methanol
  • the method of making it a solid substance is mentioned.
  • the degree of thermal history of the resultant synthetic polyisoprene can be made smaller, thereby suppressing the oxidation of the synthetic polyisoprene and, as a result, presumed to be derived from CO stretching vibration.
  • the intensity of the peak (intensity I B of the peak having the highest intensity in the range of 1,000 to 1,200 cm ⁇ 1 ) is reduced, and the intensity ratio (I B / I A ) is more appropriately controlled within the above range. From the viewpoint of being able to perform the drying, it is preferable to set the drying conditions at a lower temperature and for a shorter time.
  • the drying temperature is preferably 50 to 105 ° C, more preferably 60 to 95 ° C, and still more preferably 65 to 80 ° C.
  • the drying time is preferably 30 seconds to 30 minutes, more preferably 1 to 20 minutes, and further preferably 1 to 15 minutes.
  • the manufacturing method of this invention it is preferable to add an anti-aging agent beforehand with respect to the polymer solution obtained by solution polymerization before performing such coagulation.
  • an anti-aging agent beforehand with respect to the polymer solution obtained by solution polymerization before performing such coagulation.
  • the anti-aging agent is not particularly limited.
  • the amount of the anti-aging agent used is preferably 0.001 to 0.3 parts by weight, more preferably 0.001 parts by weight with respect to 100 parts by weight of the polymer component (synthetic polyisoprene before coagulation) in the polymer solution. 01 to 0.1 parts by weight.
  • the method for re-dissolving the solid material obtained by coagulation is not particularly limited.
  • the solid material is used in the same organic solvent as that used for the solution polymerization described above.
  • dissolve is mentioned.
  • a synthetic polyisoprene solution containing a synthetic polyisoprene in which the peak intensity ratio (I B / I A ) measured by FT-IR is controlled within the above range is prepared. Obtainable. And in the manufacturing method of this invention, synthetic polyisoprene latex is manufactured using the obtained synthetic polyisoprene solution.
  • the peak intensity ratio of (I B / I A) to produce synthetic polyisoprene solution include synthetic polyisoprene controlled in the above range, the monomer (isoprene, and optionally The polymer solution obtained by solution polymerization of the isoprene copolymerizable with the isoprene) is solidified once to obtain a solid, and then the obtained solid is recycled.
  • dissolving was illustrated, the manufacturing method of this invention is not limited to such a method.
  • a synthetic polyisoprene in which the peak intensity ratio (I B / I A ) is directly controlled within the above range can be obtained by solution polymerization of the monomer without solidification.
  • An included synthetic polyisoprene solution may be obtained.
  • the polymerization catalyst used for the solution polymerization is not particularly limited.
  • a Ziegler polymerization catalyst or an organic alkali metal is used. From the viewpoint that the polymerization conversion rate can be increased and the residual amount of unreacted monomers as impurities in the synthetic polyisoprene solution can be reduced. It is preferable to use a metal catalyst.
  • the organic solvent used for solution polymerization can be the same as described above.
  • 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 still more preferably 500 to 1500 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene obtained by solution polymerization. It is.
  • polymerization temperature at the time of solution polymerization can be the same as described above.
  • an anti-aging agent may be added to the synthetic polyisoprene solution before the production of the synthetic polyisoprene latex. preferable.
  • the anti-aging agent used may be the same as described above.
  • the amount of the anti-aging agent used is preferably 0.001 to 0.3 parts by weight, more preferably 0.002 to 0.1 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene in the synthetic polyisoprene solution. More preferably, the amount is 0.005 to 0.05 parts by weight.
  • Synthetic polyisoprene latex In the production method of the present invention, a synthetic polyisoprene latex can be obtained by emulsifying the above-described synthetic polyisoprene solution in water in the presence of a surfactant.
  • the synthetic polyisoprene latex obtained by the production method of the present invention is a synthetic polyisoprene containing a synthetic polyisoprene in which the peak intensity ratio (I B / I A ) measured by FT-IR is controlled within the above range.
  • Latex composition obtained by using this synthetic polyisoprene latex because it is obtained using a solution, can suppress the generation of aggregates when stored for a long period of time, has excellent stability The tensile strength of the dip-molded product produced from the product can be significantly improved.
  • the surfactant is not particularly limited.
  • fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, sodium rosinate, potassium rosinate; sodium dodecylbenzenesulfonate Alkylbenzenesulfonates such as potassium dodecylbenzenesulfonate, sodium decylbenzenesulfonate, potassium decylbenzenesulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate; sodium di (2-ethylhexyl) sulfosuccinate, di (2 -Ethylhexyl) alkyl sulfosuccinates such as potassium sulfosuccinate and sodium dioctyl sulfosuccinate; sodium lauryl sulfate, potassium lauryl sulfate and the like Alkyl
  • fatty acid salts alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfate esters and polyoxyethylene alkyl ether sulfate salts are preferred, fatty acid salts and alkylbenzene sulfonates are more preferred, Fatty acid salts are more preferable, and rosinates such as sodium rosinate and potassium rosinate are particularly preferable.
  • alkylbenzene since the polymerization catalyst (especially aluminum and titanium) derived from the synthetic polyisoprene can be removed more efficiently and the generation of aggregates during production of the latex composition is suppressed, alkylbenzene. It is preferable to use at least one selected from the group consisting of sulfonates, alkylsulfosuccinates, alkylsulfate esters and polyoxyethylene alkylether sulfates in combination with fatty acid salts, alkylbenzenesulfonates and It is particularly preferable to use a fatty acid salt in combination.
  • sodium rosinate and potassium rosinate are preferable as the fatty acid salt
  • sodium dodecylbenzene sulfonate and potassium dodecylbenzene sulfonate are preferable as the alkylbenzene sulfonate.
  • anionic surfactants may be used alone or in combination of two or more.
  • the fatty acid salt is used in combination with at least one selected from the group consisting of alkylbenzene sulfonate, alkylsulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt.
  • the obtained latex contains at least one selected from alkylbenzene sulfonate, alkylsulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt and a fatty acid salt.
  • surfactants other than anionic surfactants may be used, and surfactants other than such anionic surfactants include ⁇ , ⁇ -unsaturated carboxylic acid sulfoesters, ⁇ , ⁇ - Examples thereof include copolymerizable surfactants such as sulfate esters of unsaturated carboxylic acids and sulfoalkylaryl ethers.
  • non-ionic such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, etc., as long as it does not inhibit coagulation by the coagulant used for dip molding
  • a surfactant may be used in combination.
  • the amount of the surfactant used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene.
  • the total amount used is preferably within the above range. If the amount of the surfactant used is too small, a large amount of aggregates may be generated during emulsification. Conversely, if the amount is too large, foaming is likely to occur, and pinholes may be generated in the resulting dip-formed product. .
  • an anionic surfactant when used in combination with a fatty acid salt and at least one selected from alkylbenzene sulfonate, alkylsulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt
  • the ratio of use thereof is determined by changing at least one surface activity selected from “fatty acid salts”: “alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates”.
  • the weight ratio of the “total agent” is preferably in the range of 1: 1 to 10: 1, and more preferably in the range of 1: 1 to 7: 1.
  • the amount of water used for emulsifying the synthetic polyisoprene solution is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, and most preferably 50 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene solution. ⁇ 100 parts by weight.
  • Examples of the water to be used include hard water, soft water, ion exchange water, distilled water, zeolite water and the like, and soft water, ion exchange water and distilled water are preferable.
  • An apparatus 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 a surfactant is particularly suitable if it is generally marketed as an emulsifier or a disperser. Can be used without limitation.
  • the method of adding the surfactant to the synthetic polyisoprene solution or fine suspension is not particularly limited, and it is previously added to either water or the synthetic polyisoprene solution or fine suspension, or both. Alternatively, during the emulsification operation, it may be added to the emulsified liquid, or may be added all at once or dividedly.
  • emulsifier examples include batch type emulsification such as trade name “Homogenizer” (manufactured by IKA), trade name “Polytron” (manufactured by Kinematica), trade name “TK auto homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), etc.
  • a method for removing the organic solvent from the emulsion a method capable of setting the content of the organic solvent (preferably an alicyclic hydrocarbon solvent) in the obtained emulsion to 500 ppm by weight or less is preferable. 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, membrane concentration, In particular, it is preferable to perform centrifugation from the viewpoint of increasing the solid content concentration of the synthetic polyisoprene latex and reducing the residual amount of the surfactant in the synthetic polyisoprene latex.
  • Centrifugation is performed using, for example, a continuous centrifuge, centrifugal force is preferably 100 to 10,000 G, and the solid content concentration of the synthetic polyisoprene latex before centrifugation is preferably 2 to 15% by weight. It is preferable that 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. Synthetic polyisoprene latex can be obtained as a liquid. Thereby, 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 described later becomes low, so that the film thickness of the dip molded product described later becomes thin and is easily broken. On the other hand, if the solid content concentration is too high, the viscosity of the synthetic polyisoprene latex becomes high, which may make it difficult to transfer it through piping or to stir in the preparation 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.
  • Synthetic polyisoprene latex contains additives such as pH adjusters, antifoaming agents, preservatives, crosslinking agents, chelating agents, oxygen scavengers, dispersants, and anti-aging agents that are usually blended in the latex field. You may mix
  • the pH adjuster include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium bicarbonate; ammonia An organic amine compound such as trimethylamine or triethanolamine; an alkali metal hydroxide or ammonia is preferred.
  • Latex Composition The latex composition of the present invention is obtained by adding a crosslinking agent to the synthetic polyisoprene latex obtained by the production method of the present invention described above.
  • crosslinking agent examples include sulfur such as powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, and the like; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, caprolactam disulfide (N, And sulfur-containing compounds such as N′-dithio-bis (hexahydro-2H-azepinone-2)), phosphorus-containing polysulfides, polymer polysulfides, and 2- (4′-morpholinodithio) benzothiazole.
  • sulfur can be preferably used.
  • a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • the content of the crosslinking agent is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene.
  • the latex composition of this invention contains a crosslinking accelerator further.
  • a crosslinking accelerator those usually used in dip molding can be used. Acids and zinc salts thereof; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazoline, dibenzothiazyl disulfide, 2- (2,4-dinitrophenylthio) benzothiazole, 2- (N, N-diethylthio-carbylthio) benzothiazole, 2- (2,6-dimethyl-4-morpholinothio) benzothiazole, 2- (4'-morpholino-dithio) benzothia And 4-morpholinyl-2-benzothiazyl disulfide, 1,3-bis (2-benzothiazyl mercaptomethyl) urea, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc 2-mercaptobenzothiazole Is preferred.
  • the content of the crosslinking accelerator is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene.
  • the latex composition of this invention contains a zinc oxide further.
  • the content of zinc oxide is not particularly limited, but is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight with respect to 100 parts by weight of synthetic polyisoprene.
  • the latex composition of the present invention further comprises a compounding agent such as an anti-aging agent, a dispersant; a reinforcing agent such as carbon black, silica, or talc; a filler such as calcium carbonate or clay; an ultraviolet absorber; a plasticizer; It can mix
  • a compounding agent such as an anti-aging agent, a dispersant; a reinforcing agent such as carbon black, silica, or talc; a filler such as calcium carbonate or clay; an ultraviolet absorber; a plasticizer; It can mix
  • the method for preparing the latex composition of the present invention is not particularly limited.
  • a dispersing machine such as a ball mill, a kneader, a disper, etc.
  • a synthetic polyisoprene latex is blended with a crosslinking agent and various blends as needed.
  • examples thereof include a method of mixing an agent, a method of preparing an aqueous dispersion of blending components other than the synthetic polyisoprene latex using the above-mentioned disperser, and then mixing the aqueous dispersion into the synthetic polyisoprene latex.
  • the latex composition of the present invention preferably has a pH of 7 or more, more preferably in the range of 7 to 13, and still more preferably in the range of 8 to 12.
  • the solid content concentration of the latex composition is preferably in the range of 15 to 65% by weight.
  • the latex composition of the present invention is preferably aged (pre-crosslinked) before being subjected to dip molding from the viewpoint of further improving the mechanical properties of the resulting dip molded article.
  • the pre-crosslinking time is not particularly limited and depends on the pre-crosslinking temperature, but is preferably 1 to 14 days, and more preferably 1 to 7 days.
  • the pre-crosslinking temperature is preferably 20 to 40 ° C. After pre-crosslinking, it is preferably stored at a temperature of 10 to 30 ° C. until it is used for dip molding. When stored at a high temperature, the tensile strength of the resulting dip-molded product may decrease.
  • Dip Molded Body The dip molded body of the present invention is 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 mold surface is dried. is there.
  • the mold before being immersed in the latex composition may be preheated. Further, a coagulant can be used as necessary before the mold is immersed in the latex composition or after the mold is pulled up from the latex composition.
  • the method of using the coagulant include a method in which the mold before dipping in the latex composition is immersed in a solution of the coagulant to attach the coagulant to the mold (anode coagulation dipping method), and the latex composition is deposited.
  • anode coagulation dipping method There is a method of immersing the formed mold in a coagulant solution (Teag adhesion dipping method), etc., but the anode adhesion dipping method is preferable in that a dip-formed product with little thickness unevenness can be obtained.
  • coagulants 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; water-soluble polyvalent metal salts such as calcium sulfate, magnesium sulfate, and sulfates such as aluminum sulfate; Of these, calcium salts are 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 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.
  • 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 deposit formed on the mold is usually dried by heating. What is necessary is just to select drying conditions suitably.
  • the heating conditions at the time of crosslinking are not particularly limited, but are preferably 60 to 150 ° C., more preferably 100 to 130 ° C., and preferably 10 to 120 minutes.
  • the heating method is not particularly limited, and there are a method of heating with warm air in an oven, a method of heating by irradiating infrared rays, and the like.
  • the mold may be washed with water or warm water to remove water-soluble impurities (for example, excess surfactant or coagulant) before or after heating the mold on which the latex composition is deposited.
  • water-soluble impurities for example, excess surfactant or coagulant
  • the hot water used is preferably 40 ° C. to 80 ° C., more preferably 50 ° C. to 70 ° C.
  • the dip-formed body after crosslinking is detached from the mold.
  • the desorption method include a method of peeling from a mold by hand, a method of peeling by water pressure or compressed air pressure, and the like. If the dip-formed product in the middle of crosslinking has sufficient strength against desorption, it may be desorbed in the middle of crosslinking, and then the subsequent crosslinking may be continued.
  • the dip-molded product of the present invention is obtained by using the synthetic polyisoprene latex obtained by the production method of the present invention. Therefore, the dip molded product is excellent in tensile strength and has a soft texture, particularly as a glove. It can be used suitably.
  • the dip-molded body is a glove
  • the glove is made of inorganic fine particles such as talc and calcium carbonate or organic fine particles such as starch particles. It may be dispersed on the surface, an elastomer layer containing fine particles may be formed on the surface of the glove, or the surface layer of the glove may be chlorinated.
  • the dip-molded body of the present invention is a medical article such as a nipple for baby bottles, a dropper, a tube, a water pillow, a balloon sac, a catheter, and a condom; a toy such as a balloon, a doll, and a ball; It can also be used for industrial articles such as molding bags and gas storage bags;
  • Adhesive Layer Forming Base Material An adhesive layer forming base material of the present invention comprises a base material comprising an adhesive layer formed on the base material using the above-described synthetic polyisoprene solution of the present invention, and an adhesive layer. And composite material.
  • the substrate is not particularly limited, but for example, a fiber substrate can be used.
  • the kind of fiber which comprises a fiber base material is not specifically limited, For example, polyamide fibers, such as vinylon fiber, polyester fiber, nylon, and aramid (aromatic polyamide), glass fiber, cotton, rayon etc. are mentioned. These can be appropriately selected according to the application.
  • the shape of the fiber substrate is not particularly limited, and examples thereof include staples, filaments, cords, ropes, woven fabrics (such as canvas), and the like, and can be appropriately selected depending on the application.
  • the adhesive layer may be formed using the above-described synthetic polyisoprene solution of the present invention, and may be used as it is without blending a compounding agent or the like in the above-described synthetic polyisoprene solution of the present invention. Or it is set as an adhesive composition by mix
  • Examples of the compounding agent contained in the adhesive composition include an adhesive resin.
  • the adhesive resin is not particularly limited, and for example, resorcin-formaldehyde resin, melamine resin, epoxy resin and isocyanate resin can be suitably used, and among these, resorcin-formaldehyde resin is preferable.
  • As the resorcin-formaldehyde resin known ones (for example, those disclosed in JP-A-55-142635) can be used.
  • the reaction ratio of resorcin to formaldehyde is usually 1: 1 to 1: 5, preferably 1: 1 to 1: 3 in terms of a molar ratio of “resorcin: formaldehyde”.
  • the adhesive composition contains 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or a similar compound, isocyanate, block, which has been conventionally used to further increase the adhesive strength.
  • isocyanate, ethylene urea, polyepoxide, modified polyvinyl chloride resin and the like can be contained.
  • the adhesive composition can contain a vulcanization aid.
  • a vulcanization aid By including a vulcanization aid, the mechanical strength of the adhesive layer-forming substrate can be improved.
  • Vulcanization aids include quinone dioximes such as p-quinone dioxime; methacrylic acid esters such as lauryl methacrylate and methyl methacrylate; DAF (diallyl fumarate), DAP (diallyl phthalate), TAC (triallyl cyanurate), And allyl compounds such as TAIC (triallyl isocyanurate); maleimide compounds such as bismaleimide, phenylmaleimide and N, Nm-phenylene dimaleimide; sulfur; and the like.
  • the content (solid content) of the synthetic rubber in the adhesive composition is preferably 5 to 60% by weight, more preferably 10 to 30% by weight.
  • the adhesive layer-forming substrate of the present invention can be prepared, for example, by applying the synthetic polyisoprene solution of the present invention or an adhesive composition containing the same to the surface of the substrate, or by synthesizing the substrate of the present invention. It can be obtained by forming an adhesive layer on a substrate by a method of immersing in a polyisoprene solution or an adhesive composition containing the same.
  • Such an adhesive layer-forming substrate of the present invention can be used as a substrate-rubber composite by adhering to rubber via an adhesive layer, for example.
  • the base material-rubber composite is not particularly limited.
  • rubber using a base fiber-like fiber base material such as a rubber toothed belt with a core wire using a cord-like fiber base material or a canvas Examples thereof include a toothed belt.
  • the method for obtaining the base material-rubber composite is not particularly limited.
  • the synthetic polyisoprene solution of the present invention or the adhesive composition containing the base material is adhered to the base material by a coating method, a dipping treatment or the like.
  • a method of obtaining an adhesive layer-forming substrate, placing the adhesive layer-forming substrate on rubber, and heating and pressurizing it is exemplified.
  • the pressurization can be performed using a compression (press) molding machine, a metal roll, an injection molding machine or the like.
  • the pressurizing pressure is preferably 0.5 to 20 MPa, more preferably 2 to 10 MPa.
  • the heating temperature is preferably 130 to 300 ° C, more preferably 150 to 250 ° C.
  • the treatment time for heating and pressing is preferably 1 to 180 minutes, more preferably 5 to 120 minutes.
  • rubber molding and adhesion between the adhesive layer forming substrate and the rubber can be performed simultaneously.
  • a base material-rubber-base composite can be exemplified.
  • the base material-rubber-base material composite can be formed, for example, by combining a base material (may be a composite of two or more kinds of base materials) and a base material-rubber composite. Specifically, a core wire as a base material, rubber and a base fabric as a base material are stacked (in this case, the core wire and the base fabric are coated with the synthetic polyisoprene solution of the present invention or an adhesive composition containing the same).
  • a base material-rubber-base material composite can be obtained by applying it while heating and applying pressure while heating.
  • the base material-rubber composite obtained using the adhesive layer forming base material of the present invention is excellent in mechanical strength, abrasion resistance and water resistance. Therefore, a flat belt, V belt, V ribbed belt, It can be suitably used as a belt such as a round belt, a square belt, or a toothed belt.
  • the base material-rubber composite obtained using the base material for forming an adhesive layer of the present invention is excellent in oil resistance and can be suitably used as a belt in oil.
  • the substrate-rubber composite obtained 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 reinforcement hose, and a cloth wound reinforcement hose.
  • 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 uses.
  • the seal include a moving part seal such as a rotating part, a swinging part, and a reciprocating part, and a fixed part seal.
  • the motion part seal include an oil seal, a piston seal, a mechanical seal, a boot, a dust cover, a diaphragm, and an accumulator.
  • Examples of the fixed part seal include an O-ring and various gaskets.
  • rolls that are parts of OA equipment such as printing equipment and copying equipment; rolls for fiber processing such as spinning rolls for spinning and drafting rolls for spinning; rolls for iron making such as bridle rolls, snubber rolls, steering rolls, etc.
  • OA equipment printing equipment and copying equipment
  • rolls for fiber processing such as spinning rolls for spinning and drafting rolls for spinning
  • rolls for iron making such as bridle rolls, snubber rolls, steering rolls, etc.
  • Weight average molecular weight (Mw) The sample was diluted with tetrahydrofuran so that the solid content concentration was 0.1% by weight, and this solution was subjected to gel permeation chromatography analysis to calculate the weight average molecular weight (Mw) in terms of standard polystyrene.
  • Peak intensity ratio (I B / I A ) Using a synthetic polyisoprene solution, a synthetic polyisoprene film was produced, and the produced film was subjected to 2,840 to 3,000 cm ⁇ using FT-IR (model “IG-1000”, manufactured by Otsuka Electronics Co., Ltd.). the most intensity is large peak intensity I a in 1, and the strongest intensity is large peak I B in the range of 1,000 ⁇ 1,200cm -1 measured, the intensity ratio of these peaks (I B / I A ) was calculated.
  • the solid content concentration of the synthetic polyisoprene latex was measured, and about 100 g of the synthetic polyisoprene latex was precisely weighed and then filtered through a 200 mesh SUS wire mesh with a known weight.
  • the synthetic polyisoprene latex was removed by washing with water. After drying this at 105 ° C. for 60 minutes, its dry weight was measured, and the aggregate content ratio (unit: wt%) was determined based on the following formula.
  • Aggregate content ⁇ ( ⁇ ) / ( ⁇ ⁇ ⁇ ) ⁇ ⁇ 10,000
  • ⁇ represents the weight of the dried wire mesh and dried aggregate
  • ⁇ represents the weight of the wire mesh
  • ⁇ represents the weight of the synthetic polyisoprene latex
  • ⁇ represents the solid content concentration of the synthetic polyisoprene latex.
  • the latex composition was aged at 30 ° C, and after a predetermined number of days from the start of aging, the agglomerate content of the latex composition was measured according to the above method, and the agglomerate content was The stability of the latex composition was evaluated by determining the number of days that the value of 0.2 was 0.2% by weight. In addition, the stability of a latex composition is excellent, so that the days which the aggregate content rate became 0.2 weight% are long.
  • a dip-molded product having a film thickness of about 0.2 mm was obtained by dumbbell (trade name “Super Dumbbell (model: SDMK-100C). ) ", Manufactured by Dumbbell Co., Ltd.) to produce a test piece for measuring tensile strength.
  • the test piece was pulled with a Tensilon universal tester (trade name “RTG-1210”, manufactured by Orientec Co., Ltd.) at a tensile speed of 500 mm / min, tensile strength immediately before break (unit: MPa), elongation just before break (unit:%) ) And the tensile stress (unit: MPa) when the elongation is 500%.
  • RMG-1210 tensile strength immediately before break
  • unit: MPa tensile strength just before break
  • unit:% tensile stress
  • the smaller the tensile stress at 500% the better the dip-formed body becomes excellent in flexibility.
  • Example 1 (Production of synthetic polyisoprene latex) 1150 parts of normal hexane and 100 parts of isoprene were charged into an autoclave with stirring that was dried and purged with nitrogen. Next, the temperature in the autoclave was set to 30 ° C., and while stirring, 0.03 part of titanium tetrachloride, 0.03 part of triisobutylaluminum and 0.005 part of normal butyl ether were added and reacted for 2 hours. As a result, 0.05 part of methanol was added to stop the reaction to obtain a polymer solution (A-1).
  • the weight average molecular weight of the polymer component (synthetic polyisoprene before coagulation described later) in the polymer solution (A-1) was 1320,000. Further, in the obtained polymer solution (A-1), an anti-aging agent (2,6-di-tert-butyl-p-cresol (centralized) was added to 100 parts of the polymer component contained in the polymer solution.
  • the obtained polymer solution (B-1) was coagulated with methanol and then dried at 100 ° C. for 25 minutes to obtain a solid synthetic polyisoprene (C-1). Thereafter, the synthetic polyisoprene (C-1) was redissolved in cyclohexane to obtain a synthetic polyisoprene solution (D-1) having a concentration of 8% by weight. Using a portion of the resulting synthetic polyisoprene solution (D-1), the peak intensity ratio (I B / I A ) was determined according to the above method. The results are shown in Table 1.
  • the emulsion (E-1) was heated to 80 ° C. under reduced pressure to distill off the cyclohexane to obtain an aqueous dispersion of synthetic polyisoprene.
  • the obtained aqueous dispersion was centrifuged using a continuous centrifuge to obtain a synthetic polyisoprene latex (F-1) having a solid content concentration of 59.5% by weight as a light liquid.
  • the aggregate content was measured according to the above method. The results are shown in Table 1.
  • a latex composition was obtained by adjusting the pH to 10.5 by adding an aqueous potassium solution. Using a part of the obtained latex composition, the stability of the latex composition was evaluated according to the above method. On the other hand, about the latex composition which was not used for evaluation of stability of a latex composition, it age
  • Example 2 The solid synthetic polyisoprene (C-2) and the synthetic polyisoprene solution (C-2) were synthesized in the same manner as in Example 1 except that the drying conditions after solidifying with methanol for the polymer solution were changed to 83 ° C. and 18 minutes. D-2), a synthetic polyisoprene latex (F-2), a latex composition, and a dip-formed product were produced and evaluated in the same manner. The results are shown in Table 1.
  • Example 3 The amount of the anti-aging agent added to the polymer solution was changed from 0.2 part to 0.05 part, and the drying condition after solidifying with methanol for the polymer solution was changed to 65 ° C. and 13 minutes. Except for the above, in the same manner as in Example 1, a solid synthetic polyisoprene (C-3), a synthetic polyisoprene solution (D-3), a synthetic polyisoprene latex (F-3), a latex composition and a dip-molded product were obtained. Manufactured and similarly evaluated. The results are shown in Table 1.
  • Example 4 In producing the polymer solution, instead of 0.03 part of titanium tetrachloride, 0.03 part of triisobutylaluminum and 0.005 part of normal butyl ether, 0.006 part of normal butyl lithium was used, and the reaction temperature was changed.
  • a synthetic polyisoprene solution (D-4), a synthetic polyisoprene latex (F-4), a latex composition and a dip-molded body were produced in the same manner as in Example 3 except that the temperature was changed from 30 ° C to 60 ° C. Evaluation was performed in the same manner. The results are shown in Table 1.
  • Example 5 In place of 0.03 part of titanium tetrachloride, 0.03 part of triisobutylaluminum and 0.005 part of normal butyl ether, 0.006 part of normal butyl lithium was used, and the reaction temperature was changed from 30 ° C. to 60 ° C. In the same manner as in Example 1, a polymer solution (A-5) was obtained. As will be described later, this polymer solution (A-5) was directly used as a synthetic polyisoprene solution (D-5) for the production of synthetic polyisoprene latex (F-5). The weight average molecular weight of the polymer component (synthetic polyisoprene) in this synthetic polyisoprene solution (D-5) was 1,240,000. Further, the peak intensity ratio (I B / I A ) of a part of the synthetic polyisoprene solution (D-5) was determined according to the above method. The results are shown in Table 1.
  • the synthetic polyisoprene solution (D-5) was directly emulsified to obtain an emulsified liquid (E-5).
  • an anti-aging agent (2,6-di-tert-butyl-p-cresol (manufactured by Chuo Kasei Co., Ltd.) and 2,6-di- hydrate with respect to 1250 parts of the synthetic polyisoprene solution (D-5)
  • Weight ratio of tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol (trade name “IRGANOX565” manufactured by Ciba Specialty Chemicals) 22: 3
  • a mixture of 0.007 parts was heated to 60 ° C., and the flow rate was adjusted to 1: 1 by weight with 1250 parts of a 1.0 wt% sodium rosinate aqueous solution heated to 60 ° C.
  • the mixture was adjusted and mixed using a line mixer, and then emul
  • the emulsion (E-5) was heated to 80 ° C. under reduced pressure to distill off normal hexane, whereby an aqueous dispersion of synthetic polyisoprene was obtained.
  • the obtained aqueous dispersion was centrifuged using a continuous centrifuge to obtain an organic alkali metal synthetic polyisoprene latex (F-5) having a solid concentration of 62.8% by weight as a light liquid.
  • the aggregate content ratio was measured according to the above method. The results are shown in Table 1.
  • Example 5 the stability of the latex composition was evaluated. After 20 days, the aggregate content was less than 0.2% by weight, and thus the evaluation was stopped. Therefore, in Table 1, the evaluation result of the stability of the latex composition is described as “> 20”.
  • Comparative Example 1 The solid synthetic polyisoprene (C-6) and the synthetic polyisoprene solution (C-6) were prepared in the same manner as in Example 1 except that the drying conditions after the polymer solution was coagulated with methanol were changed to 120 ° C. and 45 minutes. D-6), a synthetic polyisoprene latex (F-6), a latex composition, and a dip-formed product were produced and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 2 The solid synthetic polyisoprene (C-7) and the synthetic polyisoprene solution (C-7) were prepared in the same manner as in Example 3 except that the drying conditions after solidifying with methanol for the polymer solution were changed to 110 ° C. and 35 minutes. D-7), a synthetic polyisoprene latex (F-7), a latex composition and a dip-molded product were produced and evaluated in the same manner. The results are shown in Table 1.
  • the obtained synthetic polyisoprene latex is agglomerated.
  • the product content ratio is small, and when it is a latex composition, it is excellent in stability, and the dip-molded article produced using this latex composition has excellent tensile strength and elongation, and is flexible. It had a texture (Examples 1 to 5).

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Abstract

L'invention concerne un procédé de production d'un latex de polyisoprène synthétique, comprenant une étape d'émulsification d'une solution de polyisoprène synthétique préparée par dissolution dans de l'eau d'un polyisoprène synthétique dans un solvant organique en présence d'un tensioactif pour produire un latex du polyisoprène synthétique, le polyisoprène synthétique présentant un rapport (IB/IA) entre l'intensité IB d'un pic, qui présente la plus grande intensité dans une région allant de 1 000 à 1 200 cm-1, et l'intensité IA d'un pic qui présente la plus grande intensité dans une région allant de 2 840 à 3 000 cm-1 comme mesuré par FT-IR, égal ou inférieur à 0,4.
PCT/JP2018/003209 2017-02-24 2018-01-31 Procédé de production de latex de polyisoprène synthétique Ceased WO2018155113A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110441230A (zh) * 2019-08-13 2019-11-12 吉林大学 一种基于化学特性分析的粘结结构老化预测方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009179680A (ja) * 2008-01-30 2009-08-13 Nippon Zeon Co Ltd ポリマーエマルジョンの製造方法
JP2015193685A (ja) * 2014-03-31 2015-11-05 日本ゼオン株式会社 合成イソプレン重合体ラテックスの製造方法、合成イソプレン重合体ラテックス、ディップ成形用組成物およびディップ成形体
JP2016089017A (ja) * 2014-11-04 2016-05-23 株式会社レヂテックス 柔軟性を有する高強度ポリイソプレン及びポリイソプレン組成物とその製造方法
JP2016160366A (ja) * 2015-03-03 2016-09-05 日本ゼオン株式会社 ディップ成形用合成イソプレン重合体ラテックス
WO2016140043A1 (fr) * 2015-03-03 2016-09-09 日本ゼオン株式会社 Latex de polymère d'isoprène synthétique pour moulage par immersion, composition pour moulage par immersion, et corps moulé par immersion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009179680A (ja) * 2008-01-30 2009-08-13 Nippon Zeon Co Ltd ポリマーエマルジョンの製造方法
JP2015193685A (ja) * 2014-03-31 2015-11-05 日本ゼオン株式会社 合成イソプレン重合体ラテックスの製造方法、合成イソプレン重合体ラテックス、ディップ成形用組成物およびディップ成形体
JP2016089017A (ja) * 2014-11-04 2016-05-23 株式会社レヂテックス 柔軟性を有する高強度ポリイソプレン及びポリイソプレン組成物とその製造方法
JP2016160366A (ja) * 2015-03-03 2016-09-05 日本ゼオン株式会社 ディップ成形用合成イソプレン重合体ラテックス
WO2016140043A1 (fr) * 2015-03-03 2016-09-09 日本ゼオン株式会社 Latex de polymère d'isoprène synthétique pour moulage par immersion, composition pour moulage par immersion, et corps moulé par immersion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110441230A (zh) * 2019-08-13 2019-11-12 吉林大学 一种基于化学特性分析的粘结结构老化预测方法

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