WO2011125224A1 - Copolymer latex for adhesive - Google Patents

Copolymer latex for adhesive Download PDF

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Publication number
WO2011125224A1
WO2011125224A1 PCT/JP2010/056469 JP2010056469W WO2011125224A1 WO 2011125224 A1 WO2011125224 A1 WO 2011125224A1 JP 2010056469 W JP2010056469 W JP 2010056469W WO 2011125224 A1 WO2011125224 A1 WO 2011125224A1
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phase
monomer
weight
adhesive
copolymer latex
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PCT/JP2010/056469
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French (fr)
Japanese (ja)
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淳美 種村
竹中　俊
上村　彰
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日本エイアンドエル株式会社
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Priority to JP2012509263A priority Critical patent/JP5681169B2/en
Priority to CN201080066038.9A priority patent/CN102822295B/en
Priority to PCT/JP2010/056469 priority patent/WO2011125224A1/en
Publication of WO2011125224A1 publication Critical patent/WO2011125224A1/en

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    • 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
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • C09J125/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes

Definitions

  • the present invention relates to a copolymer latex for adhesive, and more particularly to a copolymer latex for adhesive that bonds rubber and fiber.
  • fibers such as nylon, polyester, and aramid have been used as rubber reinforcing fibers for reinforcing rubber products such as tires, belts, and hoses.
  • Rubber reinforcing fibers are usually used for adhesive latex latex (generally butadiene-vinylpyridine copolymer latex or butadiene-vinylpyridine) to ensure their adhesion to rubber products.
  • RFL adhesive composition
  • RF resin resorcin-formalin resin
  • the rubber reinforcing fiber is immersed in RFL and dried, and then heat treated at a high temperature of 170 ° C. or higher for nylon fiber and 220 ° C. or higher for polyester fiber or aramid fiber.
  • a copolymer latex for adhesive used in RFL for example, a butadiene-vinylpyridine copolymer latex having a specific monomer composition has been proposed (see, for example, Patent Documents 1 and 2 below). .
  • a copolymer latex comprising a butadiene-vinylpyridine copolymer latex having a specific monomer composition and SBR having a specific monomer composition has been proposed (see, for example, Patent Documents 3, 4, and 5 below). ).
  • the above-described adhesion treatment has a problem that the strength of the rubber reinforcing fiber is reduced by the heat treatment.
  • the objective of this invention is providing the copolymer latex for adhesive agents which can improve the adhesive force of rubber
  • the copolymer latex for an adhesive of the present invention contains latex particles in which at least a part of the first phase is covered with the second phase, and the first phase is a butadiene-based polymer. Obtained by emulsion polymerization of a first phase monomer composition containing 10 to 45% by weight of monomer, 0 to 5% by weight of vinylpyridine monomer and 55 to 90% by weight of styrene monomer, The two-phase emulsion polymerization of a second-phase monomer composition containing 50 to 90% by weight of a butadiene monomer, 10 to 30% by weight of a vinylpyridine monomer and 0 to 40% by weight of a styrene monomer It is characterized by being obtained.
  • the first phase monomer composition is based on the total weight of the first phase monomer composition and the second phase monomer composition. Is preferably 10 to 50% by weight, and the second phase monomer composition is preferably 50 to 90% by weight.
  • the first phase covers 50% or more of its surface area with the second phase.
  • the first phase monomer composition contains 0 to 3% by weight of a vinylpyridine monomer.
  • copolymer latex for adhesive of the present invention it is possible to improve the adhesive strength between rubber and rubber reinforcing fiber while suppressing the strength reduction of the rubber reinforcing fiber due to heat treatment.
  • FIG. 1 is a transmission electron micrograph of latex particles showing the latex particles of Example 1.
  • FIG. 2 is a transmission electron micrograph of latex particles showing the latex particles of Example 6.
  • FIG. 3 is a transmission electron micrograph of latex particles showing the latex particles of Example 5.
  • FIG. 4 is a transmission electron micrograph of latex particles, showing the latex particles of Comparative Example 2.
  • the copolymer latex for adhesive of the present invention contains latex particles composed of a first phase and a second phase having different compositions (different phase structure).
  • the first phase is obtained by emulsion polymerization of a first phase monomer composition containing a butadiene monomer, a vinylpyridine monomer, and a styrene monomer.
  • butadiene monomer examples include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and the like, preferably 1,3-butadiene. Is mentioned. These butadiene monomers can be used alone or in combination of two or more.
  • vinylpyridine monomers examples include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, and preferably 2-vinylpyridine. These vinylpyridine monomers can be used alone or in combination of two or more.
  • styrene monomer examples include styrene, ⁇ -methylstyrene, monochlorostyrene, and preferably styrene. These styrenic monomers can be used alone or in combination of two or more.
  • the first phase monomer composition comprises 10 to 45% by weight of butadiene monomer, preferably 15 to 40% by weight, and 0 to 5% by weight of vinylpyridine monomer (that is, vinylpyridine).
  • the monomer may or may not be contained, and if it is contained, it is 5% by weight or less.), Preferably 0 to 3% by weight, and styrene monomer
  • the monomer contains 55 to 90% by weight, preferably 60 to 85% by weight.
  • the initial adhesive strength is lowered, and when it exceeds 45% by weight, the cord strength and the heat resistant adhesive strength are lowered.
  • the heat-resistant adhesive strength is lowered, and when it exceeds 90% by weight, the initial adhesive force and the heat-resistant adhesive force are lowered.
  • the first phase monomer composition is composed of other monomers (a butadiene monomer, a vinylpyridine monomer, and a styrene monomer) that can be copolymerized with other monomers. It can be replaced by a mass.
  • Examples of other copolymerizable monomers include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid.
  • Monomers for example, ethylenically unsaturated carboxylic acid alkyl ester monomers such as methyl methacrylate, ethyl acrylate and butyl acrylate, for example, ethylenically unsaturated carboxylic acids such as ⁇ -hydroxyethyl acrylate and ⁇ -hydroxyethyl methacrylate
  • ethylenically unsaturated carboxylic acids such as ⁇ -hydroxyethyl acrylate and ⁇ -hydroxyethyl methacrylate
  • hydroxyalkyl ester monomers for example, amide monomers such as acrylamide and methacrylamide, and one or two or more of them can be used.
  • the second phase is obtained by emulsion polymerization of a second phase monomer composition containing a butadiene monomer, a vinylpyridine monomer and a styrene monomer.
  • Examples of the butadiene monomer, vinylpyridine monomer, and styrene monomer include the same monomers as those exemplified in the first phase. The same applies to preferred monomers.
  • the second phase monomer composition is a copolymer of a part of the contained monomers (butadiene monomer, vinylpyridine monomer and styrene monomer) with other monomers capable of being copolymerized. It can be replaced by a mass.
  • Examples of the other copolymerizable monomer include the same monomers as the other copolymerizable monomers exemplified in the first phase.
  • the butadiene monomer is 50 to 90% by weight, preferably 60 to 80% by weight, and the vinylpyridine monomer is 10 to 30% by weight, preferably 10%. -25% by weight, and 0 to 40% by weight of styrenic monomer (that is, the styrenic monomer may or may not be contained. 40 wt% or less.), Preferably 0 to 30 wt%.
  • the blending ratio of the butadiene monomer is less than 50% by weight, the initial adhesive strength is lowered, and when it exceeds 90% by weight, the cord strength and the heat resistant adhesive force are lowered.
  • the initial adhesive strength and the heat-resistant adhesive force are reduced, and when it exceeds 30% by weight, the initial adhesive force is reduced.
  • the blending ratio of the styrene monomer exceeds 40% by weight, the initial adhesive strength and the heat resistant adhesive strength are lowered.
  • the weight ratio of the first phase monomer composition to the total weight of the first phase monomer composition and the second phase monomer composition is, for example, 10 to 50% by weight, preferably The weight ratio of the second phase monomer composition is, for example, 50 to 90% by weight, preferably 60 to 80% by weight.
  • the cord strength and the heat-resistant adhesive force may be reduced.
  • the weight ratio exceeds 50% by weight, the first phase is covered with the second phase. In some cases, the initial adhesive strength and the heat-resistant adhesive strength may be reduced.
  • the total amount of the first phase monomer composition and the second phase monomer composition is, for example, 40 to 80% by weight, preferably 50 to 70% by weight, vinyl, based on the butadiene monomer.
  • the pyridine monomer is contained in an amount of 5 to 25% by weight, preferably 7 to 17% by weight, and the styrene monomer is contained in an amount of 10 to 55% by weight, preferably 15 to 43% by weight.
  • the first phase monomer composition is emulsion-polymerized to obtain a copolymer of the first phase monomer composition (that is, the first phase).
  • the second phase monomer composition is emulsion-polymerized to obtain a copolymer of the second phase monomer composition (that is, the second phase).
  • the second phase monomer composition is preferably added when the polymerization conversion rate of the first phase monomer composition reaches 60 to 90%.
  • each monomer composition (each of the first phase monomer composition or the second phase monomer composition is used).
  • the emulsifier examples include nonionic surfactants such as polyethylene glycol alkyl ester type, alkyl phenyl ether type, and alkyl ether type, such as rosin acid salt, fatty acid salt, sulfate ester salt of higher alcohol, alkylbenzene sulfonate, Anionic surfactants such as alkyl diphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfate esters of nonionic surfactants, formalin condensates of naphthalene sulfonate, and the like, preferably, An anionic surfactant is mentioned, More preferably, the formalin condensate of a rosinate and a naphthalenesulfonate is mentioned.
  • One or more emulsifiers can be used.
  • the emulsifier is added, for example, at a ratio of, for example, 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of each monomer composition.
  • the polymerization initiator is a radical polymerization initiator, for example, a water-soluble polymerization initiator such as potassium persulfate, sodium persulfate, ammonium persulfate, such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide. And oil-soluble polymerization initiators such as acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide.
  • the water-soluble polymerization initiator includes potassium persulfate, sodium persulfate, and ammonium persulfate
  • the oil-soluble polymerization initiator includes cumene hydroperoxide.
  • the polymerization initiator is added, for example, at a ratio of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, with respect to 100 parts by weight of each monomer composition.
  • a reducing agent and a chain transfer agent can be added as necessary.
  • the reducing agent examples include sulfite, bisulfite, pyrosulfite, nitrite, nithionate, thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate, such as L-ascorbic acid, erythorbic acid
  • Carboxylic acids such as tartaric acid and citric acid and salts thereof, for example, reducing sugars such as dextrose and saccharose, and amines such as dimethylaniline and triethanolamine.
  • carboxylic acids and salts thereof are preferred, and more preferred are L-ascorbic acid and erythorbic acid.
  • the reducing agent is added, for example, at a ratio of, for example, 0 to 1 part by weight, preferably 0 to 0.7 part by weight with respect to 100 parts by weight of the polymerization initiator.
  • chain transfer agent examples include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, such as dimethylxanthogen disulfide, diisopropyl Xanthogen compounds such as xanthogen disulfide, for example, thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, such as 2,6-di-t-butyl-4-methylphenol, styrenated phenol, etc.
  • alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercapt
  • Phenolic compounds for example, allyl compounds such as allyl alcohol, such as halogenated carbons such as dichloromethane, dibromomethane, carbon tetrabromide Hydrogen compounds such as ⁇ -benzyloxystyrene, ⁇ -benzyloxyacrylonitrile, ⁇ -benzyloxyacrylamide, and other vinyl ethers such as triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2- Examples thereof include ethylhexyl thioglycolate and ⁇ -methylstyrene dimer, preferably alkyl mercaptan, and more preferably n-octyl mercaptan and t-dodecyl mercaptan.
  • One or two or more chain transfer agents can be used.
  • the chain transfer agent is added, for example, in a ratio of, for example, 0 to 5 parts by weight, preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of each monomer composition.
  • a hydrocarbon solvent can be added as necessary.
  • the hydrocarbon include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methylcyclohexene, etc.
  • An unsaturated hydrocarbon etc. are mentioned, Preferably a cyclohexene is mentioned.
  • Cyclohexene has a low boiling point and can be easily recovered and reused by, for example, steam distillation after polymerization, and is suitable from the viewpoint of environmental burden.
  • electrolytes such as sodium hydroxide and sodium carbonate
  • polymerization inhibitors such as hydroquinone
  • polymerization accelerators such as hydroquinone
  • chelating agents such as sodium citrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium sulfate, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium ne, sodium
  • a copolymer latex for adhesive is prepared as an aqueous dispersion.
  • the latex particles are preferably covered with 50% or more of the surface area of the first phase, more preferably 100% (that is, the entire surface) by the second phase.
  • the number average particle diameter of the latex particles is, for example, 50 to 200 nm, preferably 80 to 160 nm.
  • a cross section of the particles is observed using a transmission electron microscope.
  • an osmium tetroxide aqueous solution is added to the adhesive copolymer latex, and the latex particles are electron-stained (osmium dyeing). Note that osmium tetroxide is added to the double bond of 1,3-butadiene by electron staining.
  • an epoxy resin is added to the copolymer latex and then dried. Thereby, the solid substance of the epoxy resin containing latex particles can be obtained. That is, latex particles are coated (embedded) with an epoxy resin.
  • the cross section of the latex particle is 50% or more of the outer peripheral length of the first phase, more preferably 100% ( That is, the entire outer periphery) is covered with the second phase.
  • the copolymer latex for adhesive of the present invention is preferably blended in an adhesive composition for bonding rubber and rubber reinforcing fiber.
  • the rubber is not particularly limited, and examples thereof include natural rubber, SBR, NBR, chloroprene rubber, polybutadiene rubber, polyisoprene rubber, and various modified rubbers thereof.
  • well-known additives such as a filler, a softening agent, a vulcanizing agent, a vulcanization accelerator, can be mix
  • rubber reinforcing fibers examples include nylon fibers, polyester fibers, and aramid fibers. Moreover, it does not specifically limit as a form of these fibers, For example, a cord, a cable, a textile fabric, a canvas, a short fiber etc. are mentioned.
  • the adhesive composition can be obtained by mixing and mixing a copolymer latex for adhesive and a resorcin-formalin resin.
  • the adhesive copolymer latex and the resorcin-formalin resin are not particularly limited, but the resorcin-- is used with respect to 100 parts by weight (solid content) of the adhesive copolymer latex.
  • Formalin resin is blended, for example, in an amount of 5 to 100 parts by weight, preferably 5 to 90 parts by weight.
  • the adhesive composition may contain isocyanate, blocked isocyanate, ethylene urea, 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol, sulfur monochloride and resorcin, if necessary.
  • Compounding agent and modified resorcin-formalin resin such as a mixture with resorcin-formalin condensate, polyepoxide, modified polyvinyl chloride, carbon black and other adhesion aids, fillers, crosslinking agents, vulcanizing agents, vulcanization accelerator can do.
  • the adhesive composition is processed into the rubber reinforcing fiber.
  • the rubber reinforcing fiber is immersed in the adhesive composition using a dipping machine or the like. Thereafter, for example, drying is performed at 100 to 150 ° C., preferably 110 to 130 ° C., for example, 80 to 200 seconds, preferably 100 to 150 seconds, and then, for example, 180 to 300 ° C., preferably 200 to 260 ° C. For example, the baking is performed at a temperature of 30 to 100 seconds, preferably 50 to 80 seconds.
  • the adhesive strength between the rubber and the rubber reinforcing fiber is improved while suppressing the strength reduction of the rubber reinforcing fiber due to heat treatment. Can be made.
  • copolymer latex for adhesive was added with an osmium tetroxide aqueous solution and subjected to electron staining.
  • an epoxy resin was added to the adhesive copolymer latex and dried to obtain an epoxy resin solid containing latex particles.
  • latex particles of the copolymer latex for adhesive were coated (embedded) with the epoxy resin.
  • FIGS. 1 shows latex particles of Example 1
  • FIG. 2 shows latex particles of Example 6
  • FIG. 3 shows latex particles of Example 5
  • FIG. 4 shows latex particles of Comparative Example 2. Show.
  • Adhesive Composition for Polyester Tire Cord (PET / Tire Cord) After adding 4 parts of 10% aqueous sodium hydroxide to 260 parts of water and stirring, 7.9 parts of resorcin, Then, 8.6 parts of a 37% formalin aqueous solution was added, mixed with stirring, and aged at 30 ° C. for 6 hours to synthesize a resorcin-formalin resin.
  • the initial adhesive strength and heat-resistant adhesive strength between rubber and rubber reinforcing fiber were measured according to ASTM D2138-67 (H Pull Test). The results are shown in Table 2.
  • (4-2) Nylon / Tire Cord As in the case of the above-mentioned polyester / tire cord, the nylon / tyre cord treated with the adhesive composition of each Example and each Comparative Example was sandwiched with rubber, and 20 minutes at 160 ° C. Vulcanizing press was performed under the conditions of (initial adhesive strength evaluation conditions).
  • the initial adhesive strength between rubber and rubber reinforcing fiber was measured according to ASTM D2138-67 (H Pull Test). The results are shown in Table 2.
  • the copolymer latex for adhesive of the present invention is blended in an adhesive composition and used for bonding rubber and rubber reinforcing fiber.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Disclosed is a copolymer latex for an adhesive such that at least part of a first phase contains latex particles coated by a second phase. The first phase is obtained by emulsion polymerization of a first phase monomer composition that contains 10 - 45% of a butadiene monomer, 0 - 5% of a vinylpyridine monomer and 55 - 90% of a styrene monomer. The second phase is obtained by emulsion polymerization of a second phase monomer composition that contains 50 - 90% of a butadiene monomer, 10 - 30% of a vinylpyridine monomer and 0 - 40% of a styrene monomer.

Description

接着剤用共重合体ラテックスCopolymer latex for adhesive
　本発明は、接着剤用共重合体ラテックスに関し、詳しくは、ゴムと繊維とを接着する接着剤用共重合体ラテックスに関する。 The present invention relates to a copolymer latex for adhesive, and more particularly to a copolymer latex for adhesive that bonds rubber and fiber.
　従来より、タイヤ、ベルト、ホースなどのゴム製品を補強するゴム補強用繊維として、ナイロン、ポリエステル、アラミドなどの繊維が用いられている。 Conventionally, fibers such as nylon, polyester, and aramid have been used as rubber reinforcing fibers for reinforcing rubber products such as tires, belts, and hoses.
　これらゴム補強用繊維は、通常、ゴム製品に対して、それらの接着性を確保すべく、接着剤用共重合体ラテックス（一般に、ブタジエン－ビニルピリジン系共重合体ラテックス、または、ブタジエン－ビニルピリジン系共重合体ラテックスと他のゴムラテックスとの混合物）と、レゾルシン－ホルマリン樹脂（以下、ＲＦレジンとする。）とを含有する接着剤組成物（以下、ＲＦＬとする。）を用いて接着処理されている。 These rubber reinforcing fibers are usually used for adhesive latex latex (generally butadiene-vinylpyridine copolymer latex or butadiene-vinylpyridine) to ensure their adhesion to rubber products. Adhesive treatment using an adhesive composition (hereinafter referred to as RFL) containing a copolymer copolymer latex and other rubber latex) and a resorcin-formalin resin (hereinafter referred to as RF resin). Has been.
　この接着処理では、ゴム補強用繊維をＲＦＬに浸漬して、乾燥した後、ナイロン繊維では１７０℃以上、ポリエステル繊維やアラミド繊維では２２０℃以上の高温で、熱処理がなされる。 In this bonding treatment, the rubber reinforcing fiber is immersed in RFL and dried, and then heat treated at a high temperature of 170 ° C. or higher for nylon fiber and 220 ° C. or higher for polyester fiber or aramid fiber.
　このようなＲＦＬに用いられる接着剤用共重合体ラテックスとして、例えば、特定単量体組成のブタジエン－ビニルピリジン系共重合体ラテックスが提案されている（例えば、下記特許文献１、２参照。）。 As such a copolymer latex for adhesive used in RFL, for example, a butadiene-vinylpyridine copolymer latex having a specific monomer composition has been proposed (see, for example, Patent Documents 1 and 2 below). .
　また、例えば、特定単量体組成のブタジエン－ビニルピリジン系共重合体ラテックスと特定単量体組成のＳＢＲからなる共重合体ラテックスが提案されている（例えば、下記特許文献３、４、５参照）。 For example, a copolymer latex comprising a butadiene-vinylpyridine copolymer latex having a specific monomer composition and SBR having a specific monomer composition has been proposed (see, for example, Patent Documents 3, 4, and 5 below). ).
　また、例えば、特定構造を有する共重合体粒子からなる共重合体ラテックスが提案されている（例えば、下記特許文献６参照。）。 For example, a copolymer latex composed of copolymer particles having a specific structure has been proposed (see, for example, Patent Document 6 below).
　また、例えば、２種類の特定単量体組成のブタジエン－ビニルピリジン系共重合体ラテックスからなる共重合体ラテックスが提案されている（例えば、下記特許文献７参照。）。
特公平７－７８２０７号公報 特公平８－３２８６４号公報 特公平６－７４４０１号公報 特公平７－５８７１号公報 特開２００７－１５４１２６号公報 特許第３９８６６５４号公報 特開平１１－１５８２８９号公報 In addition, for example, a copolymer latex comprising a butadiene-vinylpyridine copolymer latex having two specific monomer compositions has been proposed (see, for example, Patent Document 7 below).
Japanese Patent Publication No. 7-78207 Japanese Patent Publication No. 8-32864 Japanese Patent Publication No. 6-74401 Japanese Patent Publication No. 7-5871 JP 2007-154126 A Japanese Patent No. 3986654 Japanese Patent Laid-Open No. 11-158289
　しかるに、上記した接着処理では、熱処理によって、ゴム補強用繊維の強度が低下するという不具合がある。 However, the above-described adhesion treatment has a problem that the strength of the rubber reinforcing fiber is reduced by the heat treatment.
　一方、ゴム補強用繊維の強度低下を抑制するために、上記温度よりも低温で熱処理することが検討されるが、熱処理の温度が低いと、ゴムとゴム補強用繊維との接着力が低下するという不具合がある。 On the other hand, in order to suppress the strength reduction of the rubber reinforcing fiber, it is considered that the heat treatment is performed at a temperature lower than the above temperature. There is a problem that.
　そこで、本発明の目的は、熱処理によるゴム補強用繊維の強度低下を抑制しながら、ゴムとゴム補強用繊維との接着力を向上させることができる接着剤用共重合体ラテックスを提供することにある。 Then, the objective of this invention is providing the copolymer latex for adhesive agents which can improve the adhesive force of rubber | gum and a rubber reinforcing fiber, suppressing the strength fall of the rubber reinforcing fiber by heat processing. is there.
　上記した課題を解決するため、本発明の接着剤用共重合体ラテックスは、第１相の少なくとも一部が第２相によって被覆されてなるラテックス粒子を含有し、前記第１相は、ブタジエン系単量体１０～４５重量％、ビニルピリジン系単量体０～５重量％およびスチレン系単量体５５～９０重量％を含む第１相単量体組成物の乳化重合により得られ、前記第２相は、ブタジエン系単量体５０～９０重量％、ビニルピリジン系単量体１０～３０重量％およびスチレン系単量体０～４０重量％を含む第２相単量体組成物の乳化重合により得られていることを特徴としている。 In order to solve the above-described problems, the copolymer latex for an adhesive of the present invention contains latex particles in which at least a part of the first phase is covered with the second phase, and the first phase is a butadiene-based polymer. Obtained by emulsion polymerization of a first phase monomer composition containing 10 to 45% by weight of monomer, 0 to 5% by weight of vinylpyridine monomer and 55 to 90% by weight of styrene monomer, The two-phase emulsion polymerization of a second-phase monomer composition containing 50 to 90% by weight of a butadiene monomer, 10 to 30% by weight of a vinylpyridine monomer and 0 to 40% by weight of a styrene monomer It is characterized by being obtained.
　また、本発明の接着剤用共重合体ラテックスでは、前記第１相単量体組成物と前記第２相単量体組成物との総重量に対して、前記第１相単量体組成物の重量割合が１０～５０重量％であり、前記第２相単量体組成物の重量割合が５０～９０重量％であることが好適である。 In the copolymer latex for an adhesive of the present invention, the first phase monomer composition is based on the total weight of the first phase monomer composition and the second phase monomer composition. Is preferably 10 to 50% by weight, and the second phase monomer composition is preferably 50 to 90% by weight.
　また、本発明の接着剤用共重合体ラテックスでは、前記第１相が、その表面積の５０％以上を、前記第２相により被覆されていることが好適である。 In the copolymer latex for adhesive of the present invention, it is preferable that the first phase covers 50% or more of its surface area with the second phase.
　また、本発明の接着剤用共重合体ラテックスでは、前記第１相単量体組成物が、ビニルピリジン系単量体を、０～３重量％含んでいることが好適である。 In the copolymer latex for adhesive of the present invention, it is preferable that the first phase monomer composition contains 0 to 3% by weight of a vinylpyridine monomer.
　本発明の接着剤用共重合体ラテックスによれば、熱処理によるゴム補強用繊維の強度低下を抑制しながら、ゴムとゴム補強用繊維との接着力を向上させることができる。 According to the copolymer latex for adhesive of the present invention, it is possible to improve the adhesive strength between rubber and rubber reinforcing fiber while suppressing the strength reduction of the rubber reinforcing fiber due to heat treatment.
図１は、ラテックス粒子の透過型電子顕微鏡写真であって、実施例１のラテックス粒子を示す。FIG. 1 is a transmission electron micrograph of latex particles showing the latex particles of Example 1. 図２は、ラテックス粒子の透過型電子顕微鏡写真であって、実施例６のラテックス粒子を示す。FIG. 2 is a transmission electron micrograph of latex particles showing the latex particles of Example 6. 図３は、ラテックス粒子の透過型電子顕微鏡写真であって、実施例５のラテックス粒子を示す。FIG. 3 is a transmission electron micrograph of latex particles showing the latex particles of Example 5. 図４は、ラテックス粒子の透過型電子顕微鏡写真であって、比較例２のラテックス粒子を示す。FIG. 4 is a transmission electron micrograph of latex particles, showing the latex particles of Comparative Example 2.
発明の実施形態Embodiment of the Invention
　本発明の接着剤用共重合体ラテックスは、互いに組成の異なる（異相構造の）第１相と第２相とからなるラテックス粒子を含有している。 The copolymer latex for adhesive of the present invention contains latex particles composed of a first phase and a second phase having different compositions (different phase structure).
　第１相は、ブタジエン系単量体、ビニルピリジン系単量体およびスチレン系単量体を含む第１相単量体組成物を乳化重合して得られる。 The first phase is obtained by emulsion polymerization of a first phase monomer composition containing a butadiene monomer, a vinylpyridine monomer, and a styrene monomer.
　ブタジエン系単量体としては、例えば、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエンなどが挙げられ、好ましくは、１，３－ブタジエンが挙げられる。これらブタジエン系単量体は、１種または２種以上使用することができる。 Examples of the butadiene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and the like, preferably 1,3-butadiene. Is mentioned. These butadiene monomers can be used alone or in combination of two or more.
　ビニルピリジン系単量体としては、例えば２－ビニルピリジン、３－ビニルピリジン、４－ビニルピリジン、２－メチル－５－ビニルピリジンなどが挙げられ、好ましくは、２－ビニルピリジンが挙げられる。これらビニルピリジン系単量体は、１種または２種以上使用することができる。 Examples of the vinylpyridine monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, and preferably 2-vinylpyridine. These vinylpyridine monomers can be used alone or in combination of two or more.
　スチレン系単量体としては、例えば、スチレン、α－メチルスチレン、モノクロロスチレンなどが挙げられ、好ましくは、スチレンが挙げられる。これらスチレン系単量体は、１種または２種以上使用することができる。 Examples of the styrene monomer include styrene, α-methylstyrene, monochlorostyrene, and preferably styrene. These styrenic monomers can be used alone or in combination of two or more.
　第１相単量体組成物は、ブタジエン系単量体を、１０～４５重量％、好ましくは、１５～４０重量％、ビニルピリジン系単量体を、０～５重量％（つまり、ビニルピリジン系単量体は、含有されていても含有されていなくてもよく、含有されている場合には、５重量％以下である。）、好ましくは、０～３重量％、および、スチレン系単量体を、５５～９０重量％、好ましくは、６０～８５重量％を含有している。 The first phase monomer composition comprises 10 to 45% by weight of butadiene monomer, preferably 15 to 40% by weight, and 0 to 5% by weight of vinylpyridine monomer (that is, vinylpyridine). The monomer may or may not be contained, and if it is contained, it is 5% by weight or less.), Preferably 0 to 3% by weight, and styrene monomer The monomer contains 55 to 90% by weight, preferably 60 to 85% by weight.
　ブタジエン系単量体の配合割合が、１０重量％未満では、初期接着力が低下し、４５重量％を超えると、コード強度および耐熱接着力が低下する。 When the blending ratio of the butadiene monomer is less than 10% by weight, the initial adhesive strength is lowered, and when it exceeds 45% by weight, the cord strength and the heat resistant adhesive strength are lowered.
　ビニルピリジン系単量体の配合割合が、５重量％を超過すると、初期接着力が低下する。 When the blending ratio of the vinylpyridine monomer exceeds 5% by weight, the initial adhesive strength is lowered.
　スチレン系単量体の配合割合が、５５重量％未満では、耐熱接着力が低下し、９０重量％を超えると、初期接着力および耐熱接着力が低下する。 When the blending ratio of the styrene monomer is less than 55% by weight, the heat-resistant adhesive strength is lowered, and when it exceeds 90% by weight, the initial adhesive force and the heat-resistant adhesive force are lowered.
　なお、第１相単量体組成物は、含有される単量体（ブタジエン系単量体、ビニルピリジン系単量体およびスチレン系単量体）の一部を、共重合可能な他の単量体に置き換えることもできる。 In addition, the first phase monomer composition is composed of other monomers (a butadiene monomer, a vinylpyridine monomer, and a styrene monomer) that can be copolymerized with other monomers. It can be replaced by a mass.
　共重合可能な他の単量体としては、例えば、アクリロニトリル、メタクリロニトリルなどのシアン化ビニル系単量体、例えば、アクリル酸、メタクリル酸、イタコン酸、フマル酸などのエチレン系不飽和カルボン酸単量体、例えば、メチルメタクリレート、エチルアクリレート、ブチルアクリレートなどのエチレン系不飽和カルボン酸アルキルエステル系単量体、例えば、β－ヒドロキシエチルアクリレート、β－ヒドロキシエチルメタクリレートなどのエチレン系不飽和カルボン酸ヒドロキシアルキルエステル系単量体、例えば、アクリルアミド、メタクリルアミドなどのアミド系単量体等が挙げられ、それぞれ１種または２種以上使用することができる。 Examples of other copolymerizable monomers include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid. Monomers, for example, ethylenically unsaturated carboxylic acid alkyl ester monomers such as methyl methacrylate, ethyl acrylate and butyl acrylate, for example, ethylenically unsaturated carboxylic acids such as β-hydroxyethyl acrylate and β-hydroxyethyl methacrylate Examples thereof include hydroxyalkyl ester monomers, for example, amide monomers such as acrylamide and methacrylamide, and one or two or more of them can be used.
　第２相は、ブタジエン系単量体、ビニルピリジン系単量体およびスチレン系単量体を含む第２相単量体組成物を乳化重合して得られる。 The second phase is obtained by emulsion polymerization of a second phase monomer composition containing a butadiene monomer, a vinylpyridine monomer and a styrene monomer.
　ブタジエン系単量体、ビニルピリジン系単量体およびスチレン系単量体としては、それぞれ、第１相において例示された単量体と同一の単量体を例示することができる。なお、好ましい単量体についても同様である。 Examples of the butadiene monomer, vinylpyridine monomer, and styrene monomer include the same monomers as those exemplified in the first phase. The same applies to preferred monomers.
　また、第２相単量体組成物は、含有される単量体（ブタジエン系単量体、ビニルピリジン系単量体およびスチレン系単量体）の一部を、共重合可能な他の単量体に置き換えることもできる。 In addition, the second phase monomer composition is a copolymer of a part of the contained monomers (butadiene monomer, vinylpyridine monomer and styrene monomer) with other monomers capable of being copolymerized. It can be replaced by a mass.
　共重合可能な他の単量体としては、第１相において例示された共重合可能な他の単量体と同一の単量体を例示することができる。 Examples of the other copolymerizable monomer include the same monomers as the other copolymerizable monomers exemplified in the first phase.
　第２相単量体組成物は、ブタジエン系単量体を、５０～９０重量％、好ましくは、６０～８０重量％、ビニルピリジン系単量体を、１０～３０重量％、好ましくは、１０～２５重量％、および、スチレン系単量体を、０～４０重量％（つまり、スチレン系単量体は、含有されていても含有されていなくてもよく、含有されている場合には、４０重量％以下である。）、好ましくは、０～３０重量％含有している。 In the second phase monomer composition, the butadiene monomer is 50 to 90% by weight, preferably 60 to 80% by weight, and the vinylpyridine monomer is 10 to 30% by weight, preferably 10%. -25% by weight, and 0 to 40% by weight of styrenic monomer (that is, the styrenic monomer may or may not be contained. 40 wt% or less.), Preferably 0 to 30 wt%.
　ブタジエン系単量体の配合割合が、５０重量％未満では、初期接着力が低下し、９０重量％を超えると、コード強度および耐熱接着力が低下する。 When the blending ratio of the butadiene monomer is less than 50% by weight, the initial adhesive strength is lowered, and when it exceeds 90% by weight, the cord strength and the heat resistant adhesive force are lowered.
　ビニルピリジン系単量体の配合割合が、１０重量％未満では、初期接着力および耐熱接着力が低下し、３０重量％を超えると、初期接着力が低下する。 When the blending ratio of the vinylpyridine monomer is less than 10% by weight, the initial adhesive strength and the heat-resistant adhesive force are reduced, and when it exceeds 30% by weight, the initial adhesive force is reduced.
　スチレン系単量体の配合割合が、４０重量％を超えると、初期接着力および耐熱接着力が低下する。 When the blending ratio of the styrene monomer exceeds 40% by weight, the initial adhesive strength and the heat resistant adhesive strength are lowered.
　また、第１相単量体組成物と第２相単量体組成物との総重量に対して、第１相単量体組成物の重量割合は、例えば、１０～５０重量％、好ましくは、２０～４０重量％であり、第２相単量体組成物の重量割合は、例えば、５０～９０重量％、好ましくは、６０～８０重量％である。 Further, the weight ratio of the first phase monomer composition to the total weight of the first phase monomer composition and the second phase monomer composition is, for example, 10 to 50% by weight, preferably The weight ratio of the second phase monomer composition is, for example, 50 to 90% by weight, preferably 60 to 80% by weight.
　第１相単量体組成物の重量割合が、１０重量％未満であると、コード強度および耐熱接着力が低下する場合があり、５０重量％を超えると、第１相を第２相により被覆することができず、初期接着力および耐熱接着力が低下する場合がある。 When the weight ratio of the first phase monomer composition is less than 10% by weight, the cord strength and the heat-resistant adhesive force may be reduced. When the weight ratio exceeds 50% by weight, the first phase is covered with the second phase. In some cases, the initial adhesive strength and the heat-resistant adhesive strength may be reduced.
　また、第１相単量体組成物と第２相単量体組成物との総量中に、ブタジエン系単量体は、例えば、４０～８０重量％、好ましくは、５０～７０重量％、ビニルピリジン系単量体は、５～２５重量％、好ましくは、７～１７重量％、および、スチレン系単量体は、１０～５５重量％、好ましくは、１５～４３重量％含有されている。 The total amount of the first phase monomer composition and the second phase monomer composition is, for example, 40 to 80% by weight, preferably 50 to 70% by weight, vinyl, based on the butadiene monomer. The pyridine monomer is contained in an amount of 5 to 25% by weight, preferably 7 to 17% by weight, and the styrene monomer is contained in an amount of 10 to 55% by weight, preferably 15 to 43% by weight.
　そして、共重合体ラテックスを得るには、まず、第１相単量体組成物を乳化重合して、第１相単量体組成物の共重合体（すなわち、第１相）を得た後、第１相単量体組成物の共重合体の存在下に、第２相単量体組成物を乳化重合して、第２相単量体組成物の共重合体（すなわち、第２相）を得る。 In order to obtain a copolymer latex, first, the first phase monomer composition is emulsion-polymerized to obtain a copolymer of the first phase monomer composition (that is, the first phase). In the presence of the copolymer of the first phase monomer composition, the second phase monomer composition is emulsion-polymerized to obtain a copolymer of the second phase monomer composition (that is, the second phase). )
　なお、第２相単量体組成物は、好ましくは、第１相単量体組成物の重合転化率が６０～９０％になった時点で、添加される。 The second phase monomer composition is preferably added when the polymerization conversion rate of the first phase monomer composition reaches 60 to 90%.
　第１相単量体組成物および第２相単量体組成物を乳化重合するには、各単量体組成物（第１相単量体組成物または第２相単量体組成物のそれぞれ）に乳化剤および重合開始剤を添加する。 In order to emulsion-polymerize the first phase monomer composition and the second phase monomer composition, each monomer composition (each of the first phase monomer composition or the second phase monomer composition is used). ) Is added an emulsifier and a polymerization initiator.
　乳化剤としては、例えば、ポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、アルキルエーテル型などのノニオン性界面活性剤、例えば、ロジン酸塩、脂肪酸塩、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、ノニオン性界面活性剤の硫酸エステル塩、ナフタレンスルホン酸塩のホルマリン縮合物などのアニオン性界面活性剤が挙げられ、好ましくは、アニオン性界面活性剤が挙げられ、より好ましくは、ロジン酸塩、ナフタレンスルホン酸塩のホルマリン縮合物が挙げられる。乳化剤は、１種または２種以上使用することができる。 Examples of the emulsifier include nonionic surfactants such as polyethylene glycol alkyl ester type, alkyl phenyl ether type, and alkyl ether type, such as rosin acid salt, fatty acid salt, sulfate ester salt of higher alcohol, alkylbenzene sulfonate, Anionic surfactants such as alkyl diphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfate esters of nonionic surfactants, formalin condensates of naphthalene sulfonate, and the like, preferably, An anionic surfactant is mentioned, More preferably, the formalin condensate of a rosinate and a naphthalenesulfonate is mentioned. One or more emulsifiers can be used.
　乳化剤は、例えば、各単量体組成物１００重量部に対して、例えば、０．１～２０重量部、好ましくは、０．５～１５重量部の割合で添加される。 The emulsifier is added, for example, at a ratio of, for example, 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of each monomer composition.
　重合開始剤は、ラジカル重合開始剤であって、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムなどの水溶性重合開始剤、例えば、クメンハイドロパーオキサイド、過酸化ベンゾイル、t－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイドなどの油溶性重合開始剤が挙げられる。好ましくは、水溶性重合開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムが挙げられ、油溶性重合開始剤としては、クメンハイドロパーオキサイドが挙げられる。 The polymerization initiator is a radical polymerization initiator, for example, a water-soluble polymerization initiator such as potassium persulfate, sodium persulfate, ammonium persulfate, such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide. And oil-soluble polymerization initiators such as acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide. Preferably, the water-soluble polymerization initiator includes potassium persulfate, sodium persulfate, and ammonium persulfate, and the oil-soluble polymerization initiator includes cumene hydroperoxide.
　重合開始剤は、例えば、各単量体組成物１００重量部に対して、例えば、０．０１～３重量部、好ましくは、０．０５～２重量部の割合で添加される。 The polymerization initiator is added, for example, at a ratio of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, with respect to 100 parts by weight of each monomer composition.
　また、各単量体組成物を乳化重合するには、必要により、還元剤、連鎖移動剤を添加することができる。 Further, in order to emulsion polymerize each monomer composition, a reducing agent and a chain transfer agent can be added as necessary.
　還元剤としては、例えば、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩、例えば、Ｌ－アスコルビン酸、エリソルビン酸、酒石酸、クエン酸などのカルボン酸類およびその塩、例えば、デキストロース、サッカロースなどの還元糖類、例えば、ジメチルアニリン、トリエタノールアミンなどのアミン類が挙げられる。好ましくは、カルボン酸類およびその塩が挙げられ、より好ましくは、Ｌ－アスコルビン酸、エリソルビン酸が挙げられる。 Examples of the reducing agent include sulfite, bisulfite, pyrosulfite, nitrite, nithionate, thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate, such as L-ascorbic acid, erythorbic acid Carboxylic acids such as tartaric acid and citric acid and salts thereof, for example, reducing sugars such as dextrose and saccharose, and amines such as dimethylaniline and triethanolamine. Preferred are carboxylic acids and salts thereof, and more preferred are L-ascorbic acid and erythorbic acid.
　還元剤は、例えば、重合開始剤１００重量部に対して、例えば、０～１重量部、好ましくは、０～０．７重量部の割合で添加される。 The reducing agent is added, for example, at a ratio of, for example, 0 to 1 part by weight, preferably 0 to 0.7 part by weight with respect to 100 parts by weight of the polymerization initiator.
　連鎖移動剤としては、例えば、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタンなどのアルキルメルカプタン、例えば、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイドなどのキサントゲン化合物、例えば、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィドなどのチウラム化合物、例えば、２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノールなどのフェノール化合物、例えば、アリルアルコールなどのアリル化合物、例えば、ジクロルメタン、ジブロモメタン、四臭化炭素などのハロゲン化炭化水素化合物、例えば、α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミドなどのビニルエーテル、例えば、トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、α－メチルスチレンダイマーなどが挙げられ、好ましくは、アルキルメルカプタンが挙げられ、より好ましくは、ｎ－オクチルメルカプタン、ｔ－ドデシルメルカプタンが挙げられる。連鎖移動剤は、１種または２種以上使用することができる。 Examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, such as dimethylxanthogen disulfide, diisopropyl Xanthogen compounds such as xanthogen disulfide, for example, thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, such as 2,6-di-t-butyl-4-methylphenol, styrenated phenol, etc. Phenolic compounds, for example, allyl compounds such as allyl alcohol, such as halogenated carbons such as dichloromethane, dibromomethane, carbon tetrabromide Hydrogen compounds such as α-benzyloxystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide, and other vinyl ethers such as triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2- Examples thereof include ethylhexyl thioglycolate and α-methylstyrene dimer, preferably alkyl mercaptan, and more preferably n-octyl mercaptan and t-dodecyl mercaptan. One or two or more chain transfer agents can be used.
　連鎖移動剤は、例えば、各単量体組成物１００重量部に対して、例えば、０～５重量部、好ましくは、０．０５～３重量部の割合で添加される。 The chain transfer agent is added, for example, in a ratio of, for example, 0 to 5 parts by weight, preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of each monomer composition.
　また、乳化重合において、必要により、炭化水素系溶剤を添加することができる。炭化水素としては、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタンなどの飽和炭化水素、例えば、ペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４－メチルシクロヘキセン、１－メチルシクロヘキセンなどの不飽和炭化水素などが挙げられ、好ましくは、シクロヘキセンが挙げられる。シクロへキセンは、低沸点で重合終了後に水蒸気蒸留などによって回収、再利用しやすく、環境負荷の観点から好適である。 In the emulsion polymerization, a hydrocarbon solvent can be added as necessary. Examples of the hydrocarbon include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methylcyclohexene, etc. An unsaturated hydrocarbon etc. are mentioned, Preferably a cyclohexene is mentioned. Cyclohexene has a low boiling point and can be easily recovered and reused by, for example, steam distillation after polymerization, and is suitable from the viewpoint of environmental burden.
　また、その他の添加剤として、必要により、例えば、水酸化ナトリウム、炭酸ナトリウムなどの電解質、ハイドロキノンなどの重合禁止剤、重合促進剤、キレート剤などを添加することができる。 As other additives, for example, electrolytes such as sodium hydroxide and sodium carbonate, polymerization inhibitors such as hydroquinone, polymerization accelerators, chelating agents and the like can be added as necessary.
　これにより、粒状の第１相の表面が第２相により一部被覆されるか、または、粒状の第１相の表面が第２相により完全被覆（コア・シェル構造）されてなるラテックス粒子の水分散体として、接着剤用共重合体ラテックスが調製される。 Thereby, the surface of the granular first phase is partially coated with the second phase, or the surface of the granular first phase is completely coated with the second phase (core-shell structure). A copolymer latex for adhesive is prepared as an aqueous dispersion.
　そして、ラテックス粒子は、好ましくは、第１相の表面積の５０％以上、より好ましくは、１００％（すなわち、表面すべて）が、第２相によって被覆されている。 And, the latex particles are preferably covered with 50% or more of the surface area of the first phase, more preferably 100% (that is, the entire surface) by the second phase.
　また、ラテックス粒子の数平均粒子径は、例えば、５０～２００ｎｍ、好ましくは、８０～１６０ｎｍである。 Further, the number average particle diameter of the latex particles is, for example, 50 to 200 nm, preferably 80 to 160 nm.
　ラテックス粒子において、第２相による第１相の被覆状態を判定するには、例えば、透過型電子顕微鏡を用いて粒子の断面を観察する。 In order to determine the covering state of the first phase by the second phase in the latex particles, for example, a cross section of the particles is observed using a transmission electron microscope.
　透過型電子顕微鏡を用いて粒子の断面を観察するには、まず、接着剤用共重合体ラテックスに四酸化オスミウム水溶液を添加して、ラテックス粒子を電子染色（オスミウム染色）する。なお、電子染色により、１，３－ブタジエンの二重結合に四酸化オスミウムが付加する。 In order to observe the cross section of the particles using a transmission electron microscope, first, an osmium tetroxide aqueous solution is added to the adhesive copolymer latex, and the latex particles are electron-stained (osmium dyeing). Note that osmium tetroxide is added to the double bond of 1,3-butadiene by electron staining.
　次いで、共重合体ラテックスにエポキシ樹脂を添加した後、乾燥させる。これにより、ラテックス粒子を含有するエポキシ樹脂の固形物を得ることができる。つまり、ラテックス粒子をエポキシ樹脂で被覆（包埋）する。 Next, an epoxy resin is added to the copolymer latex and then dried. Thereby, the solid substance of the epoxy resin containing latex particles can be obtained. That is, latex particles are coated (embedded) with an epoxy resin.
　そして、ウルトラミクロトームを用いて、エポキシ樹脂の固形物の切片を切り出し、切り出した切片を透過型電子顕微鏡で観察する。なお、粒子断面の透過型電子顕微鏡観察において、１，３－ブタジエンの含有量が比較的少ない第１相は薄く観察され、１，３－ブタジエンの含有量が比較的多い第２相は濃く観察される。 Then, using an ultramicrotome, a section of solid epoxy resin is cut out, and the cut out section is observed with a transmission electron microscope. In the transmission electron microscope observation of the particle cross section, the first phase with a relatively small content of 1,3-butadiene is observed thin, and the second phase with a relatively large content of 1,3-butadiene is observed deeply. Is done.
　なお、上記したように、透過型電子顕微鏡を用いてラテックス粒子の断面を観察した場合には、ラテックス粒子の断面において、第１相の外周長さの５０％以上、より好ましくは、１００％（すなわち、外周すべて）が、第２相によって被覆されている。 As described above, when the cross section of the latex particle is observed using a transmission electron microscope, the cross section of the latex particle is 50% or more of the outer peripheral length of the first phase, more preferably 100% ( That is, the entire outer periphery) is covered with the second phase.
　なお、ラテックス粒子において、第２相による第１相の被覆状態を制御するには、例えば、上記した第１相単量体組成物と第２相単量体組成物との重量割合を変更する。 In addition, in latex particle | grains, in order to control the coating state of the 1st phase by a 2nd phase, the weight ratio of an above-described 1st phase monomer composition and a 2nd phase monomer composition is changed, for example. .
　そして、本発明の接着剤用共重合体ラテックスは、好ましくは、ゴムとゴム補強繊維とを接着するための接着剤組成物に配合される。 The copolymer latex for adhesive of the present invention is preferably blended in an adhesive composition for bonding rubber and rubber reinforcing fiber.
　ゴムとしては、特に限定されず、例えば、天然ゴム、ＳＢＲ、ＮＢＲ、クロロプレンゴム、ポリブタジエンゴム、ポリイソプレンゴム、それらの各種変性ゴムなどが挙げられる。また、ゴムには、例えば、充填剤、軟化剤、加硫剤、加硫促進剤などの公知の添加剤を配合することができる。 The rubber is not particularly limited, and examples thereof include natural rubber, SBR, NBR, chloroprene rubber, polybutadiene rubber, polyisoprene rubber, and various modified rubbers thereof. Moreover, well-known additives, such as a filler, a softening agent, a vulcanizing agent, a vulcanization accelerator, can be mix | blended with rubber | gum, for example.
　ゴム補強繊維としては、例えば、ナイロン繊維、ポリエステル繊維、アラミド繊維などが挙げられる。また、これらの繊維の形態としては、特に限定されず、例えば、コード、ケーブル、織物、帆布、短繊維などが挙げられる。 Examples of rubber reinforcing fibers include nylon fibers, polyester fibers, and aramid fibers. Moreover, it does not specifically limit as a form of these fibers, For example, a cord, a cable, a textile fabric, a canvas, a short fiber etc. are mentioned.
　接着剤組成物は、接着剤用共重合体ラテックスとレゾルシン－ホルマリン樹脂とを配合し、混合することにより得られる。 The adhesive composition can be obtained by mixing and mixing a copolymer latex for adhesive and a resorcin-formalin resin.
　接着剤組成物を調製するには、接着剤用共重合体ラテックスとレゾルシン－ホルマリン樹脂とは、特に限定されないが、接着剤用共重合体ラテックス１００重量部（固形分）に対して、レゾルシン－ホルマリン樹脂を、例えば、５～１００重量部、好ましくは、５～９０重量部、配合する。 To prepare the adhesive composition, the adhesive copolymer latex and the resorcin-formalin resin are not particularly limited, but the resorcin-- is used with respect to 100 parts by weight (solid content) of the adhesive copolymer latex. Formalin resin is blended, for example, in an amount of 5 to 100 parts by weight, preferably 5 to 90 parts by weight.
　また、接着剤組成物には、必要に応じて、イソシアネート、ブロックドイソシアネート、エチレン尿素、２，６－ビス（２，４－ジヒドロキシフェニルメチル）－４－クロロフェノール、一塩化イオウとレゾルシンの縮合物およびレゾルシン－ホルマリン縮合物との混合物などの変性レゾルシン－ホルマリン樹脂、ポリエポキシド、変性ポリ塩化ビニル、カーボンブラックなどの接着助剤、充填剤、架橋剤、加硫剤、加硫促進剤などを配合することができる。 The adhesive composition may contain isocyanate, blocked isocyanate, ethylene urea, 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol, sulfur monochloride and resorcin, if necessary. Compounding agent and modified resorcin-formalin resin such as a mixture with resorcin-formalin condensate, polyepoxide, modified polyvinyl chloride, carbon black and other adhesion aids, fillers, crosslinking agents, vulcanizing agents, vulcanization accelerator can do.
　そして、ゴムとゴム補強繊維とを接着するには、まず、接着剤組成物をゴム補強繊維に処理する。 In order to bond the rubber and the rubber reinforcing fiber, first, the adhesive composition is processed into the rubber reinforcing fiber.
　接着剤組成物をゴム補強繊維に処理するには、例えば、ディッピングマシンなどを用いて、接着剤組成物にゴム補強繊維を浸漬させる。その後、例えば、１００～１５０℃、好ましくは、１１０～１３０℃で、例えば、８０～２００秒、好ましくは、１００～１５０秒乾燥させ、その後、例えば、１８０～３００℃、好ましくは、２００～２６０℃で、例えば、３０～１００秒、好ましくは、５０～８０秒加熱して焼き付けする。 In order to treat the adhesive composition into the rubber reinforcing fiber, for example, the rubber reinforcing fiber is immersed in the adhesive composition using a dipping machine or the like. Thereafter, for example, drying is performed at 100 to 150 ° C., preferably 110 to 130 ° C., for example, 80 to 200 seconds, preferably 100 to 150 seconds, and then, for example, 180 to 300 ° C., preferably 200 to 260 ° C. For example, the baking is performed at a temperature of 30 to 100 seconds, preferably 50 to 80 seconds.
　そして、上記処理の後、接着剤組成物が処理されたゴム補強繊維に、ゴムを接触させて、ゴムとゴム補強繊維とを加熱および加圧すると、ゴムとゴム補強繊維とが接着される。 After the above treatment, when the rubber is brought into contact with the rubber reinforcing fiber treated with the adhesive composition, and the rubber and the rubber reinforcing fiber are heated and pressurized, the rubber and the rubber reinforcing fiber are bonded.
　そして、本発明の接着剤用共重合体ラテックスを用いて接着剤組成物を調整すれば、熱処理によるゴム補強用繊維の強度低下を抑制しながら、ゴムとゴム補強用繊維との接着力を向上させることができる。 And, by adjusting the adhesive composition using the copolymer latex for adhesive of the present invention, the adhesive strength between the rubber and the rubber reinforcing fiber is improved while suppressing the strength reduction of the rubber reinforcing fiber due to heat treatment. Can be made.
　以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明は、これらの実施例に限定されるものではない。なお、実施例中、配合割合を示す「部」および「％」は重量基準による。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, “part” and “%” indicating the blending ratio are based on weight.
　１．接着剤用共重合体ラテックスの合成
（１）実施例１～８および比較例１
　攪拌機付きオートクレーブに、水１３５部、ナフタレンスルホン酸ナトリウム・ホルマリン縮合物１部、水酸化ナトリウム０．５部およびロジン酸カリウム５．０部を加え溶解させた。 1. Synthesis of copolymer latex for adhesive (1) Examples 1 to 8 and Comparative Example 1
In an autoclave equipped with a stirrer, 135 parts of water, 1 part of sodium naphthalenesulfonate / formalin condensate, 0.5 part of sodium hydroxide and 5.0 parts of potassium rosinate were added and dissolved.
　次いで、表１に示した第１相単量体組成物と、ｔ－ドデシルメルカプタン０．３部とを加えて乳化させた。 Next, the first phase monomer composition shown in Table 1 and 0.3 part of t-dodecyl mercaptan were added and emulsified.
　その後、過硫酸カリウム０．５部を加え、内温を５５℃に保ち、第１相単量体組成物を重合した。 Thereafter, 0.5 part of potassium persulfate was added to maintain the internal temperature at 55 ° C., and the first phase monomer composition was polymerized.
　第１相単量体組成物の重合転化率が８２％に到達した時点で、表１に示した第２相単量体組成物とｔ－ドデシルメルカプタン０．２５部とを連続的に添加して、重合を継続した。 When the polymerization conversion rate of the first phase monomer composition reached 82%, the second phase monomer composition shown in Table 1 and 0.25 part of t-dodecyl mercaptan were continuously added. The polymerization was continued.
　重合転化率が９３重量％に到達した時点で、ハイドロキノン０．１部を加え、重合を停止させ、減圧蒸留により未反応単量体を除去して、接着剤用共重合体ラテックスを得た。
（２）比較例２
　攪拌機付きオートクレーブに、水１３０部、ナフタレンスルホン酸ナトリウム・ホルマリン縮合物１部、水酸化ナトリウム０．５部およびロジン酸カリウム４部を加え溶解させた。 When the polymerization conversion rate reached 93% by weight, 0.1 part of hydroquinone was added to stop the polymerization, and the unreacted monomer was removed by distillation under reduced pressure to obtain a copolymer latex for adhesive.
(2) Comparative Example 2
In an autoclave equipped with a stirrer, 130 parts of water, 1 part of sodium naphthalenesulfonate / formalin condensate, 0.5 part of sodium hydroxide and 4 parts of potassium rosinate were added and dissolved.
　次いで、表１に示した第１相単量体組成物と、ｔ－ドデシルメルカプタン０．５５部とを加えて乳化させた。 Next, the first phase monomer composition shown in Table 1 and 0.55 part of t-dodecyl mercaptan were added and emulsified.
　その後、過硫酸カリウム０．５部を加え、内温を５０℃に保ち、第１相単量体組成物を重合した。 Thereafter, 0.5 part of potassium persulfate was added to maintain the internal temperature at 50 ° C., and the first phase monomer composition was polymerized.
　重合転化率が９３％に到達した時点で、ハイドロキノン０．１部を加え、重合を停止させ、その後、減圧蒸留により未反応単量体を除去して、接着剤用共重合体ラテックスを得た。 When the polymerization conversion rate reached 93%, 0.1 part of hydroquinone was added to stop the polymerization, and then the unreacted monomer was removed by distillation under reduced pressure to obtain a copolymer latex for adhesive. .
　２．共重合ラテックスの電子顕微鏡観察（異相構造確認）
　得られた接着剤用共重合体ラテックスに、四酸化オスミウム水溶液を加えて電子染色した。 2. Observation of copolymer latex with electron microscope (confirmation of heterogeneous structure)
The obtained copolymer latex for adhesive was added with an osmium tetroxide aqueous solution and subjected to electron staining.
　次いで、接着剤用共重合体ラテックスにエポキシ樹脂を加えて乾燥し、ラテックス粒子を含有するエポキシ樹脂の固形物を得た。これにより、接着剤用共重合体ラテックスのラテックス粒子をエポキシ樹脂で被覆（包埋）した。 Next, an epoxy resin was added to the adhesive copolymer latex and dried to obtain an epoxy resin solid containing latex particles. Thus, latex particles of the copolymer latex for adhesive were coated (embedded) with the epoxy resin.
　次いで、ウルトラミクロトームを用いて、エポキシ樹脂の切片を切り出し、透過型電子顕微鏡（日本電子　ＪＥＭ－１４００）でラテックス粒子の断面を撮影した。ラテックス粒子の透過型電子顕微鏡写真を図１～４に示す。図１は、実施例１のラテックス粒子を示し、図２は、実施例６のラテックス粒子を示し、図３は、実施例５のラテックス粒子を示し、図４は、比較例２のラテックス粒子を示す。 Next, a section of the epoxy resin was cut out using an ultramicrotome, and a cross section of the latex particles was photographed with a transmission electron microscope (JEOL JEM-1400). Transmission electron micrographs of latex particles are shown in FIGS. 1 shows latex particles of Example 1, FIG. 2 shows latex particles of Example 6, FIG. 3 shows latex particles of Example 5, and FIG. 4 shows latex particles of Comparative Example 2. Show.
　そして、粒子の断面を観察し、１）異相構造の有無、および、２）第２相による第１相の被覆状態を、目視で評価した。 Then, the cross section of the particle was observed, and 1) presence / absence of a heterogeneous structure and 2) the coating state of the first phase by the second phase were visually evaluated.
　なお、２）第２相による第１相の被覆状態については、粒子１００個を観察し、そのうち５０個以上が下記の評価基準に相当すれば、下記の評価と認定した。
＜被覆状態の評価基準＞
◎：第２相が第１相を完全に（１００％）被覆している。
○：第２相が第１相の５０％以上を覆っている。
△：第２相が第１相の５０％以下を覆っている。
×：第２相が第１相を被覆しておらず、１つの粒子中に第１相または第２相のいずれか一方のみが認められる。 2) Regarding the coating state of the first phase by the second phase, 100 particles were observed, and if 50 or more of them corresponded to the following evaluation criteria, the following evaluation was recognized.
<Evaluation criteria for coating state>
A: The second phase completely (100%) covers the first phase.
○: The second phase covers 50% or more of the first phase.
Δ: The second phase covers 50% or less of the first phase.
X: The second phase does not cover the first phase, and only one of the first phase and the second phase is recognized in one particle.
　３．接着剤組成物の調製
（１）ポリエステル・タイヤコード（ＰＥＴ・タイヤコード）用接着剤組成物
　水２６０部に１０％水酸化ナトリウム水溶液４部を添加して攪拌した後、レゾルシン７．９部、および、３７％ホルマリン水溶液８．６部を加えて攪拌混合し、３０℃にて６時間熟成し、レゾルシン－ホルマリン樹脂を合成した。 3. Preparation of Adhesive Composition (1) Adhesive Composition for Polyester Tire Cord (PET / Tire Cord) After adding 4 parts of 10% aqueous sodium hydroxide to 260 parts of water and stirring, 7.9 parts of resorcin, Then, 8.6 parts of a 37% formalin aqueous solution was added, mixed with stirring, and aged at 30 ° C. for 6 hours to synthesize a resorcin-formalin resin.
　次いで、各実施例および各比較例の接着剤用共重合体ラテックス１００部に、接着剤組成物の固形分濃度が１６．５％になるように水を添加して攪拌した後、レゾルシン－ホルマリン樹脂を全量と、２８％アンモニア水１１．４部とを添加して攪拌混合した。 Next, water was added to 100 parts of the copolymer latex for adhesives of each example and each comparative example so that the solid content concentration of the adhesive composition was 16.5% and stirred, and then resorcin-formalin was stirred. The total amount of the resin and 11.4 parts of 28% aqueous ammonia were added and mixed with stirring.
　その後、２７％ブロックドイソシアネート分散液（明成化学工業（株）製ＳＵ－１２５Ｆ）４６．３部添加して、３０℃にて４８時間熟成させ、ポリエステル・タイヤコード用の接着剤組成物を得た。
（２）６－６ナイロン・タイヤコード（ナイロン・タイヤコード）用接着剤組成物
　水２３６部に１０％水酸化ナトリウム水溶液３．０部を添加して攪拌した後、レゾルシン１１．０部、および、３７％ホルマリン水溶液１６．２部を加えて攪拌混合し、２５℃にて６時間熟成し、レゾルシン－ホルマリン樹脂を合成した。 Thereafter, 46.3 parts of 27% blocked isocyanate dispersion (SU-125F manufactured by Meisei Chemical Industry Co., Ltd.) was added and aged at 30 ° C. for 48 hours to obtain an adhesive composition for polyester tire cords. It was.
(2) Adhesive composition for 6-6 nylon tire cord (nylon tire cord) After adding 3.0 parts of 10% aqueous sodium hydroxide to 236 parts of water and stirring, 11.0 parts of resorcin, and Then, 16.2 parts of a 37% formalin aqueous solution was added, mixed with stirring, and aged at 25 ° C. for 6 hours to synthesize a resorcin-formalin resin.
　次いで、各実施例および各比較例の接着剤用共重合体ラテックス１００部に、接着剤組成物の固形分濃度が１６．５％になるように水を添加して攪拌した後、レゾルシン－ホルマリン樹脂を全量と、２８％アンモニア水１３．０部とを添加して攪拌混合した。 Next, water was added to 100 parts of the copolymer latex for adhesives of each Example and each Comparative Example so that the solid content concentration of the adhesive composition was 16.5% and stirred, and then resorcin-formalin was stirred. The total amount of the resin and 13.0 parts of 28% aqueous ammonia were added and mixed with stirring.
　その後、２５℃にて１８時間熟成させ、６－６ナイロン・タイヤコード用の接着剤組成物を得た。 Thereafter, aging was carried out at 25 ° C. for 18 hours to obtain an adhesive composition for 6-6 nylon tire cord.
　４．評価
（１）タイヤコード浸漬処理
　試験用シングルコードディッピングマシンを用いて、得られた接着剤組成物に、前処理されたポリエステル・タイヤコード（１５００Ｄ／２）または６－６ナイロン・タイヤコード（１２６０Ｄ/３）を浸漬し、その後、１２０℃で１２０秒間乾燥した後、ポリエステル・タイヤコードは２４０℃で６０秒間、６－６ナイロン・タイヤコードは２２０℃で６０秒間、焼き付けた。
（２）ゴム
　下記の配合処方によりゴムを準備した。
＜ゴム処方＞
天然ゴム　　　　　　　　　７０部
ＳＢＲゴム　　　　　　　　３０部
ＦＥＦカーボン　　　　　　４０部
プロセスオイル　　　　　　　４部
アンチゲンＲＤ（＊１）　　　２部
ステアリン酸　　　　　　１．５部
亜鉛華      　　　　　　　　５部
加硫促進剤ＤＭ（＊２）　０．９部
硫黄　　　　　　　　　　２．７部
＊１：２，２，４－トリメチル－１，２－ジヒドロキノリン重合物（住友化学（株）社製）
＊２：ジベンゾチアジルジスルフィド
（３）繊維強度の測定
　各実施例および各比較例の接着剤組成物で処理されたポリエステル・タイヤコード（１５００Ｄ／２）または６－６ナイロン・タイヤコード（１２６０Ｄ/３）の繊維強度（コード強力）を、ＪＩＳ－Ｌ１０１７に準じて測定した。結果を表２に示す。
（４）接着力の測定
（４－１）ポリエステル・タイヤコード
　各実施例および各比較例の接着剤組成物で処理されたポリエステル・タイヤコードをゴムではさみ、１６０℃で２０分（初期接着力評価条件）、および１７０℃で５０分（耐熱接着力評価条件）の条件で加硫プレスした。 4). Evaluation (1) Tire cord dipping treatment Using a test single cord dipping machine, the resulting adhesive composition was pre-treated with a polyester tire cord (1500D / 2) or 6-6 nylon tire cord (1260D). 3) and then dried at 120 ° C. for 120 seconds, and then the polyester tire cord was baked at 240 ° C. for 60 seconds and the 6-6 nylon tire cord was baked at 220 ° C. for 60 seconds.
(2) Rubber A rubber was prepared according to the following formulation.
<Rubber prescription>
Natural rubber 70 parts SBR rubber 30 parts FEF carbon 40 parts Process oil 4 parts Antigen RD (* 1) 2 parts Stearic acid 1.5 parts Zinc white 5 parts Vulcanization accelerator DM (* 2) 0.9 parts Sulfur 7 parts * 1: 2,2,4-trimethyl-1,2-dihydroquinoline polymer (manufactured by Sumitomo Chemical Co., Ltd.)
* 2: Measurement of dibenzothiazyl disulfide (3) Fiber strength Polyester tire cord (1500D / 2) or 6-6 nylon tire cord (1260D / The fiber strength (cord strength) of 3) was measured according to JIS-L1017. The results are shown in Table 2.
(4) Measurement of Adhesive Strength (4-1) Polyester / Tire Cord A polyester tire cord treated with the adhesive composition of each Example and each Comparative Example was sandwiched with rubber, and then at 160 ° C. for 20 minutes (initial adhesive strength) (Evaluation conditions), and vulcanization press was performed at 170 ° C. for 50 minutes (heat resistant adhesive strength evaluation conditions).
　ゴムとゴム補強繊維との初期接着力および耐熱接着力を、ＡＳＴＭ　Ｄ２１３８－６７（Ｈ　Ｐｕｌｌ　Ｔｅｓｔ）に準じて測定した。結果を表２に示す。
（４－２）ナイロン・タイヤコード
　上記ポリエステル・タイヤコードの場合と同様に、各実施例および各比較例の接着剤組成物で処理されたナイロン・タイヤコードをゴムではさみ、１６０℃で２０分（初期接着力評価条件）の条件で加硫プレスした。 The initial adhesive strength and heat-resistant adhesive strength between rubber and rubber reinforcing fiber were measured according to ASTM D2138-67 (H Pull Test). The results are shown in Table 2.
(4-2) Nylon / Tire Cord As in the case of the above-mentioned polyester / tire cord, the nylon / tyre cord treated with the adhesive composition of each Example and each Comparative Example was sandwiched with rubber, and 20 minutes at 160 ° C. Vulcanizing press was performed under the conditions of (initial adhesive strength evaluation conditions).
　ゴムとゴム補強繊維との初期接着力を、ＡＳＴＭ　Ｄ２１３８－６７（Ｈ　Ｐｕｌｌ　Ｔｅｓｔ）に準じて測定した。結果を表２に示す。 The initial adhesive strength between rubber and rubber reinforcing fiber was measured according to ASTM D2138-67 (H Pull Test). The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示にすぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記特許請求の範囲に含まれるものである。 Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be interpreted in a limited manner. Modifications of the present invention apparent to those skilled in the art are intended to be included within the scope of the following claims.
　本発明の接着剤用共重合体ラテックスは、接着剤組成物に配合され、ゴムとゴム補強繊維とを接着するために利用される。 The copolymer latex for adhesive of the present invention is blended in an adhesive composition and used for bonding rubber and rubber reinforcing fiber.

Claims (4)

  1. 　第１相の少なくとも一部が第２相によって被覆されてなるラテックス粒子を含有し、
    　前記第１相は、
    　　ブタジエン系単量体１０～４５重量％、ビニルピリジン系単量体０～５重量％およびスチレン系単量体５５～９０重量％を含む第１相単量体組成物の乳化重合により得られ、
    　前記第２相は、
    　　ブタジエン系単量体５０～９０重量％、ビニルピリジン系単量体１０～３０重量％およびスチレン系単量体０～４０重量％を含む第２相単量体組成物の乳化重合により得られていることを特徴とする、接着剤用共重合体ラテックス。     Containing latex particles wherein at least a portion of the first phase is coated with the second phase;
    The first phase is
    Obtained by emulsion polymerization of a first phase monomer composition comprising 10 to 45% by weight of a butadiene monomer, 0 to 5% by weight of a vinylpyridine monomer and 55 to 90% by weight of a styrene monomer,
    The second phase is
    It is obtained by emulsion polymerization of a second phase monomer composition containing 50 to 90% by weight of butadiene monomer, 10 to 30% by weight of vinylpyridine monomer and 0 to 40% by weight of styrene monomer. Copolymer latex for adhesives, characterized in that
  2. 　前記第１相単量体組成物と前記第２相単量体組成物との総重量に対して、前記第１相単量体組成物の重量割合が１０～５０重量％であり、前記第２相単量体組成物の重量割合が５０～９０重量％であることを特徴とする、請求項１に記載の接着剤用共重合体ラテックス。 The weight ratio of the first phase monomer composition is 10 to 50% by weight based on the total weight of the first phase monomer composition and the second phase monomer composition, The copolymer latex for an adhesive according to claim 1, wherein the weight ratio of the two-phase monomer composition is 50 to 90% by weight.
  3. 　前記第１相は、その表面積の５０％以上を、前記第２相により被覆されていることを特徴とする、請求項１に記載の接着剤用共重合体ラテックス。 The copolymer latex for an adhesive according to claim 1, wherein 50% or more of the surface area of the first phase is covered with the second phase.
  4. 　前記第１相単量体組成物は、ビニルピリジン系単量体を、０～３重量％、含んでいることを特徴とする、請求項１に記載の接着剤用共重合体ラテックス。 The copolymer latex for an adhesive according to claim 1, wherein the first phase monomer composition contains 0 to 3 wt% of a vinylpyridine monomer.
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WO1997013818A1 (en) * 1995-10-13 1997-04-17 Bridgestone Corporation Adhesive composition and pneumatic tire

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