WO2014073525A1 - Method for producing copolymer latex for adhesives - Google Patents

Method for producing copolymer latex for adhesives Download PDF

Info

Publication number
WO2014073525A1
WO2014073525A1 PCT/JP2013/079878 JP2013079878W WO2014073525A1 WO 2014073525 A1 WO2014073525 A1 WO 2014073525A1 JP 2013079878 W JP2013079878 W JP 2013079878W WO 2014073525 A1 WO2014073525 A1 WO 2014073525A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
monomer
monomer composition
copolymer latex
composition
Prior art date
Application number
PCT/JP2013/079878
Other languages
French (fr)
Japanese (ja)
Inventor
竹中　俊
淳美 種村
皇雄 三崎
Original Assignee
日本エイアンドエル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本エイアンドエル株式会社 filed Critical 日本エイアンドエル株式会社
Priority to KR1020157011212A priority Critical patent/KR102141789B1/en
Priority to CN201380057723.9A priority patent/CN104769066B/en
Publication of WO2014073525A1 publication Critical patent/WO2014073525A1/en

Links

Classifications

    • 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
    • C09J109/06—Copolymers with styrene

Definitions

  • the present invention relates to a method for producing a copolymer latex for adhesive, and more particularly to a method for producing a copolymer latex for adhesive that bonds rubber and fiber.
  • fibers such as nylon, polyester, aramid and glass 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
  • Examples of the copolymer latex for adhesive contained in the RFL include, for example, a conjugated diene monomer, an ethylenically unsaturated acid monomer, vinyl pyridine, and other monomers copolymerizable therewith.
  • monomers including ethylenically unsaturated acid and conjugated diene monomer
  • a copolymer latex obtained by polymerizing the remaining monomers has been proposed (see, for example, Patent Document 1 below).
  • the second-stage monomer (the remaining monomers in Patent Document 1) has a polymerization conversion rate of 60% or more of the first-stage monomer. Since then, it is polymerized.
  • an object of the present invention is to provide an adhesive that can improve the productivity of the copolymer latex for an adhesive while ensuring the adhesive force of the copolymer latex for an adhesive to a rubber reinforcing fiber.
  • Another object of the present invention is to provide a method for producing a copolymer latex.
  • the method for producing the copolymer latex for adhesive according to the present invention includes 35% by mass to 75% by mass of an aliphatic conjugated diene monomer, 5% by mass to 25% by mass of a vinylpyridine monomer, and these Emulsion polymerization of the monomer composition (a) containing 0% by mass or more and 60% by mass or less of another monomer copolymerizable with the monomer, and the polymerization conversion rate of the monomer composition (a) is 30% When the amount is less than 60%, the monomer composition (a) has an aliphatic conjugated diene monomer of 35% by mass to 75% by mass, and a vinylpyridine monomer of 5% by mass to 25% by mass. And a step of emulsion polymerization by adding a monomer composition (b) containing 0% by mass or more and 60% by mass or less of another monomer copolymerizable therewith.
  • the monomer composition (a) is a total amount of the monomer composition (a) and the monomer composition (b). Is 30 mass% or more and 70 mass% or less, and the monomer composition (b) is based on the total amount of the monomer composition (a) and the monomer composition (b).
  • the content is preferably 30% by mass or more and 70% by mass or less.
  • the method for producing a copolymer latex for an adhesive according to the present invention includes the monomer composition (a) based on the mass% of the aliphatic conjugated diene monomer in the monomer composition (b).
  • the ratio of the mass% of the aliphatic conjugated diene monomer in the composition is 0.8 or more and 1.25 or less, and is based on the mass% of the vinylpyridine monomer in the monomer composition (b).
  • the ratio by mass of the vinylpyridine monomer in the monomer composition (a) is preferably 0.8 or more and 1.25 or less.
  • the monomer composition (a) is emulsion-polymerized, and the polymerization conversion rate of the monomer composition (a) is 30% or more and 60%.
  • the monomer composition (b) is added to the monomer composition (a), and emulsion polymerization is further performed.
  • the polymerization time can be shortened.
  • a monomer comprising an aliphatic conjugated diene monomer, a vinylpyridine monomer, and another monomer copolymerizable therewith.
  • the body composition (a) (first monomer composition) is subjected to emulsion polymerization.
  • Examples of the aliphatic conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3-butadiene. And butadiene monomer.
  • butadiene monomers are preferable, and 1,3-butadiene is more preferable.
  • these aliphatic conjugated diene monomers can be used alone (one kind) or in combination of two or more kinds.
  • vinylpyridine monomer examples include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, and the like.
  • 2-vinylpyridine is preferable.
  • vinylpyridine monomers can be used alone (one kind) or in combination of two or more kinds.
  • Examples of other monomers copolymerizable with the above aliphatic conjugated diene monomers and vinylpyridine monomers include, for example, aromatic vinyl monomers, vinyl cyanide monomers, and ethylenically unsaturated monomers.
  • Examples thereof include carboxylic acid monomers, ethylenically unsaturated carboxylic acid alkyl ester monomers, unsaturated monomers containing a hydroxyalkyl group, and ethylenically unsaturated carboxylic acid amide monomers.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, and monochlorostyrene.
  • vinyl cyanide monomer examples include acrylonitrile and methacrylonitrile.
  • ethylenically unsaturated carboxylic acid monomer examples include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid, for example, ethylenically unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Saturated dicarboxylic acid monomer (or its anhydride) etc. are mentioned.
  • Examples of the ethylenically unsaturated carboxylic acid alkyl ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • Examples of the unsaturated monomer containing a hydroxyalkyl group include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate and the like.
  • Examples of the ethylenically unsaturated carboxylic acid amide monomer include acrylamide and methacrylamide.
  • an aromatic vinyl monomer is preferable, and styrene is more preferable.
  • a combination of aromatic vinyl monomers preferably a combination of aromatic vinyl monomers, a combination of an aromatic vinyl monomer and a vinyl cyanide monomer
  • a combination of an aromatic vinyl monomer and an ethylenically unsaturated carboxylic acid monomer, a combination of an aromatic vinyl monomer and an ethylenically unsaturated carboxylic acid alkyl ester monomer and more preferably, A combination of styrene and ⁇ -methylstyrene, a combination of styrene and acrylonitrile, a combination of styrene and acrylic acid, a combination of styrene and itaconic acid, or a combination of styrene and methyl methacrylate.
  • the monomer composition (a) is an aliphatic conjugated diene monomer, for example, 35% by mass or more, preferably 40% by mass or more, for example, 75% by mass or less, preferably 70% by mass or less.
  • Vinyl pyridine monomer for example, 5% by mass or more, preferably 10% by mass or more, for example, 25% by mass or less, preferably 20% by mass or less, and the remainder can be copolymerized with these.
  • 0% by mass or more preferably 10% by mass or more, for example, 60% by mass or less, and preferably 55% by mass or less.
  • the blending ratio of the aliphatic conjugated diene monomer is less than 35% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. On the other hand, when the blending ratio of the aliphatic conjugated diene monomer exceeds 75% by mass, the processing cord strength and the heat-resistant adhesive strength may decrease.
  • the blending ratio of the vinylpyridine monomer is less than 5% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. Moreover, when the mixture ratio of a vinyl pyridine-type monomer exceeds 25 mass%, an initial stage adhesive force may fall.
  • the initial adhesive strength and heat resistant adhesive strength may be reduced.
  • the ratio of the monomer composition (a) to the total amount of the monomer composition (a) and the monomer composition (b) (described later) is, for example, 30% by mass or more, preferably 35% by mass. % Or more, for example, 70% by mass or less, preferably 65% by mass or less.
  • the proportion of the monomer composition (a) is within the above range, the productivity of the copolymer latex for adhesive can be improved.
  • the ratio of the mass% of the aliphatic conjugated diene monomer in the monomer composition (a) to the mass% of the aliphatic conjugated diene monomer in the monomer composition (b) (described later). Is, for example, 0.8 or more, preferably 0.9 or more, for example, 1.25 or less, preferably 1.1 or less.
  • the productivity of the copolymer latex for adhesive can be improved and the initial adhesive force can be improved.
  • the ratio of the mass% of the vinylpyridine monomer in the monomer composition (a) to the mass% of the vinylpyridine monomer in the monomer composition (b) (described later) is, for example, 0.8 or more, preferably 0.9 or more, for example, 1.25 or less, preferably 1.1 or less.
  • the productivity of the copolymer latex for adhesive can be improved and the initial adhesive force can be improved.
  • an emulsifier and a polymerization initiator are added to the monomer composition (a).
  • 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 soap, fatty acid soap, sulfate ester salt of higher alcohol, alkylbenzene sulfonate, Examples include anionic surfactants such as alkyl diphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfate esters of nonionic surfactants, and formalin condensates of naphthalene sulfonate.
  • nonionic surfactants such as polyethylene glycol alkyl ester type, alkyl phenyl ether type, and alkyl ether type, such as rosin acid soap, fatty acid soap, sulfate ester salt of higher alcohol, alkylbenzene sulfonate
  • anionic surfactants such as alkyl
  • emulsifiers can be used alone (one kind) or in combination of two or more kinds.
  • anionic surfactants are preferable, and rosin acid soaps, fatty acid soaps, and formalin condensates of naphthalene sulfonates are more preferable.
  • the emulsifier is, for example, 0.5 parts by mass or more, preferably 2.0 parts by mass or more, for example, 10.0 parts by mass or less, preferably 8 parts by mass with respect to 100 parts by mass of the monomer composition (a). It is added at a ratio of 0.0 part by mass or less.
  • 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.
  • a water-soluble polymerization initiator such as potassium persulfate, sodium persulfate, ammonium persulfate, such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide.
  • 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, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, for example, 2.0 parts by mass or less, preferably 100 parts by mass for the monomer composition (a). And 1.0 parts by mass or less.
  • a reducing agent and a chain transfer agent can be added as necessary.
  • 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 preferable, and L-ascorbic acid and erythorbic acid are more preferable.
  • a reducing agent is 0.1 mass part or more with respect to 100 mass parts of polymerization initiators, Preferably, it is 0.3 mass parts or more, for example, 400 mass parts or less, Preferably, it is a ratio of 350 mass parts or less. Added.
  • 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 include ethylhexyl thioglycolate and ⁇ -methylstyrene dimer.
  • halogenated carbons such as dichloromethane, dibromomethane, carbon tetrabromide
  • Hydrogen compounds such as ⁇ -benzyloxystyrene, ⁇ -benzyloxyacrylonitrile, ⁇ -benzyloxyacrylamide, and other vinyl ethers
  • chain transfer agents can be used alone (only one kind) or in combination of two or more kinds.
  • alkyl mercaptans are preferable, and n-octyl mercaptan and t-dodecyl mercaptan are more preferable.
  • the chain transfer agent is, for example, 0 parts by mass or more, preferably 0.05 parts by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass with respect to 100 parts by mass of the monomer composition (a). It is added in the following ratio.
  • hydrocarbons can be added.
  • hydrocarbons examples include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methylcyclohexene and the like.
  • aromatic hydrocarbons such as benzene, toluene and xylene.
  • Preferred hydrocarbons include cyclohexene and toluene.
  • the hydrocarbon is cyclohexene or toluene, it can be recovered and reused by steam distillation after completion of polymerization at a low boiling point, which is preferable from the viewpoint of environmental load.
  • electrolytes such as sodium hydroxide and sodium carbonate, polymerization accelerators, chelating agents, and the like can be added as necessary.
  • the monomer composition (a) has a polymerization conversion rate (measured by the method described in Examples described later), for example, 30% or more, for example, less than 60%, preferably less than 50%. More preferably, the emulsion polymerization is carried out so as to be less than 45%.
  • the monomer composition (a) when the polymerization conversion rate of the monomer composition (a) falls within the above range, the monomer composition (a) is described above.
  • a monomer composition (b) (second monomer composition) containing an aliphatic conjugated diene monomer, the above-mentioned vinylpyridine monomer, and the above-mentioned other monomer, Subsequently, emulsion polymerization is performed.
  • the monomer composition (b) is added when the polymerization conversion rate of the monomer composition (a) is less than the above range (that is, less than 30%), the monomer composition is increased before the polymerization rate is increased. Since the product (b) is added, it is possible to shorten the polymerization time (the time from when the polymerization initiator is added to start the polymerization until the polymerization conversion becomes a value described later. The same applies hereinafter). It can be difficult.
  • the monomer composition (b) is added when the polymerization conversion rate of the monomer composition (a) exceeds the above range (that is, 60% or more), the monomer composition is reduced after the polymerization rate is reduced. Since (b) is added, it may be difficult to shorten the polymerization time.
  • the monomer composition (b) is an aliphatic conjugated diene monomer, for example, 35% by mass or more, preferably 40% by mass or more, for example, 75% by mass or less, preferably 70% by mass or less.
  • Vinyl pyridine monomer for example, 5% by mass or more, preferably 10% by mass or more, for example, 25% by mass or less, preferably 20% by mass or less, and the remainder can be copolymerized with these.
  • 0% by mass or more preferably 10% by mass or more, for example, 60% by mass or less, and preferably 55% by mass or less.
  • the blending ratio of the aliphatic conjugated diene monomer is less than 35% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. On the other hand, when the blending ratio of the aliphatic conjugated diene monomer exceeds 75% by mass, the processing cord strength and the heat-resistant adhesive strength may decrease.
  • the blending ratio of the vinylpyridine monomer is less than 5% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. Moreover, when the mixture ratio of a vinyl pyridine-type monomer exceeds 25 mass%, an initial stage adhesive force may fall.
  • the initial adhesive strength and heat resistant adhesive strength may be reduced.
  • the ratio of the monomer composition (b) to the total amount of the monomer composition (a) and the monomer composition (b) is, for example, 30% by mass or more, preferably 35% by mass or more, For example, it is 70 mass% or less, preferably 65 mass% or less.
  • the productivity of the copolymer latex for adhesive can be improved.
  • the above-described chain transfer agent can be added as necessary.
  • the chain transfer agent is, for example, 0 parts by mass or more, preferably 0.05 parts by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass with respect to 100 parts by mass of the monomer composition (b). It is added in the following ratio.
  • the mixture of the monomer composition (a) and the monomer composition (b) is emulsion-polymerized so that the polymerization conversion rate is, for example, 90% or more.
  • a polymerization inhibitor such as hydroquinone is added to stop the polymerization reaction, and unreacted monomers are removed by a method such as distillation under reduced pressure.
  • the copolymer latex for adhesive of the present invention is prepared.
  • the monomer composition (a) when the polymerization conversion rate of the monomer composition (a) is 30% or more and less than 60%, the monomer composition (a) is The monomer composition (b) is added.
  • the polymerization time can be shortened.
  • the obtained copolymer latex for adhesive 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
  • the rubber reinforcing fiber examples include nylon fiber, polyester fiber, aramid fiber, and glass fiber. 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 mass (solid content) of the adhesive copolymer latex.
  • Formalin resin is blended, for example, 5 parts by mass or more, for example, 100 parts by mass or less, preferably 90 parts by mass or less.
  • 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 a mixture of resorcin-formalin condensate, etc. 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, 100 ° C. or higher, preferably 110 ° C. or higher, such as 150 ° C. or lower, preferably 130 ° C. or lower, for example, 80 seconds or longer, preferably 100 seconds or longer, for example 200 seconds or shorter, preferably 150 seconds or less, and then dried, for example, 180 ° C. or higher, preferably 200 ° C. or higher, such as 300 ° C. or lower, preferably 260 ° C. or lower, such as 30 seconds or longer, preferably 50 seconds or longer. For example, baking is performed by heating for 100 seconds or less, preferably 80 seconds or less.
  • Example 4 In an autoclave equipped with a stirrer, 100 parts of water, 1 part of a sodium naphthalenesulfonate / formalin condensate, 0.1 part of sodium hydroxide and 4.0 parts of potassium rosinate were added and dissolved.
  • the obtained film was put into an aluminum pan of a differential scanning calorimeter (DSC) and cooled to ⁇ 100 ° C. at 10 ° C./min.
  • DSC differential scanning calorimeter
  • 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 Tables 1 and 2.
  • the method for producing a copolymer latex for adhesive according to the present invention is used, for example, for producing a copolymer latex for adhesive to be blended in an adhesive composition for adhering rubber and rubber reinforcing fibers. It is done.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

This method for producing a copolymer latex for adhesives comprises: a step for subjecting a monomer composition (a) to emulsion polymerization, said monomer composition (a) containing from 35% by mass to 75% by mass (inclusive) of an aliphatic conjugated diene monomer, from 5% by mass to 25% by mass (inclusive) of a vinyl pyridine monomer and from 0% by mass to 60% by mass (inclusive) of another monomer that is copolymerizable with the aliphatic conjugated diene monomer and the vinyl pyridine monomer; and a step for adding a monomer composition (b) to the monomer composition (a) and subjecting the resulting mixture to emulsion polymerization when the polymer conversion rate of the monomer composition (a) is 30% or more but less than 60%, said monomer composition (b) containing from 35% by mass to 75% by mass (inclusive) of an aliphatic conjugated diene monomer, from 5% by mass to 25% by mass (inclusive) of a vinyl pyridine monomer and from 0% by mass to 60% by mass (inclusive) of another monomer that is copolymerizable with the aliphatic conjugated diene monomer and the vinyl pyridine monomer.

Description

接着剤用共重合体ラテックスの製造方法Method for producing copolymer latex for adhesive
　本発明は、接着剤用共重合体ラテックスの製造方法、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の製造方法に関する。 The present invention relates to a method for producing a copolymer latex for adhesive, and more particularly to a method for producing 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、ガラスなどの繊維が用いられている。 Conventionally, fibers such as nylon, polyester, aramid and glass 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.
　このようなＲＦＬに含有される接着剤用共重合体ラテックスとして、例えば、共役ジエン系単量体、エチレン系不飽和酸単量体、ビニルピリジン、および、これらと共重合可能な他の単量体を、まず、全単量体の２．５～６０質量％にあたる単量体（エチレン系不飽和酸および共役ジエン系単量体を含む）を、重合転化率が少なくとも６０％に達するまで重合し、次いで、残りの単量体を重合することにより得られ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１参照。）。 Examples of the copolymer latex for adhesive contained in the RFL include, for example, a conjugated diene monomer, an ethylenically unsaturated acid monomer, vinyl pyridine, and other monomers copolymerizable therewith. First, monomers (including ethylenically unsaturated acid and conjugated diene monomer) corresponding to 2.5 to 60% by mass of all monomers are polymerized until the polymerization conversion rate reaches at least 60%. Then, a copolymer latex obtained by polymerizing the remaining monomers has been proposed (see, for example, Patent Document 1 below).
特公平６－９９４８７号公報Japanese Patent Publication No. 6-99487
　しかるに、上記した特許文献１に記載のラテックスでは、２段目の単量体（上記特許文献１における残りの単量体）を、１段目の単量体の重合転化率が６０％以上となってから、重合させている。 However, in the latex described in Patent Document 1, the second-stage monomer (the remaining monomers in Patent Document 1) has a polymerization conversion rate of 60% or more of the first-stage monomer. Since then, it is polymerized.
　そのため、１段目の単量体の重合時間を短縮することが困難であり、ラテックスの生産性を向上させることが困難である。 Therefore, it is difficult to shorten the polymerization time of the first-stage monomer, and it is difficult to improve latex productivity.
　そこで、本発明の目的は、接着剤用共重合体ラテックスのゴム補強用繊維に対する接着力を確保することができながら、接着剤用共重合体ラテックスの生産性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の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide an adhesive that can improve the productivity of the copolymer latex for an adhesive while ensuring the adhesive force of the copolymer latex for an adhesive to a rubber reinforcing fiber. Another object of the present invention is to provide a method for producing a copolymer latex.
　本発明の接着剤用共重合体ラテックスの製造方法は、脂肪族共役ジエン系単量体３５質量％以上７５質量％以下、ビニルピリジン系単量体５質量％以上２５質量％以下、および、これらと共重合可能な他の単量体０質量％以上６０質量％以下を含む単量体組成物（ａ）を乳化重合する工程と、単量体組成物（ａ）の重合転化率が３０％以上６０％未満となったときに、単量体組成物（ａ）に、脂肪族共役ジエン系単量体３５質量％以上７５質量％以下、ビニルピリジン系単量体５質量％以上２５質量％以下、および、これらと共重合可能な他の単量体０質量％以上６０質量％以下を含む単量体組成物（ｂ）を添加し、乳化重合する工程とを含むことを特徴としている。 The method for producing the copolymer latex for adhesive according to the present invention includes 35% by mass to 75% by mass of an aliphatic conjugated diene monomer, 5% by mass to 25% by mass of a vinylpyridine monomer, and these Emulsion polymerization of the monomer composition (a) containing 0% by mass or more and 60% by mass or less of another monomer copolymerizable with the monomer, and the polymerization conversion rate of the monomer composition (a) is 30% When the amount is less than 60%, the monomer composition (a) has an aliphatic conjugated diene monomer of 35% by mass to 75% by mass, and a vinylpyridine monomer of 5% by mass to 25% by mass. And a step of emulsion polymerization by adding a monomer composition (b) containing 0% by mass or more and 60% by mass or less of another monomer copolymerizable therewith.
　また、本発明の接着剤用共重合体ラテックスの製造方法は、前記単量体組成物（ａ）は、前記単量体組成物（ａ）と前記単量体組成物（ｂ）との総量に対して、３０質量％以上７０質量％以下であり、前記単量体組成物（ｂ）は、前記単量体組成物（ａ）と前記単量体組成物（ｂ）との総量に対して、３０質量％以上７０質量％以下であることが好適である。 In the method for producing a copolymer latex for an adhesive according to the present invention, the monomer composition (a) is a total amount of the monomer composition (a) and the monomer composition (b). Is 30 mass% or more and 70 mass% or less, and the monomer composition (b) is based on the total amount of the monomer composition (a) and the monomer composition (b). The content is preferably 30% by mass or more and 70% by mass or less.
　また、本発明の接着剤用共重合体ラテックスの製造方法は、前記単量体組成物（ｂ）中の脂肪族共役ジエン系単量体の質量％に対する、前記単量体組成物（ａ）中の脂肪族共役ジエン系単量体の質量％の比率は、０．８以上１．２５以下であり、前記単量体組成物（ｂ）中のビニルピリジン系単量体の質量％に対する、前記単量体組成物（ａ）中のビニルピリジン系単量体の質量％の比率は、０．８以上１．２５以下であることが好適である。 The method for producing a copolymer latex for an adhesive according to the present invention includes the monomer composition (a) based on the mass% of the aliphatic conjugated diene monomer in the monomer composition (b). The ratio of the mass% of the aliphatic conjugated diene monomer in the composition is 0.8 or more and 1.25 or less, and is based on the mass% of the vinylpyridine monomer in the monomer composition (b). The ratio by mass of the vinylpyridine monomer in the monomer composition (a) is preferably 0.8 or more and 1.25 or less.
　本発明の接着剤用共重合体ラテックスの製造方法によれば、まず、単量体組成物（ａ）を乳化重合し、単量体組成物（ａ）の重合転化率が３０％以上６０％未満となったときに、その単量体組成物（ａ）に単量体組成物（ｂ）を添加して、さらに乳化重合している。 According to the method for producing an adhesive copolymer latex of the present invention, first, the monomer composition (a) is emulsion-polymerized, and the polymerization conversion rate of the monomer composition (a) is 30% or more and 60%. When the ratio is less than 1, the monomer composition (b) is added to the monomer composition (a), and emulsion polymerization is further performed.
　そのため、少なくとも、単量体組成物（ａ）を乳化重合する工程において、重合時間を短縮することができる。 Therefore, at least in the step of emulsion polymerization of the monomer composition (a), the polymerization time can be shortened.
　その結果、接着剤用共重合体ラテックスのゴム補強用繊維に対する接着力を確保することができながら、接着剤用共重合体ラテックスの生産性を向上させることができる。 As a result, it is possible to improve the productivity of the adhesive copolymer latex while ensuring the adhesive force of the adhesive copolymer latex to the rubber reinforcing fiber.
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の製造方法では、まず、脂肪族共役ジエン系単量体、ビニルピリジン系単量体、および、これらと共重合可能な他の単量体を含む単量体組成物（ａ）（第１単量体組成物）を乳化重合する。 In the method for producing a copolymer latex for an adhesive according to the present invention, first, a monomer comprising an aliphatic conjugated diene monomer, a vinylpyridine monomer, and another monomer copolymerizable therewith. The body composition (a) (first monomer composition) is subjected to emulsion polymerization.
　脂肪族共役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、２－クロル－１，３－ブタジエンなどのブタジエン系単量体などが挙げられる。 Examples of the aliphatic conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3-butadiene. And butadiene monomer.
　これらの脂肪族共役ジエン系単量体のうち、好ましくは、ブタジエン系単量体が挙げられ、より好ましくは、１，３－ブタジエンが挙げられる。 Of these aliphatic conjugated diene monomers, butadiene monomers are preferable, and 1,3-butadiene is more preferable.
　また、これらの脂肪族共役ジエン系単量体は、単独（１種類）のみで用いることもでき、２種以上併用することもできる。 Moreover, these aliphatic conjugated diene monomers can be used alone (one kind) or in combination of two or more kinds.
　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る。 Examples of the vinylpyridine monomer include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, and the like.
　これらのビニルピリジン系単量体のうち、好ましくは、２－ビニルピリジンが挙げられる。 Of these vinylpyridine monomers, 2-vinylpyridine is preferable.
　また、これらのビニルピリジン系単量体は、単独（１種類）のみで用いることもでき、２種以上併用することもできる。 Moreover, these vinylpyridine monomers can be used alone (one kind) or in combination of two or more kinds.
　上記した脂肪族共役ジエン系単量体およびビニルピリジン系単量体と共重合可能な他の単量体としては、例えば、芳香族ビニル単量体、シアン化ビニル単量体、エチレン系不飽和カルボン酸単量体、エチレン系不飽和カルボン酸アルキルエステル単量体、ヒドロキシアルキル基を含有する不飽和単量体、エチレン系不飽和カルボン酸アミド単量体などが挙げられる。 Examples of other monomers copolymerizable with the above aliphatic conjugated diene monomers and vinylpyridine monomers include, for example, aromatic vinyl monomers, vinyl cyanide monomers, and ethylenically unsaturated monomers. Examples thereof include carboxylic acid monomers, ethylenically unsaturated carboxylic acid alkyl ester monomers, unsaturated monomers containing a hydroxyalkyl group, and ethylenically unsaturated carboxylic acid amide monomers.
　芳香族ビニル単量体としては、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る。 Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and monochlorostyrene.
　シアン化ビニル単量体としては、例えば、アクリロニトリル、メタクリロニトリルなどが挙げられる。 Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.
　エチレン系不飽和カルボン酸単量体としては、例えば、アクリル酸、メタクリル酸、クロトン酸などのエチレン系不飽和モノカルボン酸単量体、例えば、マレイン酸、フマル酸、イタコン酸などのエチレン系不飽和ジカルボン酸単量体（またはその無水物）などが挙げられる。 Examples of the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid, for example, ethylenically unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Saturated dicarboxylic acid monomer (or its anhydride) etc. are mentioned.
　エチレン系不飽和カルボン酸アルキルエステル単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレートなどが挙げられる。 Examples of the ethylenically unsaturated carboxylic acid alkyl ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
　ヒドロキシアルキル基を含有する不飽和単量体としては、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が挙げられる。 Examples of the unsaturated monomer containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate and the like.
　エチレン系不飽和カルボン酸アミド単量体としては、例えば、アクリルアミド、メタクリルアミドなどが挙げられる。 Examples of the ethylenically unsaturated carboxylic acid amide monomer include acrylamide and methacrylamide.
　また、他の単量体として、上記した単量体の他に、エチレン、プロピレン、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデンなど、通常の乳化重合において使用される単量体が挙げられる。 In addition to the above-mentioned monomers, other monomers used in normal emulsion polymerization such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, and vinylidene chloride can be cited as other monomers. .
　これらの他の単量体は、単独（１種類）のみで用いることもでき、２種以上併用することもできる。 These other monomers can be used alone (one kind) or in combination of two or more kinds.
　また、これらの他の単量体のうち、単独（１種類）のみで用いる場合には、好ましくは、芳香族ビニル単量体、より好ましくは、スチレンが挙げられる。 Of these other monomers, when used alone (one kind), an aromatic vinyl monomer is preferable, and styrene is more preferable.
　また、これらの他の単量体のうち、２種以上併用する場合には、好ましくは、芳香族ビニル単量体同士の組み合わせ、芳香族ビニル単量体とシアン化ビニル単量体との組み合わせ、芳香族ビニル単量体とエチレン系不飽和カルボン酸単量体との組み合わせ、芳香族ビニル単量体とエチレン系不飽和カルボン酸アルキルエステル単量体との組み合わせが挙げられ、より好ましくは、スチレンとα－メチルスチレンとの組み合わせ、スチレンとアクリロニトリルとの組み合わせ、スチレンとアクリル酸との組み合わせ、スチレンとイタコン酸との組み合わせ、スチレンとメチルメタクリレートとの組み合わせが挙げられる。 In addition, when two or more of these other monomers are used in combination, preferably a combination of aromatic vinyl monomers, a combination of an aromatic vinyl monomer and a vinyl cyanide monomer , A combination of an aromatic vinyl monomer and an ethylenically unsaturated carboxylic acid monomer, a combination of an aromatic vinyl monomer and an ethylenically unsaturated carboxylic acid alkyl ester monomer, and more preferably, A combination of styrene and α-methylstyrene, a combination of styrene and acrylonitrile, a combination of styrene and acrylic acid, a combination of styrene and itaconic acid, or a combination of styrene and methyl methacrylate.
　単量体組成物（ａ）は、脂肪族共役ジエン系単量体を、例えば、３５質量％以上、好ましくは、４０質量％以上、例えば、７５質量％以下、好ましくは、７０質量％以下と、ビニルピリジン系単量体を、例えば、５質量％以上、好ましくは、１０質量％以上、例えば、２５質量％以下、好ましくは、２０質量％以下と、残部として、これらと共重合可能な他の単量体を、例えば、０質量％以上、好ましくは、１０質量％以上、例えば、６０質量％以下、好ましくは、５５質量％以下とを含有している。 The monomer composition (a) is an aliphatic conjugated diene monomer, for example, 35% by mass or more, preferably 40% by mass or more, for example, 75% by mass or less, preferably 70% by mass or less. , Vinyl pyridine monomer, for example, 5% by mass or more, preferably 10% by mass or more, for example, 25% by mass or less, preferably 20% by mass or less, and the remainder can be copolymerized with these. For example, 0% by mass or more, preferably 10% by mass or more, for example, 60% by mass or less, and preferably 55% by mass or less.
　脂肪族共役ジエン系単量体の配合割合が３５質量％未満であると、初期接着力、耐熱接着力が低下する場合がある。また、脂肪族共役ジエン系単量体の配合割合が７５質量％を超えると、処理コード強度および耐熱接着力が低下する場合がある。 If the blending ratio of the aliphatic conjugated diene monomer is less than 35% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. On the other hand, when the blending ratio of the aliphatic conjugated diene monomer exceeds 75% by mass, the processing cord strength and the heat-resistant adhesive strength may decrease.
　ビニルピリジン系単量体の配合割合が５質量％未満であると、初期接着力および耐熱接着力が低下する場合がある。また、ビニルピリジン系単量体の配合割合が２５質量％を超えると、初期接着力が低下する場合がある。 When the blending ratio of the vinylpyridine monomer is less than 5% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. Moreover, when the mixture ratio of a vinyl pyridine-type monomer exceeds 25 mass%, an initial stage adhesive force may fall.
　他の単量体の配合割合が、６０質量％を超えると、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 blending ratio of other monomers exceeds 60% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced.
　また、単量体組成物（ａ）と単量体組成物（ｂ）（後述）との総量に対する単量体組成物（ａ）の割合は、例えば、３０質量％以上、好ましくは、３５質量％以上、例えば、７０質量％以下、好ましくは、６５質量％以下である。 The ratio of the monomer composition (a) to the total amount of the monomer composition (a) and the monomer composition (b) (described later) is, for example, 30% by mass or more, preferably 35% by mass. % Or more, for example, 70% by mass or less, preferably 65% by mass or less.
　単量体組成物（ａ）の割合が上記範囲内であると、接着剤用共重合体ラテックスの生産性を向上させることができる。 When the proportion of the monomer composition (a) is within the above range, the productivity of the copolymer latex for adhesive can be improved.
　また、単量体組成物（ｂ）（後述）中の脂肪族共役ジエン系単量体の質量％に対する単量体組成物（ａ）中の脂肪族共役ジエン系単量体の質量％の比率は、例えば、０．８以上、好ましくは、０．９以上、例えば、１．２５以下、好ましくは、１．１以下である。 Further, the ratio of the mass% of the aliphatic conjugated diene monomer in the monomer composition (a) to the mass% of the aliphatic conjugated diene monomer in the monomer composition (b) (described later). Is, for example, 0.8 or more, preferably 0.9 or more, for example, 1.25 or less, preferably 1.1 or less.
　脂肪族共役ジエン系単量体の比率が上記範囲内であると、接着剤用共重合体ラテックスの生産性を向上させることができるとともに、初期接着力を向上させることができる。 When the ratio of the aliphatic conjugated diene monomer is within the above range, the productivity of the copolymer latex for adhesive can be improved and the initial adhesive force can be improved.
　また、単量体組成物（ｂ）（後述）中のビニルピリジン系単量体の質量％に対する単量体組成物（ａ）中のビニルピリジン系単量体の質量％の比率は、例えば、０．８以上、好ましくは、０．９以上、例えば、１．２５以下、好ましくは、１．１以下である。 The ratio of the mass% of the vinylpyridine monomer in the monomer composition (a) to the mass% of the vinylpyridine monomer in the monomer composition (b) (described later) is, for example, 0.8 or more, preferably 0.9 or more, for example, 1.25 or less, preferably 1.1 or less.
　ビニルピリジン系単量体の比率が上記範囲内であると、接着剤用共重合体ラテックスの生産性を向上させることができるとともに、初期接着力を向上させることができる。 When the ratio of the vinylpyridine monomer is within the above range, the productivity of the copolymer latex for adhesive can be improved and the initial adhesive force can be improved.
　そして、単量体組成物（ａ）を乳化重合するには、単量体組成物（ａ）に乳化剤および重合開始剤を添加する。 In order to emulsion polymerize the monomer composition (a), an emulsifier and a polymerization initiator are added to the monomer composition (a).
　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、ロジン酸石鹸、脂肪酸石鹸、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 soap, fatty acid soap, sulfate ester salt of higher alcohol, alkylbenzene sulfonate, Examples include anionic surfactants such as alkyl diphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfate esters of nonionic surfactants, and formalin condensates of naphthalene sulfonate.
　これらの乳化剤は、単独（１種類）のみで用いることもでき、２種以上併用することもできる。 These emulsifiers can be used alone (one kind) or in combination of two or more kinds.
　また、これらの乳化剤のうち、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、ロジン酸石鹸、脂肪酸石鹸、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。 Of these emulsifiers, anionic surfactants are preferable, and rosin acid soaps, fatty acid soaps, and formalin condensates of naphthalene sulfonates are more preferable.
　乳化剤は、単量体組成物（ａ）１００質量部に対して、例えば、０．５質量部以上、好ましくは、２．０質量部以上、例えば、１０．０質量部以下、好ましくは、８．０質量部以下の割合で添加される。 The emulsifier is, for example, 0.5 parts by mass or more, preferably 2.0 parts by mass or more, for example, 10.0 parts by mass or less, preferably 8 parts by mass with respect to 100 parts by mass of the monomer composition (a). It is added at a ratio of 0.0 part by mass or less.
　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。 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.
　これらの重合開始剤のうち、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。 Of these polymerization initiators, 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、単量体組成物（ａ）１００質量部に対して、例えば、０．０５質量部以上、好ましくは、０．１質量部以上、例えば、２．０質量部以下、好ましくは、１．０質量部以下の割合で添加される。 The polymerization initiator is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, for example, 2.0 parts by mass or less, preferably 100 parts by mass for the monomer composition (a). And 1.0 parts by mass or less.
　また、単量体組成物（ａ）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。 In addition, in order to emulsion-polymerize the monomer composition (a), 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。 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.
　これらの還元剤のうち、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。 Of these reducing agents, carboxylic acids and salts thereof are preferable, and L-ascorbic acid and erythorbic acid are more preferable.
　還元剤は、重合開始剤１００質量部に対して、例えば、０．１質量部以上、好ましくは、０．３質量部以上、例えば、４００質量部以下、好ましくは、３５０質量部以下の割合で添加される。 A reducing agent is 0.1 mass part or more with respect to 100 mass parts of polymerization initiators, Preferably, it is 0.3 mass parts or more, for example, 400 mass parts or less, Preferably, it is a ratio of 350 mass parts or less. Added.
　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 include ethylhexyl thioglycolate and α-methylstyrene dimer.
　これらの連鎖移動剤は、単独（１種類のみ）で用いることもでき、２種以上併用することもできる。 These chain transfer agents can be used alone (only one kind) or in combination of two or more kinds.
　これらの連鎖移動剤のうち、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。 Of these chain transfer agents, alkyl mercaptans are preferable, and n-octyl mercaptan and t-dodecyl mercaptan are more preferable.
　連鎖移動剤は、単量体組成物（ａ）１００質量部に対して、例えば、０質量部以上、好ましくは、０．０５質量部以上、例えば、１０質量部以下、好ましくは、７質量部以下の割合で添加される。 The chain transfer agent is, for example, 0 parts by mass or more, preferably 0.05 parts by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass with respect to 100 parts by mass of the monomer composition (a). It is added in the following ratio.
　また、乳化重合において、必要により、炭化水素類を添加することができる。 In the emulsion polymerization, if necessary, hydrocarbons can be added.
　炭化水素類としては、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、例えば、ベンゼン、トルエン、キシレンなどの芳香族炭化水素などが挙げられる。 Examples of hydrocarbons include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methylcyclohexene and the like. For example, aromatic hydrocarbons such as benzene, toluene and xylene.
　炭化水素類としては、好ましくは、シクロヘキセン、トルエンが挙げられる。炭化水素類がシクロへキセンまたはトルエンであると、低沸点で重合終了後に水蒸気蒸留などによって回収、再利用することができ、環境負荷の観点から好適である。 Preferred hydrocarbons include cyclohexene and toluene. When the hydrocarbon is cyclohexene or toluene, it can be recovered and reused by steam distillation after completion of polymerization at a low boiling point, which is preferable from the viewpoint of environmental load.
　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、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 accelerators, chelating agents, and the like can be added as necessary.
　そして、単量体組成物（ａ）を、その重合転化率（後述する実施例に記載の方法により測定する。）が、例えば、３０％以上、例えば、６０％未満、好ましくは、５０％未満、より好ましくは、４５％未満となるように乳化重合する。 The monomer composition (a) has a polymerization conversion rate (measured by the method described in Examples described later), for example, 30% or more, for example, less than 60%, preferably less than 50%. More preferably, the emulsion polymerization is carried out so as to be less than 45%.
　次いで、本発明の接着剤用共重合体ラテックスの製造方法では、単量体組成物（ａ）の重合転化率が上記範囲となったときに、単量体組成物（ａ）に、上記した脂肪族共役ジエン系単量体、上記したビニルピリジン系単量体、および、上記した他の単量体を含む単量体組成物（ｂ）（第２単量体組成物）を添加し、引き続き乳化重合する。 Next, in the method for producing a copolymer latex for adhesive according to the present invention, when the polymerization conversion rate of the monomer composition (a) falls within the above range, the monomer composition (a) is described above. Add a monomer composition (b) (second monomer composition) containing an aliphatic conjugated diene monomer, the above-mentioned vinylpyridine monomer, and the above-mentioned other monomer, Subsequently, emulsion polymerization is performed.
　単量体組成物（ａ）の重合転化率が上記範囲未満（すなわち、３０％未満）であるときに単量体組成物（ｂ）を添加すると、重合速度が上昇する前に単量体組成物（ｂ）が添加されるため、重合時間（重合開始剤を加えて重合を開始してから、重合転化率が後述する値となるまでの時間。以下、同じ。）の短縮を図ることが困難な場合がある。 If the monomer composition (b) is added when the polymerization conversion rate of the monomer composition (a) is less than the above range (that is, less than 30%), the monomer composition is increased before the polymerization rate is increased. Since the product (b) is added, it is possible to shorten the polymerization time (the time from when the polymerization initiator is added to start the polymerization until the polymerization conversion becomes a value described later. The same applies hereinafter). It can be difficult.
　単量体組成物（ａ）の重合転化率が上記範囲を超過（すなわち、６０％以上）したときに単量体組成物（ｂ）を添加すると、重合速度が低下した後に単量体組成物（ｂ）が添加されるため、重合時間の短縮を図ることが困難な場合がある。 If the monomer composition (b) is added when the polymerization conversion rate of the monomer composition (a) exceeds the above range (that is, 60% or more), the monomer composition is reduced after the polymerization rate is reduced. Since (b) is added, it may be difficult to shorten the polymerization time.
　単量体組成物（ｂ）は、脂肪族共役ジエン系単量体を、例えば、３５質量％以上、好ましくは、４０質量％以上、例えば、７５質量％以下、好ましくは、７０質量％以下と、ビニルピリジン系単量体を、例えば、５質量％以上、好ましくは、１０質量％以上、例えば、２５質量％以下、好ましくは、２０質量％以下と、残部として、これらと共重合可能な他の単量体を、例えば、０質量％以上、好ましくは、１０質量％以上、例えば、６０質量％以下、好ましくは、５５質量％以下とを含有している。 The monomer composition (b) is an aliphatic conjugated diene monomer, for example, 35% by mass or more, preferably 40% by mass or more, for example, 75% by mass or less, preferably 70% by mass or less. , Vinyl pyridine monomer, for example, 5% by mass or more, preferably 10% by mass or more, for example, 25% by mass or less, preferably 20% by mass or less, and the remainder can be copolymerized with these. For example, 0% by mass or more, preferably 10% by mass or more, for example, 60% by mass or less, and preferably 55% by mass or less.
　脂肪族共役ジエン系単量体の配合割合が３５質量％未満であると、初期接着力、耐熱接着力が低下する場合がある。また、脂肪族共役ジエン系単量体の配合割合が７５質量％を超えると、処理コード強度および耐熱接着力が低下する場合がある。 If the blending ratio of the aliphatic conjugated diene monomer is less than 35% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. On the other hand, when the blending ratio of the aliphatic conjugated diene monomer exceeds 75% by mass, the processing cord strength and the heat-resistant adhesive strength may decrease.
　ビニルピリジン系単量体の配合割合が５質量％未満であると、初期接着力および耐熱接着力が低下する場合がある。また、ビニルピリジン系単量体の配合割合が２５質量％を超えると、初期接着力が低下する場合がある。 When the blending ratio of the vinylpyridine monomer is less than 5% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced. Moreover, when the mixture ratio of a vinyl pyridine-type monomer exceeds 25 mass%, an initial stage adhesive force may fall.
　他の単量体の配合割合が、６０質量％を超えると、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 blending ratio of other monomers exceeds 60% by mass, the initial adhesive strength and heat resistant adhesive strength may be reduced.
　また、単量体組成物（ａ）と単量体組成物（ｂ）との総量に対する単量体組成物（ｂ）の割合は、例えば、３０質量％以上、好ましくは、３５質量％以上、例えば、７０質量％以下、好ましくは、６５質量％以下である。 Further, the ratio of the monomer composition (b) to the total amount of the monomer composition (a) and the monomer composition (b) is, for example, 30% by mass or more, preferably 35% by mass or more, For example, it is 70 mass% or less, preferably 65 mass% or less.
　単量体組成物（ｂ）の割合が上記範囲内であると、接着剤用共重合体ラテックスの生産性を向上させることができる。 When the ratio of the monomer composition (b) is within the above range, the productivity of the copolymer latex for adhesive can be improved.
　また、単量体組成物（ｂ）を乳化重合するには、必要により、上記した連鎖移動剤を添加することができる。 Further, in order to emulsion polymerize the monomer composition (b), the above-described chain transfer agent can be added as necessary.
　連鎖移動剤は、単量体組成物（ｂ）１００質量部に対して、例えば、０質量部以上、好ましくは、０．０５質量部以上、例えば、１０質量部以下、好ましくは、７質量部以下の割合で添加される。 The chain transfer agent is, for example, 0 parts by mass or more, preferably 0.05 parts by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass with respect to 100 parts by mass of the monomer composition (b). It is added in the following ratio.
　そして、単量体組成物（ａ）および単量体組成物（ｂ）の混合物を、その重合転化率が、例えば、９０％以上となるように乳化重合する。 Then, the mixture of the monomer composition (a) and the monomer composition (b) is emulsion-polymerized so that the polymerization conversion rate is, for example, 90% or more.
　その後、例えば、ハイドロキノンなどの重合禁止剤を添加して重合反応を停止させて、例えば、減圧蒸留などの方法により未反応の単量体を除去する。 Thereafter, a polymerization inhibitor such as hydroquinone is added to stop the polymerization reaction, and unreacted monomers are removed by a method such as distillation under reduced pressure.
　これにより、本発明の接着剤用共重合体ラテックスが調製される。 Thereby, the copolymer latex for adhesive of the present invention is prepared.
　この接着剤用共重合体ラテックスの製造方法によれば、単量体組成物（ａ）の重合転化率が３０％以上６０％未満となったときに、単量体組成物（ａ）に単量体組成物（ｂ）を添加している。 According to this method for producing an adhesive copolymer latex, when the polymerization conversion rate of the monomer composition (a) is 30% or more and less than 60%, the monomer composition (a) is The monomer composition (b) is added.
　そのため、少なくとも、単量体組成物（ａ）を乳化重合する工程において、重合時間を短縮することができる。 Therefore, at least in the step of emulsion polymerization of the monomer composition (a), the polymerization time can be shortened.
　その結果、接着剤用共重合体ラテックスのゴム補強用繊維に対する接着力を確保することができながら、接着剤用共重合体ラテックスの生産性を向上させることができる。 As a result, it is possible to improve the productivity of the adhesive copolymer latex while ensuring the adhesive force of the adhesive copolymer latex to the rubber reinforcing fiber.
　そして、得られた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。 Then, the obtained copolymer latex for adhesive 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、ガラス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 the rubber reinforcing fiber include nylon fiber, polyester fiber, aramid fiber, and glass fiber. 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質量部（固形分）に対して、レゾルシン－ホルマリン樹脂を、例えば、５質量部以上、例えば、１００質量部以下、好ましくは、９０質量部以下、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 mass (solid content) of the adhesive copolymer latex. Formalin resin is blended, for example, 5 parts by mass or more, for example, 100 parts by mass or less, preferably 90 parts by mass or less.
　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 a mixture of resorcin-formalin condensate, etc. 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℃以上、好ましくは、１１０℃以上、例えば、１５０℃以下、好ましくは、１３０℃以下で、例えば、８０秒以上、好ましくは、１００秒以上、例えば、２００秒以下、好ましくは、１５０秒以下、乾燥させ、その後、例えば、１８０℃以上、好ましくは、２００℃以上、例えば、３００℃以下、好ましくは、２６０℃以下で、例えば、３０秒以上、好ましくは、５０秒以上、例えば、１００秒以下、好ましくは、８０秒以下、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, 100 ° C. or higher, preferably 110 ° C. or higher, such as 150 ° C. or lower, preferably 130 ° C. or lower, for example, 80 seconds or longer, preferably 100 seconds or longer, for example 200 seconds or shorter, preferably 150 seconds or less, and then dried, for example, 180 ° C. or higher, preferably 200 ° C. or higher, such as 300 ° C. or lower, preferably 260 ° C. or lower, such as 30 seconds or longer, preferably 50 seconds or longer. For example, baking is performed by heating for 100 seconds or less, preferably 80 seconds or less.
　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.
　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％は質量基準によるものである。
１．共重合体ラテックスの合成
（１）実施例１
　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０．１部およびロジン酸カリウム５．０部を加え溶解させた。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the examples, parts and% indicating the blending ratio are based on mass.
1. Synthesis of copolymer latex (1) Example 1
In an autoclave equipped with a stirrer, 130 parts of water, 1 part of sodium naphthalene sulfonate / formalin condensate, 0.1 part of sodium hydroxide and 5.0 parts of potassium rosinate were added and dissolved.
　次いで、表１に示す単量体組成物（ａ）とｔ－ドデシルメルカプタン０．３部を加えて乳化させた。 Subsequently, the monomer composition (a) shown in Table 1 and 0.3 part of t-dodecyl mercaptan were added and emulsified.
　次いで、過硫酸カリウム０．５部を加え、内温を６０℃に保ち、単量体組成物（ａ）を重合した。 Next, 0.5 part of potassium persulfate was added, the internal temperature was kept at 60 ° C., and the monomer composition (a) was polymerized.
　単量体組成物（ａ）の重合転化率が表１に示す重合転化率に達した時点で、表１に示す単量体組成物（ｂ）とｔ－ドデシルメルカプタン０．３５部を添加して、引き続き重合した。 When the polymerization conversion rate of the monomer composition (a) reached the polymerization conversion rate shown in Table 1, the monomer composition (b) shown in Table 1 and 0.35 parts of t-dodecyl mercaptan were added. The polymerization continued.
　重合転化率が９３％に達した時点で、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の単量体を除去して、共重合体ラテックスを得た。過硫酸カリウムを加えてからハイドロキノンを加えるまでの時間（重合時間）を表１に示す。
（２）実施例２、３
　表１に示す単量体組成物（ａ）を表１に示す重合転化率に達するまで重合させた後、表１に示す単量体組成物（ｂ）を添加して、引き続き重合した以外は、上記した実施例１と同様にして、共重合体ラテックスを得た。重合時間を表１に示す。
（３）実施例４
　攪拌機付きオートクレーブに、水１００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０．１部およびロジン酸カリウム４．０部を加え溶解させた。 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. Table 1 shows the time (polymerization time) from the addition of potassium persulfate to the addition of hydroquinone.
(2) Examples 2 and 3
After polymerizing the monomer composition (a) shown in Table 1 until the polymerization conversion rate shown in Table 1 was reached, the monomer composition (b) shown in Table 1 was added and the polymerization was continued. In the same manner as in Example 1 described above, a copolymer latex was obtained. The polymerization time is shown in Table 1.
(3) Example 4
In an autoclave equipped with a stirrer, 100 parts of water, 1 part of a sodium naphthalenesulfonate / formalin condensate, 0.1 part of sodium hydroxide and 4.0 parts of potassium rosinate were added and dissolved.
　次いで、表１に示す単量体組成物（ａ）とｔ－ドデシルメルカプタン０．２部を加えて乳化させた。 Next, the monomer composition (a) shown in Table 1 and 0.2 part of t-dodecyl mercaptan were added and emulsified.
　次いで、過硫酸カリウム０．５部を加え、内温を６０℃に保ち、単量体組成物（ａ）を重合した。 Next, 0.5 part of potassium persulfate was added, the internal temperature was kept at 60 ° C., and the monomer composition (a) was polymerized.
　単量体組成物（ａ）の重合転化率が表１に示す重合転化率に達した時点で、表１に示す単量体組成物（ｂ）とｔ－ドデシルメルカプタン０．３部を添加して、引き続き重合した。 When the polymerization conversion rate of the monomer composition (a) reaches the polymerization conversion rate shown in Table 1, the monomer composition (b) shown in Table 1 and 0.3 part of t-dodecyl mercaptan were added. The polymerization continued.
　重合転化率が９３％に達した時点で、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の単量体を除去して、共重合体ラテックスを得た。重合時間を表１に示す。
（４）比較例１
　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０．１部およびロジン酸カリウム５．０部を加え溶解させた。 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. The polymerization time is shown in Table 1.
(4) Comparative Example 1
In an autoclave equipped with a stirrer, 130 parts of water, 1 part of sodium naphthalene sulfonate / formalin condensate, 0.1 part of sodium hydroxide and 5.0 parts of potassium rosinate were added and dissolved.
　次いで、表２に示す単量体組成物（ａ）とｔ－ドデシルメルカプタン０．６部を加えて乳化させた。 Next, the monomer composition (a) shown in Table 2 and 0.6 part of t-dodecyl mercaptan were added and emulsified.
　次いで、過硫酸カリウム０．５部を加え、内温を５０℃に保ち、単量体組成物（ａ）を重合した。 Next, 0.5 part of potassium persulfate was added, the internal temperature was kept at 50 ° C., and the monomer composition (a) was polymerized.
　重合転化率が９３％に達した時点で、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の単量体を除去して、共重合体ラテックスを得た。重合時間を表２に示す。
（５）比較例２～５
　表２に示す単量体組成物（ａ）を表２に示す重合転化率に達するまで重合させた後、表２に示す単量体組成物（ｂ）を添加して、引き続き重合した以外は、上記した実施例１と同様にして、共重合体ラテックスを得た。重合時間を表２に示す。
２．共重合体ラテックスの物性評価
（１）重合転化率の測定方法
　重合中にサンプリングした共重合体ラテックス約２ｇを秤量し、この値を「乾燥前重量」とする。これを１５０℃で３０分乾燥して秤量し、この値を「乾燥後重量」とする。重合槽へ仕込む単量体以外の固形分部数をＳとし、Ｓと「重合水部数」と「単量体合計部数」との合計を「仕込み総部数」とし、下記の式（１）と式（２）を経て、式（３）によって、重合転化率が計算される。
式（１）　重合転化部数＝仕込み総部数×乾燥後重量／乾燥前重量－Ｓ
式（２）　単量体合計部数＝仕込み総部数－（重合水部数＋Ｓ）
式（３）　重合転化率＝重合転化部数／単量体合計部数×１００
（２）共重合体ラテックスの光子相関法による平均粒子径の測定
　共重合体ラテックスの光子相関法による平均粒子径を動的光散乱法により測定した。尚、測定に際しては、ＦＰＡＲ－１０００（大塚電子製）を使用した（ＪＩＳ　Ｚ８８２６）。結果を表１および表２に示す。
（３）ムーニー粘度
　各実施例および各比較例の共重合体ラテックスを乾燥して、得られた固形分（樹脂分）のムーニー粘度（ＭＬ１＋４、１００℃）を、ＪＩＳ　Ｋ６３００に従って測定した。結果を表１および表２に示す。
（４）ガラス転移温度
　各実施例および各比較例の共重合体ラテックス０．５ｇをガラス板に塗布し、７０℃で４時間乾燥してフィルムを作製した。 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. The polymerization time is shown in Table 2.
(5) Comparative Examples 2-5
After polymerizing the monomer composition (a) shown in Table 2 until the polymerization conversion rate shown in Table 2 was reached, the monomer composition (b) shown in Table 2 was added and subsequently polymerized. In the same manner as in Example 1 described above, a copolymer latex was obtained. The polymerization time is shown in Table 2.
2. Evaluation of Physical Properties of Copolymer Latex (1) Method for Measuring Polymerization Conversion Rate About 2 g of copolymer latex sampled during polymerization is weighed, and this value is defined as “weight before drying”. This is dried at 150 ° C. for 30 minutes and weighed, and this value is defined as “weight after drying”. The solid content part other than the monomer charged into the polymerization tank is S, and the total of S, the “polymerization water part” and the “total monomer part” is “total charge part”, and the following formula (1) and formula Through (2), the polymerization conversion is calculated by equation (3).
Formula (1) Number of polymerization conversion parts = total number of charged parts × weight after drying / weight before drying−S
Formula (2) Total number of monomers = total number of charged parts-(number of polymerization water parts + S)
Formula (3) Polymerization conversion rate = number of polymerization conversion parts / total number of monomers × 100
(2) Measurement of average particle diameter of copolymer latex by photon correlation method The average particle diameter of copolymer latex by the photon correlation method was measured by a dynamic light scattering method. In the measurement, FPAR-1000 (manufactured by Otsuka Electronics) was used (JIS Z8826). The results are shown in Tables 1 and 2.
(3) Mooney viscosity The copolymer latex of each Example and each Comparative Example was dried, and the Mooney viscosity (ML1 + 4, 100 ° C.) of the obtained solid content (resin content) was measured according to JIS K6300. The results are shown in Tables 1 and 2.
(4) Glass transition temperature 0.5 g of copolymer latex of each Example and each Comparative Example was applied to a glass plate and dried at 70 ° C. for 4 hours to prepare a film.
　得られたフィルムを、示差走査熱分析装置（ＤＳＣ）のアルミニウム製パンに投入し、１０℃／ｍｉｎで－１００℃まで冷却した。 The obtained film was put into an aluminum pan of a differential scanning calorimeter (DSC) and cooled to −100 ° C. at 10 ° C./min.
　次いで、－１００℃から１５０℃まで１０℃／ｍｉｎで昇温し、相変化の吸熱の開始点を読み取ってガラス転移温度（℃）とした。結果を表１および表２に示す。
３．接着剤組成物の調製
　水２３９部に水酸化ナトリウム０．３部を添加して攪拌した後、レゾルシン１１部、および、３７％ホルマリン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。 Next, the temperature was raised from −100 ° C. to 150 ° C. at 10 ° C./min, and the end point of the endothermic phase change was read to obtain the glass transition temperature (° C.). The results are shown in Tables 1 and 2.
3. Preparation of Adhesive Composition After adding 0.3 part of sodium hydroxide to 239 parts of water and stirring, add 11 parts of resorcin and 16.2 parts of 37% formalin and stir and mix at 25 ° C. After aging, resorcin-formalin resin was synthesized.
　次いで、各実施例および各比較例で得られた共重合体ラテックスに、共重合体ラテックスの固形分１００部に対して、得られたレゾルシン－ホルマリン樹脂を全量と、２８％アンモニア水１２．６部とを添加して攪拌した後、水を加えて、固形分濃度を２０質量％に調整し、２５℃で１８時間熟成させて、接着剤組成物を得た。
４．接着剤組成物の接着性評価
（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、得られた各接着剤組成物に、前処理されたナイロンタイヤコード（１２６０Ｄ／３）を浸漬し、１２０℃で１２０秒間乾燥した後、２００℃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
（２）初期接着力の測定
　各実施例および各比較例の接着剤組成物で処理されたナイロンタイヤコードをゴムではさみ、１４０℃で４５分の条件で加硫プレスした。 Next, in the copolymer latex obtained in each Example and each Comparative Example, the total amount of the obtained resorcin-formalin resin with respect to 100 parts of the solid content of the copolymer latex, 28% aqueous ammonia 12.6. Then, water was added to adjust the solid content concentration to 20% by mass and aged at 25 ° C. for 18 hours to obtain an adhesive composition.
4). Adhesive evaluation of adhesive composition (1) Tire cord dipping treatment A pretreated nylon tire cord (1260D / 3) was dipped in each obtained adhesive composition using a test single cord dipping machine. After drying at 120 ° C. for 120 seconds, baking was performed at 200 ° 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: Dibenzothiazyl disulfide (2) Measurement of initial adhesive strength Nylon tire cord treated with the adhesive composition of each example and each comparative example was sandwiched with rubber and vulcanized press at 140 ° C for 45 minutes did.
　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１および表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 Tables 1 and 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過ぎず、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。 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. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.
　本発明の接着剤用共重合体ラテックスの製造方法は、例えば、ゴムとゴム補強用繊維とを接着するための接着剤組成物に配合される接着剤用共重合体ラテックスを製造するために用いられる。 The method for producing a copolymer latex for adhesive according to the present invention is used, for example, for producing a copolymer latex for adhesive to be blended in an adhesive composition for adhering rubber and rubber reinforcing fibers. It is done.

Claims (3)

  1. 　脂肪族共役ジエン系単量体３５質量％以上７５質量％以下、ビニルピリジン系単量体５質量％以上２５質量％以下、および、これらと共重合可能な他の単量体０質量％以上６０質量％以下を含む単量体組成物（ａ）を乳化重合する工程と、
    　単量体組成物（ａ）の重合転化率が３０％以上６０％未満となったときに、単量体組成物（ａ）に、脂肪族共役ジエン系単量体３５質量％以上７５質量％以下、ビニルピリジン系単量体５質量％以上２５質量％以下、および、これらと共重合可能な他の単量体０質量％以上６０質量％以下を含む単量体組成物（ｂ）を添加して、乳化重合する工程と
    を含むことを特徴とする、接着剤用共重合体ラテックスの製造方法。     Aliphatic conjugated diene monomer 35% by mass to 75% by mass, vinylpyridine monomer 5% by mass to 25% by mass, and other monomers copolymerizable therewith 0% by mass or more 60% A step of emulsion polymerization of the monomer composition (a) containing at most mass%,
    When the polymerization conversion rate of the monomer composition (a) is 30% or more and less than 60%, the monomer composition (a) is added to 35% by mass to 75% by mass of the aliphatic conjugated diene monomer. Hereinafter, a monomer composition (b) containing 5% by mass to 25% by mass of a vinylpyridine monomer and 0% by mass to 60% by mass of another monomer copolymerizable therewith is added. And a step of emulsion polymerization. A method for producing a copolymer latex for an adhesive.
  2. 　前記単量体組成物（ａ）は、前記単量体組成物（ａ）と前記単量体組成物（ｂ）との総量に対して、３０質量％以上７０質量％以下であり、
    　前記単量体組成物（ｂ）は、前記単量体組成物（ａ）と前記単量体組成物（ｂ）との総量に対して、３０質量％以上７０質量％以下である
    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の製造方法。     The monomer composition (a) is 30% by mass or more and 70% by mass or less based on the total amount of the monomer composition (a) and the monomer composition (b).
    The monomer composition (b) is 30% by mass or more and 70% by mass or less based on the total amount of the monomer composition (a) and the monomer composition (b). The method for producing a copolymer latex for an adhesive according to claim 1.
  3. 　前記単量体組成物（ｂ）中の脂肪族共役ジエン系単量体の質量％に対する、前記単量体組成物（ａ）中の脂肪族共役ジエン系単量体の質量％の比率は、０．８以上１．２５以下であり、
    　前記単量体組成物（ｂ）中のビニルピリジン系単量体の質量％に対する、前記単量体組成物（ａ）中のビニルピリジン系単量体の質量％の比率は、０．８以上１．２５以下である
    ことを特徴とする、請求項１または２に記載の接着剤用共重合体ラテックスの製造方法。     The ratio of the mass% of the aliphatic conjugated diene monomer in the monomer composition (a) to the mass% of the aliphatic conjugated diene monomer in the monomer composition (b) is: 0.8 or more and 1.25 or less,
    The ratio of the mass% of the vinylpyridine monomer in the monomer composition (a) to the mass% of the vinylpyridine monomer in the monomer composition (b) is 0.8 or more. The method for producing a copolymer latex for an adhesive according to claim 1 or 2, wherein the content is 1.25 or less.
PCT/JP2013/079878 2012-11-06 2013-11-05 Method for producing copolymer latex for adhesives WO2014073525A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020157011212A KR102141789B1 (en) 2012-11-06 2013-11-05 Producing method of copolymer latex for adhesives
CN201380057723.9A CN104769066B (en) 2012-11-06 2013-11-05 The manufacture method of bonding agent copolymer emulsion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012244370A JP5715109B2 (en) 2012-11-06 2012-11-06 Method for producing copolymer latex for adhesive
JP2012-244370 2012-11-06

Publications (1)

Publication Number Publication Date
WO2014073525A1 true WO2014073525A1 (en) 2014-05-15

Family

ID=50684628

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/079878 WO2014073525A1 (en) 2012-11-06 2013-11-05 Method for producing copolymer latex for adhesives

Country Status (4)

Country Link
JP (1) JP5715109B2 (en)
KR (1) KR102141789B1 (en)
CN (1) CN104769066B (en)
WO (1) WO2014073525A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019049075A (en) * 2017-09-11 2019-03-28 東レ株式会社 Fiber cord for reinforcing rubber
JP2019049074A (en) * 2017-09-11 2019-03-28 東レ株式会社 Fiber cord for reinforcing rubber
CN111094648A (en) * 2017-09-11 2020-05-01 东丽株式会社 Fiber cord for rubber reinforcement
JP2019049076A (en) * 2017-09-11 2019-03-28 東レ株式会社 Fiber cord for rubber reinforcement
JP7304753B2 (en) * 2019-07-02 2023-07-07 日本エイアンドエル株式会社 Adhesive copolymer latex and adhesive composition
CN116515026A (en) * 2023-04-28 2023-08-01 金发科技股份有限公司 Polybutadiene latex and ABS resin and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0699487B2 (en) * 1986-03-31 1994-12-07 日本ゼオン株式会社 Method for producing copolymer latex
JPH11130912A (en) * 1997-08-29 1999-05-18 Sumika Abs Latex Kk Copolymer latex for rubber-to-fiber adhesive
JPH11263958A (en) * 1998-03-16 1999-09-28 Sumika Abs Latex Kk Copolymeric latex for adhesive used for adhering rubber to polyester fiber
JP2004204088A (en) * 2002-12-26 2004-07-22 Denki Kagaku Kogyo Kk Method for producing polychloroprene-based polymer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2576059B2 (en) * 1987-03-31 1997-01-29 日本合成ゴム株式会社 Method for producing copolymer latex
JP2845680B2 (en) 1992-09-21 1999-01-13 出光石油化学株式会社 Easy tearable laminate film and easy tearable bag using the same
JP4275205B2 (en) * 1997-07-09 2009-06-10 日本エイアンドエル株式会社 Copolymer latex for rubber and polyester fiber adhesives
WO2003089511A1 (en) * 2002-04-19 2003-10-30 Denki Kagaku Kogyo Kabushiki Kaisha Latex composition
JP5677942B2 (en) * 2009-04-28 2015-02-25 株式会社ブリヂストン Adhesive composition for organic fiber cord, rubber reinforcing material, tire and bonding method using the same
JP5481225B2 (en) * 2010-02-19 2014-04-23 日本エイアンドエル株式会社 Copolymer latex for adhesive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0699487B2 (en) * 1986-03-31 1994-12-07 日本ゼオン株式会社 Method for producing copolymer latex
JPH11130912A (en) * 1997-08-29 1999-05-18 Sumika Abs Latex Kk Copolymer latex for rubber-to-fiber adhesive
JPH11263958A (en) * 1998-03-16 1999-09-28 Sumika Abs Latex Kk Copolymeric latex for adhesive used for adhering rubber to polyester fiber
JP2004204088A (en) * 2002-12-26 2004-07-22 Denki Kagaku Kogyo Kk Method for producing polychloroprene-based polymer

Also Published As

Publication number Publication date
KR20150083086A (en) 2015-07-16
JP5715109B2 (en) 2015-05-07
CN104769066A (en) 2015-07-08
JP2014091801A (en) 2014-05-19
CN104769066B (en) 2017-06-13
KR102141789B1 (en) 2020-08-06

Similar Documents

Publication Publication Date Title
JP5715109B2 (en) Method for producing copolymer latex for adhesive
JP5481225B2 (en) Copolymer latex for adhesive
JP5671188B1 (en) Copolymer latex for adhesive and adhesive composition
JP2004204147A (en) Copolymer latex for adhesive between rubber and fiber
JP5681169B2 (en) Copolymer latex for adhesive
JP7304752B2 (en) Adhesive copolymer latex and adhesive composition
JP5238454B2 (en) Copolymer latex for rubber and polyester fiber adhesives
JP4578077B2 (en) Copolymer latex for rubber and fiber adhesives
JP5000887B2 (en) Copolymer latex for rubber and fiber adhesives
JP6113530B2 (en) Copolymer latex for adhesive and adhesive composition
JP7304753B2 (en) Adhesive copolymer latex and adhesive composition
KR102166231B1 (en) Copolymer latex for adhesive, and adhesive composition
JPH1192730A (en) Copolymer latex for adhesive for bonding rubber to polyester fiber
JP4578078B2 (en) Copolymer latex for rubber and fiber adhesives
JP5200279B2 (en) Method for producing copolymer latex for rubber and fiber adhesive
JP5602215B2 (en) Copolymer latex for adhesive of rubber and fiber and composition for adhesive
JPH1121414A (en) Copolymer latex for adhesive used for adhering rubber to fiber
JP2007186585A (en) Latex composition for adhesive for ethylene-propylene rubber and fiber

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13852748

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20157011212

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13852748

Country of ref document: EP

Kind code of ref document: A1