WO2010055877A1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
WO2010055877A1
WO2010055877A1 PCT/JP2009/069265 JP2009069265W WO2010055877A1 WO 2010055877 A1 WO2010055877 A1 WO 2010055877A1 JP 2009069265 W JP2009069265 W JP 2009069265W WO 2010055877 A1 WO2010055877 A1 WO 2010055877A1
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group
meth
adhesive composition
rubber latex
natural rubber
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PCT/JP2009/069265
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French (fr)
Japanese (ja)
Inventor
康三 佐々木
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株式会社ブリヂストン
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Publication of WO2010055877A1 publication Critical patent/WO2010055877A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
    • 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
    • C09J109/08—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex

Definitions

  • the present invention relates to an adhesive composition used for bonding industrial fibers and rubber, and more particularly to an adhesive composition for organic fiber cords used for bonding to rubber.
  • resorcinol / formaldehyde latex has been used as an adhesive composition (dip solution) in order to ensure adhesion between the organic fiber cord and rubber.
  • Patent Documents 2 and 3 the addition of natural rubber latex to the adhesive composition has a problem that the adhesive strength after rubber vulcanization is reduced.
  • the present invention has been made under such circumstances, and provides an adhesive composition that improves the adhesive strength after rubber vulcanization without lowering the adhesion between the organic fiber cord and the unvulcanized rubber. For the purpose.
  • the present inventor has found that the object of the present invention can be achieved by improving the natural rubber latex.
  • the present invention has been completed based on such findings. That is, the present invention reacts with a modified natural rubber latex obtained by graft polymerization of a polar group-containing monomer, a butadiene-styrene-vinylpyridine terpolymer rubber latex, a dihydric phenol, and a hydroxy group of the dihydric phenol.
  • An adhesive composition comprising a compound having a functional group is provided.
  • the adhesive composition of the present invention comprises a modified natural rubber latex obtained by graft polymerization of a polar group-containing monomer, a butadiene-styrene-vinylpyridine terpolymer rubber latex, a dihydric phenol and a hydroxy of the dihydric phenol. It contains a compound having a functional group that reacts with a group.
  • the polar group-containing monomer in the present invention is not particularly limited as long as it has at least one polar group in the molecule and can be graft polymerized with a natural rubber molecule. Therefore, it is preferable to have a carbon-carbon double bond in the molecule, and a polar group-containing vinyl monomer is preferable.
  • polar groups include amino groups, imino groups, ammonium groups, imide groups, amide groups, pyridyl groups, isocyanate groups, hydrazo groups, azo groups, diazo groups, hydroxy groups, carboxy groups, carbonyl groups, epoxy groups, Examples thereof include an oxycarbonyl group, a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group, an alkoxysilyl group, and a tin-containing group.
  • polar groups those that react with the hydroxy group of dihydric phenols are more preferred, and are amino groups, hydroxy groups, nitrogen-containing heterocyclic groups, carboxy groups, epoxy groups, amide groups, or isocyanate groups. It is particularly preferred. These monomers containing polar groups may be used alone or in combination of two or more.
  • the polar group-containing monomer containing an amino group as a polar group is a polymerizable monomer containing at least one amino group selected from the first, second and third amino groups in one molecule.
  • the body is mentioned.
  • a tertiary amino group-containing monomer such as dialkylaminoalkyl (meth) acrylate is particularly preferable.
  • These amino group-containing monomers may be used alone or in combination of two or more.
  • the amide group-containing monomer is included in the amino group-containing monomer and exemplified together.
  • (Meth) acrylate refers to acrylate or methacrylate. The same applies to (meth) acrylic acid, (meth) allyl alcohol, (meth) allyl glycidyl, (meth) acryloxy and the like described later.
  • acrylamide methacrylamide, 4-vinylaniline, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) An acrylate etc. are mentioned.
  • Examples of the secondary amino group-containing monomer include (1) anilinostyrene, ⁇ -phenyl-p-anilinostyrene, ⁇ -cyano-p-anilinostyrene, ⁇ -cyano- ⁇ -methyl-p- Anilinostyrene, ⁇ -chloro-p-anilinostyrene, ⁇ -carboxy-p-anilinostyrene, ⁇ -methoxycarbonyl-p-anilinostyrene, ⁇ - (2-hydroxyethoxy) carbonyl-p-anilinostyrene , Anilinostyrenes such as ⁇ -formyl-p-anilinostyrene, ⁇ -formyl- ⁇ -methyl-p-anilinostyrene, ⁇ -carboxy- ⁇ -carboxy- ⁇ -phenyl-p-anilinostyrene, ( 2) 1-anilinophenyl-1,3-butadiene, 1-anilinopheny
  • examples of the tertiary amino group-containing monomer include N, N-disubstituted aminoalkyl (meth) acrylate and N, N-disubstituted aminoalkyl (meth) acrylamide.
  • examples of the N, N-disubstituted aminoalkyl (meth) acrylate include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N-methyl -N-ethylaminoethyl (
  • N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate and the like are particularly preferable.
  • N, N-disubstituted aminoalkyl (meth) acrylamide examples include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( (Meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N -Methyl-N-ethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibuty
  • N, N-dimethyl Particularly preferred are aminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide and the like.
  • examples of the polar group-containing monomer containing a hydroxy group as a polar group include polymerizable monomers having at least one primary, secondary, and tertiary hydroxy group in one molecule. It is done. Examples of such monomers include hydroxy group-containing unsaturated carboxylic acid monomers, hydroxy group-containing vinyl ether monomers, and hydroxy group-containing vinyl ketone monomers.
  • hydroxy group-containing monomer 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 23 Mono (meth) acrylates; N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxymethyl) (meth) acrylamide, etc.
  • hydroxy group-containing unsaturated amides o-hydroxys Hydroxy group-containing vinyl such as len, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy- ⁇ -methylstyrene, m-hydroxy- ⁇ -methylstyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzyl alcohol Aromatic compounds etc. are mentioned. Among these, hydroxy group-containing unsaturated carboxylic acid monomers, hydroxyalkyl (meth) acrylates, and hydroxy group-containing vinyl aromatic compounds are preferable, and hydroxy group-containing unsaturated carboxylic acid monomers are particularly preferable.
  • examples of the hydroxy group-containing unsaturated carboxylic acid monomer include esters such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, amides, and anhydrides. Among these, Particularly preferred are esters such as acrylic acid and methacrylic acid. These hydroxy group-containing monomers may be used alone or in a combination of two or more.
  • the nitrogen-containing heterocyclic ring includes pyrrole, histidine, imidazole, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indole. Quinoline, purine, phenazine, pteridine, melamine and the like.
  • the nitrogen-containing heterocycle may contain other heteroatoms in the ring.
  • a monomer containing a pyridyl group as a nitrogen-containing heterocyclic group is preferable.
  • These nitrogen-containing heterocyclic group-containing monomers may be used alone or in a combination of two or more.
  • the polar group-containing monomer containing a carboxy group as a polar group includes unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid and cinnamic acid; phthalic acid , Free carboxyl group-containing esters such as monoesters of non-polymerizable polyvalent carboxylic acids such as succinic acid and adipic acid and hydroxyl-containing unsaturated compounds such as (meth) allyl alcohol and 2-hydroxyethyl (meth) acrylate And salts thereof. Of these, unsaturated carboxylic acids are particularly preferred. These carboxyl group-containing monomers may be used alone or in a combination of two or more.
  • unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid and cinnamic acid
  • phthalic acid Free carboxyl group-containing esters such as
  • examples of the polar group-containing monomer containing an epoxy group as a polar group include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. These epoxy group-containing monomers may be used alone or in combination of two or more.
  • the polar group-containing monomer containing an alkoxysilyl group as a polar group includes (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethylmethyldimethoxysilane, (meth) acryloxymethyldimethylmethoxy.
  • Silane (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethyldimethylethoxysilane, (meth) acryloxymethyltripropoxysilane, (meth) acryloxymethylmethylmethyl Dipropoxysilane, (meth) acryloxymethyldimethylpropoxysilane, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropyldimethylmethoxysilane, ⁇ - (meta) act Roxypropyltriethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane, ⁇ - (meth) acryloxypropyldimethylethoxysilane, ⁇ - (meth) acryloxypropyltripropoxysilane, ⁇
  • polar group-containing monomers containing a tin-containing group as a polar group include allyltri-n-butyltin, allyltrimethyltin, allyltriphenyltin, allyltri-n-octyltin, (meth) acryloxy-n -Butyltin, (meth) acryloxytrimethyltin, (meth) acryloxytriphenyltin, (meth) acryloxy-n-octyltin, vinyltri-n-butyltin, vinyltrimethyltin, vinyltriphenyltin, vinyltri-n-octyltin And tin-containing monomers such as These tin-containing olefins may be used alone or in combination of two or more.
  • the natural rubber latex used in the production of the modified natural rubber latex is not particularly limited.
  • field latex, ammonia-treated latex, centrifugal concentrated latex, deproteinized latex treated with a surfactant or enzyme, and a combination thereof. Can be used.
  • an emulsifier may be added to the natural rubber latex in advance, or the polar group-containing monomer is emulsified with the emulsifier and then the natural rubber is added. It may be added to the latex.
  • the emulsifier that can be used for emulsification of the natural rubber latex and / or the polar group-containing monomer is not particularly limited, and nonionic surfactants such as polyoxyethylene alkyl ethers, for example, polyoxyethylene lauryl ether, can be used. Can be mentioned.
  • the modified natural rubber latex used in the present invention is obtained by adding the above polar group-containing monomer to the natural rubber latex, and using, for example, tert-butyl hydroperoxide and tetraethylenepentamine as a polymerization initiator. What is necessary is just to graft-polymerize a group containing monomer to the natural rubber molecule in natural rubber latex.
  • the above-mentioned components are charged in a reaction vessel and reacted at 30 to 80 ° C. for 10 minutes to 24 hours to obtain a modified natural rubber latex in which the polar group is introduced into natural rubber molecules.
  • the graft amount of the polar group-containing monomer in the obtained modified natural rubber latex is preferably 0.01 to 5.0% by mass with respect to the rubber content of the modified natural rubber latex. If the graft amount is within this range, the adhesion after rubber vulcanization is improved without lowering the adhesion between the organic fiber cord and the unvulcanized rubber, which is preferable.
  • the butadiene-styrene-vinylpyridine terpolymer rubber latex used in the adhesive composition of the present invention is a terpolymer of a butadiene compound, a vinylpyridine compound and a styrene compound.
  • examples of the butadiene compound include 1,3-butadiene, 2-methyl-1,3-butadiene and the like, and among these, 1,3-butadiene is preferable. These butadiene compounds may be used alone or in combination of two or more.
  • the vinyl pyridine-based compound includes vinyl pyridine and substituted vinyl pyridine in which a hydrogen atom in the vinyl pyridine is substituted with a substituent.
  • the vinylpyridine compounds include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. Among these, 2 -Vinylpyridine is preferred. These vinylpyridine compounds may be used alone or in combination of two or more.
  • the styrene compound includes styrene and substituted styrene in which a hydrogen atom in the styrene is substituted with a substituent.
  • the styrenic compound include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Examples thereof include hydroxymethylstyrene, and among these, styrene is preferable. These styrene compounds may be used alone or in combination of two or more.
  • the butadiene-styrene-vinylpyridine terpolymer rubber latex has a mass ratio of a constituent unit derived from butadiene, a constituent unit derived from vinylpyridine, and a constituent unit derived from styrene from 80/10/10 to 30/20/50. It is preferable that This butadiene-styrene-vinylpyridine terpolymer rubber latex can be obtained as a commercial product, and examples thereof include those manufactured by Japan A & L, trade name “PYRATEX”, and a solid content of 41% by mass.
  • the mass ratio of the rubber content of the modified natural rubber latex and the rubber content of the butadiene-styrene-vinylpyridine terpolymer rubber latex is 10/90 to 70/30. It is preferable. If the mass ratio is within this range, the adhesion between the organic fiber cord and the unvulcanized rubber is not lowered, and the adhesive strength after rubber vulcanization is improved, which is preferable.
  • one or more other rubber latexes are appropriately used as long as the effects of the present invention are not impaired. can do.
  • examples of other rubber latex include modified latex obtained by modifying a butadiene-styrene-vinylpyridine terpolymer with a carboxy group, styrene-butadiene latex and modified latex thereof, acrylate copolymer latex, butyl rubber latex, chloroprene.
  • latex prepared by dispersing a rubber component of the same type as the rubber component blended in the adherent rubber in water or an organic solvent can be used.
  • dihydric phenol used in the adhesive composition of the present invention an unsubstituted dihydric phenol and a substituted dihydric phenol substituted with an alkyl group having 1 to 10 carbon atoms are preferable.
  • the dihydric phenol include resorcin, catechol, and hydroquinone.
  • the substituted dihydric phenol include 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, and the like. Can be mentioned. Of these, resorcin is preferred.
  • the dihydric phenols When the dihydric phenols are present in the adhesive composition of the present invention, the dihydric phenols and the polar group-containing monomer graft-polymerized with the modified natural rubber latex can be bonded, so that the adhesive strength after rubber vulcanization is increased. It will be improved.
  • a resorcin-formaldehyde resin in addition to the dihydric phenols, may be blended as desired within a range not impairing the object of the present invention.
  • a resorcin-formaldehyde initial condensate can be used as the resorcin-formaldehyde resin.
  • This resorcin-formaldehyde initial condensate contains a formaldehyde-derived structural unit and a resorcin-derived structural unit, and it is important to maintain a stoichiometrically shortage of formaldehyde-derived structural units. That is, the resin can be kept soluble at a low molecular weight.
  • any compound that reacts with the hydroxy group of the dihydric phenol to produce a resin may be used.
  • the functional group an aldehyde group or a primary amino group is preferable. Formaldehyde is preferred as the compound having a functional group that reacts with the hydroxy group of dihydric phenols.
  • the dihydric phenol is used with respect to 100 parts by mass of the rubber component comprising the rubber component of the modified natural rubber latex and the rubber component of the butadiene-styrene-vinylpyridine terpolymer rubber latex. It is preferable that 10 to 30 parts by mass of a resin component made of a compound having a functional group capable of reacting with the hydroxy group of the dihydric phenol and the dihydric phenol is contained. If the content of the resin component is within this range, the adhesive strength after rubber vulcanization is improved without lowering the adhesion between the organic fiber cord and the unvulcanized rubber, which is preferable. If desired, other rubber latex is added to the rubber component, and if desired, a resin such as resorcin-formaldehyde resin is added to the resin component.
  • the above-mentioned modified natural rubber latex, butadiene-styrene-vinylpyridine terpolymer rubber latex, dihydric phenols and functional groups that react with hydroxy groups of the dihydric phenols It is preferable to use a basic compound as a catalyst when the compound having aging is aged.
  • a basic compound for example, ammonia or sodium hydroxide can be used.
  • the compounding amount of the basic compound depends on the type of the basic compound, but in the case of ammonia, the above-mentioned modified natural rubber latex, butadiene-styrene-vinylpyridine terpolymer rubber latex, in terms of solid content,
  • the amount is usually about 1 to 8 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the total amount of the dihydric phenols and the compound having a functional group that reacts with the hydroxy group of the dihydric phenols.
  • sodium hydroxide in the case of sodium hydroxide, it reacts with the above-mentioned modified natural rubber latex, butadiene-styrene-vinylpyridine terpolymer rubber latex, dihydric phenols and hydroxy groups of the dihydric phenols in terms of solid content.
  • the amount is usually about 0.1 to 2 parts by weight, preferably 0.2 to 1 part by weight, based on 100 parts by weight of the total amount of the compounds having functional groups.
  • the basic compound is in the form of an aqueous solution, the modified natural rubber latex, the butadiene-styrene-vinylpyridine terpolymer rubber latex, the dihydric phenol, and the hydroxy group of the dihydric phenol. It may be added to a mixed solution of a compound having a functional group that reacts with or may be added simultaneously with other components.
  • the industrial fiber to which the adhesive composition of the present invention is applied is not particularly limited and can be applied to various organic fiber cords and inorganic fiber cords, but is preferably applied to organic fiber cords.
  • Organic fiber cords such as cotton, rayon, polyamide (nylon-6, nylon-6,6), polyester (polyethylene terephthalate, polyethylene naphthalate), aramid (m-phenylene isophthalamide, p-phenylene terephthalamide), etc. Can be mentioned. These cords are treated with the adhesive composition of the present invention as a reinforcing material for rubber products.
  • the method of using the adhesive composition of the present invention is not particularly limited, a method of immersing the fiber material in the adhesive composition, a method of applying with a doctor knife or a brush, a method of spray coating, a method of spraying powdered and spraying Any of these methods may be used.
  • heat treatment is performed, and then the organic fiber cord is embedded in unvulcanized rubber, and then the unvulcanized rubber is vulcanized or electron beamed.
  • the rubber product reinforced with the organic fiber cord is manufactured by integrating the organic fiber cord and the rubber by treatment with microwave or plasma.
  • the temperature for the above heat treatment is preferably 100 to 260 ° C., more preferably 220 to 255 ° C., and particularly preferably 230 to 250 ° C. from the viewpoint of effectively imparting adhesiveness to the organic fiber cord.
  • the adhesion amount of the adhesive composition to the organic fiber cord is preferably 1 to 15% by mass. More preferably, it is 6 mass%. Further, the unvulcanized rubber is appropriately selected according to the use of the obtained rubber product.
  • an adhesive composition in which the adhesive strength after rubber vulcanization is improved without lowering the adhesion between the organic fiber cord and the unvulcanized rubber.
  • Example 1 Manufacture of modified natural rubber latex> The field latex was centrifuged at a rotational speed of 7500 rpm using a latex separator (manufactured by Saito Centrifugal Industries) to obtain a concentrated latex having a dry rubber concentration of 60% by mass.
  • a latex separator manufactured by Saito Centrifugal Industries
  • Formic acid was added to the resulting modified natural rubber latex to adjust the pH to 4.7 to coagulate the modified natural rubber latex.
  • the solid material thus obtained was treated 5 times with a creper, passed through a shredder, crushed, and then dried at 110 ° C. for 210 minutes with a hot air dryer as a monomer. It was confirmed that the conversion of added N, N-diethylaminoethyl methacrylate was 100%.
  • this solid rubber was extracted with petroleum ether and further extracted with a 2: 1 mixed solvent of acetone and methanol. However, when the extract was analyzed, no homopolymer was detected and added. It was confirmed that 100% of the obtained monomer was introduced into the natural rubber molecule. Accordingly, the polar group content of the resulting modified natural rubber latex A is 0.027 mmol / g with respect to the rubber component in the natural rubber latex.
  • a 6-nylon 1400 dtex raw yarn was twisted at a lower twist of 39 times / 10 cm and an upper twist of 39 times / 10 cm to form a twisted structure of 1400 dtex / 2 and immersed in the adhesive composition of Example 1 at 160 ° C. was dried for 60 seconds, and further heat treated at 240 ° C. for 60 seconds to obtain an adhesive-treated fiber cord.
  • the fiber cord was evaluated for adhesion and adhesion. The results are shown in Table 3.
  • Examples 2-8 Instead of 3.0 g of N, N-diethylaminoethyl methacrylate in Example 1, 2.1 g of 2-hydroxyethyl methacrylate in Example 2, 1.7 g of 4-vinylpyridine in Example 3, and 2.1 g of itaconic acid, 1.4 g of methacrylic acid in Example 5, 1.7 g of acrylonitrile in Example 6, 2.3 g of glycidyl methacrylate in Example 7, and 2.8 g of methacrylamide in Example 8
  • Modified natural rubber latex used in Examples 2 to 8 was obtained in the same manner as Example 1 except that it was used.
  • Example 9 Manufacture of modified natural rubber latex> The field latex was centrifuged at a rotational speed of 7500 rpm using a latex separator [manufactured by Saito Centrifugal Co., Ltd.] to obtain a concentrated latex having a dry rubber concentration of 60%.
  • Example 9 an adhesive composition of Example 9 was obtained in the same manner as Example 1. Using this adhesive composition, the adhesive strength and the adhesive strength of the same fiber cord as in Example 1 subjected to the same adhesive treatment as in Example 1 were evaluated. The results are shown in Table 3.
  • Example 10 A modified natural rubber latex was obtained by the same operation and conditions as in Example 9, except that 60.0 g of 2-hydroxyethyl methacrylate was used instead of 60.0 g of N, N-diethylaminoethyl methacrylate in Example 9.
  • the modified natural rubber latex was analyzed by the same method as in Example 1, it was confirmed that the conversion rate of the added monomer was 98.7%. Moreover, when the amount of homopolymer was analyzed by extraction, it was 4.1% of the monomer.
  • an adhesive composition of Example 10 was obtained in the same manner as Example 1. Using this adhesive composition, the adhesive strength and the adhesive strength of the same fiber cord as in Example 1 subjected to the same adhesive treatment as in Example 1 were evaluated. The results are shown in Table 3.
  • Examples 11 to 34 Adhesive compositions were prepared from the modified natural rubber latex obtained in Examples 1 to 8 with the compositions shown in Table 3. Using these adhesive compositions of Examples 11 to 34, the same fiber cord as in Example 1 treated with the same adhesive as in Example 1 was evaluated for adhesive strength and adhesion. The results are shown in Table 3.
  • Comparative Examples 1-7 The natural rubber latex was not modified, only the solid content was adjusted and used as it was, and adhesive compositions of Comparative Examples 1 to 7 were obtained in the same manner as in Example 1. Using these adhesive compositions, the adhesive strength and the adhesive strength were evaluated for the same fiber cord as in Example 1 that was subjected to the same adhesive treatment as in Example 1. The results are shown in Table 3.
  • the adhesive compositions of Examples 1 to 27 of the present invention were both made of organic fiber cord and unvulcanized rubber as compared with the adhesive compositions of Comparative Examples 1 to 7.
  • the adhesive strength after rubber vulcanization was improved without lowering the adhesion.
  • the adhesive composition of the present invention is used for adhesion treatment of a composite of an industrial fiber, in particular, an organic fiber cord and a sulfur vulcanizable rubber vulcanizate, and is used for all kinds of tires, conveyor belts, hoses, air springs, etc. It is suitably used for the production of rubber products. Particularly in tires, the composite is used as a belt material, carcass material, ply material, cap ply material, layer material, or the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Disclosed is an adhesive composition that is characterized by containing modified natural rubber latex to which a polar group-containing monomer is graft polymerized, a butadiene-styrene-vinylpyridine terpolymer rubber latex, a dihydric phenol, and a compound having a functional group that reacts with the hydroxyl group of the dihydric phenol. With the adhesive compound, adhesion between organic fiber cords and unvulcanized rubber does not decrease, and adhesive strength after rubber vulcanization is improved.

Description

接着剤組成物Adhesive composition
　本発明は、工業用繊維とゴムとの接着に用いられる接着剤組成物に関し、特に、ゴムとの接着に用いられる有機繊維コード用接着剤組成物に関する。 The present invention relates to an adhesive composition used for bonding industrial fibers and rubber, and more particularly to an adhesive composition for organic fiber cords used for bonding to rubber.
　従来、有機繊維コードとゴムとの接着を確保するためには、接着剤組成物（ディップ液）としてレゾルシン・ホルムアルデヒド・ラテックス（ＲＦＬ）が使用されている。（例えば、特許文献１参照）
　そして、上記の接着剤組成物で被覆された有機繊維コードと未加硫ゴムとの密着性を改良するため接着剤組成物に天然ゴムラテックスを加えることも試みられている。（例えば、特許文献２及び３参照）
　しかしながら、接着剤組成物に天然ゴムラテックスを加えることにより、かえってゴム加硫後の接着力が低下するという問題があった。 Conventionally, resorcinol / formaldehyde latex (RFL) has been used as an adhesive composition (dip solution) in order to ensure adhesion between the organic fiber cord and rubber. (For example, see Patent Document 1)
An attempt has been made to add natural rubber latex to the adhesive composition in order to improve the adhesion between the organic fiber cord coated with the adhesive composition and the unvulcanized rubber. (For example, see Patent Documents 2 and 3)
However, the addition of natural rubber latex to the adhesive composition has a problem that the adhesive strength after rubber vulcanization is reduced.
特開昭４８－１１３３５号公報Japanese Patent Laid-Open No. 48-11335 特開平２－９１２７６号公報JP-A-2-91276 特開平８－３２５９５３号公報JP-A-8-325953
　本発明は、このような状況下になされたもので、有機繊維コードと未加硫ゴムとの密着性が低下することなく、ゴム加硫後の接着力が向上する接着剤組成物を提供することを目的とする。 The present invention has been made under such circumstances, and provides an adhesive composition that improves the adhesive strength after rubber vulcanization without lowering the adhesion between the organic fiber cord and the unvulcanized rubber. For the purpose.
　本発明者は、前記目的を達成するために鋭意研究を重ねた結果、天然ゴムラテックスを改良することにより、本発明の課題を達成し得ることを見出した。
　本発明は、かかる知見に基づいて完成したものである。
　すなわち、本発明は、極性基含有単量体をグラフト重合した変性天然ゴムラテックス、ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス、二価フェノール類及び該二価フェノール類のヒドロキシ基と反応する官能基を有する化合物を含有することを特徴とする接着剤組成物を提供するものである。 As a result of intensive studies to achieve the above object, the present inventor has found that the object of the present invention can be achieved by improving the natural rubber latex.
The present invention has been completed based on such findings.
That is, the present invention reacts with a modified natural rubber latex obtained by graft polymerization of a polar group-containing monomer, a butadiene-styrene-vinylpyridine terpolymer rubber latex, a dihydric phenol, and a hydroxy group of the dihydric phenol. An adhesive composition comprising a compound having a functional group is provided.
　本発明の接着剤組成物は、極性基含有単量体をグラフト重合した変性天然ゴムラテックス、ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス、二価フェノール類及び該二価フェノール類のヒドロキシ基と反応する官能基を有する化合物を含有することを特徴とする。 The adhesive composition of the present invention comprises a modified natural rubber latex obtained by graft polymerization of a polar group-containing monomer, a butadiene-styrene-vinylpyridine terpolymer rubber latex, a dihydric phenol and a hydroxy of the dihydric phenol. It contains a compound having a functional group that reacts with a group.
　本発明における極性基含有単量体は、分子内に少なくとも一つの極性基を有し、天然ゴム分子とグラフト重合できる単量体である限り特に制限されるものでないが、天然ゴム分子とグラフト重合するために、分子内に炭素－炭素二重結合を有することが好ましく、極性基含有ビニル系単量体であることが好ましい。極性基の具体例としては、アミノ基、イミノ基、アンモニウム基、イミド基、アミド基、ピリジル基、イソシアネート基、ヒドラゾ基、アゾ基、ジアゾ基、ヒドロキシ基、カルボキシ基、カルボニル基、エポキシ基、オキシカルボニル基、スルフィド基、ジスルフィド基、スルホニル基、スルフィニル基、チオカルボニル基、含窒素複素環基、含酸素複素環基、アルコキシシリル基、及びスズ含有基等を挙げることができる。これらの極性基の内、二価フェノール類のヒドロキシ基と反応するものであることがより好ましく、アミノ基、ヒドロキシ基、含窒素複素環基、カルボキシ基、エポキシ基、アミド基又はイソシアネート基であることが特に好ましい。
　これら極性基を含有する単量体は、一種単独で用いても良く、二種以上を組み合せて用いても良い。 The polar group-containing monomer in the present invention is not particularly limited as long as it has at least one polar group in the molecule and can be graft polymerized with a natural rubber molecule. Therefore, it is preferable to have a carbon-carbon double bond in the molecule, and a polar group-containing vinyl monomer is preferable. Specific examples of polar groups include amino groups, imino groups, ammonium groups, imide groups, amide groups, pyridyl groups, isocyanate groups, hydrazo groups, azo groups, diazo groups, hydroxy groups, carboxy groups, carbonyl groups, epoxy groups, Examples thereof include an oxycarbonyl group, a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group, an alkoxysilyl group, and a tin-containing group. Of these polar groups, those that react with the hydroxy group of dihydric phenols are more preferred, and are amino groups, hydroxy groups, nitrogen-containing heterocyclic groups, carboxy groups, epoxy groups, amide groups, or isocyanate groups. It is particularly preferred.
These monomers containing polar groups may be used alone or in combination of two or more.
　本発明において、極性基としてアミノ基を含有する極性基含有単量体としては、１分子中に第１、第２及び第３アミノ基から選ばれる少なくとも１つのアミノ基を含有する重合性単量体が挙げられる。該アミノ基を有する重合性単量体の中でも、ジアルキルアミノアルキル(メタ)アクリレート等の第３アミノ基含有単量体が特に好ましい。これらアミノ基含有単量体は、一種単独で用いても良く、二種以上を組み合せて用いても良い。なお、アミド基含有単量体は、アミノ基含有単量体に包含され、併せて例示される。(メタ)アクリレートとは、アクリレート又はメタクリレートをいう。後述する(メタ)アクリル酸、(メタ)アリルアルコール、(メタ)アリルグリシジル、(メタ)アクリロキシ等も同様である。 In the present invention, the polar group-containing monomer containing an amino group as a polar group is a polymerizable monomer containing at least one amino group selected from the first, second and third amino groups in one molecule. The body is mentioned. Among the polymerizable monomers having an amino group, a tertiary amino group-containing monomer such as dialkylaminoalkyl (meth) acrylate is particularly preferable. These amino group-containing monomers may be used alone or in combination of two or more. The amide group-containing monomer is included in the amino group-containing monomer and exemplified together. (Meth) acrylate refers to acrylate or methacrylate. The same applies to (meth) acrylic acid, (meth) allyl alcohol, (meth) allyl glycidyl, (meth) acryloxy and the like described later.
　ここで、第１アミノ基含有単量体としては、アクリルアミド、メタクリルアミド、４-ビニルアニリン、アミノメチル(メタ)アクリレート、アミノエチル(メタ)アクリレート、アミノプロピル(メタ)アクリレート、アミノブチル(メタ)アクリレート等が挙げられる。 Here, as the first amino group-containing monomer, acrylamide, methacrylamide, 4-vinylaniline, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) An acrylate etc. are mentioned.
　また、第２アミノ基含有単量体としては、（１）アニリノスチレン、β-フェニル-ｐ-アニリノスチレン、β-シアノ-ｐ-アニリノスチレン、β-シアノ-β-メチル-ｐ-アニリノスチレン、β-クロロ-ｐ-アニリノスチレン、β-カルボキシ-ｐ-アニリノスチレン、β-メトキシカルボニル-ｐ-アニリノスチレン、β-(２-ヒドロキシエトキシ)カルボニル-ｐ-アニリノスチレン、β-ホルミル-ｐ-アニリノスチレン、β-ホルミル-β-メチル-ｐ-アニリノスチレン、α-カルボキシ-β-カルボキシ-β-フェニル-ｐ-アニリノスチレン等のアニリノスチレン類、（２）１-アニリノフェニル-１,３-ブタジエン、１-アニリノフェニル-３-メチル-１,３-ブタジエン、１-アニリノフェニル-３-クロロ-１,３-ブタジエン、３-アニリノフェニル-２-メチル-１,３-ブタジエン、１-アニリノフェニル-２-クロロ-１,３-ブタジエン、２-アニリノフェニル-１,３-ブタジエン、２-アニリノフェニル-３-メチル-１,３-ブタジエン、２-アニリノフェニル-３-クロロ-１,３-ブタジエン等のアニリノフェニルブタジエン類、（３）Ｎ-メチル(メタ)アクリルアミド、Ｎ-エチル(メタ)アクリルアミド、Ｎ-メチロールアクリルアミド、Ｎ-(４-アニリノフェニル)メタクリルアミド等のＮ-モノ置換(メタ)アクリルアミド類等が挙げられる。 Examples of the secondary amino group-containing monomer include (1) anilinostyrene, β-phenyl-p-anilinostyrene, β-cyano-p-anilinostyrene, β-cyano-β-methyl-p- Anilinostyrene, β-chloro-p-anilinostyrene, β-carboxy-p-anilinostyrene, β-methoxycarbonyl-p-anilinostyrene, β- (2-hydroxyethoxy) carbonyl-p-anilinostyrene , Anilinostyrenes such as β-formyl-p-anilinostyrene, β-formyl-β-methyl-p-anilinostyrene, α-carboxy-β-carboxy-β-phenyl-p-anilinostyrene, ( 2) 1-anilinophenyl-1,3-butadiene, 1-anilinophenyl-3-methyl-1,3-butadiene, 1-anilinophenyl-3-chloro-1,3-butadiene, 3-anilino Phenyl-2-methyl-1,3-butadiene, 1-anilinov Nyl-2-chloro-1,3-butadiene, 2-anilinophenyl-1,3-butadiene, 2-anilinophenyl-3-methyl-1,3-butadiene, 2-anilinophenyl-3-chloro- Anilinophenylbutadienes such as 1,3-butadiene, (3) N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide, N- (4-anilinophenyl) methacrylamide, etc. N-mono substituted (meth) acrylamides and the like can be mentioned.
　更に、第３アミノ基含有単量体としては、Ｎ,Ｎ-ジ置換アミノアルキル(メタ)アクリレート及びＮ,Ｎ-ジ置換アミノアルキル(メタ)アクリルアミド等が挙げられる。上記Ｎ,Ｎ-ジ置換アミノアルキル(メタ)アクリレートとしては、Ｎ,Ｎ-ジメチルアミノメチル(メタ)アクリレート、Ｎ,Ｎ-ジメチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジメチルアミノプロピル(メタ)アクリレート、Ｎ,Ｎ-ジメチルアミノブチル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノプロピル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノブチル(メタ)アクリレート、Ｎ-メチル-Ｎ-エチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジプロピルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジブチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジブチルアミノプロピル(メタ)アクリレート、Ｎ,Ｎ-ジブチルアミノブチル(メタ)アクリレート、Ｎ,Ｎ-ジヘキシルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジオクチルアミノエチル(メタ)アクリレート、アクリロイルモルフォリン等のアクリル酸又はメタクリル酸のエステル等が挙げられ、これらの中でも、Ｎ,Ｎ-ジメチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジプロピルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジオクチルアミノエチル(メタ)アクリレート、Ｎ-メチル-Ｎ-エチルアミノエチル(メタ)アクリレート等が特に好ましい。 Furthermore, examples of the tertiary amino group-containing monomer include N, N-disubstituted aminoalkyl (meth) acrylate and N, N-disubstituted aminoalkyl (meth) acrylamide. Examples of the N, N-disubstituted aminoalkyl (meth) acrylate include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N-methyl -N-ethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate, N, N-dibutylaminobutyl (meth) acrylate, N, N-dihexylaminoethyl (meth) acrylate, N, N-dioctyl Examples include acrylic acid or methacrylic acid esters such as aminoethyl (meth) acrylate and acryloylmorpholine. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate and the like are particularly preferable.
　また、上記Ｎ,Ｎ-ジ置換アミノアルキル(メタ)アクリルアミドとしては、Ｎ,Ｎ-ジメチルアミノメチル(メタ)アクリルアミド、Ｎ,Ｎ-ジメチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジメチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジメチルアミノブチル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノブチル(メタ)アクリルアミド、Ｎ-メチル-Ｎ-エチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジプロピルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジブチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジブチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジブチルアミノブチル(メタ)アクリルアミド、Ｎ,Ｎ-ジヘキシルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジヘキシルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジオクチルアミノプロピル(メタ)アクリルアミド等のアクリルアミド化合物又はメタクリルアミド化合物等が挙げられ、これらの中でも、Ｎ,Ｎ-ジメチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジオクチルアミノプロピル(メタ)アクリルアミド等が特に好ましい。 Examples of the N, N-disubstituted aminoalkyl (meth) acrylamide include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( (Meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N -Methyl-N-ethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dibutylaminobutyl (meth) acrylamide, N, N-dihexylaminoethyl Examples include (meth) acrylamide, N, N-dihexylaminopropyl (meth) acrylamide, acrylamide compounds such as N, N-dioctylaminopropyl (meth) acrylamide, and methacrylamide compounds. Among these, N, N-dimethyl Particularly preferred are aminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide and the like.
　本発明において、極性基としてヒドロキシ基を含有する極性基含有単量体としては、１分子中に少なくとも１つの第１級、第２級及び第３級ヒドロキシ基を有する重合性単量体が挙げられる。かかる単量体としては、ヒドロキシ基含有不飽和カルボン酸系単量体、ヒドロキシ基含有ビニルエーテル系単量体、ヒドロキシ基含有ビニルケトン系単量体等が挙げられる。 In the present invention, examples of the polar group-containing monomer containing a hydroxy group as a polar group include polymerizable monomers having at least one primary, secondary, and tertiary hydroxy group in one molecule. It is done. Examples of such monomers include hydroxy group-containing unsaturated carboxylic acid monomers, hydroxy group-containing vinyl ether monomers, and hydroxy group-containing vinyl ketone monomers.
　ここで、ヒドロキシ基含有単量体の具体例としては、２-ヒドロキシエチル(メタ)アクリレート、２-ヒドロキシプロピル(メタ)アクリレート、３-ヒドロキシプロピル(メタ)アクリレート、２-ヒドロキシブチル(メタ)アクリレート、３-ヒドロキシブチル(メタ)アクリレート、４-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類；ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール（アルキレングリコール単位数は、例えば、２～２３である）のモノ(メタ)アクリレート類；Ｎ-ヒドロキシメチル(メタ)アクリルアミド、Ｎ-(２-ヒドロキシエチル)(メタ)アクリルアミド、Ｎ,Ｎ-ビス(２-ヒドロキシメチル)(メタ)アクリルアミド等のヒドロキシ基含有不飽和アミド類；ｏ-ヒドロキシスチレン、ｍ-ヒドロキシスチレン、ｐ-ヒドロキシスチレン、ｏ-ヒドロキシ-α-メチルスチレン、ｍ-ヒドロキシ-α-メチルスチレン、ｐ-ヒドロキシ-α-メチルスチレン、ｐ-ビニルベンジルアルコール等のヒドロキシ基含有ビニル芳香族化合物類等が挙げられる。これらの中でも、ヒドロキシ基含有不飽和カルボン酸系単量体、ヒドロキシアルキル(メタ)アクリレート類、ヒドロキシ基含有ビニル芳香族化合物が好ましく、ヒドロキシ基含有不飽和カルボン酸系単量体が特に好ましい。ここで、ヒドロキシ基含有不飽和カルボン酸系単量体としては、アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸等のエステル、アミド、無水物等の誘導体が挙げられ、これらの中でも、アクリル酸、メタクリル酸等のエステルが特に好ましい。これらヒドロキシ基含有単量体は、一種単独で用いても良く、二種以上を組み合せて用いても良い。 Here, as specific examples of the hydroxy group-containing monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 23 Mono (meth) acrylates; N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxymethyl) (meth) acrylamide, etc. Hydroxy group-containing unsaturated amides; o-hydroxys Hydroxy group-containing vinyl such as len, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl alcohol Aromatic compounds etc. are mentioned. Among these, hydroxy group-containing unsaturated carboxylic acid monomers, hydroxyalkyl (meth) acrylates, and hydroxy group-containing vinyl aromatic compounds are preferable, and hydroxy group-containing unsaturated carboxylic acid monomers are particularly preferable. Here, examples of the hydroxy group-containing unsaturated carboxylic acid monomer include esters such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, amides, and anhydrides. Among these, Particularly preferred are esters such as acrylic acid and methacrylic acid. These hydroxy group-containing monomers may be used alone or in a combination of two or more.
　本発明において、極性基として含窒素複素環基を含有する極性基含有単量体において、該含窒素複素環としては、ピロール、ヒスチジン、イミダゾール、トリアゾリジン、トリアゾール、トリアジン、ピリジン、ピリミジン、ピラジン、インドール、キノリン、プリン、フェナジン、プテリジン、メラミン等が挙げられる。なお、該含窒素複素環は、他のヘテロ原子を環中に含んでいても良い。ここで、含窒素複素環基としてピリジル基を含有する単量体が好ましく、具体的には、２-ビニルピリジン、３-ビニルピリジン、４-ビニルピリジン、５-メチル-２-ビニルピリジン、５-エチル-２-ビニルピリジン等のピリジル基含有ビニル化合物等が挙げられ、これらの中でも、２-ビニルピリジン、４-ビニルピリジン等が特に好ましい。これら含窒素複素環基含有単量体は、一種単独で用いても良く、二種以上を組み合せて用いても良い。 In the present invention, in the polar group-containing monomer containing a nitrogen-containing heterocyclic group as a polar group, the nitrogen-containing heterocyclic ring includes pyrrole, histidine, imidazole, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indole. Quinoline, purine, phenazine, pteridine, melamine and the like. The nitrogen-containing heterocycle may contain other heteroatoms in the ring. Here, a monomer containing a pyridyl group as a nitrogen-containing heterocyclic group is preferable. Specifically, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5 Examples include pyridyl group-containing vinyl compounds such as 2-ethyl-2-vinylpyridine, and among these, 2-vinylpyridine, 4-vinylpyridine and the like are particularly preferable. These nitrogen-containing heterocyclic group-containing monomers may be used alone or in a combination of two or more.
　本発明において、極性基としてカルボキシ基を含有する極性基含有単量体としては、(メタ)アクリル酸、マレイン酸、フマル酸、イタコン酸、テトラコン酸、桂皮酸等の不飽和カルボン酸類；フタル酸、コハク酸、アジピン酸等の非重合性多価カルボン酸と、(メタ)アリルアルコール、２-ヒドロキシエチル(メタ)アクリレート等の水酸基含有不飽和化合物とのモノエステルのような遊離カルボキシル基含有エステル類及びその塩等が挙げられる。これらの中でも、不飽和カルボン酸類が特に好ましい。これらカルボキシル基含有単量体は、一種単独で用いても良く、二種以上を組み合せて用いても良い。 In the present invention, the polar group-containing monomer containing a carboxy group as a polar group includes unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid and cinnamic acid; phthalic acid , Free carboxyl group-containing esters such as monoesters of non-polymerizable polyvalent carboxylic acids such as succinic acid and adipic acid and hydroxyl-containing unsaturated compounds such as (meth) allyl alcohol and 2-hydroxyethyl (meth) acrylate And salts thereof. Of these, unsaturated carboxylic acids are particularly preferred. These carboxyl group-containing monomers may be used alone or in a combination of two or more.
　本発明において、極性基としてエポキシ基を含有する極性基含有単量体としては、(メタ)アリルグリシジルエーテル、グリシジル(メタ)アクリレート、３,４-エポキシシクロヘキシル(メタ)アクリレート等が挙げられる。これらエポキシ基含有単量体は、一種単独で用いても良く、二種以上を組み合せて用いても良い。 In the present invention, examples of the polar group-containing monomer containing an epoxy group as a polar group include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. These epoxy group-containing monomers may be used alone or in combination of two or more.
　本発明において、極性基としてアルコキシシリル基を含有する極性基含有単量体としては、(メタ)アクリロキシメチルトリメトキシシラン、(メタ)アクリロキシメチルメチルジメトキシシラン、(メタ)アクリロキシメチルジメチルメトキシシラン、(メタ)アクリロキシメチルトリエトキシシラン、(メタ)アクリロキシメチルメチルジエトキシシラン、(メタ)アクリロキシメチルジメチルエトキシシラン、(メタ)アクリロキシメチルトリプロポキシシラン、(メタ)アクリロキシメチルメチルジプロポキシシラン、(メタ)アクリロキシメチルジメチルプロポキシシラン、γ-(メタ)アクリロキシプロピルトリメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジメトキシシラン、γ-(メタ)アクリロキシプロピルジメチルメトキシシラン、γ-(メタ)アクリロキシプロピルトリエトキシシラン、γ-(メタ)アクリロキシプロピルメチルジエトキシシラン、γ-(メタ)アクリロキシプロピルジメチルエトキシシラン、γ-(メタ)アクリロキシプロピルトリプロポキシシラン、γ-(メタ)アクリロキシプロピルメチルジプロポキシシラン、γ-(メタ)アクリロキシプロピルジメチルプロポキシシラン、γ-(メタ)アクリロキシプロピルメチルジフェノキシシラン、γ-(メタ)アクリロキシプロピルジメチルフェノキシシラン、γ-(メタ)アクリロキシプロピルメチルジベンジロキシシラン、γ-(メタ)アクリロキシプロピルジメチルベンジロキシシラン、トリメトキシビニルシラン、トリエトキシビニルシラン、６-トリメトキシシリル-１,２-ヘキセン、ｐ-トリメトキシシリルスチレン等が挙げられる。これらアルコキシシリル基含有オレフィンは、一種単独で用いても良く、二種以上を組み合せて用いても良い。 In the present invention, the polar group-containing monomer containing an alkoxysilyl group as a polar group includes (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethylmethyldimethoxysilane, (meth) acryloxymethyldimethylmethoxy. Silane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethyldimethylethoxysilane, (meth) acryloxymethyltripropoxysilane, (meth) acryloxymethylmethyl Dipropoxysilane, (meth) acryloxymethyldimethylpropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meta) act Roxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxy Propylmethyldipropoxysilane, γ- (meth) acryloxypropyldimethylpropoxysilane, γ- (meth) acryloxypropylmethyldiphenoxysilane, γ- (meth) acryloxypropyldimethylphenoxysilane, γ- (meth) acryloxy Examples include propylmethyldibenzyloxysilane, γ- (meth) acryloxypropyldimethylbenzyloxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 6-trimethoxysilyl-1,2-hexene, and p-trimethoxysilylstyrene. . These alkoxysilyl group-containing olefins may be used alone or in a combination of two or more.
　本発明において、極性基としてスズ含有基を含有する極性基含有単量体としては、アリルトリ-ｎ-ブチルスズ、アリルトリメチルスズ、アリルトリフェニルスズ、アリルトリ-ｎ-オクチルスズ、(メタ)アクリルオキシ-ｎ-ブチルスズ、(メタ)アクリルオキシトリメチルスズ、(メタ)アクリルオキシトリフェニルスズ、(メタ)アクリルオキシ-ｎ-オクチルスズ、ビニルトリ-ｎ-ブチルスズ、ビニルトリメチルスズ、ビニルトリフェニルスズ、ビニルトリ-ｎ-オクチルスズ等のスズ含有単量体を挙げることができる。これらスズ含有オレフィンは、一種単独で用いても良く、二種以上を組み合せて用いても良い。 In the present invention, polar group-containing monomers containing a tin-containing group as a polar group include allyltri-n-butyltin, allyltrimethyltin, allyltriphenyltin, allyltri-n-octyltin, (meth) acryloxy-n -Butyltin, (meth) acryloxytrimethyltin, (meth) acryloxytriphenyltin, (meth) acryloxy-n-octyltin, vinyltri-n-butyltin, vinyltrimethyltin, vinyltriphenyltin, vinyltri-n-octyltin And tin-containing monomers such as These tin-containing olefins may be used alone or in combination of two or more.
　上記変性天然ゴムラテックスの製造に用いる天然ゴムラテックスとしては、特に限定されず、例えば、フィールドラテックス、アンモニア処理ラテックス、遠心分離濃縮ラテックス、界面活性剤や酵素で処理した脱タンパク質ラテックス、及びこれらを組み合せたもの等を用いることができる。 The natural rubber latex used in the production of the modified natural rubber latex is not particularly limited. For example, field latex, ammonia-treated latex, centrifugal concentrated latex, deproteinized latex treated with a surfactant or enzyme, and a combination thereof. Can be used.
　また、ここで、上記極性基含有単量体の天然ゴムラテックスへの添加においては、予め天然ゴムラテックス中に乳化剤を加えても良いし、極性基含有単量体を乳化剤で乳化した後に天然ゴムラテックス中に加えても良い。なお、天然ゴムラテックス及び／又は極性基含有単量体の乳化に使用できる乳化剤としては、特に限定されず、ポリオキシエチレンアルキルエーテル、例えば、ポリオキシエチレンラウリルエーテル等のノニオン系の界面活性剤が挙げられる。 Here, in the addition of the polar group-containing monomer to the natural rubber latex, an emulsifier may be added to the natural rubber latex in advance, or the polar group-containing monomer is emulsified with the emulsifier and then the natural rubber is added. It may be added to the latex. The emulsifier that can be used for emulsification of the natural rubber latex and / or the polar group-containing monomer is not particularly limited, and nonionic surfactants such as polyoxyethylene alkyl ethers, for example, polyoxyethylene lauryl ether, can be used. Can be mentioned.
　本発明に用いられる変性天然ゴムラテックスは、天然ゴムラテックスに上述の極性基含有単量体を添加し、例えば、重合開始剤としてｔｅｒｔ－ブチルヒドロペルオキシドとテトラエチレンペンタミンとを用いて、該極性基含有単量体を天然ゴムラテックス中の天然ゴム分子にグラフト重合させれば良い。
　上述した各成分を反応容器に仕込み、３０～８０℃で１０分～２４時間反応させることで、天然ゴム分子に上記極性基が導入された変性天然ゴムラテックスが得られる。 The modified natural rubber latex used in the present invention is obtained by adding the above polar group-containing monomer to the natural rubber latex, and using, for example, tert-butyl hydroperoxide and tetraethylenepentamine as a polymerization initiator. What is necessary is just to graft-polymerize a group containing monomer to the natural rubber molecule in natural rubber latex.
The above-mentioned components are charged in a reaction vessel and reacted at 30 to 80 ° C. for 10 minutes to 24 hours to obtain a modified natural rubber latex in which the polar group is introduced into natural rubber molecules.
　得られた変性天然ゴムラテックス中の極性基含有単量体のグラフト量は、前記変性天然ゴムラテックスのゴム分に対して、０．０１～５．０質量％であることが好ましい。グラフト量がこの範囲であれば、有機繊維コードと未加硫ゴムとの密着性が低下することなく、ゴム加硫後の接着力が向上するので好ましい。 The graft amount of the polar group-containing monomer in the obtained modified natural rubber latex is preferably 0.01 to 5.0% by mass with respect to the rubber content of the modified natural rubber latex. If the graft amount is within this range, the adhesion after rubber vulcanization is improved without lowering the adhesion between the organic fiber cord and the unvulcanized rubber, which is preferable.
　本発明の接着剤組成物に用いられるブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスは、ブタジエン化合物と、ビニルピリジン系化合物と、スチレン系化合物とを三元共重合させたものである。ここで、ブタジエン化合物としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン等が挙げられ、これらの中でも、１，３－ブタジエンが好ましい。これらブタジエン化合物は、１種単独で使用しても、２種以上を組み合わせて使用しても良い。 The butadiene-styrene-vinylpyridine terpolymer rubber latex used in the adhesive composition of the present invention is a terpolymer of a butadiene compound, a vinylpyridine compound and a styrene compound. Here, examples of the butadiene compound include 1,3-butadiene, 2-methyl-1,3-butadiene and the like, and among these, 1,3-butadiene is preferable. These butadiene compounds may be used alone or in combination of two or more.
　上記ビニルピリジン系化合物は、ビニルピリジンと、該ビニルピリジン中の水素原子が置換基で置換された置換ビニルピリジンとを包含する。該ビニルピリジン系化合物としては、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、５－エチル－２－ビニルピリジン等が挙げられ、これらの中でも、２－ビニルピリジンが好ましい。これらビニルピリジン系化合物は、１種単独で使用しても、２種以上を組み合わせて使用しても良い。 The vinyl pyridine-based compound includes vinyl pyridine and substituted vinyl pyridine in which a hydrogen atom in the vinyl pyridine is substituted with a substituent. Examples of the vinylpyridine compounds include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. Among these, 2 -Vinylpyridine is preferred. These vinylpyridine compounds may be used alone or in combination of two or more.
　上記スチレン系化合物は、スチレンと、該スチレン中の水素原子が置換基で置換された置換スチレンとを包含する。該スチレン系化合物としては、スチレン、α－メチルスチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、２，４－ジイソプロピルスチレン、２，４－ジメチルスチレン、４－ｔ－ブチルスチレン、ヒドロキシメチルスチレン等が挙げられ、これらの中でも、スチレンが好ましい。これらスチレン系化合物は、１種単独で使用しても、２種以上を組み合わせて使用しても良い。 The styrene compound includes styrene and substituted styrene in which a hydrogen atom in the styrene is substituted with a substituent. Examples of the styrenic compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Examples thereof include hydroxymethylstyrene, and among these, styrene is preferable. These styrene compounds may be used alone or in combination of two or more.
　上記ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスは、ブタジエン由来の構成単位、ビニルピリジン由来の構成単位及びスチレン由来の構成単位の質量比が、８０／１０／１０～３０／２０／５０であることが好ましい。
　このブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスは市販品として入手することが可能であり、例えば、日本Ａ＆Ｌ社製、商品名「ＰＹＲＡＴＥＸ」、固形分４１質量％のものが挙げられる。
　本発明の接着剤組成物においては、上記変性天然ゴムラテックスのゴム分と上記ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスのゴム分との質量比が１０／９０～７０／３０であることが好ましい。質量比がこの範囲であれば、有機繊維コードと未加硫ゴムとの密着性が低下することなく、ゴム加硫後の接着力が向上するので好ましい。 The butadiene-styrene-vinylpyridine terpolymer rubber latex has a mass ratio of a constituent unit derived from butadiene, a constituent unit derived from vinylpyridine, and a constituent unit derived from styrene from 80/10/10 to 30/20/50. It is preferable that
This butadiene-styrene-vinylpyridine terpolymer rubber latex can be obtained as a commercial product, and examples thereof include those manufactured by Japan A & L, trade name “PYRATEX”, and a solid content of 41% by mass.
In the adhesive composition of the present invention, the mass ratio of the rubber content of the modified natural rubber latex and the rubber content of the butadiene-styrene-vinylpyridine terpolymer rubber latex is 10/90 to 70/30. It is preferable. If the mass ratio is within this range, the adhesion between the organic fiber cord and the unvulcanized rubber is not lowered, and the adhesive strength after rubber vulcanization is improved, which is preferable.
　本発明においては、上述の変性天然ゴムラテックス及びブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスに加えて、本発明の効果が損なわれない範囲で、他のゴムラテックス１種以上を適宜併用することができる。
　他のゴムラテックスとしては、例えばブタジエン－スチレン－ビニルピリジン三元共重合体をカルボキシ基等で変性した変性ラテックス、スチレン－ブタジエンラテックス及びその変性ラテックス、アクリル酸エステル共重合体系ラテックス、ブチルゴムラテックス、クロロプレンゴムラテックスの他、被着ゴムに配合されるゴム成分と同種のゴム成分を水又は有機溶媒に分散させて調製したラテックス等を用いることができる。 In the present invention, in addition to the above-mentioned modified natural rubber latex and butadiene-styrene-vinylpyridine terpolymer rubber latex, one or more other rubber latexes are appropriately used as long as the effects of the present invention are not impaired. can do.
Examples of other rubber latex include modified latex obtained by modifying a butadiene-styrene-vinylpyridine terpolymer with a carboxy group, styrene-butadiene latex and modified latex thereof, acrylate copolymer latex, butyl rubber latex, chloroprene. In addition to rubber latex, latex prepared by dispersing a rubber component of the same type as the rubber component blended in the adherent rubber in water or an organic solvent can be used.
　本発明の接着剤組成物に用いられる二価フェノール類としては、無置換の二価フェノール及び炭素数１～１０のアルキル基等で置換された置換二価フェノールが好ましい。二価フェノールとしては、レゾルシン、カテコール及びヒドロキノンが挙げられ、置換二価フェノールとしては、３－メチルレゾルシン、３－エチルレゾルシン、３－プロピルレゾルシン、３－ブチルレゾルシン、３－ｔ－ブチルレゾルシン等が挙げられる。これらの内、レゾルシンが好ましい。
　本発明の接着剤組成物に二価フェノール類が存在すると、この二価フェノール類と変性天然ゴムラテックスのグラフト重合した極性基含有単量体とが結合できるため、ゴム加硫後の接着力が改良されることとなる。
　本発明の接着剤組成物においては、二価フェノール類に加えて、本発明の目的を損なわない範囲で、所望によりレゾルシン－ホルムアルデヒド樹脂を配合しても良い。
　レゾルシン－ホルムアルデヒド樹脂としては、レゾルシン－ホルムアルデヒド初期縮合物を用いることができる。このレゾルシン－ホルムアルデヒド初期縮合物は、ホルムアルデヒド由来の構成単位とレゾルシン由来の構成単位とを含有し、ホルムアルデヒド由来の構成単位が化学量論的に不足する状態を維持することが重要である。即ちこれにより樹脂を低分子量で可溶性に維持することができる。 As the dihydric phenol used in the adhesive composition of the present invention, an unsubstituted dihydric phenol and a substituted dihydric phenol substituted with an alkyl group having 1 to 10 carbon atoms are preferable. Examples of the dihydric phenol include resorcin, catechol, and hydroquinone. Examples of the substituted dihydric phenol include 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, and the like. Can be mentioned. Of these, resorcin is preferred.
When the dihydric phenols are present in the adhesive composition of the present invention, the dihydric phenols and the polar group-containing monomer graft-polymerized with the modified natural rubber latex can be bonded, so that the adhesive strength after rubber vulcanization is increased. It will be improved.
In the adhesive composition of the present invention, in addition to the dihydric phenols, a resorcin-formaldehyde resin may be blended as desired within a range not impairing the object of the present invention.
As the resorcin-formaldehyde resin, a resorcin-formaldehyde initial condensate can be used. This resorcin-formaldehyde initial condensate contains a formaldehyde-derived structural unit and a resorcin-derived structural unit, and it is important to maintain a stoichiometrically shortage of formaldehyde-derived structural units. That is, the resin can be kept soluble at a low molecular weight.
　本発明の接着剤組成物に用いられる、二価フェノール類のヒドロキシ基と反応する官能基を有する化合物としては、二価フェノール類のヒドロキシ基と反応し樹脂を生成するものであれば何でも良い。官能基としては、アルデヒド基又は第１アミノ基が好ましい。二価フェノール類のヒドロキシ基と反応する官能基を有する化合物としては、ホルムアルデヒドが好ましい。 As the compound having a functional group that reacts with the hydroxy group of the dihydric phenol used in the adhesive composition of the present invention, any compound that reacts with the hydroxy group of the dihydric phenol to produce a resin may be used. As the functional group, an aldehyde group or a primary amino group is preferable. Formaldehyde is preferred as the compound having a functional group that reacts with the hydroxy group of dihydric phenols.
　本発明の接着剤組成物においては、上記変性天然ゴムラテックスのゴム分及び上記ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスのゴム分からなるゴム成分１００質量部に対して、前記二価フェノール類及び前記二価フェノール類のヒドロキシ基と反応する官能基を有する化合物からなる樹脂成分が１０～３０質量部含まれることが好ましい。樹脂成分の含有量がこの範囲であれば、有機繊維コードと未加硫ゴムとの密着性が低下することなく、ゴム加硫後の接着力が向上するので好ましい。
　なお、所望により他のゴムラテックスが加えられる場合は、そのゴム分もゴム成分に加えられ、所望によりレゾルシン－ホルムアルデヒド樹脂等の樹脂が加えられる場合は、その樹脂分も樹脂成分に加えられる。 In the adhesive composition of the present invention, the dihydric phenol is used with respect to 100 parts by mass of the rubber component comprising the rubber component of the modified natural rubber latex and the rubber component of the butadiene-styrene-vinylpyridine terpolymer rubber latex. It is preferable that 10 to 30 parts by mass of a resin component made of a compound having a functional group capable of reacting with the hydroxy group of the dihydric phenol and the dihydric phenol is contained. If the content of the resin component is within this range, the adhesive strength after rubber vulcanization is improved without lowering the adhesion between the organic fiber cord and the unvulcanized rubber, which is preferable.
If desired, other rubber latex is added to the rubber component, and if desired, a resin such as resorcin-formaldehyde resin is added to the resin component.
　本発明の接着剤組成物においては、上記の変性天然ゴムラテックス、ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス、二価フェノール類及び該二価フェノール類のヒドロキシ基と反応する官能基を有する化合物を熟成させる際に触媒として塩基性化合物を用いることが好ましい。この塩基性化合物としては、例えばアンモニアや水酸化ナトリウム等を用いることができる。この当該塩基性化合物の配合量は、塩基性化合物の種類にもよるが、アンモニアの場合、固形分換算で、上記の変性天然ゴムラテックス、ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス、二価フェノール類及び該二価フェノール類のヒドロキシ基と反応する官能基を有する化合物の合計量１００質量部に対して、通常１～８質量部程度、好ましくは２～６質量部である。一方、水酸化ナトリウムの場合は、固形分換算で、上記の変性天然ゴムラテックス、ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス、二価フェノール類及び該二価フェノール類のヒドロキシ基と反応する官能基を有する化合物の合計量１００質量部に対して、通常０．１～２質量部程度、好ましくは０．２～１質量部である。
　本発明においては、塩基性化合物は、水溶液の形態で、前記上記の変性天然ゴムラテックス、ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス、二価フェノール類及び該二価フェノール類のヒドロキシ基と反応する官能基を有する化合物の混合液に加えても良いし、他の成分と同時に加えても良い。 In the adhesive composition of the present invention, the above-mentioned modified natural rubber latex, butadiene-styrene-vinylpyridine terpolymer rubber latex, dihydric phenols and functional groups that react with hydroxy groups of the dihydric phenols. It is preferable to use a basic compound as a catalyst when the compound having aging is aged. As this basic compound, for example, ammonia or sodium hydroxide can be used. The compounding amount of the basic compound depends on the type of the basic compound, but in the case of ammonia, the above-mentioned modified natural rubber latex, butadiene-styrene-vinylpyridine terpolymer rubber latex, in terms of solid content, The amount is usually about 1 to 8 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the total amount of the dihydric phenols and the compound having a functional group that reacts with the hydroxy group of the dihydric phenols. On the other hand, in the case of sodium hydroxide, it reacts with the above-mentioned modified natural rubber latex, butadiene-styrene-vinylpyridine terpolymer rubber latex, dihydric phenols and hydroxy groups of the dihydric phenols in terms of solid content. The amount is usually about 0.1 to 2 parts by weight, preferably 0.2 to 1 part by weight, based on 100 parts by weight of the total amount of the compounds having functional groups.
In the present invention, the basic compound is in the form of an aqueous solution, the modified natural rubber latex, the butadiene-styrene-vinylpyridine terpolymer rubber latex, the dihydric phenol, and the hydroxy group of the dihydric phenol. It may be added to a mixed solution of a compound having a functional group that reacts with or may be added simultaneously with other components.
　本発明の接着剤組成物が適用される工業用繊維については特に制限はなく、種々の有機繊維コードや無機繊維コードに適用されるが、有機繊維コードに適用されることが好ましい。有機繊維コードとしては、木綿、レーヨン、ポリアミド（ナイロン－６、ナイロン－６，６）、ポリエステル（ポリエチレンテレフタレート、ポリエチレンナフタレート）、アラミド（ｍ－フェニレンイソフタルアミド、ｐ－フェニレンテレフタルアミド）等のコードを挙げることができる。これらのコードはゴム製品の補強材として本発明の接着剤組成物にて処理される。 The industrial fiber to which the adhesive composition of the present invention is applied is not particularly limited and can be applied to various organic fiber cords and inorganic fiber cords, but is preferably applied to organic fiber cords. Organic fiber cords such as cotton, rayon, polyamide (nylon-6, nylon-6,6), polyester (polyethylene terephthalate, polyethylene naphthalate), aramid (m-phenylene isophthalamide, p-phenylene terephthalamide), etc. Can be mentioned. These cords are treated with the adhesive composition of the present invention as a reinforcing material for rubber products.
　本発明の接着剤組成物の使用方法は特に制限がなく、繊維材料を接着剤組成物に浸漬する方法、ドクターナイフ又はハケで塗布する方法、スプレー塗布する方法、粉体化して吹き付け塗布する方法等のいずれの方法でも良い。具体的には、例えば、有機繊維コードに含浸付着させた後、加熱処理し、その後に上記有機繊維コードを未加硫ゴムに埋設し、次いで該未加硫ゴムを加硫処理、又は電子線、マイクロ波もしくはプラズマによる処理をして有機繊維コードとゴムとを一体化することにより、有機繊維コードで補強されたゴム製品を製造する。
　上記の加熱処理をする温度としては、該有機繊維コードに、接着性を効果的に付与する観点から、１００～２６０℃が好ましく、２２０～２５５℃がより好ましく、２３０～２５０℃が特に好ましい。 The method of using the adhesive composition of the present invention is not particularly limited, a method of immersing the fiber material in the adhesive composition, a method of applying with a doctor knife or a brush, a method of spray coating, a method of spraying powdered and spraying Any of these methods may be used. Specifically, for example, after impregnating and adhering to an organic fiber cord, heat treatment is performed, and then the organic fiber cord is embedded in unvulcanized rubber, and then the unvulcanized rubber is vulcanized or electron beamed. The rubber product reinforced with the organic fiber cord is manufactured by integrating the organic fiber cord and the rubber by treatment with microwave or plasma.
The temperature for the above heat treatment is preferably 100 to 260 ° C., more preferably 220 to 255 ° C., and particularly preferably 230 to 250 ° C. from the viewpoint of effectively imparting adhesiveness to the organic fiber cord.
　また、該有機繊維コードに対する接着剤組成物の付着量（乾燥後の含浸処理済コードの質量を基準として、接着剤組成物による増加質量）は１～１５質量％であることが好ましく、２～６質量％であることが更に好ましい。更に、未加硫ゴムは、得られるゴム製品の用途に応じて、適宜選定される。 The adhesion amount of the adhesive composition to the organic fiber cord (increased mass by the adhesive composition based on the mass of the impregnated cord after drying) is preferably 1 to 15% by mass. More preferably, it is 6 mass%. Further, the unvulcanized rubber is appropriately selected according to the use of the obtained rubber product.
　本発明により、有機繊維コードと未加硫ゴムとの密着性が低下することなく、ゴム加硫後の接着力が向上する接着剤組成物を提供することができる。 According to the present invention, it is possible to provide an adhesive composition in which the adhesive strength after rubber vulcanization is improved without lowering the adhesion between the organic fiber cord and the unvulcanized rubber.
　次に、本発明を実施例により、更に詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。なお、接着力及び密着力の評価法は下記の方法に基づいて行った。
＜接着力＞
　供試接着剤組成物により接着剤処理した繊維コードを第１表に示す配合組成の接着試験用の未加硫ゴム組成物の表面近傍に埋め込み、加硫条件１５５℃×２０分、２ＭＰａの加圧下で加硫し、短冊状の形状を有するサンプルを作製した。得られた加硫物サンプルから繊維コードを掘り起こし、ＪＩＳ Ｋ ６２５６：１９９９のａ）に準拠して、毎分３０ｃｍの速度で繊維コードを加硫ゴムから剥離した。このときの剥離強さを室温（２３℃）で測定し、コード１本当りの接着力（ｋｇ／本）を算出した。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In addition, the evaluation method of adhesive force and contact | adhesion power was performed based on the following method.
<Adhesive strength>
The fiber cord treated with the test adhesive composition was embedded in the vicinity of the surface of the unvulcanized rubber composition for the adhesion test shown in Table 1, and vulcanized under conditions of 155 ° C. × 20 minutes and 2 MPa applied. A sample having a strip shape was prepared by vulcanization under pressure. A fiber cord was dug up from the obtained vulcanized sample, and the fiber cord was peeled from the vulcanized rubber at a speed of 30 cm per minute in accordance with JIS K 6256: 1999 a). The peel strength at this time was measured at room temperature (23 ° C.), and the adhesive strength (kg / piece) per cord was calculated.
Figure JPOXMLDOC01-appb-T000001
 ［注］
＊１：ＪＳＲ株式会社製、商品名「ＩＲ２２００」
＊２：Ｎ－フェニル－Ｎ'－イソプロピル－ｐ－フェニレンジアミン、精工化学（株）製、商品名「オゾノン３Ｃ」
＊３：ＨＡＦ、東海カーボン（株）製、商品名「シースト３」
＊４：富士興産（株）製、商品名「フツコールＡＲＯＭＡＸ＃１」
＊５：Ｎ－シクロヘキシル－２－ベンゾチアジルスルフェンアミド、大内新興化学工業（株）製、商品名「ノクセラーＣＺ」
Figure JPOXMLDOC01-appb-T000001
 [note]
* 1: Product name “IR2200” manufactured by JSR Corporation.
* 2: N-phenyl-N′-isopropyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd., trade name “Ozonon 3C”
* 3: HAF, manufactured by Tokai Carbon Co., Ltd., trade name “Seast 3”
* 4: Product name “Futscall AROMAX # 1” manufactured by Fuji Kosan Co., Ltd.
* 5: N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller CZ”
＜密着力＞
　上記接着力の評価試験の手順において、加硫を実施せずに、繊維コードを剥離した場合の剥離強さからコード１本当りの密着力（ｋｇ／本）を算出した。 <Adhesion>
In the procedure of the adhesive strength evaluation test, the adhesion strength (kg / piece) per cord was calculated from the peel strength when the fiber cord was peeled off without performing vulcanization.
実施例１
＜変性天然ゴムラテックスの製造＞
　フィールドラテックスをラテックスセパレーター［斎藤遠心工業製］を用いて回転数７５００ｒｐｍで遠心分離して、乾燥ゴム濃度６０質量％の濃縮ラテックスを得た。この濃縮ラテックス１０００ｇを、撹拌機及び温調ジャケットを備えたステンレス製反応容器に投入し、予め１０ｍＬの水と９０ｍｇの乳化剤ポリオキシエチレンラウリルエーテル［エマルゲン１０８，花王株式会社製］をＮ,Ｎ-ジエチルアミノエチルメタクリレート ３．０ｇに加えて乳化したものを９９０ｍＬの水と共に添加し、これらを窒素置換しながら常温で３０分間撹拌した。次いで、重合開始剤としてｔｅｒｔ－ブチルヒドロペルオキシド １．２ｇとテトラエチレンペンタミン １．２ｇとを添加し、４０℃で３０分間反応させ、その後、水を添加することにより固形分を４１質量％に調整し、目的とする変性天然ゴムラテックスを得た。 Example 1
<Manufacture of modified natural rubber latex>
The field latex was centrifuged at a rotational speed of 7500 rpm using a latex separator (manufactured by Saito Centrifugal Industries) to obtain a concentrated latex having a dry rubber concentration of 60% by mass. 1000 g of this concentrated latex was put into a stainless steel reaction vessel equipped with a stirrer and a temperature control jacket, and 10 mL of water and 90 mg of an emulsifier polyoxyethylene lauryl ether [Emulgen 108, manufactured by Kao Corporation] were added in advance to N, N What was emulsified in addition to 3.0 g of diethylaminoethyl methacrylate was added together with 990 mL of water, and these were stirred at room temperature for 30 minutes while purging with nitrogen. Next, 1.2 g of tert-butyl hydroperoxide and 1.2 g of tetraethylenepentamine are added as polymerization initiators, reacted at 40 ° C. for 30 minutes, and then water is added to obtain a solid content of 41% by mass. The desired modified natural rubber latex was obtained.
　得られた変性天然ゴムラテックスにギ酸を加えｐＨを４．７に調整し、変性天然ゴムラテックスを凝固させた。このようにして得られた固形物をクレーパーで５回処理し、シュレッダーに通してクラム化した後、熱風式乾燥機により１１０℃で２１０分間乾燥して得られた固形ゴムから、単量体として加えたＮ,Ｎ-ジエチルアミノエチルメタクリレートの転化率が１００％であることが確認された。また、この固形ゴムを石油エーテルで抽出し、更にアセトンとメタノールの２：１混合溶媒で抽出することによりホモポリマーの分離を試みたが、抽出物を分析したところホモポリマーは検出されず、添加した単量体の１００％が天然ゴム分子に導入されていることが確認された。従って、得られた変性天然ゴムラテックスＡの極性基含有量は、天然ゴムラテックス中のゴム成分に対して０．０２７ｍｍｏｌ／ｇである。 Formic acid was added to the resulting modified natural rubber latex to adjust the pH to 4.7 to coagulate the modified natural rubber latex. The solid material thus obtained was treated 5 times with a creper, passed through a shredder, crushed, and then dried at 110 ° C. for 210 minutes with a hot air dryer as a monomer. It was confirmed that the conversion of added N, N-diethylaminoethyl methacrylate was 100%. In addition, this solid rubber was extracted with petroleum ether and further extracted with a 2: 1 mixed solvent of acetone and methanol. However, when the extract was analyzed, no homopolymer was detected and added. It was confirmed that 100% of the obtained monomer was introduced into the natural rubber molecule. Accordingly, the polar group content of the resulting modified natural rubber latex A is 0.027 mmol / g with respect to the rubber component in the natural rubber latex.
＜接着剤組成物の製造＞
　第２表の組成内容の内、軟水にレゾルシンを溶解させ、これに水酸化ナトリウム水溶液を加え、ついでホルムアルデヒドを加え、２７℃、８時間熟成し、レゾルシン－ホルムアルデヒド樹脂液を得た。得られたレゾルシン－ホルムアルデヒド樹脂液に、上記の変性天然ゴムラテックス（固形分４１質量％）及びブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス（固形分４１質量％）［日本Ａ＆Ｌ社製、商品名「ＰＹＲＡＴＥＸ」など］の第２表に示す質量部を第３表に示す質量比にて加えた後、更に、２３℃で１６時間熟成して、実施例１の接着剤組成物を得た。 <Manufacture of adhesive composition>
Of the composition shown in Table 2, resorcin was dissolved in soft water, an aqueous sodium hydroxide solution was added thereto, and then formaldehyde was added, followed by aging at 27 ° C. for 8 hours to obtain a resorcin-formaldehyde resin solution. To the obtained resorcin-formaldehyde resin liquid, the above modified natural rubber latex (solid content 41% by mass) and butadiene-styrene-vinylpyridine terpolymer rubber latex (solid content 41% by mass) [manufactured by Japan A & L, After adding the mass parts shown in Table 2 of the trade name “PYRATEX” etc. at the mass ratio shown in Table 3, the mixture was further aged at 23 ° C. for 16 hours to obtain the adhesive composition of Example 1 It was.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
＜繊維コードの製造と接着剤処理＞
　繊維コードとして、６－ナイロンの１４００ｄｔｅｘの原糸を下撚り３９回／１０ｃｍ、上撚り３９回／１０ｃｍで撚り、撚り構造１４００ｄｔｅｘ／２として、実施例１の接着剤組成物に浸漬し、１６０℃で６０秒間乾燥し、更に２４０℃で６０秒間熱処理して、接着剤処理した繊維コードを得た。この繊維コードについて、接着力及び密着力を評価した。結果を第３表に示す。 <Manufacture of fiber cords and adhesive treatment>
As a fiber cord, a 6-nylon 1400 dtex raw yarn was twisted at a lower twist of 39 times / 10 cm and an upper twist of 39 times / 10 cm to form a twisted structure of 1400 dtex / 2 and immersed in the adhesive composition of Example 1 at 160 ° C. Was dried for 60 seconds, and further heat treated at 240 ° C. for 60 seconds to obtain an adhesive-treated fiber cord. The fiber cord was evaluated for adhesion and adhesion. The results are shown in Table 3.
実施例２～８
　実施例１における３．０ｇのＮ,Ｎ-ジエチルアミノエチルメタクリレートの代わりに、実施例２では２－ヒドロキシエチルメタクリレートを２．１ｇ、実施例３では４－ビニルピリジンを１．７ｇ、実施例４ではイタコン酸を２．１ｇ、実施例５ではメタクリル酸を１．４ｇ、実施例６ではアクリルニトリルを１．７ｇ、実施例７ではグリシジルメタクリレートを２．３ｇ、実施例８ではメタクリルアミドを２．８ｇ用いた以外は実施例１と同様にして、実施例２～８に用いられる変性天然ゴムラテックスを得た。実施例１と同じ方法により天然ゴムラテックスを分析した所、添加した単量体の１００％が天然ゴム分子に導入されていることを確認した。
　これらの変性天然ゴムラテックスを用い、実施例１と同様にして実施例２～８の接着剤組成物を得た。これらの接着剤組成物を用い、実施例１と同じ接着剤処理をした実施例１と同じ繊維コードについて、接着力及び密着力を評価した。結果を第３表に示す。 Examples 2-8
Instead of 3.0 g of N, N-diethylaminoethyl methacrylate in Example 1, 2.1 g of 2-hydroxyethyl methacrylate in Example 2, 1.7 g of 4-vinylpyridine in Example 3, and 2.1 g of itaconic acid, 1.4 g of methacrylic acid in Example 5, 1.7 g of acrylonitrile in Example 6, 2.3 g of glycidyl methacrylate in Example 7, and 2.8 g of methacrylamide in Example 8 Modified natural rubber latex used in Examples 2 to 8 was obtained in the same manner as Example 1 except that it was used. When the natural rubber latex was analyzed by the same method as in Example 1, it was confirmed that 100% of the added monomer was introduced into the natural rubber molecule.
Using these modified natural rubber latexes, adhesive compositions of Examples 2 to 8 were obtained in the same manner as Example 1. Using these adhesive compositions, the adhesive strength and the adhesive strength were evaluated for the same fiber cord as in Example 1 that was subjected to the same adhesive treatment as in Example 1. The results are shown in Table 3.
実施例９
＜変性天然ゴムラテックスの製造＞
　フィールドラテックスをラテックスセパレーター［斎藤遠心工業製など］を用いて回転数７５００ｒｐｍで遠心分離して、乾燥ゴム濃度６０％の濃縮ラテックスを得た。この濃縮ラテックス１０００ｇを、撹拌機及び温調ジャケットを備えたステンレス製反応容器に投入し、予め１０ｍＬの水と１．８ｇの乳化剤ポリオキシエチレンラウリルエーテル［エマルゲン１０８，花王株式会社製］をＮ,Ｎ-ジエチルアミノエチルメタクリレート ６０．０ｇに加えて乳化したものを９９０ｍＬの水と共に添加し、これらを窒素置換しながら常温で３０分間撹拌した。次いで、重合開始剤としてｔｅｒｔ－ブチルヒドロペルオキシド ０．６ｇとテトラエチレンペンタミン ０．６ｇとを加え、４０℃で２時間反応させ、その後、水を添加することにより固形分を４１質量％に調整し、目的とする変性天然ゴムラテックスを得た。
　実施例１と同じ方法により変性天然ゴムラテックスを分析したところ、添加した単量体の転化率は９８．２％であることを確認した。また、抽出によりホモポリマーの量を分析したところ、単量体の４．８％であった。
　この変性天然ゴムラテックスを用い、実施例１と同様にして実施例９の接着剤組成物を得た。この接着剤組成物を用い、実施例１と同じ接着剤処理をした実施例１と同じ繊維コードについて、接着力及び密着力を評価した。結果を第３表に示す。 Example 9
<Manufacture of modified natural rubber latex>
The field latex was centrifuged at a rotational speed of 7500 rpm using a latex separator [manufactured by Saito Centrifugal Co., Ltd.] to obtain a concentrated latex having a dry rubber concentration of 60%. 1000 g of this concentrated latex was put into a stainless steel reaction vessel equipped with a stirrer and a temperature control jacket, and 10 mL of water and 1.8 g of an emulsifier polyoxyethylene lauryl ether [Emulgen 108, manufactured by Kao Corporation] What was emulsified in addition to 60.0 g of N-diethylaminoethyl methacrylate was added with 990 mL of water, and these were stirred at room temperature for 30 minutes while purging with nitrogen. Next, 0.6 g of tert-butyl hydroperoxide and 0.6 g of tetraethylenepentamine were added as polymerization initiators, reacted at 40 ° C. for 2 hours, and then the solid content was adjusted to 41 mass% by adding water. Thus, the desired modified natural rubber latex was obtained.
When the modified natural rubber latex was analyzed by the same method as in Example 1, it was confirmed that the conversion rate of the added monomer was 98.2%. Moreover, when the amount of homopolymer was analyzed by extraction, it was 4.8% of the monomer.
Using this modified natural rubber latex, an adhesive composition of Example 9 was obtained in the same manner as Example 1. Using this adhesive composition, the adhesive strength and the adhesive strength of the same fiber cord as in Example 1 subjected to the same adhesive treatment as in Example 1 were evaluated. The results are shown in Table 3.
実施例１０
　実施例９における６０．０ｇのＮ,Ｎ-ジエチルアミノエチルメタクリレートの代わりに、２－ヒドロキシエチルメタクリレートを６０．０ｇ用いた以外は実施例９と同じ操作、条件により変性天然ゴムラテックスを得た。実施例１と同じ方法により変性天然ゴムラテックスを分析したところ、添加した単量体の転化率は９８．７％であることを確認した。また、抽出によりホモポリマーの量を分析したところ、単量体の４．１％であった。
　この変性天然ゴムラテックスを用い、実施例１と同様にして実施例１０の接着剤組成物を得た。この接着剤組成物を用い、実施例１と同じ接着剤処理をした実施例１と同じ繊維コードについて、接着力及び密着力を評価した。結果を第３表に示す。 Example 10
A modified natural rubber latex was obtained by the same operation and conditions as in Example 9, except that 60.0 g of 2-hydroxyethyl methacrylate was used instead of 60.0 g of N, N-diethylaminoethyl methacrylate in Example 9. When the modified natural rubber latex was analyzed by the same method as in Example 1, it was confirmed that the conversion rate of the added monomer was 98.7%. Moreover, when the amount of homopolymer was analyzed by extraction, it was 4.1% of the monomer.
Using this modified natural rubber latex, an adhesive composition of Example 10 was obtained in the same manner as Example 1. Using this adhesive composition, the adhesive strength and the adhesive strength of the same fiber cord as in Example 1 subjected to the same adhesive treatment as in Example 1 were evaluated. The results are shown in Table 3.
実施例１１～３４
　実施例１～８において得られた変性天然ゴムラテックスを第３表記載の組成にて接着剤組成物を調製した。これら実施例１１～３４の接着剤組成物を用い、実施例１と同じ接着剤処理をした実施例１と同じ繊維コードについて、接着力及び密着力を評価した。結果を第３表に示す。 Examples 11 to 34
Adhesive compositions were prepared from the modified natural rubber latex obtained in Examples 1 to 8 with the compositions shown in Table 3. Using these adhesive compositions of Examples 11 to 34, the same fiber cord as in Example 1 treated with the same adhesive as in Example 1 was evaluated for adhesive strength and adhesion. The results are shown in Table 3.
比較例１～７
　天然ゴムラテックスを変性することなく、固形分調整のみ実施してそのまま使用し、実施例１と同様にして比較例１～７の接着剤組成物を得た。これらの接着剤組成物を用い、実施例１と同じ接着剤処理をした実施例１と同じ繊維コードについて、接着力及び密着力を評価した。結果を第３表に示す。 Comparative Examples 1-7
The natural rubber latex was not modified, only the solid content was adjusted and used as it was, and adhesive compositions of Comparative Examples 1 to 7 were obtained in the same manner as in Example 1. Using these adhesive compositions, the adhesive strength and the adhesive strength were evaluated for the same fiber cord as in Example 1 that was subjected to the same adhesive treatment as in Example 1. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
 ［注］
Ａ：Ｎ,Ｎ-ジエチルアミノエチルメタクリレート
Ｂ：２－ヒドロキシエチルメタクリレート
Ｃ：４－ビニルピリジン
Ｄ：イタコン酸
Ｅ：メタクリル酸
Ｆ：アクリルニトリル
Ｇ：グリシジルメタクリレート
Ｈ：メタクリルアミド
Figure JPOXMLDOC01-appb-T000003
 [note]
A: N, N-diethylaminoethyl methacrylate B: 2-hydroxyethyl methacrylate C: 4-vinylpyridine D: itaconic acid E: methacrylic acid F: acrylonitrile G: glycidyl methacrylate H: methacrylamide
Figure JPOXMLDOC01-appb-T000004
 ［注］
　Ａ、Ｂ、Ｃ、Ｄ、Ｅ、Ｆ、Ｇ，Ｈは、いずれも第３表－１と同じ。
Figure JPOXMLDOC01-appb-T000004
 [note]
All of A, B, C, D, E, F, G, and H are the same as those in Table 3.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　第３表から分かるように、本発明の実施例１～２７の接着剤組成物は、比較例１～７の接着剤組成物と比較して、いずれも有機繊維コードと未加硫ゴムとの密着性が低下することなく、ゴム加硫後の接着力が向上した。 As can be seen from Table 3, the adhesive compositions of Examples 1 to 27 of the present invention were both made of organic fiber cord and unvulcanized rubber as compared with the adhesive compositions of Comparative Examples 1 to 7. The adhesive strength after rubber vulcanization was improved without lowering the adhesion.
　本発明の接着剤組成物は、工業用繊維、特に有機繊維コードと硫黄架橋可能なゴムの加硫体との複合体の接着処理に用いられ、タイヤ、コンベアベルト、ホース、空気バネ等のあらゆるゴム製品の製造に好適に用いられる。特にタイヤでは前記複合体としてベルト材、カーカス材、プライ材、キャッププライ材、レイヤー材等として使用される。 The adhesive composition of the present invention is used for adhesion treatment of a composite of an industrial fiber, in particular, an organic fiber cord and a sulfur vulcanizable rubber vulcanizate, and is used for all kinds of tires, conveyor belts, hoses, air springs, etc. It is suitably used for the production of rubber products. Particularly in tires, the composite is used as a belt material, carcass material, ply material, cap ply material, layer material, or the like.

Claims (9)

  1. 　極性基含有単量体をグラフト重合した変性天然ゴムラテックス、ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックス、二価フェノール類及び該二価フェノール類のヒドロキシ基と反応する官能基を有する化合物を含有することを特徴とする接着剤組成物。 Modified natural rubber latex obtained by graft polymerization of polar group-containing monomer, butadiene-styrene-vinylpyridine terpolymer rubber latex, dihydric phenols, and compounds having functional groups that react with hydroxy groups of the dihydric phenols An adhesive composition comprising:
  2. 　前記二価フェノール類が、レゾルシンである請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the dihydric phenol is resorcin.
  3. 　前記官能基が、アルデヒド基又は第１アミノ基である請求項１又は２に記載の接着剤組成物。 The adhesive composition according to claim 1 or 2, wherein the functional group is an aldehyde group or a primary amino group.
  4. 　前記二価フェノール類のヒドロキシ基と反応する官能基を有する化合物が、ホルムアルデヒドである請求項１又は２に記載の接着剤組成物。 The adhesive composition according to claim 1 or 2, wherein the compound having a functional group that reacts with a hydroxy group of the dihydric phenol is formaldehyde.
  5. 　前記極性基が、前記二価フェノール類のヒドロキシ基と反応するものである請求項１～４のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, wherein the polar group reacts with a hydroxy group of the dihydric phenol.
  6. 　前記極性基が、アミノ基、ヒドロキシ基、含窒素複素環基、カルボキシ基、エポキシ基、アミド基又はイソシアネート基である請求項１～５のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 5, wherein the polar group is an amino group, a hydroxy group, a nitrogen-containing heterocyclic group, a carboxy group, an epoxy group, an amide group or an isocyanate group.
  7. 　前記極性基含有単量体のグラフト量が、前記変性天然ゴムラテックスのゴム分に対して、０．０１～５．０質量％である請求項１～６のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 6, wherein a graft amount of the polar group-containing monomer is 0.01 to 5.0 mass% with respect to a rubber content of the modified natural rubber latex. .
  8. 　前記変性天然ゴムラテックスのゴム分と前記ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスのゴム分との質量比が１０／９０～７０／３０である請求項１～７のいずれかに記載の接着剤組成物。 The mass ratio of the rubber content of the modified natural rubber latex and the rubber content of the butadiene-styrene-vinylpyridine terpolymer rubber latex is 10/90 to 70/30. Adhesive composition.
  9. 　前記変性天然ゴムラテックスのゴム分及び前記ブタジエン－スチレン－ビニルピリジン三元共重合体ゴムラテックスのゴム分からなるゴム成分１００質量部に対して、前記二価フェノール類及び前記二価フェノール類のヒドロキシ基と反応する官能基を有する化合物からなる樹脂成分が１０～３０質量部含まれる請求項１～８のいずれかに記載の接着剤組成物。 The dihydric phenols and the hydroxy groups of the dihydric phenols with respect to 100 parts by mass of the rubber component comprising the rubber component of the modified natural rubber latex and the rubber component of the butadiene-styrene-vinylpyridine terpolymer rubber latex The adhesive composition according to any one of claims 1 to 8, wherein 10 to 30 parts by mass of a resin component comprising a compound having a functional group that reacts with the compound is contained.
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