WO2010055877A1 - Composition adhésive - Google Patents

Composition adhésive 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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English (en)
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/fr

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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

L'invention porte sur une composition adhésive qui est caractérisée en ce qu'elle contient un latex de caoutchouc naturel modifié auquel un monomère à teneur en groupe polaire est soumis à une polymérisation de greffage, un latex de caoutchouc terpolymère butadiène-styrène-vinylpyridine, un phénol divalent et un composé ayant un groupe fonctionnel qui réagit avec le groupe hydroxyle du phénol divalent. Avec le composé adhésif, une adhérence entre des cordons de fibre organique et un caoutchouc non vulcanisé ne diminue pas, et la force d'adhérence après la vulcanisation de caoutchouc est améliorée.
PCT/JP2009/069265 2008-11-12 2009-11-12 Composition adhésive WO2010055877A1 (fr)

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JP2011241363A (ja) * 2010-05-21 2011-12-01 Bridgestone Corp セメント組成物、ゴム組成物の接着方法及びタイヤ
CN102898984A (zh) * 2012-09-11 2013-01-30 苏州市胶粘剂厂有限公司 一种硫化鞋水性胶粘剂的制备方法
US20130296493A1 (en) * 2012-05-01 2013-11-07 Bridgestone Corporation Modified natural rubber and method of manufacturing the same, rubber composition and tire
WO2021002182A1 (fr) * 2019-07-02 2021-01-07 日本エイアンドエル株式会社 Latex copolymère pour adhésif et composition adhésive
WO2021002181A1 (fr) * 2019-07-02 2021-01-07 日本エイアンドエル株式会社 Latex copolymère pour adhésif et composition adhésive

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FR2978770B1 (fr) * 2011-08-04 2013-09-27 Michelin Soc Tech Composition adhesive aqueuse a base de polyaldehyde et phloroglucinol

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JP2011241363A (ja) * 2010-05-21 2011-12-01 Bridgestone Corp セメント組成物、ゴム組成物の接着方法及びタイヤ
US20130296493A1 (en) * 2012-05-01 2013-11-07 Bridgestone Corporation Modified natural rubber and method of manufacturing the same, rubber composition and tire
US9181378B2 (en) * 2012-05-01 2015-11-10 Bridgestone Corporation Modified natural rubber and method of manufacturing the same, rubber composition and tire
CN102898984A (zh) * 2012-09-11 2013-01-30 苏州市胶粘剂厂有限公司 一种硫化鞋水性胶粘剂的制备方法
CN102898984B (zh) * 2012-09-11 2014-04-02 苏州市胶粘剂厂有限公司 一种硫化鞋水性胶粘剂的制备方法
WO2021002181A1 (fr) * 2019-07-02 2021-01-07 日本エイアンドエル株式会社 Latex copolymère pour adhésif et composition adhésive
WO2021002182A1 (fr) * 2019-07-02 2021-01-07 日本エイアンドエル株式会社 Latex copolymère pour adhésif et composition adhésive
JP2021008575A (ja) * 2019-07-02 2021-01-28 日本エイアンドエル株式会社 接着剤用共重合体ラテックスおよび接着剤組成物
JP2021008574A (ja) * 2019-07-02 2021-01-28 日本エイアンドエル株式会社 接着剤用共重合体ラテックスおよび接着剤組成物
CN114040931A (zh) * 2019-07-02 2022-02-11 日本A&L株式会社 粘接剂用共聚物胶乳以及粘接剂组合物
CN114040954A (zh) * 2019-07-02 2022-02-11 日本A&L株式会社 粘接剂用共聚物胶乳以及粘接剂组合物
JP7304753B2 (ja) 2019-07-02 2023-07-07 日本エイアンドエル株式会社 接着剤用共重合体ラテックスおよび接着剤組成物
JP7304752B2 (ja) 2019-07-02 2023-07-07 日本エイアンドエル株式会社 接着剤用共重合体ラテックスおよび接着剤組成物

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