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.

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

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