WO2019131467A1 - Reinforcement fiber and molded body using same - Google Patents

Reinforcement fiber and molded body using same Download PDF

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Publication number
WO2019131467A1
WO2019131467A1 PCT/JP2018/047123 JP2018047123W WO2019131467A1 WO 2019131467 A1 WO2019131467 A1 WO 2019131467A1 JP 2018047123 W JP2018047123 W JP 2018047123W WO 2019131467 A1 WO2019131467 A1 WO 2019131467A1
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WIPO (PCT)
Prior art keywords
fiber
reinforcing fiber
multiple bond
acid
rubber
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PCT/JP2018/047123
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French (fr)
Japanese (ja)
Inventor
徹 浅田
正博 馬場
祐貴 立花
慎一 竹本
利章 小林
川井　弘之
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株式会社クラレ
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Priority to JP2019561621A priority Critical patent/JP7090102B2/en
Publication of WO2019131467A1 publication Critical patent/WO2019131467A1/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
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall

Definitions

  • the present invention relates to a reinforcing fiber excellent in adhesion to rubber, and a molded article using the same.
  • Patent Document 3 proposes a technique using an adhesive containing an adhesive compound having an unsaturated carbon bond and an epoxy group, which react with a vulcanizing agent used for vulcanizing rubber.
  • Patent Document 4 includes an (blocked) isocyanate compound and / or an amine curing agent (A), an epoxy compound (B), and a rubber latex (C), and does not contain resorcin and formalin.
  • a bonding method using a fiber cord adhesive composition has been proposed.
  • the method using the adhesive described in Patent Document 3 is inferior in adhesion to the method using a conventional adhesive containing resorcin / formalin resin and rubber latex as main components, as described in Patent Document 4
  • the method using the adhesive described in the above has an adhesive power equal to or higher than the method using the conventional adhesive based on resorcinol formalin resin and rubber latex, the surface of the organic fiber cord After forming the adhesive layer, it was necessary to carry out heat treatment substantially at high temperatures (180.degree. C. and 240.degree. C.).
  • Adhesive layer can be formed and heat-treated at a temperature at which general-purpose resins do not deteriorate while having the same adhesive strength as the method using an adhesive containing a conventional resorcin-formalin resin and rubber latex as the main components A method was sought.
  • the object of the present invention is to provide a reinforcing fiber using a bonding component which does not contain resorcinol and formalin and is excellent in adhesion to rubber. It is in.
  • the present invention relates to the following [1] to [2].
  • a reinforcing fiber comprising a hydrophilic fiber having an adhesive component on at least a part of the fiber surface, wherein the adhesive component is selected from reactive carbon-carbon double bonds and reactive carbon-carbon triple bonds in the molecule
  • Reinforcing fiber comprising a vinyl alcohol polymer having one or more multiple bonds.
  • the present invention is a reinforcing fiber using an adhesive component not containing resorcin and formalin, and can provide a reinforcing fiber having excellent adhesion to rubber.
  • the reinforcing fiber of the present invention is a reinforcing fiber consisting of a hydrophilic fiber having an adhesive component on at least a part of the fiber surface, and the adhesive component comprises a reactive carbon-carbon double bond and a reactive carbon- in the molecule. It includes a vinyl alcohol polymer having one or more kinds of multiple bonds selected from carbon triple bonds. According to the present invention, since the vinyl alcohol polymer having multiple bonds is present in at least a part of the hydrophilic fiber surface, the multiple bonds react with rubber and the like to form bonds, which is excellent. It is possible to obtain a reinforcing fiber having good adhesion.
  • reactive carbon-carbon double bond means a carbon-carbon double bond that can react with other components by external energy such as heat or light, and is usually contained in an aromatic ring. Does not include the carbon-carbon double bond, but refers to an aliphatic carbon-carbon double bond. The same applies to “reactive carbon-carbon triple bond”.
  • the adhesive component used in the present invention is particularly preferably one containing a vinyl alcohol polymer having in its molecule one or more multiple bonds selected from reactive carbon-carbon double bonds and reactive carbon-carbon triple bonds.
  • the vinyl alcohol polymer the multiple bond may be present in the main chain or the multiple bond may be present in the side chain, but from the viewpoint of further improving the adhesion.
  • at least a part of the multiple bond is present in the side chain of the vinyl alcohol polymer.
  • the multiple bond since the multiple bond is considered to exhibit adhesiveness by forming a covalent bond with the rubber by vulcanization, the multiple bond is not the main chain of the vinyl alcohol polymer, If it is present in the side chain, the adhesion between the reinforcing fiber and the rubber becomes better.
  • the number of multiple bonds contained in each side chain of the vinyl alcohol polymer is not particularly limited, and is, for example, 1 to 5.
  • the distance from the main chain of the vinyl alcohol polymer to the multiple bond is from the oxygen or carbon atom connecting the main chain and the side chain
  • the number of atoms up to the carbon atom constituting the multiple bond of the side chain is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, preferably 20 or less, more preferably 15 or less, 13 or less More preferably, 10 or less is even more preferable.
  • the larger the number of atoms up to the carbon atom that constitutes the multiple bond of the side chain the longer the distance from the main chain of the vinyl alcohol polymer to the multiple bond, and the reaction between the multiple bond and the rubber is more likely to occur.
  • the adhesion between fiber and rubber is improved. From such a point of view, it is also preferred that multiple bonds be present at the end of the side chain. Further, from the viewpoint of reducing steric hindrance in the vicinity of multiple bonds and facilitating reaction with rubber, it is also preferable that the side chain in which multiple bonds exist be linear rather than branched. On the other hand, when the number of atoms up to the carbon atom constituting the multiple bond of the side chain is less than the upper limit value, the solubility of the vinyl alcohol polymer in water and the like becomes high, and the handleability is improved.
  • production method Also referred to as “(1)”
  • an amine compound having multiple bonds with polyvinyl alcohol having a lactone ring structure in the molecule which is obtained by copolymerizing a vinyl ester and a (meth) acrylic acid ester and then saponifying
  • production method (2) an amine compound having multiple bonds with polyvinyl alcohol having a lactone ring structure in the molecule
  • production method (2) an amine compound having multiple bonds with polyvinyl alcohol having a lactone ring structure in the molecule
  • production method (2) A method obtained by modifying with an amine compound having a reactive carbon-carbon double bond
  • production method (3) A method obtained by modifying with an amine compound having a reactive carbon-carbon double bond
  • the multiple bond-containing compound is not particularly limited, but is preferably a compound having 3 to 30, more preferably 3 to 20, still more preferably 5 to 15, and still more preferably 5 to 10 carbon atoms.
  • the carbon number of the multiple bond-containing compound is at least the lower limit value, the distance from the main chain of the resulting vinyl alcohol polymer to the multiple bond is long, and the reaction between the multiple bond and the rubber is likely to occur. The adhesion between fiber and rubber is improved.
  • the carbon number of the multiple bond-containing compound is less than or equal to the above upper limit, the solubility of the resulting vinyl alcohol polymer in water and the like is increased, and the handleability is improved.
  • the compound containing no multiple bond is preferably a compound having no branched chain, and from the viewpoint of reactivity with rubber, multiple bonds are preferred. It is preferably present at the end of the compound.
  • the number of multiple bonds in the multiple bond-containing compound is not particularly limited, and is, for example, 1 to 5.
  • the said multiple bond containing compound may have substituents, such as a hydroxyl group, a nitro group, and an aromatic group, for example.
  • the multiple bond-containing compound include an aldehyde having the multiple bond, an acetalized form of the aldehyde, a carboxylic acid having the multiple bond, a salt of the carboxylic acid, an esterified form of the carboxylic acid, and the carboxylic acid At least one selected from an acid anhydride of the above, a dicarboxylic acid having the multiple bond, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, an acid anhydride of the dicarboxylic acid, and an amine compound having the multiple bond; It can be mentioned.
  • the adhesive component used in the present invention can provide a reinforcing fiber having excellent adhesion to rubber even if it does not contain a resorcinol-formaldehyde component which is harmful to the human body. Therefore, in the adhesive component, the content of the resorcinol-formaldehyde component is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less with respect to 100 parts by mass of the vinyl alcohol polymer. 1 part by mass or less is still more preferable, and it is particularly preferable that it is substantially free.
  • Examples of the multiple bond compound used in the production method (1) include an aldehyde having the multiple bond, an acetalized form of the aldehyde, a carboxylic acid having the multiple bond, a salt of the carboxylic acid, and an esterified form of the carboxylic acid And an acid anhydride of the carboxylic acid, a dicarboxylic acid having the multiple bond, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid.
  • aldehydes having multiple bonds examples include acrolein, methacrolein, crotonaldehyde, 3-butenal, 2-methyl-2-butenal, 2-methyl-3.
  • the acetalized form of the aldehyde having a reactive carbon-carbon double bond among the acetalized forms of the aldehyde having a multiple bond includes the acetalized form of the aldehyde, specifically, 2-methyl-3-butenal 3- (1,3-dioxalan-2-yl-)-3-methyl-1-propene which is acetalized form, 3- (1,3-dioxalane- which is acetalized form of 3-methyl-3-butenal 2-yl) -2-methyl-1-propene and the like.
  • aldehyde having multiple bonds and the acetalized form of the aldehyde examples include aldehydes having a carbon-carbon triple bond such as 1-al, acetalized products of the aldehydes, and the like.
  • aldehydes having a reactive carbon-carbon double bond and acetalized products of the aldehydes are preferable.
  • acrolein, methacrolein, crotonaldehyde, 3-butenal, 2-methyl-2- Butenal, 2-methyl-3-butenal, 2,2-dimethyl-3-butenal, 3-methyl-2-butenal, 3-methyl-3-butenal, 2-pentenal, 2-methyl-2-pentenal, 3- 3-pentenal, 3-methyl-4-pentenal, 4-pentenal, 4-methyl-4-pentenal, 2-hexenal, 3-hexenal, 4-hexenal, 5-hexenal, 7-octenal, 2-ethyl crotonaldehyde, 3- (Dimethylamino) acrolein, 2,4-pentadie Lumpur, and one or more selected from acetalization body of these aldehydes are preferred.
  • aldehydes having 3 to 25 carbon atoms and acetalized products of the aldehydes are preferable because they have good reactivity with rubber, and one type selected from 5-hexenal, 7-octenal, and acetalized products of these aldehydes The above is more preferable.
  • the carboxylic acid having the multiple bond, the salt of the carboxylic acid, the esterified form of the carboxylic acid, and the acid anhydride of the carboxylic acid include, for example, (meth) acrylic acid and sodium salt of (meth) acrylic acid, Potassium salt of (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) Vinyl acrylate, 2- (trifluoromethyl) acrylic acid, 2-trifluoromethyl acrylic acid Ethyl, 2-trifluoromethyl ethyl acrylate, propyl 2-tri
  • Examples of the dicarboxylic acid having a multiple bond, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid include, for example, maleic acid, sodium salt of maleic acid, potassium salt of maleic acid, and maleic acid Reactive carbon-carbon double bonds such as methyl, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, helic acid, helic acid methyl, helic acid dimethyl, helic acid anhydride, and helic acid anhydride And a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid.
  • Examples of the multiple bond compound used in the production method (2) include amine compounds having a reactive carbon-carbon double bond.
  • Examples of the amine compound having a reactive carbon-carbon double bond include allylamine, 3-butenylamine, 4-pentenylamine, 5-hexenylamine, 6-heptenylamine, 7-octenylamine, oleylamine, 2-methylallylamine, and the like.
  • Reactive carbons such as aminostyrene, 4-vinylbenzylamine, 2-allylglycine, S-allylcysteine, ⁇ -allylalanine, 2-allylaniline, geranylamine, vigabatrin, 4-vinylaniline, and 4-vinyloxyaniline -Amine compounds having a carbon double bond are mentioned.
  • the amine compound at least one member selected from 5-hexenylamine, 6-heptenylamine and 7-octenylamine is preferable because of good reactivity with rubber.
  • Examples of the multiple bond compound used in the production method (3) include monomers having two or more double bonds.
  • diene compounds such as pentadiene, hexadiene, heptadiene, octadiene, nonadiene, and decadiene;
  • glycerin diallyl ether diethylene glycol diallyl ether, ethylene glycol diallyl ether, triethylene glycol diallyl ether, polyethylene Diallyl ether compounds such as glycol diallyl ether, trimethylolpropane diallyl ether, and pentaerythritol diallyl ether, glycerin triallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, and 1,3,5-triallyl-1, Triallyl ether compounds such as 3,5-triazine-2,4,6 (1H, 3H, 5H)
  • Diallyl ammonium salt such as diallyldimethyl ammonium chloride
  • Monomers having an allyl ammonium group such as: triaryl isocyanurate; 1,3-diallylurea; triallyl phosphate; diallyl disulfide etc.
  • diallyl amine diallyl amine, diallyl amine, diallyl methyl amine, ethylene glycol di (meta ) Acrylate, hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and butanediol di (meth) acrylate
  • ethylene glycol di (meta ) Acrylate ethylene glycol di (meta ) Acrylate
  • hexanediol di (meth) acrylate tripropylene glycol di (meth) acrylate
  • butanediol di (meth) acrylate One or more kinds selected from over preparative is preferred.
  • the total content of structural units derived from the multiple bond-containing compound (hereinafter also referred to as “multiple bond content”) is 0.01 mol% or more and 30 mol% or less based on the total structural units of the vinyl alcohol polymer Is preferred.
  • the adhesiveness of an adhesive component and a hydrophilic fiber can also be maintained, improving the adhesiveness of a vinyl alcohol polymer and rubber
  • the total content of structural units derived from the multiple bond-containing compound is preferably 0.05% by mol or more, more preferably 0.1% by mol or more, based on the total structural units of the vinyl alcohol polymer.
  • the multiple bond content is a value determined by 1 H-NMR spectrum, and more specifically, a value determined according to the method described in the examples.
  • the vinyl alcohol polymer may contain other structural units in addition to the structural unit derived from the multiple bond-containing compound and the vinyl alcohol unit.
  • a structural unit derived from an ethylenically unsaturated monomer copolymerizable with a vinyl ester monomer such as vinyl acetate as a raw material of polyvinyl alcohol can be mentioned.
  • the ethylenically unsaturated monomer include olefins such as ethylene, 1-butene, and isobutylene; acrylic acid and its derivatives; methacrylic acid and its derivatives; acrylamide and its derivatives; methacrylamide and its derivatives; Derivatives thereof; maleic anhydride and derivatives thereof; and the like.
  • the vinyl alcohol polymer contains another structural unit derived from the above-mentioned ethylenically unsaturated monomer, its content is preferably 10 mol% or less, more preferably 5 mol% or less, and 3 mol% or less. More preferable.
  • the viscosity average polymerization degree of the vinyl alcohol polymer is not particularly limited, but is preferably 4000 or less, more preferably 3500 or less, still more preferably 3000 or less from the viewpoint of handling, and from the viewpoint of improving adhesion, The above is preferable, 1000 or more is more preferable, and 1500 or more is still more preferable.
  • the viscosity average polymerization degree of the vinyl alcohol polymer can be measured, for example, by a method according to JIS K 6726.
  • Production method (1) is a method obtained by modifying polyvinyl alcohol with a multiple bond-containing compound having one or more multiple bonds selected from reactive carbon-carbon double bonds and reactive carbon-carbon triple bonds Specifically, it is a method of reacting polyvinyl alcohol with the multiple bond-containing compound to acetalize or esterify polyvinyl alcohol.
  • one or more selected from the multiple bond-containing compounds is reacted with polyvinyl alcohol in the presence of an acid catalyst, and then neutralized with a basic substance to obtain a vinyl alcohol polymer
  • an acid catalyst As a method of acetalizing polyvinyl alcohol, one or more selected from the multiple bond-containing compounds is reacted with polyvinyl alcohol in the presence of an acid catalyst, and then neutralized with a basic substance to obtain a vinyl alcohol polymer
  • the method etc. of obtaining an aqueous solution are mentioned.
  • the acid catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; and organic acids such as formic acid, acetic acid, oxalic acid and p-toluenesulfonic acid.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid
  • organic acids such as formic acid, acetic acid, oxalic acid and p-toluenesulfonic acid.
  • its use amount is preferably about 0.01 to 20 parts by mass with respect to 100 parts by mass of polyvinyl alcohol.
  • the basic substance used for the neutralization is not particularly limited, but, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate, monoethanolamine Primary alkanolamines such as aminoethylethanolamine and monoisopropanolamine; secondary alkanolamines such as diethanolamine, methylethanolamine and butylmethanolamine; firsts such as triethanolamine, methyldiethanolamine and dimethylethanolamine Organic amines such as tertiary alkanolamines can be mentioned.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • monoethanolamine Primary alkanolamines such as aminoethylethanolamine and monoisopropanolamine
  • secondary alkanolamines such as diethanolamine, methylethanolamine and butylmethanolamine
  • firsts such as triethanolamine, methyldi
  • esterifying polyvinyl alcohol carboxylic acid having the multiple bond, salt of the carboxylic acid, esterified product of the carboxylic acid, acid anhydride of the carboxylic acid, dicarboxylic acid having the multiple bond
  • Examples thereof include a method of reacting one or more selected from a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid in the presence of an esterification catalyst.
  • esterification catalyst used for producing a vinyl alcohol polymer in addition to the above-mentioned acid catalyst, for example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and the like; Carbonates and hydrogencarbonates of alkali metals or alkaline earth metals such as sodium hydrogen, potassium carbonate and calcium hydrogencarbonate; phosphates and hydrogenphosphates of alkali metals or alkaline earth metals such as potassium dihydrogenphosphate; Alkali metal or alkaline earth metal borates such as sodium tetraborate; alkali metal or alkaline earth metal carboxylates such as sodium acetate, potassium acetate, sodium benzoate and magnesium acetate; sodium methoxide, potassium methoxy Alkali metal or alkaline earth such as magnesium methoxide Alkoxide compounds of the genus; ammonium salts such as ammonium hydroxide, tetramethyl ammonium hydroxide, am
  • the amount of use of the multiple bond-containing compound as a raw material is, for example, preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, with respect to 100 parts by mass of polyvinyl alcohol. Further preferred is 1 to 10 parts by mass.
  • Production method (2) is a compound having multiple bonds and polyvinyl alcohol having a lactone ring structure in the molecule, which is obtained by copolymerizing a vinyl ester and a (meth) acrylic acid ester and then saponifying the compound, particularly a reaction It is a method of modifying with an amine compound having a carbon-carbon double bond, specifically, a method of amidating polyvinyl alcohol having a lactone ring structure in the molecule with the above-mentioned amine compound.
  • a specific amidation method a method of mixing a polyvinyl alcohol having a lactone ring structure and the amine compound having a reactive carbon-carbon double bond, and heating and reacting them may be mentioned.
  • the production method (3) is a method obtained by copolymerizing a monomer having two or more double bonds and a vinyl alcohol compound. There is no particular limitation on the method of copolymerizing the monomer having two or more double bonds and the vinyl alcohol compound, and a general method for producing a copolymer can be adopted.
  • the reinforcing fiber of the present invention comprises a hydrophilic fiber having an adhesive component on at least a part of the fiber surface.
  • a hydrophilic fiber By using a hydrophilic fiber, the adhesion between the reinforcing fiber and the rubber can be improved.
  • hydrophilic fibers that can be used in the present invention include synthetic fibers, natural fibers, and regenerated fibers. The hydrophilic fibers may be used alone or in combination of two or more.
  • hydrophilic synthetic fiber a synthetic fiber composed of a thermoplastic resin having a hydrophilic functional group such as a hydroxyl group, a carboxyl group, a sulfonic acid and an amino group and / or a hydrophilic bond such as an amide bond Can be mentioned.
  • thermoplastic resins are polyvinyl alcohol resins, polyamide resins [polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 9 C (polyamide composed of nonane diamine and cyclohexane dicarboxylic acid)] Aliphatic polyamides such as: Semi aromatic polyamides synthesized from aromatic dicarboxylic acids and aliphatic diamines such as polyamide 9T (polyamide consisting of nonane diamine and terephthalic acid); Aromatic dicarboxylic acids such as poly paraphenylene terephthalamide and aroma Aromatic polyamide etc. which are synthesized from a group diamine and the like], polyacrylamide based resins and the like.
  • hydrophilic synthetic fibers may be used alone or in combination of two or more.
  • these hydrophilic synthetic fibers may be further subjected to a hydrophilization treatment described later in order to further enhance the hydrophilicity.
  • hydrophilic natural fibers examples include wood pulp such as kraft pulp and natural cellulose fibers such as non-wood pulp such as cotton pulp and straw pulp.
  • Hydrophilic regenerated fibers include regenerated cellulose fibers such as rayon, lyocell, cupra and polynozic. These natural fibers and regenerated fibers may be used alone or in combination of two or more. In addition, these hydrophilic natural fibers may be further subjected to a hydrophilization treatment described later in order to further enhance the hydrophilicity.
  • the hydrophilic fiber may be at least the surface having hydrophilicity, and for example, a fiber obtained by hydrophilizing the surface of a hydrophobic resin, or a core having a hydrophobic resin as a core and a sheath having a hydrophilic resin It may be sheath type composite fiber or the like.
  • the description of hydrophilic synthetic fibers is cited as an example of the hydrophilic resin constituting the sheath part.
  • hydrophobic fibers made of hydrophobic resin include polyolefin fibers such as polyethylene and polypropylene, polyester fibers such as polyethylene terephthalate, and wholly aromatic polyester fibers, among which polyester fibers are preferable. .
  • the hydrophilization treatment is not particularly limited as long as it is a treatment that chemically or physically imparts a hydrophilic functional group to the fiber surface, but for example, a fiber composed of the hydrophobic resin is an isocyanate group, an epoxy group, and a hydroxy group And the like, and a method of modifying the surface by electron beam irradiation, and the like.
  • the hydrophilic fiber used in the present invention is preferably a synthetic fiber or a regenerated fiber from the viewpoint of being used as a reinforcing fiber, and among them, the surface of polyvinyl alcohol fiber made from polyvinyl alcohol resin, regenerated cellulose fiber, hydrophobic fiber
  • the fiber which carried out the hydrophilization process is preferable, and a polyvinyl alcohol-type fiber is especially preferable.
  • the vinyl alcohol-based polymer as the adhesive component and the hydrophilic fiber exhibit a strong affinity effect, and the adhesive component and the fiber are strongly coupled, so adhesion to the object to be reinforced is achieved. The power can be made better.
  • polyvinyl alcohol fibers from the viewpoint of suitably using the reinforcing fiber of the present invention for automobile hoses, particularly automobile brake oil hoses, commercially available from Kuraray Co., Ltd. under the trade name "Vinylon", and having a single fiber fineness Those having about 0.1 to 30 dtex can be suitably used.
  • the reinforcing fiber of the present invention is not particularly limited as long as it has an adhesive component on at least a part of the fiber surface, but a reinforcing fiber having an adhesive layer consisting of the adhesive component on at least a part of the fiber surface
  • the reinforcing fiber which contains the said adhesion component as a part of raw material is preferable.
  • the manufacturing method of said 2 types of reinforcement fiber is demonstrated.
  • the method for producing a reinforcing fiber having an adhesive layer comprising the adhesive component on at least a part of the fiber surface includes the above-mentioned hydrophilicity by one or more methods selected from immersion, roll coater, nozzle (spray) application, brushing and the like.
  • the adhesive component can be attached to the adhesive fiber and then dried by heating at about 100 to 180 ° C. for about 0.1 second to 2 minutes.
  • the adhesive component When the adhesive component is attached to the hydrophilic fiber, water, ethanol, propanol, butanol, methanol, toluene, xylene, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, ethyl acetate and the like are used as solvents in addition to the adhesive component. It is also good.
  • an acid, an alkali, a curing agent, a dispersing agent, an oil and the like may be mixed together with the adhesive component and dissolved or dispersed.
  • the amount thereof used is preferably 50 to 99.9% by mass, more preferably 60 to 99.5% by mass, still more preferably 70 to 99.0% by mass in the total of the adhesive component and the solvent. It is.
  • the amount of the adhesive component to be attached to the hydrophilic fiber is preferably 0.01% by mass or more, from the viewpoint of improving the adhesion between the reinforcing fiber and the rubber, % Or more is more preferable, 0.1% by mass or more is further preferable, and 10% by mass or less is preferable, 5% by mass or less is more preferable, and 3% by mass or less from the viewpoint of the balance between manufacturing costs and effects. More preferable.
  • the reinforcing fiber of the present invention may be produced by providing an adhesive layer comprising the adhesive component on the surface of a hydrophilic fiber as described above, but it is produced as a fiber containing the adhesive component as a part of the raw material It is also good.
  • raw materials other than the adhesive component in the case where the fiber contains the adhesive component as a part of the raw material but examples thereof include polyvinyl alcohol, polyester, nylon, triacetate, diacetate, polyamide, and mixtures thereof. Among them, polyvinyl alcohol is preferable from the viewpoint of the easiness of mixing with the adhesive component and the strength of the reinforcing fiber.
  • the content of the adhesive component in the fiber raw material is preferably 20% by mass or more from the viewpoint of improving the adhesion between the reinforcing fiber and the rubber, More preferably, it is 30% by mass or more, and more preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less from the viewpoint of the balance between the production cost and the effect.
  • the content of multiple bonds in the fiber raw material is the structural unit derived from the multiple bond-containing compound with respect to all constituent units of the polymer constituting the raw material.
  • it is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, still more preferably 0.08 mol% or more, still more preferably 0.1 mol% or more, still more preferably 0.12 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, still more preferably 5 mol% or less, still more preferably 3 mol%
  • the following is more preferably 2 mol% or less.
  • the manufacturing method of the fiber in the case of manufacturing as a fiber which contains the said adhesion component as a part of raw material, According to the manufacturing method of a general synthetic fiber, it can manufacture.
  • a polyvinyl alcohol having a degree of polymerization of 1,500 or more and a degree of saponification of 99 mol% or more and a method for performing wet, dry, or dry and wet spinning by dissolving or semi-melting the adhesive component in water or an organic solvent may be mentioned.
  • the reinforcing fiber is preferably a multifilament having a single yarn fineness of 0.1 dtex or more and 30 dtex or less.
  • the single yarn fineness may be less than 0.1 dtex, but is preferably 0.1 dtex or more because it is difficult to industrially produce.
  • the single yarn fineness is 30 dtex or less, the surface area of the fiber in the case of the reinforcing fiber is increased, and the adhesion to rubber is improved.
  • the reinforcing fiber of the present invention preferably has a single yarn fineness of 0.3 dtex or more, more preferably 0.5 dtex or more, still more preferably 1 dtex or more, and preferably 20 dtex or less, more preferably 15 dtex or less More preferably, it is a multifilament which is 10 dtex or less.
  • the initial tensile resistance measured according to JIS L 1013: 2010 is preferably 70 cN / dtex or more.
  • gum improves that the initial stage tensile resistance degree of the reinforcement fiber of this invention is more than the said lower limit.
  • the initial tensile resistance of the present invention is preferably 100 cN / dtex or more, more preferably 130 cN / dtex or more, still more preferably 160 cN / dtex or more, still more preferably 190 cN / dtex or more, 200 cN / dtex or more Even more preferable.
  • the upper limit value of the initial tensile resistance degree of the present invention is not particularly limited, but is usually 1000 cN / dtex or less.
  • the reinforcing fiber of the present invention can be used, for example, as a fiber adhering to rubber as described later, and as a reinforcing fiber to be mixed. In addition, it can also be used as a reinforcing fiber to be mixed into cement, concrete or the like.
  • the molded article of the present invention is not particularly limited as long as it uses the reinforcing fiber.
  • a molded article using a reinforcing fiber and a rubber is preferable because the reinforcing fiber of the present invention has excellent adhesion to the rubber.
  • Molded articles using reinforcing fibers and rubber can be used as members of rubber products such as automobile tires, conveyor belts, rubber hoses, timing belts, and vibration-proof rubbers, among which rubber hoses and vibration-proof rubbers are used. Is more preferred.
  • the rubber hose can be used to transport various fluids in various applications, and is suitable, for example, as a fluid transport hose for automobiles, and in particular, a liquid fuel hose for automobiles, a brake for automobiles It is preferable to use for an oil hose and a hose for refrigerant
  • the rubber constituting the molded article using the reinforcing fiber and rubber of the present invention is preferably one obtained by blending a compounding agent which is usually used in the rubber industry with a rubber component.
  • the rubber component is not particularly limited.
  • NR natural rubber
  • IR polyisoprene rubber
  • BR polybutadiene rubber
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • EPM ethylene-) Propylene copolymer rubber
  • EPDM ethylene-propylene non-conjugated diene copolymer rubber
  • IIR butyl rubber
  • CR chloroprene rubber
  • the reinforcing fiber may be produced by bonding to rubber in the form of a fiber bundle, a woven fabric or a knitted fabric.
  • Production Example 2 A vinyl alcohol polymer (the same as in Production Example 1) except that 1.07 g of 7-octenal was changed to 1.82 g of 3- (1,3-dioxalan-2-yl) -2-methyl-1-propene B) was synthesized. As a result of quantifying the double bond content by 1 H-NMR, the double bond content of the vinyl alcohol polymer (B) was 1.1 mol%.
  • Adhesive component adhesion amount [(BA) / A] x 100 (mass%)
  • reinforcing fibers having an adhesive layer composed of an adhesive component on at least a part of the fiber surface were produced and evaluated as follows. In 98.0 g of water, 2.0 g of the adhesive component consisting of the vinyl alcohol polymers (A) to (C) produced as described above was dissolved. After immersing vinylon fiber ("Kuraray 1239", 1330 dtex made by Kuraray Co., Ltd.) which is a polyvinyl alcohol-based fiber in this solution, it was squeezed with a roller. The resulting fibers were then dried at 120 ° C. for 30 seconds and heat treated at 140 ° C. for 30 seconds. The vinylon to which the adhesive component was attached in this manner was twisted at a twist number of 80 T / m to produce a fiber cord. The adhesion amount of the adhesive component in Examples 1 to 3 was adjusted as described in Table 1.
  • Comparative Example 1 The same as Examples 1 to 3 except that polyvinyl alcohol (saponification degree of 99 mol% or more, average polymerization degree of 1700) was used as an adhesive component, and the adhesion amount of the adhesive component was adjusted as described in Table 1.
  • the fiber cord was made by the method.
  • Comparative Example 2 As Examples 1 to 3 except that polyvinyl alcohol (saponification degree 94.5 mol% or more, average polymerization degree 1700) was used as the adhesive component, and the adhesion amount of the adhesive component was adjusted as described in Table 1 A fiber cord was made in the same manner.
  • polyvinyl alcohol saponification degree 94.5 mol% or more, average polymerization degree 1700
  • Comparative Example 3 A fiber cord was produced in the same manner as in Examples 1 to 3 except that RFL prepared by the following method was used as an adhesive component, and the adhesion amount of the adhesive component was adjusted as described in Table 1.
  • Solution B SBR latex (concentration 40%): 43 parts Vinylpyridine-modified SBR latex (concentration 40%): 244 parts The solution B was mixed with the solution A and then aged at 25 ° C. for 16 hours for RFL The solution was made.
  • the initial tensile resistance of the obtained sheet for adhesive strength evaluation was measured according to JIS L 1013: 2010 using a measuring machine (Instron 3365).
  • the peeling test was performed by moving 200 mm at a peeling speed of 50 mm / min to peel the fiber cord and the rubber. Five peaks and five lowest points were taken from a number of peaks appearing in the range of 10 mm from the first peak appearing in the chart and 10 mm from the last peak, and the average value was taken as the initial tensile resistance of fiber and rubber. .
  • the value was extract
  • the evaluation results of the initial degree of tensile resistance show that the larger the numerical value, the greater the adhesion between the reinforcing fiber and the rubber.
  • Example 4 As Example 4, the reinforcing fiber in which the fiber contains the adhesive component as a part of the raw material was manufactured and evaluated as follows.
  • the boric acid was added in the ratio of 2 mass parts with respect to a total of 100 mass parts of OEL modified PVA and a PVA homopolymer, and the undiluted
  • the stock solution is wet-spun into a 70 ° C. coagulation bath (one bath) bathed in water at a ratio of 20 g / L of sodium hydroxide and 320 g / L of sodium sulfate, roller stretching, neutralization, wet heat stretching, It was washed with water and dried. Subsequently, dry heat drawing was performed at 240 ° C., and winding on a bobbin was performed to obtain a PVA-based fiber (2000 dTex). The obtained fiber was twisted at 80 T / m to produce a fiber cord.
  • Comparative Example 4 A fiber cord comprising PVA fiber was obtained in the same manner as in Example 4 except that the stock solution was prepared so as to have a solid content concentration of 12% by weight using only the PVA homopolymer without using OEL-modified PVA.
  • the reinforcing fiber of the present invention obtains a reinforcing fiber having excellent adhesion to rubber without using an adhesive containing resorcinol formalin resin and rubber latex as main components. be able to.

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Abstract

A reinforcement fiber comprising a hydrophilic fiber having an adhesive component in at least a part of the fiber surface, wherein the adhesive component includes a vinyl alcohol polymer having, within a molecule, at least one multiple bond selected from among a reactive carbon-carbon double bond and a reactive carbon-carbon triple bond.

Description

補強繊維、及びこれを用いた成形体Reinforcing fiber and molded article using the same
　本発明は、ゴムとの接着性に優れる補強繊維、及びこれを用いた成形体に関する。 The present invention relates to a reinforcing fiber excellent in adhesion to rubber, and a molded article using the same.
　一般的に、タイヤ、コンベアベルト、及びホース（例えば、自動車用オイルブレーキホース）等の工業用ゴム製品は、ビニロン及びレーヨン等の合成繊維や綿等の天然繊維を用いて補強されている。これらの製品において、ゴムが有する優れた物理的特性（例えば、高強度及び高弾性率）等を十分に発揮させるためには、繊維とゴムとを強固に接着させる必要がある。従来、かかる方法として、レゾルシン・ホルマリン樹脂とゴムラテックスとを主成分とする接着剤を用いる方法が広く知られている（特許文献１及び２）。 In general, industrial rubber products such as tires, conveyor belts, and hoses (for example, oil brake hoses for automobiles) are reinforced with synthetic fibers such as vinylon and rayon or natural fibers such as cotton. In these products, in order to fully exhibit the excellent physical properties (for example, high strength and high elastic modulus) possessed by the rubber, it is necessary to firmly bond the fiber and the rubber. Conventionally, as such a method, a method using an adhesive containing resorcinol formalin resin and rubber latex as main components is widely known (Patent Documents 1 and 2).
　しかしながら、ホルマリンは発がん性の疑いがあり、レゾルシンは環境ホルモンの疑いがあることから代替材料の開発が望まれている。具体的に、特許文献３には、ゴムの加硫に用いられる加硫剤と反応する不飽和炭素結合及びエポキシ基を有する接着化合物を含む接着剤を用いる技術が提案されている。また、特許文献４には、（ブロックド）イソシアネート化合物及び／又はアミン系硬化剤（Ａ）と、エポキシ化合物（Ｂ）と、ゴムラテックス（Ｃ）と、を含み、レゾルシン及びホルマリンを含まない有機繊維コード用接着剤組成物を用いた接着方法が提案されている。 However, formalin is suspected to be carcinogenic, and resorcinol is suspected to be an environmental hormone, so development of alternative materials is desired. Specifically, Patent Document 3 proposes a technique using an adhesive containing an adhesive compound having an unsaturated carbon bond and an epoxy group, which react with a vulcanizing agent used for vulcanizing rubber. In addition, Patent Document 4 includes an (blocked) isocyanate compound and / or an amine curing agent (A), an epoxy compound (B), and a rubber latex (C), and does not contain resorcin and formalin. A bonding method using a fiber cord adhesive composition has been proposed.
特開昭５４－４９７６号公報JP-A-54-4976 特開昭５８－２３７０号公報Japanese Patent Application Laid-Open No. 58-2370 特開２０１１－１１１５６３号公報JP, 2011-111563, A 国際公開第２０１０／１２５９９２号International Publication No. 2010/125992
　特許文献３に記載された接着剤を用いた方法は、従来のレゾルシン・ホルマリン樹脂とゴムラテックスとを主成分とする接着剤を用いた方法に比べて、接着性が劣っており、特許文献４に記載された接着剤を用いた方法は、従来のレゾルシン・ホルマリン樹脂とゴムラテックスとを主成分とする接着剤を用いた方法と同等かそれ以上の接着力を有するものの、有機繊維コードの表面に接着剤層を形成した後、実質的には高温（１８０℃及び２４０℃）によって加熱処理する必要があった。補強繊維としてしばしば用いられるＰＶＡ系繊維やＰＥＴ系繊維といった有機繊維をかかる方法で処理した場合、劣化によって補強繊維としての性能が落ちる危険性があった。従来のレゾルシン・ホルマリン樹脂とゴムラテックスとを主成分とする接着剤を用いた方法と同程度の接着力を有しながら、汎用的な樹脂が劣化しない温度で接着層の形成及び熱処理が可能な方法が求められていた。 The method using the adhesive described in Patent Document 3 is inferior in adhesion to the method using a conventional adhesive containing resorcin / formalin resin and rubber latex as main components, as described in Patent Document 4 Although the method using the adhesive described in the above has an adhesive power equal to or higher than the method using the conventional adhesive based on resorcinol formalin resin and rubber latex, the surface of the organic fiber cord After forming the adhesive layer, it was necessary to carry out heat treatment substantially at high temperatures (180.degree. C. and 240.degree. C.). When an organic fiber such as a PVA-based fiber or a PET-based fiber, which is often used as a reinforcing fiber, is treated by such a method, there is a risk that the performance as the reinforcing fiber may be deteriorated due to deterioration. Adhesive layer can be formed and heat-treated at a temperature at which general-purpose resins do not deteriorate while having the same adhesive strength as the method using an adhesive containing a conventional resorcin-formalin resin and rubber latex as the main components A method was sought.
　本発明の課題は、前記従来の問題を鑑みてなされたものであって、レゾルシン及びホルマリンを含有しない接着成分を用いた補強繊維であって、ゴムとの接着性に優れる補強繊維を提供することにある。 The object of the present invention is to provide a reinforcing fiber using a bonding component which does not contain resorcinol and formalin and is excellent in adhesion to rubber. It is in.
　本発明者らは、前記従来の課題を解決するために鋭意検討した結果、反応性炭素－炭素二重結合及び反応性炭素－炭素三重結合から選ばれる１種以上の多重結合を有するビニルアルコール系重合体を用いることにより、レゾルシン及びホルマリンを使用しなくても、ゴムとの接着性に優れる補強繊維が得られることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above-mentioned conventional problems, the present inventors have found that vinyl alcohol systems having one or more multiple bonds selected from reactive carbon-carbon double bonds and reactive carbon-carbon triple bonds. By using a polymer, it discovered that the reinforcement fiber which is excellent in adhesiveness with rubber | gum is obtained, even if it does not use a resorcin and formalin, and completed this invention.
　すなわち、本発明は以下［１］～［２］に関する。
［１］繊維表面の少なくとも一部に接着成分を有する親水性繊維からなる補強繊維であって、該接着成分が分子内に反応性炭素－炭素二重結合及び反応性炭素－炭素三重結合から選ばれる１種以上の多重結合を有するビニルアルコール系重合体を含む補強繊維。
［２］前記［１］に記載の補強繊維を用いた成形体。 That is, the present invention relates to the following [1] to [2].
[1] A reinforcing fiber comprising a hydrophilic fiber having an adhesive component on at least a part of the fiber surface, wherein the adhesive component is selected from reactive carbon-carbon double bonds and reactive carbon-carbon triple bonds in the molecule Reinforcing fiber comprising a vinyl alcohol polymer having one or more multiple bonds.
[2] A molded article using the reinforcing fiber according to the above [1].
　本発明は、レゾルシン及びホルマリンを含有しない接着成分を用いた補強繊維であって、ゴムとの接着性に優れる補強繊維を提供することができる。 The present invention is a reinforcing fiber using an adhesive component not containing resorcin and formalin, and can provide a reinforcing fiber having excellent adhesion to rubber.
［補強繊維］
　本発明の補強繊維は、繊維表面の少なくとも一部に接着成分を有する親水性繊維からなる補強繊維であって、該接着成分が、分子内に反応性炭素－炭素二重結合及び反応性炭素－炭素三重結合から選ばれる１種以上の多重結合を有するビニルアルコール系重合体を含むものである。本発明によれば、前記多重結合を有するビニルアルコール系重合体が親水性の繊維表面の少なくとも一部に存在しているため、前記多重結合とゴム等とが反応し結合を形成するため、優れた接着力を有する補強繊維を得ることができる。
　なお、本発明において「反応性炭素－炭素二重結合」とは、熱又は光等の外部エネルギーにより他の成分と反応し得る炭素－炭素二重結合を意味し、通常、芳香族環に含まれる炭素－炭素二重結合は含まず、脂肪族炭素－炭素二重結合を指す。「反応性炭素－炭素三重結合」についても同様の意味を示す。 [Reinforcement fiber]
The reinforcing fiber of the present invention is a reinforcing fiber consisting of a hydrophilic fiber having an adhesive component on at least a part of the fiber surface, and the adhesive component comprises a reactive carbon-carbon double bond and a reactive carbon- in the molecule. It includes a vinyl alcohol polymer having one or more kinds of multiple bonds selected from carbon triple bonds. According to the present invention, since the vinyl alcohol polymer having multiple bonds is present in at least a part of the hydrophilic fiber surface, the multiple bonds react with rubber and the like to form bonds, which is excellent. It is possible to obtain a reinforcing fiber having good adhesion.
In the present invention, "reactive carbon-carbon double bond" means a carbon-carbon double bond that can react with other components by external energy such as heat or light, and is usually contained in an aromatic ring. Does not include the carbon-carbon double bond, but refers to an aliphatic carbon-carbon double bond. The same applies to “reactive carbon-carbon triple bond”.
＜接着成分＞
　本発明において用いる接着成分は、分子内に反応性炭素－炭素二重結合及び反応性炭素－炭素三重結合から選ばれる１種以上の多重結合を有するビニルアルコール系重合体を含むものであれば特に制限はない。前記ビニルアルコール系重合体としては、主鎖に前記多重結合が存在するものであってもよく、側鎖に前記多重結合が存在するものであってもよいが、接着力をより向上させる観点から、前記多重結合の少なくとも一部が前記ビニルアルコール系重合体の側鎖に存在するものが好ましい。本発明によれば、前記多重結合がゴムと加硫により共有結合を形成することにより接着性を発現していると考えられることから、前記多重結合がビニルアルコール系重合体の主鎖ではなく、側鎖に存在した方が補強繊維とゴムとの接着性が良好になる。前記ビニルアルコール系重合体の各側鎖が有する多重結合の数は特に限定されず、例えば１～５個等である。 <Adhesive component>
The adhesive component used in the present invention is particularly preferably one containing a vinyl alcohol polymer having in its molecule one or more multiple bonds selected from reactive carbon-carbon double bonds and reactive carbon-carbon triple bonds. There is no limit. As the vinyl alcohol polymer, the multiple bond may be present in the main chain or the multiple bond may be present in the side chain, but from the viewpoint of further improving the adhesion. Preferably, at least a part of the multiple bond is present in the side chain of the vinyl alcohol polymer. According to the present invention, since the multiple bond is considered to exhibit adhesiveness by forming a covalent bond with the rubber by vulcanization, the multiple bond is not the main chain of the vinyl alcohol polymer, If it is present in the side chain, the adhesion between the reinforcing fiber and the rubber becomes better. The number of multiple bonds contained in each side chain of the vinyl alcohol polymer is not particularly limited, and is, for example, 1 to 5.
　前記多重結合の少なくとも一部が側鎖に存在するビニルアルコール系重合体において、ビニルアルコール系重合体の主鎖から多重結合までの距離は、主鎖と側鎖とを結合する酸素又は炭素原子から数えて、側鎖の多重結合を構成する炭素原子までの原子数は、２以上が好ましく、３以上がより好ましく、５以上が更に好ましく、２０以下が好ましく、１５以下がより好ましく、１３以下が更に好ましく、１０以下がより更に好ましい。側鎖の多重結合を構成する炭素原子までの原子数が多いほど、ビニルアルコール系重合体の主鎖からの多重結合までの距離が遠くなり、多重結合とゴムとの反応が生じやすくなるため補強繊維とゴムとの接着性が向上する。このような観点から、多重結合が側鎖の末端に存在することも好ましい。また、多重結合の近傍の立体障害を小さくし、ゴムと反応しやすくする観点から、多重結合が存在する側鎖は、分岐鎖ではなく直鎖状であることも好ましい。
　一方、側鎖の多重結合を構成する炭素原子までの原子数が、前記上限値以下であると、ビニルアルコール系重合体の水等への溶解性が高くなり、取り扱い性が向上する。 In the vinyl alcohol polymer in which at least a part of the multiple bond is present in the side chain, the distance from the main chain of the vinyl alcohol polymer to the multiple bond is from the oxygen or carbon atom connecting the main chain and the side chain When counting, the number of atoms up to the carbon atom constituting the multiple bond of the side chain is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, preferably 20 or less, more preferably 15 or less, 13 or less More preferably, 10 or less is even more preferable. The larger the number of atoms up to the carbon atom that constitutes the multiple bond of the side chain, the longer the distance from the main chain of the vinyl alcohol polymer to the multiple bond, and the reaction between the multiple bond and the rubber is more likely to occur. The adhesion between fiber and rubber is improved. From such a point of view, it is also preferred that multiple bonds be present at the end of the side chain. Further, from the viewpoint of reducing steric hindrance in the vicinity of multiple bonds and facilitating reaction with rubber, it is also preferable that the side chain in which multiple bonds exist be linear rather than branched.
On the other hand, when the number of atoms up to the carbon atom constituting the multiple bond of the side chain is less than the upper limit value, the solubility of the vinyl alcohol polymer in water and the like becomes high, and the handleability is improved.
　側鎖に前記多重結合の少なくとも一部が存在するビニルアルコール系重合体を得る方法としては、例えば、前記多重結合を有する多重結合含有化合物でポリビニルアルコールを変性することにより得る方法（以下「製造方法（１）」ともいう）、ビニルエステルと（メタ）アクリル酸エステルとを共重合した後、けん化することで得られる、分子内にラクトン環構造を有するポリビニルアルコールを多重結合を有するアミン化合物、特に反応性炭素－炭素二重結合を有するアミン化合物で変性することにより得る方法（以下「製造方法（２）」ともいう）、二重結合を２つ以上有する単量体とビニルアルコール系化合物とを共重合することにより得る方法（以下「製造方法（３）」ともいう）が挙げられる。中でも、前記多重結合を有する多重結合含有化合物でポリビニルアルコールを変性することにより得る方法（製造方法（１））が好ましい。各製造方法の詳細については後述する。 As a method of obtaining a vinyl alcohol polymer in which at least a part of the multiple bond is present in a side chain, for example, a method of obtaining the vinyl alcohol polymer by modifying polyvinyl alcohol with a multiple bond-containing compound having the multiple bond (hereinafter referred to as “production method (Also referred to as “(1)”), an amine compound having multiple bonds with polyvinyl alcohol having a lactone ring structure in the molecule, which is obtained by copolymerizing a vinyl ester and a (meth) acrylic acid ester and then saponifying A method obtained by modifying with an amine compound having a reactive carbon-carbon double bond (hereinafter also referred to as “production method (2)”), a monomer having two or more double bonds and a vinyl alcohol compound The method (Hereafter, it is also called "manufacturing method (3)") obtained by copolymerizing is mentioned. Among them, the method (production method (1)) obtained by modifying polyvinyl alcohol with the multiple bond-containing compound having multiple bonds is preferable. Details of each manufacturing method will be described later.
　前記多重結合含有化合物に特に制限はないが、好ましくは炭素数が３～３０、より好ましくは３～２０、更に好ましくは５～１５、より更に好ましくは５～１０である化合物が好ましい。多重結合含有化合物の炭素数が前記下限値以上であると、得られるビニルアルコール系重合体の主鎖からの多重結合までの距離が遠くなり、多重結合とゴムとの反応が生じやすくなるため補強繊維とゴムとの接着性が向上する。一方、多重結合含有化合物の炭素数が前記上限値以下であると、得られるビニルアルコール系重合体の水等への溶解性が高くなり、取り扱い性が向上する。なお、多重結合の近傍の立体障害を小さくし、ゴムと反応しやすくする観点から、多重結合含有化合物は分岐鎖を有しない化合物が好ましく、また、ゴムとの反応性の観点から、多重結合が化合物の末端に存在することが好ましい。 The multiple bond-containing compound is not particularly limited, but is preferably a compound having 3 to 30, more preferably 3 to 20, still more preferably 5 to 15, and still more preferably 5 to 10 carbon atoms. When the carbon number of the multiple bond-containing compound is at least the lower limit value, the distance from the main chain of the resulting vinyl alcohol polymer to the multiple bond is long, and the reaction between the multiple bond and the rubber is likely to occur. The adhesion between fiber and rubber is improved. On the other hand, when the carbon number of the multiple bond-containing compound is less than or equal to the above upper limit, the solubility of the resulting vinyl alcohol polymer in water and the like is increased, and the handleability is improved. From the viewpoint of reducing steric hindrance in the vicinity of multiple bonds and making it easy to react with rubber, the compound containing no multiple bond is preferably a compound having no branched chain, and from the viewpoint of reactivity with rubber, multiple bonds are preferred. It is preferably present at the end of the compound.
　前記多重結合含有化合物中の多重結合の数は特に限定されず、例えば１～５個等である。なお、前記多重結合含有化合物は、例えば、水酸基、ニトロ基、及び芳香族基等の置換基を有していてもよい。 The number of multiple bonds in the multiple bond-containing compound is not particularly limited, and is, for example, 1 to 5. In addition, the said multiple bond containing compound may have substituents, such as a hydroxyl group, a nitro group, and an aromatic group, for example.
　前記多重結合含有化合物の具体例としては、前記多重結合を有するアルデヒド、該アルデヒドのアセタール化体、前記多重結合を有するカルボン酸、該カルボン酸の塩、該カルボン酸のエステル化体、該カルボン酸の酸無水物、前記多重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、該ジカルボン酸の酸無水物、及び前記多重結合を有するアミン化合物から選ばれる１種以上が挙げられる。 Specific examples of the multiple bond-containing compound include an aldehyde having the multiple bond, an acetalized form of the aldehyde, a carboxylic acid having the multiple bond, a salt of the carboxylic acid, an esterified form of the carboxylic acid, and the carboxylic acid At least one selected from an acid anhydride of the above, a dicarboxylic acid having the multiple bond, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, an acid anhydride of the dicarboxylic acid, and an amine compound having the multiple bond; It can be mentioned.
　なお、本発明において用いる接着成分は、人体に有害なレゾルシン－ホルムアルデヒド成分を含まなくてもゴムとの接着性に優れる補強繊維を得ることができる。したがって、前記接着成分において、前記レゾルシン－ホルムアルデヒド成分の含有量は前記ビニルアルコール系重合体１００質量部に対して１０質量部以下が好ましく、５質量部以下がより好ましく、３質量部以下が更に好ましく、１質量部以下がより更に好ましく、実質的に含まないことが特に好ましい。 The adhesive component used in the present invention can provide a reinforcing fiber having excellent adhesion to rubber even if it does not contain a resorcinol-formaldehyde component which is harmful to the human body. Therefore, in the adhesive component, the content of the resorcinol-formaldehyde component is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less with respect to 100 parts by mass of the vinyl alcohol polymer. 1 part by mass or less is still more preferable, and it is particularly preferable that it is substantially free.
〔製造方法（１）において用いる多重結合含有化合物〕
　製造方法（１）において用いる多重結合化合物としては、例えば、前記多重結合を有するアルデヒド、該アルデヒドのアセタール化体、前記多重結合を有するカルボン酸、該カルボン酸の塩、該カルボン酸のエステル化体、該カルボン酸の酸無水物、前記多重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、及び該ジカルボン酸の酸無水物が挙げられる。 [Multiple bond containing compound used in production method (1)]
Examples of the multiple bond compound used in the production method (1) include an aldehyde having the multiple bond, an acetalized form of the aldehyde, a carboxylic acid having the multiple bond, a salt of the carboxylic acid, and an esterified form of the carboxylic acid And an acid anhydride of the carboxylic acid, a dicarboxylic acid having the multiple bond, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid.
　前記多重結合を有するアルデヒドのうち、反応性炭素－炭素二重結合を有するアルデヒドとしては、例えば、アクロレイン、メタクロレイン、クロトンアルデヒド、３－ブテナール、２－メチル－２－ブテナール、２－メチル－３－ブテナール、２，２－ジメチル－３－ブテナール、３－メチル－２－ブテナール、３－メチル－３－ブテナール、２－ペンテナール、２－メチル－２－ペンテナール、３－ペンテナール、３－メチル－４－ペンテナール、４－ペンテナール、４－メチル－４－ペンテナール、２－ヘキセナール、３－ヘキセナール、４－ヘキセナール、５－ヘキセナール、７－オクテナール、１０－ウンデセナール、２－エチルクロトンアルデヒド、３－（ジメチルアミノ）アクロレイン、ミリストレインアルデヒド、パルミトレインアルデヒド、オレインアルデヒド、エライジンアルデヒド、バクセンアルデヒド、ガドレインアルデヒド、エルカアルデヒド、ネルボンアルデヒド、リノールアルデヒド、シトロネラール、シンナムアルデヒド、及びバニリン等の炭素数３～３０のアルケナール、好ましくは炭素数３～２５のアルケナール；
　２，４－ペンタジエナール、２，４－ヘキサジエナール、２，６－ノナジエナール、及びシトラール等の炭素数５～３０のアルカジエナール、好ましくは炭素数５～２５のアルカジエナール；
　リノレンアルデヒド、エレオステアリンアルデヒド等の炭素数７～３０のアルカトリエナール、好ましくは炭素数７～２５のアルカトリエナール；
　ステアリドンアルデヒド、アラキドンアルデヒド等の炭素数９～３０のアルカテトラエナール、好ましくは炭素数９～２５のアルカテトラエナール；
　エイコサペンタエンアルデヒド等の炭素数１１～３０のアルカペンタエナール、好ましくは炭素数１１～２５のアルカペンタエナール；等の不飽和アルデヒド等が挙げられる。
　なお、前記アルデヒドにおいてシス－トランス異性体が存在するものは、シス体及びトランス体の両方を含む。これらのアルデヒドは、単独でも、２種以上を組み合わせて用いてもよい。 Among aldehydes having multiple bonds, examples of aldehydes having a reactive carbon-carbon double bond include acrolein, methacrolein, crotonaldehyde, 3-butenal, 2-methyl-2-butenal, 2-methyl-3. -Butenal, 2,2-dimethyl-3-butenal, 3-methyl-2-butenal, 3-methyl-3-butenal, 2-pentenal, 2-methyl-2-pentenal, 3-pentenal, 3-methyl-4 -Pentenal, 4-pentenal, 4-methyl-4-pentenal, 2-hexenal, 3-hexenal, 4-hexenal, 5-hexenal, 7-octenal, 10-undecenal, 2-ethyl crotonaldehyde, 3- (dimethylamino) ) Acrolein, myristolein aldehyde, palmito C3-C30 alkenals such as C3-C25, preferably C3-C25, such as inaldehyde, olealdehyde, elaidaldehyde, baccene aldehyde, gadrainaldehyde, erucaldehyde, nervone aldehyde, linolealdehyde, citronellal, cinnamaldehyde, and vanillin Alkenal;
Alkadienal having 5 to 30 carbon atoms such as 2,4-pentadienal, 2,4-hexadienal, 2,6-nonadienal, and citral, preferably alkadienal having 5 to 25 carbon atoms;
C 10 -C 30 alcatrienals such as linolein aldehyde, eleostearaldehyde, etc., preferably C 7 -25 alcatrienals;
Alkytetra enal having 9 to 30 carbon atoms such as stearidone aldehyde, arachidon aldehyde, preferably alky tetra enal having 9 to 25 carbon atoms;
And unsaturated aldehydes such as alkapentaenal having 11 to 30 carbon atoms such as eicosapentaene aldehyde, preferably alkapentaenal having a carbon number of 11 to 25, and the like.
Among the aldehydes, those in which cis-trans isomers exist include both cis and trans isomers. These aldehydes may be used alone or in combination of two or more.
　前記多重結合を有するアルデヒドのアセタール化体のうち、反応性炭素－炭素二重結合を有するアルデヒドのアセタール化体としては、前記アルデヒドのアセタール化体、具体的には２－メチル－３－ブテナールのアセタール化体である３－（１，３－ジオキサラン－２－イル－）－３－メチル－１－プロペン、３－メチル－３－ブテナールのアセタール化体である３－（１，３－ジオキサラン－２－イル）－２－メチル－１－プロペン等が挙げられる。 The acetalized form of the aldehyde having a reactive carbon-carbon double bond among the acetalized forms of the aldehyde having a multiple bond includes the acetalized form of the aldehyde, specifically, 2-methyl-3-butenal 3- (1,3-dioxalan-2-yl-)-3-methyl-1-propene which is acetalized form, 3- (1,3-dioxalane- which is acetalized form of 3-methyl-3-butenal 2-yl) -2-methyl-1-propene and the like.
　前記多重結合を有するアルデヒド及び該アルデヒドのアセタール化体のうち、反応性炭素－炭素三重結合を有するアルデヒド及びアセタール化体としては、プロピオルアルデヒド、２－ブチン－１－アール、及び２－ペンチン－１－アール等の炭素－炭素三重結合を有するアルデヒド、及び該アルデヒドのアセタール化体等が挙げられる。 Among the aldehyde having multiple bonds and the acetalized form of the aldehyde, as the aldehyde having a reactive carbon-carbon triple bond and the acetalized form, propiolaldehyde, 2-butyne-1-al, and 2-pentyne- Examples thereof include aldehydes having a carbon-carbon triple bond such as 1-al, acetalized products of the aldehydes, and the like.
　前記多重結合を有するアルデヒドの中でも、反応性炭素－炭素二重結合を有するアルデヒド及び該アルデヒドのアセタール化体が好ましく、例えば、アクロレイン、メタクロレイン、クロトンアルデヒド、３－ブテナール、２－メチル－２－ブテナール、２－メチル－３－ブテナール、２，２－ジメチル－３－ブテナール、３－メチル－２－ブテナール、３－メチル－３－ブテナール、２－ペンテナール、２－メチル－２－ペンテナール、３－ペンテナール、３－メチル－４－ペンテナール、４－ペンテナール、４－メチル－４－ペンテナール、２－ヘキセナール、３－ヘキセナール、４－ヘキセナール、５－ヘキセナール、７－オクテナール、２－エチルクロトンアルデヒド、３－（ジメチルアミノ）アクロレイン、２，４－ペンタジエナール、及びこれらのアルデヒドのアセタール化体から選ばれる１種以上が好ましい。中でもゴムとの反応性が良好なことから、炭素数３～２５のアルデヒド及び該アルデヒドのアセタール化体が好ましく、５－ヘキセナール、７－オクテナール、及びこれらのアルデヒドのアセタール化体から選ばれる１種以上がより好ましい。 Among the aldehydes having multiple bonds, aldehydes having a reactive carbon-carbon double bond and acetalized products of the aldehydes are preferable. For example, acrolein, methacrolein, crotonaldehyde, 3-butenal, 2-methyl-2- Butenal, 2-methyl-3-butenal, 2,2-dimethyl-3-butenal, 3-methyl-2-butenal, 3-methyl-3-butenal, 2-pentenal, 2-methyl-2-pentenal, 3- 3-pentenal, 3-methyl-4-pentenal, 4-pentenal, 4-methyl-4-pentenal, 2-hexenal, 3-hexenal, 4-hexenal, 5-hexenal, 7-octenal, 2-ethyl crotonaldehyde, 3- (Dimethylamino) acrolein, 2,4-pentadie Lumpur, and one or more selected from acetalization body of these aldehydes are preferred. Among them, aldehydes having 3 to 25 carbon atoms and acetalized products of the aldehydes are preferable because they have good reactivity with rubber, and one type selected from 5-hexenal, 7-octenal, and acetalized products of these aldehydes The above is more preferable.
　前記多重結合を有するカルボン酸、該カルボン酸の塩、該カルボン酸のエステル化体、及び該カルボン酸の酸無水物としては、例えば、（メタ）アクリル酸、（メタ）アクリル酸のナトリウム塩、（メタ）アクリル酸のカリウム塩、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸２－ヒドロキシルエチル、（メタ）アクリル酸２－ヒドロキシルプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシルブチル、（メタ）アクリル酸３－ヒドロキシルブチル、（メタ）アクリル酸４－ヒドロキシルブチル、（メタ）アクリル酸ビニル、２－（トリフルオロメチル）アクリル酸、２－トリフルオロメチルアクリル酸メチル、２－トリフルオロメチルアクリル酸エチル、２－トリフルオロメチルアクリル酸プロピル、２－トリフルオロメチルアクリル酸２ブチル、２－トリフルオロメチルアクリル酸２－ヒドロキシルエチル、２－トリフルオロメチルアクリル酸ビニル、けい皮酸メチル、けい皮酸ビニル、クロトン酸メチル、クロトン酸ビニル、３－メチル－３－ブテン酸メチル、３－メチル－３－ブテン酸ビニル、４－ペンテン酸メチル、４－ペンテン酸ビニル、２－メチル－４－ペンテン酸メチル、２－メチル－４－ペンテン酸ビニル、５－ヘキセン酸メチル、５－ヘキセン酸ビニル、３，３－ジメチル－４－ペンテン酸メチル、３，３－ジメチル－４－ペンテン酸ビニル、７－オクテン酸メチル、７－オクテン酸ビニル、ｔｒａｎｓ－３－ペンテン酸メチル、ｔｒａｎｓ－３－ペンテン酸ビニル、ｔｒａｎｓ－４－デセン酸メチル、ｔｒａｎｓ－４－デセン酸ビニル、３－メチル－３－ブテン酸エチル、４－ペンテン酸エチル、２－メチル－４－ペンテン酸エチル、５－ヘキセン酸エチル、３，３－ジメチル－４－ペンテン酸エチル、７－オクテン酸エチル、ｔｒａｎｓ－３－ペンテン酸エチル、ｔｒａｎｓ－４－デセン酸エチル、１０－ウンデセン酸メチル、１０－ウンデセン酸ビニル、（メタ）アクリル酸無水物、２－（トリフルオロメチル）アクリル酸無水物、けい皮酸無水物、クロトン酸無水物、３－メチル－３－ブテン酸無水物、４－ペンテン酸無水物、２－メチル－４－ペンテン酸無水物、５－ヘキセン酸無水物、３，３－ジメチル－４－ペンテン酸無水物、７－オクテン酸無水物、ｔｒａｎｓ－３－ペンテン酸無水物、ｔｒａｎｓ－４－デセン酸無水物、３－メチル－３－ブテン酸無水物、４－ペンテン酸無水物、２－メチル－４－ペンテン酸無水物、及び１０－ウンデセン酸無水物等の反応性炭素－炭素二重結合を有するカルボン酸、該カルボン酸の塩、該カルボン酸のエステル化体、及び該カルボン酸の酸無水物；
　プロピオール酸、プロピオール酸メチル、プロピオール酸エチル、プロピオール酸ビニル、テトロール酸、テトロール酸メチル、テトロール酸エチル、及びテトロール酸ビニル等の反応性炭素－炭素三重結合を有するカルボン酸及び該カルボン酸のエステル化体が挙げられる。 The carboxylic acid having the multiple bond, the salt of the carboxylic acid, the esterified form of the carboxylic acid, and the acid anhydride of the carboxylic acid include, for example, (meth) acrylic acid and sodium salt of (meth) acrylic acid, Potassium salt of (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) Vinyl acrylate, 2- (trifluoromethyl) acrylic acid, 2-trifluoromethyl acrylic acid Ethyl, 2-trifluoromethyl ethyl acrylate, propyl 2-trifluoromethyl acrylate, 2-butyl 2-trifluoromethyl acrylate, 2-hydroxy ethyl 2-trifluoromethyl acrylate, vinyl 2-trifluoromethyl acrylate , Methyl cinnamate, vinyl cinnamate, methyl crotonate, vinyl crotonate, methyl 3-methyl-3-butenoate, vinyl 3-methyl-3-butenoate, methyl 4-pentenoate, vinyl 4-pentenoate , Methyl 2-methyl-4-pentenoate, vinyl 2-methyl-4-pentenoate, methyl 5-hexenoate, vinyl 5-hexenoate, methyl 3,3-dimethyl-4-pentenoate, 3,3-dimethyl Vinyl -4-pentenoate, methyl 7-octenoate, vinyl 7-octenoate, trans-3-pentenoate , Vinyl trans-3-pentenoate, methyl trans-4-decenoate, vinyl trans-4-decenoate, ethyl 3-methyl-3-butenoate, ethyl 4-pentenoate, 2-methyl-4-pentenoic acid Ethyl, ethyl 5-hexenoate, ethyl 3,3-dimethyl-4-pentenoate, ethyl 7-octenoate, ethyl trans-3-pentenoate, ethyl trans-4-decenoate, methyl 10-undecenoate, 10- Vinyl undecenoate, (meth) acrylic anhydride, 2- (trifluoromethyl) acrylic anhydride, cinnamic anhydride, crotonic anhydride, 3-methyl-3-butenoic anhydride, 4-pentenoic acid Anhydride, 2-Methyl-4-pentenoic anhydride, 5-hexenoic anhydride, 3,3-dimethyl-4-pentenoic anhydride, 7-octanoic anhydride Trans-3-pentenoic anhydride, trans-4-decenoic anhydride, 3-methyl-3-butenoic anhydride, 4-pentenoic anhydride, 2-methyl-4-pentenoic anhydride, and 10 A carboxylic acid having a reactive carbon-carbon double bond such as undecenoic acid anhydride, a salt of the carboxylic acid, an esterified form of the carboxylic acid, and an acid anhydride of the carboxylic acid;
Carboxylic acids having reactive carbon-carbon triple bonds such as propiolic acid, methyl propiolate, ethyl propiolate, vinyl propiolate, tetrolate, methyl tetrolate, ethyl tetrolate, and vinyl tetrolate, and esterification of the carboxylic acid Body is mentioned.
　前記多重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、及び該ジカルボン酸の酸無水物としては、例えば、マレイン酸、マレイン酸ナトリウム塩、マレイン酸カリウム塩、マレイン酸メチル、マレイン酸ジメチル、無水マレイン酸、イタコン酸、イタコン酸メチル、イタコン酸ジメチル、無水イタコン酸、ハイミック酸、ハイミック酸メチル、ハイミック酸ジメチル、及び無水ハイミック酸等の反応性炭素－炭素二重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、及び該ジカルボン酸の酸無水物が挙げられる。 Examples of the dicarboxylic acid having a multiple bond, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid include, for example, maleic acid, sodium salt of maleic acid, potassium salt of maleic acid, and maleic acid Reactive carbon-carbon double bonds such as methyl, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, helic acid, helic acid methyl, helic acid dimethyl, helic acid anhydride, and helic acid anhydride And a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid.
　前記多重結合を有するカルボン酸、該カルボン酸の塩、該カルボン酸のエステル化体、該カルボン酸無水物、前記多重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、及び該ジカルボン酸の酸無水物としては、反応性炭素－炭素二重結合を有する化合物が好ましく、中でも、ポリビニルアルコールとの反応性が良好であることから、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸２－ヒドロキシルエチル、（メタ）アクリル酸２－ヒドロキシルプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシルブチル、（メタ）アクリル酸３－ヒドロキシルブチル、（メタ）アクリル酸４－ヒドロキシルブチル、（メタ）アクリル酸ビニル、（メタ）アクリル酸無水物、２－（トリフルオロメチル）アクリル酸無水物、けい皮酸無水物、クロトン酸無水物、３－メチル－３－ブテン酸無水物、４－ペンテン酸無水物、２－メチル－４－ペンテン酸無水物、５－ヘキセン酸無水物、３，３－ジメチル－４－ペンテン酸無水物、７－オクテン酸無水物、ｔｒａｎｓ－３－ペンテン酸無水物、ｔｒａｎｓ－４－デセン酸無水物、３－メチル－３－ブテン酸無水物、４－ペンテン酸無水物、２－メチル－４－ペンテン酸無水物、マレイン酸、マレイン酸メチル、マレイン酸ジメチル、無水マレイン酸、イタコン酸、イタコン酸メチル、イタコン酸ジメチル、無水イタコン酸、及び無水ハイミック酸から選ばれる１種以上がより好ましい。 Carboxylic acid having the multiple bond, salt of the carboxylic acid, esterified form of the carboxylic acid, carboxylic anhydride, dicarboxylic acid having the multiple bond, salt of the dicarboxylic acid, esterified form of the dicarboxylic acid, And as the acid anhydride of the dicarboxylic acid, a compound having a reactive carbon-carbon double bond is preferable. Among them, (meth) acrylic acid and (meth) acrylic acid are preferable because of their good reactivity with polyvinyl alcohol. Methyl acid, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid 3 -Hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate 4-hydroxybutyl (meth) acrylate, vinyl (meth) acrylate, (meth) acrylic anhydride, 2- (trifluoromethyl) acrylic anhydride, cinnamic anhydride, crotonic anhydride, 3 -Methyl-3-butenoic anhydride, 4-pentenoic anhydride, 2-methyl-4-pentenoic anhydride, 5-hexenoic anhydride, 3,3-dimethyl-4-pentenoic anhydride, 7- Octenoic anhydride, trans-3-pentenoic anhydride, trans-4-decenoic anhydride, 3-methyl-3-butenoic anhydride, 4-pentenoic anhydride, 2-methyl-4-pentenoic anhydride Selected from maleic acid, methyl maleate, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, and helicic anhydride And more preferably equal to or greater than the species.
〔製造方法（２）において用いる多重結合含有化合物〕
　製造方法（２）において用いる多重結合化合物としては、例えば、反応性炭素－炭素二重結合を有するアミン化合物が挙げられる。
　反応性炭素－炭素二重結合を有するアミン化合物としては、例えば、アリルアミン、３－ブテニルアミン、４－ペンテニルアミン、５－ヘキセニルアミン、６－ヘプテニルアミン、７－オクテニルアミン、オレイルアミン、２－メチルアリルアミン、４－アミノスチレン、４－ビニルベンジルアミン、２－アリルグリシン、Ｓ－アリルシステイン、α－アリルアラニン、２－アリルアニリン、ゲラニルアミン、ビガバトリン、４－ビニルアニリン、及び４－ビニロキシアニリン等の反応性炭素－炭素二重結合を有するアミン化合物が挙げられる。これらの中でも、該アミン化合物としては、ゴムとの反応性が良好なことから、５－ヘキセニルアミン、６－ヘプテニルアミン、及び７－オクテニルアミンから選ばれる１種以上が好ましい。 [Multiple bond containing compound used in production method (2)]
Examples of the multiple bond compound used in the production method (2) include amine compounds having a reactive carbon-carbon double bond.
Examples of the amine compound having a reactive carbon-carbon double bond include allylamine, 3-butenylamine, 4-pentenylamine, 5-hexenylamine, 6-heptenylamine, 7-octenylamine, oleylamine, 2-methylallylamine, and the like. Reactive carbons such as aminostyrene, 4-vinylbenzylamine, 2-allylglycine, S-allylcysteine, α-allylalanine, 2-allylaniline, geranylamine, vigabatrin, 4-vinylaniline, and 4-vinyloxyaniline -Amine compounds having a carbon double bond are mentioned. Among these, as the amine compound, at least one member selected from 5-hexenylamine, 6-heptenylamine and 7-octenylamine is preferable because of good reactivity with rubber.
〔製造方法（３）において用いる多重結合含有化合物〕
　製造方法（３）において用いる多重結合化合物としては、例えば、二重結合を２つ以上有する単量体が挙げられる。
　二重結合を２つ以上有する単量体としてはペンタジエン、ヘキサジエン、ヘプタジエン、オクタジエン、ノナジエン、及びデカジエン等のジエン化合物；グリセリンジアリルエーテル、ジエチレングリコールジアリルエーテル、エチレングリコールジアリルエーテル、トリエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテル、トリメチロールプロパンジアリルエーテル、及びペンタエリスリトールジアリルエーテル等のジアリルエーテル化合物、グリセリントリアリルエーテル、トリメチロールプロパントリアリルエーテル、ペンタエリスリトールトリアリルエーテル、及び１，３，５－トリアリル－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン等のトリアリルエーテル化合物、ペンタエリスリトールテトラアリルエーテル等のテトラアリルエーテル化合物のようなアリルエーテル基を含有する単量体；炭酸ジアリル、コハク酸ジアリル、フタル酸ジアリル、マレイン酸ジアリル、イタコン酸ジアリル、テレフタル酸ジアリル、及びアジピン酸ジアリル等カルボン酸ジアリルのようなアリルエステル基を含有する単量体；ジアリルアミン、及びジアリルメチルアミン等のジアリルアミン化合物、トリアリルアミン等のアリルアミノ基を含有する単量体；ジアリルジメチルアンモニウムクロライド等のジアリルアンモニウム塩のようなアリルアンモニウム基を含有する単量体；イソシアヌル酸トリアリル；１，３－ジアリル尿素；リン酸トリアリル；ジアリルジスルフィド等；エチレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート等のジ（メタ）アクリレート化合物、トリプロピレングリコールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等のトリ（メタ）アクリレート化合物、ペンタエリスリトールテトラ（メタ）アクリレート等のテトラ（メタ）アクリレート化合物、グルコースペンタ（メタ）アクリレート等のペンタ（メタ）アクリレート化合物のようなアクリレート基を含有する単量体；アリル（メタ）アクリレートブタジエンのようなビニルアクリレート等が挙げられる。 [Multiple bond containing compound used in production method (3)]
Examples of the multiple bond compound used in the production method (3) include monomers having two or more double bonds.
As monomers having two or more double bonds, diene compounds such as pentadiene, hexadiene, heptadiene, octadiene, nonadiene, and decadiene; glycerin diallyl ether, diethylene glycol diallyl ether, ethylene glycol diallyl ether, triethylene glycol diallyl ether, polyethylene Diallyl ether compounds such as glycol diallyl ether, trimethylolpropane diallyl ether, and pentaerythritol diallyl ether, glycerin triallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, and 1,3,5-triallyl-1, Triallyl ether compounds such as 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pen Monomers containing an allyl ether group such as tetraallyl ether compounds such as erythritol tetraallyl ether; diallyl carbonate, diallyl succinate, diallyl phthalate, diallyl maleate, diallyl itaconate, diallyl terephthalate, diallyl terephthalate, and diallyl adipate Monomer containing allyl ester group such as diallyl carboxylate etc. Diallylamine, diallylamine compound such as diallyl methylamine etc., monomer containing allylamino group such as triallylamine, etc. Diallyl ammonium salt such as diallyldimethyl ammonium chloride Monomers having an allyl ammonium group such as: triaryl isocyanurate; 1,3-diallylurea; triallyl phosphate; diallyl disulfide etc. ethylene glycol di (meth) acrylate, Sandiol di (meth) acrylate, tripropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene Di (meth) acrylate compounds such as glycol di (meth) acrylate, tri (meth) acrylate compounds such as tripropylene glycol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, penta Tetra (meth) acrylate compounds such as erythritol tetra (meth) acrylate, and penta (meth) acrylates such as glucose penta (meth) acrylate Monomers containing an acrylate group such as compounds; vinyl acrylates such as allyl (meth) acrylate butadiene and the like.
　これらの中でも、前記二重結合を２つ以上有する単量体としては、取り扱い性が良好なことから、ペンタジエン、ヘキサジエン、ヘプタジエン、オクタジエン、ノナジエン、デカジエン、グリセリンジアリルエーテル、ジエチレングリコールジアリルエーテル、エチレングリコールジアリルエーテル、トリエチレングリコールジアリルエーテル、炭酸ジアリル、コハク酸ジアリル、フタル酸ジアリル、マレイン酸ジアリル、イタコン酸ジアリル、テレフタル酸ジアリル、アジピン酸ジアリル等カルボン酸ジアリル、ジアリルアミン、ジアリルメチルアミン、エチレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、及びブタンジオールジ（メタ）アクリレートから選ばれる１種以上が好ましい。 Among these, as a monomer having two or more double bonds, since the handling property is good, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, glycerin diallyl ether, diethylene glycol diallyl ether, ethylene glycol diallyl Ether, triethylene glycol diallyl ether, diallyl carbonate, diallyl succinate, diallyl phthalate, diallyl maleate, diallyl itaconate, diallyl terephthalate, diallyl adipate, diallyl carboxylate, etc. diallyl amine, diallyl amine, diallyl methyl amine, ethylene glycol di (meta ) Acrylate, hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and butanediol di (meth) acrylate One or more kinds selected from over preparative is preferred.
＜多重結合含有量＞
　前記ビニルアルコール系重合体の全構造単位に対する前記多重結合含有化合物に由来する構造単位の合計の含有量（以下、「多重結合含有量」ともいう）は０．０１モル％以上、３０モル％以下であることが好ましい。前記多重結合含有量が３０モル％以下であると、ビニルアルコール系重合体とゴムとの接着性を向上させつつ、接着成分と親水性繊維との接着性も維持することができる。すなわち、前記多重結合含有量が３０モル％を超えると、ビニルアルコール系重合体とゴムとの接着性を向上させることができるものの、接着成分と親水性繊維との接着に寄与する水素結合を形成する水酸基の量が少なくなるため接着成分と親水性繊維との接着性が低下する。また、ビニルアルコール系重合体が水に溶けにくくなるため、取り扱い性が悪化する。前記観点から、前記ビニルアルコール系重合体の全構造単位に対する前記多重結合含有化合物に由来する構造単位の合計の含有量は、好ましくは０．０５モル％以上、より好ましくは０．１モル％以上、更に好ましくは０．２モル％以上、より更に好ましくは０．３モル％以上、より更に好ましくは０．４モル％以上、より更に好ましくは０．５モル％以上であり、そして、好ましくは２５モル％以下、より好ましくは２０モル％以下、更に好ましくは１５モル％以下、より更に好ましくは１０モル％以下、より更に好ましくは５モル％以下、より更に好ましくは３モル％以下、より更に好ましくは２モル％以下、より更に好ましくは１モル％以下である。
　なお、多重結合含有量は１Ｈ－ＮＭＲスペクトルにより求めた値であり、より詳細には実施例に記載の方法に従って測定した値である。 <Multiple bond content>
The total content of structural units derived from the multiple bond-containing compound (hereinafter also referred to as “multiple bond content”) is 0.01 mol% or more and 30 mol% or less based on the total structural units of the vinyl alcohol polymer Is preferred. The adhesiveness of an adhesive component and a hydrophilic fiber can also be maintained, improving the adhesiveness of a vinyl alcohol polymer and rubber | gum as the said multiple bond content is 30 mol% or less. That is, when the multiple bond content exceeds 30 mol%, the adhesion between the vinyl alcohol polymer and the rubber can be improved, but a hydrogen bond contributing to the adhesion between the adhesive component and the hydrophilic fiber is formed. As the amount of hydroxyl groups decreases, the adhesion between the adhesive component and the hydrophilic fiber decreases. In addition, since the vinyl alcohol polymer becomes difficult to dissolve in water, the handling property is deteriorated. From the above viewpoint, the total content of structural units derived from the multiple bond-containing compound is preferably 0.05% by mol or more, more preferably 0.1% by mol or more, based on the total structural units of the vinyl alcohol polymer. , More preferably 0.2 mol% or more, still more preferably 0.3 mol% or more, still more preferably 0.4 mol% or more, still more preferably 0.5 mol% or more, and preferably 25 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less, still more preferably 10 mol% or less, still more preferably 5 mol% or less, still more preferably 3 mol% or less, still more Preferably it is 2 mol% or less, still more preferably 1 mol% or less.
The multiple bond content is a value determined by 1 H-NMR spectrum, and more specifically, a value determined according to the method described in the examples.
　ビニルアルコール系重合体は、前記多重結合含有化合物に由来する構造単位及びビニルアルコール単位の他に、その他の構造単位を含んでいてもよい。その他の構造単位としては、ポリビニルアルコールの原料となる酢酸ビニル等のビニルエステル単量体と共重合可能なエチレン不飽和単量体に由来する構成単位が挙げられる。
　前記エチレン不飽和単量体としては、例えば、エチレン、１－ブテン、及びイソブチレン等のオレフィン；アクリル酸及びその誘導体；メタクリル酸及びその誘導体；アクリルアミド及びその誘導体；メタクリルアミド及びその誘導体；マレイン酸及びその誘導体；無水マレイン酸及びその誘導体；等が挙げられる。これらは、単独でも、２種以上を組み合わせて用いてもよい。
　ビニルアルコール系重合体が前記エチレン性不飽和単量体に由来する他の構造単位を含有する場合、その含有量は１０モル％以下が好ましく、５モル％以下がより好ましく、３モル％以下が更に好ましい。 The vinyl alcohol polymer may contain other structural units in addition to the structural unit derived from the multiple bond-containing compound and the vinyl alcohol unit. As another structural unit, a structural unit derived from an ethylenically unsaturated monomer copolymerizable with a vinyl ester monomer such as vinyl acetate as a raw material of polyvinyl alcohol can be mentioned.
Examples of the ethylenically unsaturated monomer include olefins such as ethylene, 1-butene, and isobutylene; acrylic acid and its derivatives; methacrylic acid and its derivatives; acrylamide and its derivatives; methacrylamide and its derivatives; Derivatives thereof; maleic anhydride and derivatives thereof; and the like. These may be used alone or in combination of two or more.
When the vinyl alcohol polymer contains another structural unit derived from the above-mentioned ethylenically unsaturated monomer, its content is preferably 10 mol% or less, more preferably 5 mol% or less, and 3 mol% or less. More preferable.
　ビニルアルコール系重合体の粘度平均重合度は特に制限されないが、取り扱い性の観点から、４０００以下が好ましく、３５００以下がより好ましく、３０００以下が更に好ましく、そして、接着性を向上させる観点から、５００以上が好ましく、１０００以上がより好ましく、１５００以上が更に好ましい。
　ビニルアルコール系重合体の粘度平均重合度は、例えばＪＩＳ　Ｋ　６７２６に準拠した方法により測定できる。 The viscosity average polymerization degree of the vinyl alcohol polymer is not particularly limited, but is preferably 4000 or less, more preferably 3500 or less, still more preferably 3000 or less from the viewpoint of handling, and from the viewpoint of improving adhesion, The above is preferable, 1000 or more is more preferable, and 1500 or more is still more preferable.
The viscosity average polymerization degree of the vinyl alcohol polymer can be measured, for example, by a method according to JIS K 6726.
＜ビニルアルコール系重合体の製造方法＞
　ビニルアルコール系重合体の製造方法に特に制限はないが、前記製造方法（１）～（３）により製造することが好ましく、前記製造方法（１）により製造することがより好ましい。
〔製造方法（１）〕
　製造方法（１）は、反応性炭素－炭素二重結合及び反応性炭素－炭素三重結合から選ばれる１種以上の多重結合を有する多重結合含有化合物によりポリビニルアルコールを変性することにより得る方法であり、具体的には、ポリビニルアルコールと前記多重結合含有化合物とを反応させ、ポリビニルアルコールをアセタール化又はエステル化する方法である。 <Method of producing vinyl alcohol polymer>
The method for producing the vinyl alcohol polymer is not particularly limited, but it is preferably produced by the production methods (1) to (3), and more preferably produced by the production method (1).
[Production Method (1)]
Production method (1) is a method obtained by modifying polyvinyl alcohol with a multiple bond-containing compound having one or more multiple bonds selected from reactive carbon-carbon double bonds and reactive carbon-carbon triple bonds Specifically, it is a method of reacting polyvinyl alcohol with the multiple bond-containing compound to acetalize or esterify polyvinyl alcohol.
　ポリビニルアルコールをアセタール化する方法としては、前記多重結合含有化合物から選ばれる１種以上とポリビニルアルコールとを酸触媒存在下で反応させ、その後塩基性物質で中和することによりビニルアルコール系重合体の水溶液を得る方法等が挙げられる。 As a method of acetalizing polyvinyl alcohol, one or more selected from the multiple bond-containing compounds is reacted with polyvinyl alcohol in the presence of an acid catalyst, and then neutralized with a basic substance to obtain a vinyl alcohol polymer The method etc. of obtaining an aqueous solution are mentioned.
　前記酸触媒としては、例えば、塩酸、硫酸、硝酸、及びリン酸等の無機酸；ギ酸、酢酸、シュウ酸、及びｐ－トルエンスルホン酸等の有機酸等が挙げられる。
　酸触媒を使用する場合、その使用量は、ポリビニルアルコール１００質量部に対して、０．０１～２０質量部程度が好ましい。 Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; and organic acids such as formic acid, acetic acid, oxalic acid and p-toluenesulfonic acid.
When an acid catalyst is used, its use amount is preferably about 0.01 to 20 parts by mass with respect to 100 parts by mass of polyvinyl alcohol.
　前記中和に用いる塩基性物質としては、特に制限されないが、例えば、水酸化ナトリウム、及び水酸化カリウム等のアルカリ金属水酸化物；炭酸ナトリウム、及び炭酸カリウム等のアルカリ金属炭酸塩、モノエタノールアミン、アミノエチルエタノールアミン、及びモノイソプロパノールアミン等の第一級アルカノールアミン；ジエタノールアミン、メチルエタノールアミン、及びブチルメタノールアミン等の第二級アルカノールアミン；トリエタノールアミン、メチルジエタノールアミン、及びジメチルエタノールアミン等の第三級アルカノールアミン等の有機アミン類等を挙げることができる。 The basic substance used for the neutralization is not particularly limited, but, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate, monoethanolamine Primary alkanolamines such as aminoethylethanolamine and monoisopropanolamine; secondary alkanolamines such as diethanolamine, methylethanolamine and butylmethanolamine; firsts such as triethanolamine, methyldiethanolamine and dimethylethanolamine Organic amines such as tertiary alkanolamines can be mentioned.
　一方、ポリビニルアルコールをエステル化する方法としては、前記多重結合を有するカルボン酸、該カルボン酸の塩、該カルボン酸のエステル化体、該カルボン酸の酸無水物、前記多重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、及び該ジカルボン酸の酸無水物から選ばれる１種以上とポリビニルアルコールとをエステル化触媒存在下で反応させる方法等が挙げられる。 On the other hand, as a method of esterifying polyvinyl alcohol, carboxylic acid having the multiple bond, salt of the carboxylic acid, esterified product of the carboxylic acid, acid anhydride of the carboxylic acid, dicarboxylic acid having the multiple bond, Examples thereof include a method of reacting one or more selected from a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid in the presence of an esterification catalyst.
　ビニルアルコール系重合体の製造に用いるエステル化触媒としては、上記の酸触媒に加え、例えば、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム等のアルカリ金属又はアルカリ土類金属の水酸化物；炭酸水素ナトリウム、炭酸カリウム、炭酸水素カルシウム等のアルカリ金属又はアルカリ土類金属の炭酸塩及び炭酸水素塩；リン酸二水素カリウム等のアルカリ金属又はアルカリ土類金属のリン酸塩及びリン酸水素塩；四ホウ酸ナトリウム等のアルカリ金属又はアルカリ土類金属のホウ酸塩；酢酸ナトリウム、酢酸カリウム、安息香酸ナトリウム、酢酸マグネシウム等のアルカリ金属又はアルカリ土類金属のカルボン酸塩；ナトリウムメトキシド、カリウムメトキシド、マグネシウムメトキシド等のアルカリ金属又はアルカリ土類金属のアルコキシド化合物；水酸化アンモニウム、水酸化テトラメチルアンモニウム、炭酸アンモニウム、炭酸水素アンモニウム、テトラメチルアンモニウムメチルカーボネート、メチルトリｎ－オクチルメチルカーボネート等のアンモニウム塩；水酸化テトラメチルホスホニウム、テトラメチルホスホニウムメチルカーボネート等のホスホニウム塩；ｎ－ブチルアミン、アニリン、ジエチルアミン、トリエチルアミン、１，８－ジアザビシクロ［５，４，０］－７－ウンデセン等のアミン化合物；ピリジン、Ｎ，Ｎ－ジメチルアミノピリジン等の含窒素芳香族複素環式化合物；塩化亜鉛、酢酸亜鉛、トリフルオロ酢酸亜鉛、硝酸亜鉛、炭酸亜鉛、アセチルアセトン亜鉛（II）、オキソ［ヘキサ（トリフルオロアセタト）］テトラ亜鉛等の亜鉛系化合物；塩化鉄、酢酸鉄、アセチルアセトン鉄（III）、Ｎ，Ｎ’－ビス（サリチリデン）エチレンジアミン鉄（II）等の鉄系化合物；塩化ランタン、酢酸ランタン、硝酸ランタン、ランタンアルコキシド、アセチルアセトンランタン（III）等のランタン系化合物
等が挙げられる。
　エステル化触媒を使用する場合、その使用量は、ポリビニルアルコール１００質量部に対して、０．０１～２０質量部程度が好ましい。 As an esterification catalyst used for producing a vinyl alcohol polymer, in addition to the above-mentioned acid catalyst, for example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and the like; Carbonates and hydrogencarbonates of alkali metals or alkaline earth metals such as sodium hydrogen, potassium carbonate and calcium hydrogencarbonate; phosphates and hydrogenphosphates of alkali metals or alkaline earth metals such as potassium dihydrogenphosphate; Alkali metal or alkaline earth metal borates such as sodium tetraborate; alkali metal or alkaline earth metal carboxylates such as sodium acetate, potassium acetate, sodium benzoate and magnesium acetate; sodium methoxide, potassium methoxy Alkali metal or alkaline earth such as magnesium methoxide Alkoxide compounds of the genus; ammonium salts such as ammonium hydroxide, tetramethyl ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, tetramethyl ammonium methyl carbonate, methyl tri n-octyl methyl carbonate, etc .; tetramethyl phosphonium hydroxide, tetramethyl phosphonium methyl carbonate Phosphonium salts such as n-butylamine, aniline, diethylamine, triethylamine, amine compounds such as 1,8-diazabicyclo [5,4,0] -7-undecene; nitrogen-containing aromas such as pyridine, N, N-dimethylaminopyridine Group heterocyclic compounds; zinc such as zinc chloride, zinc acetate, zinc trifluoroacetate, zinc nitrate, zinc carbonate, zinc (II) acetylacetone, oxo [hexa (trifluoroacetato)] tetrazinc Iron compounds such as iron chloride, iron acetate, acetylacetonatoiron (III), N, N'-bis (salicylidene) ethylenediamine iron (II); lanthanum chloride, lanthanum acetate, lanthanum nitrate, lanthanum alkoxide, acetylacetonate lanthanum ( And lanthanum compounds such as III).
When an esterification catalyst is used, the amount thereof used is preferably about 0.01 to 20 parts by mass with respect to 100 parts by mass of polyvinyl alcohol.
　前記製造方法において、原料となる多重結合含有化合物の使用量は、ポリビニルアルコール１００質量部に対して、例えば、０．０１～２０質量部が好ましく、０．０５～１５質量部がより好ましく、０．１～１０質量部が更に好ましい。 In the above-mentioned production method, the amount of use of the multiple bond-containing compound as a raw material is, for example, preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, with respect to 100 parts by mass of polyvinyl alcohol. Further preferred is 1 to 10 parts by mass.
〔製造方法（２）〕
　製造方法（２）は、ビニルエステルと（メタ）アクリル酸エステルとを共重合した後、けん化することで得られる、分子内にラクトン環構造を有するポリビニルアルコールを、多重結合を有する化合物、特に反応性炭素－炭素二重結合を有するアミン化合物で変性する方法であり、具体的には、分子内にラクトン環構造を有するポリビニルアルコールを前記アミン化合物によりアミド化する方法である。
　具体的なアミド化方法としては、ラクトン環構造を有するポリビニルアルコールと前記反応性炭素－炭素二重結合を有するアミン化合物とを混合し、加熱して反応させる方法等が挙げられる。 [Production Method (2)]
Production method (2) is a compound having multiple bonds and polyvinyl alcohol having a lactone ring structure in the molecule, which is obtained by copolymerizing a vinyl ester and a (meth) acrylic acid ester and then saponifying the compound, particularly a reaction It is a method of modifying with an amine compound having a carbon-carbon double bond, specifically, a method of amidating polyvinyl alcohol having a lactone ring structure in the molecule with the above-mentioned amine compound.
As a specific amidation method, a method of mixing a polyvinyl alcohol having a lactone ring structure and the amine compound having a reactive carbon-carbon double bond, and heating and reacting them may be mentioned.
〔製造方法（３）〕
　製造方法（３）は、二重結合を２つ以上有する単量体とビニルアルコール系化合物とを共重合することで得る方法である。二重結合を２つ以上有する単量体とビニルアルコール系化合物との共重合方法について特に制限はなく、一般的な共重合体の製造方法を採用することができる。 [Production method (3)]
The production method (3) is a method obtained by copolymerizing a monomer having two or more double bonds and a vinyl alcohol compound. There is no particular limitation on the method of copolymerizing the monomer having two or more double bonds and the vinyl alcohol compound, and a general method for producing a copolymer can be adopted.
＜親水性繊維＞
　本発明の補強繊維は、繊維表面の少なくとも一部に接着成分を有する親水性繊維からなるものである。親水性繊維を用いることにより補強繊維とゴムとの接着性を向上させることができる。
　本発明に用いることができる親水性繊維としては、合成繊維、天然繊維、及び再生繊維等を挙げることができる。親水性繊維は、単独でも、２種以上を組み合わせて用いてもよい。 <Hydrophilic fiber>
The reinforcing fiber of the present invention comprises a hydrophilic fiber having an adhesive component on at least a part of the fiber surface. By using a hydrophilic fiber, the adhesion between the reinforcing fiber and the rubber can be improved.
Examples of hydrophilic fibers that can be used in the present invention include synthetic fibers, natural fibers, and regenerated fibers. The hydrophilic fibers may be used alone or in combination of two or more.
　親水性の合成繊維としては、水酸基、カルボキシル基、スルホン酸、及びアミノ基のような親水性官能基、及び／又は、アミド結合のような親水性結合を有する熱可塑性樹脂で構成される合成繊維を挙げることができる。
　このような熱可塑性樹脂の具体例は、ポリビニルアルコール系樹脂、ポリアミド系樹脂〔ポリアミド６、ポリアミド６６、ポリアミド１１、ポリアミド１２、ポリアミド６１０、ポリアミド６１２、ポリアミド９Ｃ（ノナンジアミンとシクロヘキサンジカルボン酸からなるポリアミド）等の脂肪族ポリアミド；ポリアミド９Ｔ（ノナンジアミンとテレフタル酸からなるポリアミド）等の芳香族ジカルボン酸と脂肪族ジアミンとから合成される半芳香族ポリアミド；ポリパラフェニレンテレフタルアミド等の芳香族ジカルボン酸と芳香族ジアミンとから合成される全芳香族ポリアミド等〕、ポリアクリルアミド系樹脂等が挙げられる。
　これらの中でも、ポリビニルアルコール系樹脂、及びポリアミド系樹脂が好ましい。親水性の合成繊維は、単独でも、２種以上を組み合わせて用いてもよい。また、これらの親水性の合成繊維は、親水性をより高めるべく、後述する親水化処理をさらに施してもよい。 As a hydrophilic synthetic fiber, a synthetic fiber composed of a thermoplastic resin having a hydrophilic functional group such as a hydroxyl group, a carboxyl group, a sulfonic acid and an amino group and / or a hydrophilic bond such as an amide bond Can be mentioned.
Specific examples of such thermoplastic resins are polyvinyl alcohol resins, polyamide resins [polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 9 C (polyamide composed of nonane diamine and cyclohexane dicarboxylic acid)] Aliphatic polyamides such as: Semi aromatic polyamides synthesized from aromatic dicarboxylic acids and aliphatic diamines such as polyamide 9T (polyamide consisting of nonane diamine and terephthalic acid); Aromatic dicarboxylic acids such as poly paraphenylene terephthalamide and aroma Aromatic polyamide etc. which are synthesized from a group diamine and the like], polyacrylamide based resins and the like.
Among these, polyvinyl alcohol resins and polyamide resins are preferable. The hydrophilic synthetic fibers may be used alone or in combination of two or more. In addition, these hydrophilic synthetic fibers may be further subjected to a hydrophilization treatment described later in order to further enhance the hydrophilicity.
　親水性の天然繊維としては、クラフトパルプ等の木材パルプや木綿パルプ、ワラパルプ等の非木材パルプ等の天然セルロース繊維が挙げられる。
　親水性の再生繊維としては、レーヨン、リヨセル、キュプラ、及びポリノジック等の再生セルロース繊維が挙げられる。
　これらの天然繊維、及び再生繊維は、それぞれ、単独でも、２種以上を組み合わせて用いてもよい。また、これらの親水性の天然繊維は、親水性をより高めるべく、後述する親水化処理をさらに施してもよい。 Examples of hydrophilic natural fibers include wood pulp such as kraft pulp and natural cellulose fibers such as non-wood pulp such as cotton pulp and straw pulp.
Hydrophilic regenerated fibers include regenerated cellulose fibers such as rayon, lyocell, cupra and polynozic.
These natural fibers and regenerated fibers may be used alone or in combination of two or more. In addition, these hydrophilic natural fibers may be further subjected to a hydrophilization treatment described later in order to further enhance the hydrophilicity.
　親水性繊維は、少なくとも表面が親水性を有していればよく、例えば、疎水性樹脂の表面を親水化処理した繊維や、疎水性樹脂を芯部とし、鞘部を親水性樹脂とした芯鞘型複合繊維等であってもよい。鞘部を構成する親水性樹脂の例については、親水性の合成繊維についての記述が引用される。疎水性樹脂からなる疎水性繊維としては、例えば、ポリエチレン及びポリプロピレン等のポリオレフィン系繊維、ポリエチレンテレフタレート等のポリエステル系繊維、及び全芳香族ポリエステ系繊維等が挙げられ、これらの中でもポリエステル系繊維が好ましい。 The hydrophilic fiber may be at least the surface having hydrophilicity, and for example, a fiber obtained by hydrophilizing the surface of a hydrophobic resin, or a core having a hydrophobic resin as a core and a sheath having a hydrophilic resin It may be sheath type composite fiber or the like. The description of hydrophilic synthetic fibers is cited as an example of the hydrophilic resin constituting the sheath part. Examples of hydrophobic fibers made of hydrophobic resin include polyolefin fibers such as polyethylene and polypropylene, polyester fibers such as polyethylene terephthalate, and wholly aromatic polyester fibers, among which polyester fibers are preferable. .
　親水化処理は、化学的又は物理的に繊維表面に親水性官能基を付与する処理であれば特に限定はされないが、例えば、前記疎水性樹脂からなる繊維をイソシアネート基、エポキシ基、及びヒドロキシ基等の親水性官能基を含む化合物により修飾する方法や、電子線照射により表面を改質する方法等で行うことができる。 The hydrophilization treatment is not particularly limited as long as it is a treatment that chemically or physically imparts a hydrophilic functional group to the fiber surface, but for example, a fiber composed of the hydrophobic resin is an isocyanate group, an epoxy group, and a hydroxy group And the like, and a method of modifying the surface by electron beam irradiation, and the like.
　本発明に用いられる親水性繊維としては、補強繊維として用いられる観点から、合成繊維及び再生繊維が好ましく、中でもポリビニルアルコール系樹脂を原料とするポリビニルアルコール系繊維、再生セルロース繊維、疎水性繊維の表面を親水化処理した繊維が好ましく、ポリビニルアルコール系繊維が特に好ましい。
　本発明においては、親水性繊維を用いることにより接着成分であるビニルアルコール系重合体と親水性繊維とが強い親和効果を発現し、接着成分と繊維が強固に結びつくことから、被補強体に対する接着力をより優れたものとすることができる。
　なお、ポリビニルアルコール系繊維としては、本発明の補強繊維を自動車用ホース、特に自動車用ブレーキオイルホースに好適に用いる観点から、株式会社クラレから商品名「ビニロン」として市販されており、単繊維繊度が０．１～３０ｄｔｅｘ程度のものを好適に用いることができる。 The hydrophilic fiber used in the present invention is preferably a synthetic fiber or a regenerated fiber from the viewpoint of being used as a reinforcing fiber, and among them, the surface of polyvinyl alcohol fiber made from polyvinyl alcohol resin, regenerated cellulose fiber, hydrophobic fiber The fiber which carried out the hydrophilization process is preferable, and a polyvinyl alcohol-type fiber is especially preferable.
In the present invention, by using a hydrophilic fiber, the vinyl alcohol-based polymer as the adhesive component and the hydrophilic fiber exhibit a strong affinity effect, and the adhesive component and the fiber are strongly coupled, so adhesion to the object to be reinforced is achieved. The power can be made better.
As polyvinyl alcohol fibers, from the viewpoint of suitably using the reinforcing fiber of the present invention for automobile hoses, particularly automobile brake oil hoses, commercially available from Kuraray Co., Ltd. under the trade name "Vinylon", and having a single fiber fineness Those having about 0.1 to 30 dtex can be suitably used.
＜補強繊維の製造方法＞
　本発明の補強繊維は、繊維表面の少なくとも一部に接着成分を有するものであれば特に制限はないが、繊維表面の少なくとも一部に前記接着成分からなる接着層を有する補強繊維、及び繊維が前記接着成分を原料の一部として含有する補強繊維が好ましい。以下、前記２種の補強繊維の製造方法について説明する。 <Method of manufacturing reinforcing fiber>
The reinforcing fiber of the present invention is not particularly limited as long as it has an adhesive component on at least a part of the fiber surface, but a reinforcing fiber having an adhesive layer consisting of the adhesive component on at least a part of the fiber surface The reinforcing fiber which contains the said adhesion component as a part of raw material is preferable. Hereinafter, the manufacturing method of said 2 types of reinforcement fiber is demonstrated.
　繊維表面の少なくとも一部に前記接着成分からなる接着層を有する補強繊維の製造方法としては、浸漬、ロールコーター、ノズル（スプレー）塗布、及び刷毛塗り等から選ばれる１種以上の方法により前記親水性繊維に対して前記接着成分を付着させた後、１００～１８０℃程度で０．１秒～２分程度加熱乾燥させることにより製造することができる。 The method for producing a reinforcing fiber having an adhesive layer comprising the adhesive component on at least a part of the fiber surface includes the above-mentioned hydrophilicity by one or more methods selected from immersion, roll coater, nozzle (spray) application, brushing and the like. The adhesive component can be attached to the adhesive fiber and then dried by heating at about 100 to 180 ° C. for about 0.1 second to 2 minutes.
　親水性繊維に対して接着成分を付着させる場合、接着成分の他に溶媒として、水、エタノール、プロパノール、ブタノール、メタノール、トルエン、キシレン、アセトン、メチルエチルケトン、ジオキサン、テトラヒドロフラン、及び酢酸エチル等を用いてもよい。また、必要に応じて、酸、アルカリ、硬化剤、分散剤、及び油剤等を接着成分と一緒に混合して溶解又は分散させてもよい。溶媒を用いる場合、その使用量は、接着成分と溶媒との合計中、好ましくは５０～９９．９質量％、より好ましくは６０～９９．５質量％、更に好ましくは７０～９９．０質量％である。 When the adhesive component is attached to the hydrophilic fiber, water, ethanol, propanol, butanol, methanol, toluene, xylene, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, ethyl acetate and the like are used as solvents in addition to the adhesive component. It is also good. In addition, if necessary, an acid, an alkali, a curing agent, a dispersing agent, an oil and the like may be mixed together with the adhesive component and dissolved or dispersed. When a solvent is used, the amount thereof used is preferably 50 to 99.9% by mass, more preferably 60 to 99.5% by mass, still more preferably 70 to 99.0% by mass in the total of the adhesive component and the solvent. It is.
　親水性繊維に付着させる接着成分の付着量、すなわち、補強繊維中の接着成分の量は、補強繊維とゴムとの接着性を向上させる観点から、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、そして、製造コストと効果とのバランスの観点から、１０質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下が更に好ましい。 The amount of the adhesive component to be attached to the hydrophilic fiber, that is, the amount of the adhesive component in the reinforcing fiber is preferably 0.01% by mass or more, from the viewpoint of improving the adhesion between the reinforcing fiber and the rubber, % Or more is more preferable, 0.1% by mass or more is further preferable, and 10% by mass or less is preferable, 5% by mass or less is more preferable, and 3% by mass or less from the viewpoint of the balance between manufacturing costs and effects. More preferable.
　本発明の補強繊維は、前述のとおり親水性繊維の表面に前記接着成分からなる接着層を設けることにより製造してもよいが、前記接着成分を原料の一部として含有する繊維として製造してもよい。
　前記繊維が前記接着成分を原料の一部として含有する場合の接着成分以外の原料について特に制限はないが、例えば、ポリビニルアルコール、ポリエステル、ナイロン、トリアセテート、ジアセテート、ポリアミド、及びこれらの混合物が挙げられ、中でも、接着成分との混合のし易さ、及び補強繊維の強度の観点から、ポリビニルアルコールが好ましい。 The reinforcing fiber of the present invention may be produced by providing an adhesive layer comprising the adhesive component on the surface of a hydrophilic fiber as described above, but it is produced as a fiber containing the adhesive component as a part of the raw material It is also good.
There is no particular limitation on raw materials other than the adhesive component in the case where the fiber contains the adhesive component as a part of the raw material, but examples thereof include polyvinyl alcohol, polyester, nylon, triacetate, diacetate, polyamide, and mixtures thereof. Among them, polyvinyl alcohol is preferable from the viewpoint of the easiness of mixing with the adhesive component and the strength of the reinforcing fiber.
　前記繊維が前記接着成分を原料の一部として含有する場合、繊維原料中の前記接着成分の含有量は、補強繊維とゴムとの接着性を向上させる観点から、２０質量％以上が好ましく、２５質量％以上がより好ましく、３０質量％以上が更に好ましく、製造コストと効果とのバランスの観点から、７０質量％以下が好ましく、６５質量％以下がより好ましく、６０質量％以下が更に好ましい。 When the fiber contains the adhesive component as a part of the raw material, the content of the adhesive component in the fiber raw material is preferably 20% by mass or more from the viewpoint of improving the adhesion between the reinforcing fiber and the rubber, More preferably, it is 30% by mass or more, and more preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less from the viewpoint of the balance between the production cost and the effect.
　前記繊維が前記接着成分を原料の一部として含有する場合、繊維原料中の多重結合の含有量は、原料を構成する重合体の全ての構成単位に対する前記多重結合含有化合物に由来する構造単位の量として換算して、好ましくは０．０１モル％以上、より好ましくは０．０３モル％以上、更に好ましくは０．０８モル％以上、より更に好ましくは０．１モル％以上、より更に好ましくは０．１２モル％以上であり、そして、好ましくは２０モル％以下、より好ましくは１５モル％以下、更に好ましくは１０モル％以下、より更に好ましくは５モル％以下、より更に好ましくは３モル％以下、より更に好ましくは２モル％以下である。 When the fiber contains the adhesive component as a part of the raw material, the content of multiple bonds in the fiber raw material is the structural unit derived from the multiple bond-containing compound with respect to all constituent units of the polymer constituting the raw material. In terms of amount, it is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, still more preferably 0.08 mol% or more, still more preferably 0.1 mol% or more, still more preferably 0.12 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, still more preferably 5 mol% or less, still more preferably 3 mol% The following is more preferably 2 mol% or less.
　前記接着成分を原料の一部として含有する繊維として製造する場合の繊維の製造方法に特に制限はなく、一般的な合成繊維の製造方法にしたがって製造することができる。例えば、重合度１５００以上及び鹸化度９９モル％以上のポリビニルアルコール及び前記接着成分を、水又は有機溶媒に溶解又は半溶融させて、湿式、乾式又は乾湿式紡糸する方法が挙げられる。 There is no restriction | limiting in particular in the manufacturing method of the fiber in the case of manufacturing as a fiber which contains the said adhesion component as a part of raw material, According to the manufacturing method of a general synthetic fiber, it can manufacture. For example, a polyvinyl alcohol having a degree of polymerization of 1,500 or more and a degree of saponification of 99 mol% or more and a method for performing wet, dry, or dry and wet spinning by dissolving or semi-melting the adhesive component in water or an organic solvent may be mentioned.
＜補強繊維の物性＞
　前記補強繊維は単糸繊度が０．１ｄｔｅｘ以上、３０ｄｔｅｘ以下のマルチフィラメントであることが好ましい。単糸繊度は０．１ｄｔｅｘ未満であってもよいが工業的に製造することが難しいことから０．１ｄｔｅｘ以上が好ましい。一方、単糸繊度が３０ｄｔｅｘ以下であると、補強繊維とした場合における繊維の表面積が大きくなるため、ゴムとの接着性が向上する。前記観点から、本発明の補強繊維は、単糸繊度が好ましくは０．３ｄｔｅｘ以上、より好ましくは０．５ｄｔｅｘ以上、更に好ましくは１ｄｔｅｘ以上であり、そして、好ましくは２０ｄｔｅｘ以下、より好ましくは１５ｄｔｅｘ以下、更に好ましくは１０ｄｔｅｘ以下であるマルチフィラメントであることが好ましい。 <Physical properties of reinforcing fiber>
The reinforcing fiber is preferably a multifilament having a single yarn fineness of 0.1 dtex or more and 30 dtex or less. The single yarn fineness may be less than 0.1 dtex, but is preferably 0.1 dtex or more because it is difficult to industrially produce. On the other hand, when the single yarn fineness is 30 dtex or less, the surface area of the fiber in the case of the reinforcing fiber is increased, and the adhesion to rubber is improved. From the above viewpoint, the reinforcing fiber of the present invention preferably has a single yarn fineness of 0.3 dtex or more, more preferably 0.5 dtex or more, still more preferably 1 dtex or more, and preferably 20 dtex or less, more preferably 15 dtex or less More preferably, it is a multifilament which is 10 dtex or less.
　本発明の補強繊維について、ＪＩＳ　Ｌ　１０１３：２０１０に従って測定した初期引張抵抗度が７０ｃＮ／ｄｔｅｘ以上であることが好ましい。本発明の補強繊維の初期引張抵抗度が前記下限値以上であると、補強繊維とゴムとを接着した際の補強強度が向上する。前記観点から、本発明の初期引張抵抗度は、１００ｃＮ／ｄｔｅｘ以上が好ましく、１３０ｃＮ／ｄｔｅｘ以上がより好ましく、１６０ｃＮ／ｄｔｅｘ以上が更に好ましく、１９０ｃＮ／ｄｔｅｘ以上がより更に好ましく、２００ｃＮ／ｄｔｅｘ以上がより更に好ましい。本発明の初期引張抵抗度の上限値に特に制限はないが、通常、１０００ｃＮ／ｄｔｅｘ以下である。 For the reinforcing fiber of the present invention, the initial tensile resistance measured according to JIS L 1013: 2010 is preferably 70 cN / dtex or more. The reinforcement strength at the time of adhering a reinforcement fiber and rubber | gum improves that the initial stage tensile resistance degree of the reinforcement fiber of this invention is more than the said lower limit. From the above viewpoint, the initial tensile resistance of the present invention is preferably 100 cN / dtex or more, more preferably 130 cN / dtex or more, still more preferably 160 cN / dtex or more, still more preferably 190 cN / dtex or more, 200 cN / dtex or more Even more preferable. The upper limit value of the initial tensile resistance degree of the present invention is not particularly limited, but is usually 1000 cN / dtex or less.
　本発明の補強繊維は、例えば、後述するとおりゴムに接着する繊維、及び混ぜ込む補強繊維として使用できる。また、セメントやコンクリート等に混ぜ込む補強繊維として使用することもできる。 The reinforcing fiber of the present invention can be used, for example, as a fiber adhering to rubber as described later, and as a reinforcing fiber to be mixed. In addition, it can also be used as a reinforcing fiber to be mixed into cement, concrete or the like.
［成形体］
　本発明の成形体は前記補強繊維を用いたものであれば特に限定されない。中でも、本発明の補強繊維がゴムとの優れた接着性を有することから、特に補強繊維とゴムとを用いた成形体が好ましい。
　補強繊維及びゴムを用いた成形体は、例えば自動車用タイヤ、コンベアベルト、ゴムホース、タイミングベルト、及び防振ゴム等のゴム製品の部材として使用することができ、中でも、ゴムホース、防振ゴムとして用いることがより好ましい。
　前記ゴムホースとしては、種々の用途における各種流体の輸送を目的に使用することができ、例えば、自動車用の流体輸送用ホースに好適であり、特に、自動車用の液体燃料用ホース、自動車用のブレーキオイルホース、及び冷媒用ホースに用いることが好ましく、自動車用のブレーキオイルホースに用いることがより好ましい。 [Molded body]
The molded article of the present invention is not particularly limited as long as it uses the reinforcing fiber. Among them, in particular, a molded article using a reinforcing fiber and a rubber is preferable because the reinforcing fiber of the present invention has excellent adhesion to the rubber.
Molded articles using reinforcing fibers and rubber can be used as members of rubber products such as automobile tires, conveyor belts, rubber hoses, timing belts, and vibration-proof rubbers, among which rubber hoses and vibration-proof rubbers are used. Is more preferred.
The rubber hose can be used to transport various fluids in various applications, and is suitable, for example, as a fluid transport hose for automobiles, and in particular, a liquid fuel hose for automobiles, a brake for automobiles It is preferable to use for an oil hose and a hose for refrigerant | coolants, and it is more preferable to use for the brake oil hose for motor vehicles.
　本発明の補強繊維及びゴムを用いた成形体を構成するゴムは、ゴム成分に通常ゴム業界で用いられる配合剤を配合してなるものが好ましい。ゴム成分としては、特に限定はされないが、例えば、ＮＲ（天然ゴム）、ＩＲ（ポリイソプレンゴム）、ＢＲ（ポリブタジエンゴム）、ＳＢＲ（スチレン－ブタジエンゴム）、ＮＢＲ（ニトリルゴム）、ＥＰＭ（エチレン－プロピレン共重合体ゴム）ＥＰＤＭ（エチレン－プロピレン－非共役ジエン共重合体ゴム）、ＩＩＲ（ブチルゴム）、ＣＲ（クロロプレンゴム）等が挙げられ、これらの中でも、ＮＲ、ＩＲ、ＢＲ、ＳＢＲ、ＥＰＤＭ、ＣＲを用いることが好ましく、ＥＰＤＭを用いることがより好ましい。また、これらのゴム成分は一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The rubber constituting the molded article using the reinforcing fiber and rubber of the present invention is preferably one obtained by blending a compounding agent which is usually used in the rubber industry with a rubber component. The rubber component is not particularly limited. For example, NR (natural rubber), IR (polyisoprene rubber), BR (polybutadiene rubber), SBR (styrene-butadiene rubber), NBR (nitrile rubber), EPM (ethylene-) Propylene copolymer rubber) EPDM (ethylene-propylene non-conjugated diene copolymer rubber), IIR (butyl rubber), CR (chloroprene rubber), etc. are mentioned, and among them, NR, IR, BR, SBR, EPDM, It is preferable to use CR, and more preferable to use EPDM. These rubber components may be used alone or in combination of two or more.
　本発明の補強繊維及びゴムを用いた成形体において、前記補強繊維は、繊維束、織物又は編み物の形状でゴムに接着する事によって製造してもよい。また、補強繊維を短繊維にカットし、ゴムに混ぜ込む事によって成形体を製造することもできる。 In the molded article using the reinforcing fiber and rubber of the present invention, the reinforcing fiber may be produced by bonding to rubber in the form of a fiber bundle, a woven fabric or a knitted fabric. In addition, it is also possible to manufacture a molded body by cutting reinforcing fibers into short fibers and mixing it with rubber.
　以下、実施例等により本発明をさらに具体的に説明するが、本発明はかかる実施例等により何ら限定されない。
＜ビニルアルコール系重合体の製造＞
・下記一般式（１ａ）で表される構造単位を有するビニルアルコール系重合体（Ａ）の製造 Hereinafter, the present invention will be described more specifically by Examples and the like, but the present invention is not limited at all by the Examples and the like.
<Production of vinyl alcohol polymers>
-Production of vinyl alcohol polymer (A) having a structural unit represented by the following general formula (1a)
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
製造例１
　還流冷却管、及び温度計を備え付けた三つ口フラスコに、アセトニトリル１９３ｇ、７－オクテナール（ＯＥＬ）１．０７ｇを加え、マグネティックスターラーで攪拌しながらポリビニルアルコール（けん化度９９モル％、平均重合度１７００）５０ｇを徐々に添加した。水３９．５ｇ、４７質量％硫酸１６．５ｇの混合溶液を滴下漏斗から５分間かけて滴下し、３０℃に昇温して５時間反応を行った。１モル／Ｌ水酸化ナトリウム水溶液をｐＨが８になるまで加えた後、ろ過により固形物を取り出し、アセトニトリルと水の重量比９：１の混合溶媒で５回洗浄を行った後、１２０℃、圧力０．００５ＭＰａで６時間乾燥させ、ビニルアルコール系重合体（Ａ）を得た。１Ｈ－ＮＭＲにより二重結合含有量を定量した結果、ビニルアルコール系重合体（Ａ）の二重結合含有量は、０．６２モル％であった。 Production Example 1
Acetonitrile 193g and 1.07 g of 7-octenal (OEL) are added to a three-necked flask equipped with a reflux condenser and a thermometer, and polyvinyl alcohol (saponification degree 99 mol%, average polymerization degree 1700) while stirring with a magnetic stirrer. 50g was added gradually. A mixed solution of 39.5 g of water and 16.5 g of 47% by mass sulfuric acid was added dropwise over 5 minutes from the dropping funnel, and the temperature was raised to 30 ° C. to carry out a reaction for 5 hours. After adding a 1 mol / L aqueous solution of sodium hydroxide until pH reaches 8, the solid is taken out by filtration, washed 5 times with a mixed solvent of acetonitrile and water in a weight ratio of 9: 1, and then 120 ° C. It was dried at a pressure of 0.005 MPa for 6 hours to obtain a vinyl alcohol polymer (A). The double bond content was determined by 1 H-NMR, and as a result, the double bond content of the vinyl alcohol polymer (A) was 0.62 mol%.
・下記一般式（１ｂ）で表される構造単位を有するビニルアルコール系重合体（Ｂ）の製造 -Production of vinyl alcohol polymer (B) having a structural unit represented by the following general formula (1b)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　製造例２
　７－オクテナール１．０７ｇを３－（１，３－ジオキサラン－２－イル）－２－メチル－１－プロペン１．８２ｇに変更したこと以外は製造例１と同様にしてビニルアルコール系重合体（Ｂ）を合成した。１Ｈ－ＮＭＲにより二重結合含有量を定量した結果、ビニルアルコール系重合体（Ｂ）の二重結合含有量は、１．１モル％であった。 Production Example 2
A vinyl alcohol polymer (the same as in Production Example 1) except that 1.07 g of 7-octenal was changed to 1.82 g of 3- (1,3-dioxalan-2-yl) -2-methyl-1-propene B) was synthesized. As a result of quantifying the double bond content by 1 H-NMR, the double bond content of the vinyl alcohol polymer (B) was 1.1 mol%.
・下記一般式（１ｃ）で表される構造単位を有するビニルアルコール系重合体（Ｃ）の製造 -Production of vinyl alcohol polymer (C) having a structural unit represented by the following general formula (1c)
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　製造例３
　還流冷却管、及び温度計を備え付けた三つ口フラスコに、ジメチルスルホキシド（超脱水）（ＤＭＳＯ）を３６質量部、ポリビニルアルコール（けん化度９９モル％、平均重合度１７００）９質量部を加え、攪拌しながら１００℃に昇温することで均一溶液を得た。そこへ、メタクリル酸メチル（ＭＭＡ）を６．０質量部、フェノチアジンを０．１質量部加え、均一になるまで攪拌した。均一になった後、エステル交換触媒として酢酸ナトリウムを０．１７質量部加え、４時間反応させた後、室温に放冷した。反応溶液にＤＭＳＯを１００質量部加え希釈した後、１０００質量部のメタノールに滴下することで、ビニルアルコール系重合体を析出させた。析出させたビニルアルコール系重合体を１０００質量部のメタノールで２回洗浄したのち、４０℃で真空乾燥させ、ビニルアルコール系重合体（Ｃ）を得た。１Ｈ－ＮＭＲにより二重結合含有量を定量した結果、ビニルアルコール系重合体（Ｃ）の二重結合含有量は、２．８モル％であった。 Production Example 3
36 parts by mass of dimethyl sulfoxide (superdehydrated) (DMSO) and 9 parts by mass of polyvinyl alcohol (degree of saponification 99 mol%, average degree of polymerization 1700) are added to a three-necked flask equipped with a reflux condenser and a thermometer, The homogeneous solution was obtained by raising the temperature to 100 ° C. while stirring. Thereto, 6.0 parts by mass of methyl methacrylate (MMA) and 0.1 parts by mass of phenothiazine were added, and the mixture was stirred until it became uniform. After becoming homogeneous, 0.17 parts by mass of sodium acetate was added as a transesterification catalyst, reacted for 4 hours, and allowed to cool to room temperature. 100 parts by mass of DMSO was added to the reaction solution to dilute, and then the solution was added dropwise to 1000 parts by mass of methanol to precipitate a vinyl alcohol polymer. The precipitated vinyl alcohol polymer was washed twice with 1000 parts by mass of methanol, and then vacuum dried at 40 ° C. to obtain a vinyl alcohol polymer (C). The double bond content was determined by 1 H-NMR, and as a result, the double bond content of the vinyl alcohol polymer (C) was 2.8 mol%.
＜１Ｈ－ＮＭＲ測定条件＞
　装置名：超伝導核磁気共鳴装置（日本電子株式会社の「Ｌａｍｂｄａ５００」）
　観測周波数　　：５００ＭＨｚ
　溶媒　　　　　：ＤＭＳＯ－ｄ６
　ポリマー濃度　：４質量％
　測定温度　　　：８０℃
　積算回数　　　：６００回
　パルス遅延時間：３．８３６秒
　サンプル回転速度：１０Ｈｚ～１２Ｈｚ
　パルス幅（９０°パルス）：６．７５μｓｅｃ < 1 H-NMR measurement conditions>
Device name: Superconductivity nuclear magnetic resonance device ("Lambda 500" of Nippon Denshi Co., Ltd.)
Observation frequency: 500 MHz
Solvent: DMSO-d6
Polymer concentration: 4% by mass
Measurement temperature: 80 ° C
Integration number: 600 times Pulse delay time: 3.836 seconds Sample rotation speed: 10 Hz to 12 Hz
Pulse width (90 ° pulse): 6.75 μsec
＜解析方法＞
　得られた１Ｈ－ＮＭＲスペクトルにおいて、炭素－炭素二重結合を形成する炭素に結合している水素に相当するピーク（通常、４．５～６．５ｐｐｍで観察される）、ビニルアルコール単位の水酸基が結合したメチン水素に相当するピーク（通常、３．０～４．０で観察される）、及びビニルアルコール単位のメチレン水素に相当するピーク（通常、１．０～２．０で観察される）から、ビニルアルコール系重合体に含まれる二重結合含有量を測定した。
　　　二重結合含有量［モル％］＝［（二重結合のモル数）／（全構成単位のモル数）］×１００ <Analysis method>
In the obtained 1 H-NMR spectrum, a peak corresponding to hydrogen bonded to carbon forming a carbon-carbon double bond (usually observed at 4.5 to 6.5 ppm), of a vinyl alcohol unit A peak corresponding to hydroxyl group-bound methine hydrogen (usually observed at 3.0 to 4.0) and a peak corresponding to methylene hydrogen of vinyl alcohol units (usually observed at 1.0 to 2.0) ), The content of double bonds contained in the vinyl alcohol polymer was measured.
Double bond content [mol%] = [(mole number of double bond) / (mole number of all constituent units)] × 100
＜接着成分付着量の測定＞
　３０ｍあたりの繊維重量（Ａ）を予め測定しておき、接着成分を付着させた後の同一長さの繊維重量（Ｂ）を測定することで、差分としての以下の計算式の通り接着成分の付着量を計算した。
接着成分付着量＝［（Ｂ－Ａ）／Ａ］×１００（質量％） <Measurement of adhesive component adhesion amount>
By measuring the fiber weight (A) per 30 m in advance and measuring the fiber weight (B) of the same length after attaching the adhesive component, the adhesive component can be obtained according to the following formula as a difference: The amount of adhesion was calculated.
Adhesive component adhesion amount = [(BA) / A] x 100 (mass%)
＜実施例１～３＞
　実施例１～３として、繊維表面の少なくとも一部に接着成分からなる接着層を有する補強繊維を製造し、以下のとおり評価した。
　前述のとおり製造したビニルアルコール系重合体（Ａ）～（Ｃ）からなる接着成分２．０ｇを、それぞれ水９８．０ｇに溶解させた。この溶液に対してポリビニルアルコール系繊維であるビニロン繊維（株式会社クラレ製「クラロン１２３９」、１３３０ｄｔｅｘ）を浸漬した後、ローラーで搾液した。次いで、得られた繊維を１２０℃で３０秒間乾燥し、更に１４０℃で３０秒間熱処理した。このようにして接着成分を付着させたビニロンを撚り数８０Ｔ／ｍで撚って繊維コードを作製した。
　なお、実施例１～３における接着成分の付着量は表１に記載のとおりに調整した。 <Examples 1 to 3>
As Examples 1 to 3, reinforcing fibers having an adhesive layer composed of an adhesive component on at least a part of the fiber surface were produced and evaluated as follows.
In 98.0 g of water, 2.0 g of the adhesive component consisting of the vinyl alcohol polymers (A) to (C) produced as described above was dissolved. After immersing vinylon fiber ("Kuraray 1239", 1330 dtex made by Kuraray Co., Ltd.) which is a polyvinyl alcohol-based fiber in this solution, it was squeezed with a roller. The resulting fibers were then dried at 120 ° C. for 30 seconds and heat treated at 140 ° C. for 30 seconds. The vinylon to which the adhesive component was attached in this manner was twisted at a twist number of 80 T / m to produce a fiber cord.
The adhesion amount of the adhesive component in Examples 1 to 3 was adjusted as described in Table 1.
＜比較例１＞
　接着成分としてポリビニルアルコール（けん化度９９モル％以上、平均重合度１７００）を用いたこと、及び接着成分の付着量を表１に記載のとおりに調整したこと以外は実施例１～３と同様の方法で繊維コードを作製した。 Comparative Example 1
The same as Examples 1 to 3 except that polyvinyl alcohol (saponification degree of 99 mol% or more, average polymerization degree of 1700) was used as an adhesive component, and the adhesion amount of the adhesive component was adjusted as described in Table 1. The fiber cord was made by the method.
＜比較例２＞
　接着成分としてポリビニルアルコール（けん化度９４．５モル％以上、平均重合度１７００）を用いたこと、及び接着成分の付着量を表１に記載のとおりに調整したこと以外は実施例１～３と同様の方法で繊維コードを作製した。 Comparative Example 2
As Examples 1 to 3 except that polyvinyl alcohol (saponification degree 94.5 mol% or more, average polymerization degree 1700) was used as the adhesive component, and the adhesion amount of the adhesive component was adjusted as described in Table 1 A fiber cord was made in the same manner.
＜比較例３＞
　接着成分として下記方法にて調製したＲＦＬを用いたこと、及び接着成分の付着量を表１に記載のとおりに調整したこと以外は実施例１～３と同様の方法で繊維コードを作製した。 Comparative Example 3
A fiber cord was produced in the same manner as in Examples 1 to 3 except that RFL prepared by the following method was used as an adhesive component, and the adhesion amount of the adhesive component was adjusted as described in Table 1.
＜ＲＦＬ液の組成＞
Ａ液　　水　　　　　　　　　　　　　　　　　：３００部
　　　　レゾルシン　　　　　　　　　　　　　：　２２部
　　　　ホルムアルデヒド（濃度３７％）　　　：　３３部
　　　　水酸化ナトリウム水溶液（濃度１０％）：　　７部
　上記Ａ液を２５℃の温度で６時間熟成した。 <Composition of RFL solution>
Solution A Water: 300 parts Resorcinol: 22 parts Formaldehyde (concentration 37%): 33 parts Sodium hydroxide aqueous solution (concentration 10%): 7 parts The above solution A was aged at a temperature of 25 ° C. for 6 hours.
Ｂ液　　ＳＢＲラテックス（濃度４０％）　　　　　　　　　：　４３部
　　　　ビニルピリジン変性ＳＢＲラテックス（濃度４０％）：２４４部
　上記Ｂ液を熟成済みのＡ液と混合した後、２５℃の温度で１６時間熟成してＲＦＬ液を製造した。 Solution B SBR latex (concentration 40%): 43 parts Vinylpyridine-modified SBR latex (concentration 40%): 244 parts The solution B was mixed with the solution A and then aged at 25 ° C. for 16 hours for RFL The solution was made.
＜接着力の評価＞
　前述の方法により接着成分を付着させた繊維コードを、繊維コード同士が重ならないようにスダレ状にマスキングテープ上に並べて固定した後、これとＥＰＤＭ未加硫ゴム（幅２５．４ｍｍ、長さ２４０ｍｍ）とを重ね合わせた（繊維とＥＰＤＭ未加硫ゴムとの重ね合わせた部分の長さは１９０ｍｍであった）。次いで、加圧下１５０℃、圧力２０ｋｇ／ｃｍ２の条件で３０分間プレス加硫することにより接着力評価用シートを作成した。 <Evaluation of adhesive strength>
The fiber cords to which the adhesive component is attached by the above-mentioned method are arranged and fixed on the masking tape in a staggered manner so that the fiber cords do not overlap each other, and this and EPDM unvulcanized rubber (width 25.4 mm, length 240 mm) (The length of the overlapped portion of the fiber and the EPDM unvulcanized rubber was 190 mm). Subsequently, the sheet for adhesive force evaluation was created by press-curing for 30 minutes on condition of 150 degreeC under pressure, and pressure 20 kg / cm < 2 >.
＜初期引張抵抗度の測定＞
　得られた接着力評価用シートの初期引張抵抗度を測定機（インストロン３３６５）を使用してＪＩＳ　Ｌ　１０１３：２０１０に従って測定した。剥離速度５０ｍｍ／ｍｉｎで２００ｍｍ動かして剥離試験を行い、繊維コードとゴムとを剥離した。
　チャートに現れる最初のピークから１０ｍｍと最後のピークから１０ｍｍを除いた範囲で現れる多数のピークから最高点５点と最低点５点を取り出して平均した値を繊維とゴムの初期引張抵抗度とした。なお、ピーク同士が２ｍｍ以上離れているもののみから値を採取した。結果を表１に示す。
　初期引張抵抗度の評価結果は、数値が大きい方が補強繊維とゴムとの接着力が大きいことを示す。 <Measurement of initial tensile resistance>
The initial tensile resistance of the obtained sheet for adhesive strength evaluation was measured according to JIS L 1013: 2010 using a measuring machine (Instron 3365). The peeling test was performed by moving 200 mm at a peeling speed of 50 mm / min to peel the fiber cord and the rubber.
Five peaks and five lowest points were taken from a number of peaks appearing in the range of 10 mm from the first peak appearing in the chart and 10 mm from the last peak, and the average value was taken as the initial tensile resistance of fiber and rubber. . In addition, the value was extract | collected only from what the peaks mutually separated 2 mm or more. The results are shown in Table 1.
The evaluation results of the initial degree of tensile resistance show that the larger the numerical value, the greater the adhesion between the reinforcing fiber and the rubber.
＜ゴム接着力の測定＞
　得られた接着力評価用シートについて、繊維コードをゴムからＴ型剥離させるときに要した力（Ｎ／２５．４ｍｍ）を測定し、ゴム接着力として評価した。結果を表１に示す。
　ゴム接着力の評価結果は、数値が大きいほど補強繊維とゴムとの接着力が大きいことを示す。 <Measurement of rubber adhesion>
About the obtained sheet | seat for adhesive force evaluation, the force (N / 25.4 mm) required when making a fiber cord T-type peeling from rubber was measured, and it evaluated as rubber adhesive force. The results are shown in Table 1.
The evaluation results of the rubber adhesion show that the larger the numerical value, the larger the adhesion between the reinforcing fiber and the rubber.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＜実施例４＞
　実施例４として、繊維が接着成分を原料の一部として含有する補強繊維を以下のとおり製造し、評価した。
　製造例１と同様の方法で製造した多重結合（二重結合）含有量が０．２７モル％のＯＥＬ変性ＰＶＡとＰＶＡ単独重合体（粘度平均重合度：１７００、鹸化度：９９モル％以上）とを１対１の割合で混合して固形分濃度が１６重量％になるように水に浴解した。更にＯＥＬ変性ＰＶＡとＰＶＡ単独重合体の合計１００質量部に対してホウ酸を２質量部の割合で添加して原液を作製した。
　次いで、水酸化ナトリウム２０ｇ／Ｌ、及び硫酸ナトリウム３２０ｇ／Ｌの割合で水に浴解した７０℃の凝固浴（一浴）中へ該原液を湿式紡糸し、ローラー延伸、中和、湿熱延伸、水洗、乾燥した。
　次いで、２４０℃で乾熱延伸を行ってボビンに巻取ることによりＰＶＡ系繊維（２０００ｄＴｅｘ）を得た。得られた繊維を８０Ｔ／ｍで撚糸して繊維コードを作製した。 Example 4
As Example 4, the reinforcing fiber in which the fiber contains the adhesive component as a part of the raw material was manufactured and evaluated as follows.
OEL-modified PVA and PVA homopolymer having a multiple bond (double bond) content of 0.27 mol% prepared by the same method as Production Example 1 (viscosity average degree of polymerization: 1700, degree of saponification: 99 mol% or more) Were mixed in a ratio of 1 to 1 and dissolved in water so as to have a solid content concentration of 16% by weight. Furthermore, the boric acid was added in the ratio of 2 mass parts with respect to a total of 100 mass parts of OEL modified PVA and a PVA homopolymer, and the undiluted | stock solution was produced.
Then, the stock solution is wet-spun into a 70 ° C. coagulation bath (one bath) bathed in water at a ratio of 20 g / L of sodium hydroxide and 320 g / L of sodium sulfate, roller stretching, neutralization, wet heat stretching, It was washed with water and dried.
Subsequently, dry heat drawing was performed at 240 ° C., and winding on a bobbin was performed to obtain a PVA-based fiber (2000 dTex). The obtained fiber was twisted at 80 T / m to produce a fiber cord.
＜比較例４＞
　ＯＥＬ変性ＰＶＡを用いず、ＰＶＡ単独重合体のみを用いて固形分濃度１２重量％になるよう原液を作製したこと以外は実施例４と同様にしてＰＶＡ繊維からなる繊維コードを得た。 Comparative Example 4
A fiber cord comprising PVA fiber was obtained in the same manner as in Example 4 except that the stock solution was prepared so as to have a solid content concentration of 12% by weight using only the PVA homopolymer without using OEL-modified PVA.
＜ゴム接着力＞
　実施例４及び比較例４で得られた繊維コードについて、前記と同様の方法でゴム接着力を評価した。結果を表２に示す。 Rubber adhesion
Rubber adhesion of the fiber cords obtained in Example 4 and Comparative Example 4 was evaluated in the same manner as described above. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実施例及び比較例の結果より明らかなように、本発明の補強繊維はレゾルシン・ホルマリン樹脂とゴムラテックスとを主成分とする接着剤を用いることなく、ゴムとの接着性に優れる補強繊維を得ることができる。 As apparent from the results of Examples and Comparative Examples, the reinforcing fiber of the present invention obtains a reinforcing fiber having excellent adhesion to rubber without using an adhesive containing resorcinol formalin resin and rubber latex as main components. be able to.

Claims (12)

  1. 　繊維表面の少なくとも一部に接着成分を有する親水性繊維からなる補強繊維であって、該接着成分が分子内に反応性炭素－炭素二重結合及び反応性炭素－炭素三重結合から選ばれる１種以上の多重結合を有するビニルアルコール系重合体を含む補強繊維。 A reinforcing fiber comprising a hydrophilic fiber having an adhesive component on at least a part of the fiber surface, wherein the adhesive component is selected from a reactive carbon-carbon double bond and a reactive carbon-carbon triple bond in the molecule. A reinforcing fiber comprising a vinyl alcohol polymer having multiple bonds as described above.
  2. 　前記親水性繊維が、ポリビニルアルコール系繊維、再生セルロース系繊維、及び疎水性繊維の表面を親水化処理した繊維から選ばれる１種以上である、請求項１に記載の補強繊維。 The reinforcing fiber according to claim 1, wherein the hydrophilic fiber is at least one selected from polyvinyl alcohol fibers, regenerated cellulose fibers, and fibers obtained by hydrophilizing the surface of hydrophobic fibers.
  3. 　前記疎水性繊維がポリエステル系繊維である、請求項２に記載の補強繊維。 The reinforcing fiber according to claim 2, wherein the hydrophobic fiber is a polyester fiber.
  4. 　前記補強繊維が、単糸繊度が０．１ｄｔｅｘ以上、３０ｄｔｅｘ以下のマルチフィラメントである、請求項１～３のいずれかに記載の補強繊維。 The reinforcing fiber according to any one of claims 1 to 3, wherein the reinforcing fiber is a multifilament having a single yarn fineness of 0.1 dtex or more and 30 dtex or less.
  5. 　ＪＩＳ　Ｌ　１０１３：２０１０に従って測定した前記補強繊維の初期引張抵抗度が７０ｃＮ／ｄｔｅｘ以上である、請求項１～４のいずれかに記載の補強繊維。 The reinforcing fiber according to any one of claims 1 to 4, wherein the initial tensile resistance of the reinforcing fiber measured according to JIS L 1013: 2010 is 70 cN / dtex or more.
  6. 　前記多重結合の少なくとも一部が前記ビニルアルコール系重合体の側鎖に存在する、請求項１～５のいずれかに記載の補強繊維。 The reinforcing fiber according to any one of claims 1 to 5, wherein at least a part of the multiple bond is present in the side chain of the vinyl alcohol polymer.
  7. 　前記ビニルアルコール系重合体が、前記多重結合を有する多重結合含有化合物により変性したものであり、該多重結合含有化合物が、前記多重結合を有するアルデヒド、該アルデヒドのアセタール化体、前記多重結合を有するカルボン酸、該カルボン酸の塩、該カルボン酸のエステル化体、該カルボン酸の酸無水物、前記多重結合を有するジカルボン酸、該ジカルボン酸の塩、該ジカルボン酸のエステル化体、該ジカルボン酸の酸無水物、及び前記多重結合を有するアミン化合物から選ばれる１種以上である、請求項１～６のいずれかに記載の補強繊維。 The vinyl alcohol polymer is modified with a multiple bond-containing compound having the multiple bond, and the multiple bond-containing compound is an aldehyde having the multiple bond, an acetalized form of the aldehyde, and the multiple bond. Carboxylic acid, salt of the carboxylic acid, esterified form of the carboxylic acid, acid anhydride of the carboxylic acid, dicarboxylic acid having the multiple bond, salt of the dicarboxylic acid, esterified form of the dicarboxylic acid, the dicarboxylic acid The reinforcing fiber according to any one of claims 1 to 6, which is at least one selected from an acid anhydride of and an amine compound having the multiple bond.
  8. 　前記繊維表面の少なくとも一部に前記接着成分からなる接着層を有する、請求項１～７のいずれかに記載の補強繊維。 The reinforcing fiber according to any one of claims 1 to 7, further comprising an adhesive layer composed of the adhesive component on at least a part of the fiber surface.
  9. 　前記繊維が前記接着成分を原料の一部として含有する、請求項１～８のいずれかに記載の補強繊維。 The reinforcing fiber according to any one of claims 1 to 8, wherein the fiber contains the adhesive component as a part of the raw material.
  10. 　請求項１～９のいずれかに記載の補強繊維を用いた成形体。 A molded article using the reinforcing fiber according to any one of claims 1 to 9.
  11. 　請求項１～９のいずれかに記載の補強繊維及びゴムを用いた成形体。 A molded article using the reinforcing fiber and rubber according to any one of claims 1 to 9.
  12. 　前記成形体がゴムホースである請求項１０又は１１に記載の成形体。 The molded article according to claim 10, wherein the molded article is a rubber hose.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4632498B1 (en) * 1967-04-11 1971-09-22
JPH1121726A (en) * 1997-07-08 1999-01-26 Kuraray Co Ltd Polyvinyl alcohol synthetic fiber and its production
JP2007063383A (en) * 2005-08-31 2007-03-15 Mitsui Chemicals Inc Method for producing (meth)acrylate-modified polyvinyl alcohol
WO2015182567A1 (en) * 2014-05-28 2015-12-03 日本酢ビ・ポバール株式会社 Dispersion stabilizer for suspension polymerization, method for producing vinyl polymer, and vinyl chloride resin

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* Cited by examiner, † Cited by third party
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JP4632498B2 (en) 2000-08-22 2011-02-16 ケミプロ化成株式会社 Method for producing tris [(alkylthioalkanoyloxy) ethyl] isocyanurate derivative

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4632498B1 (en) * 1967-04-11 1971-09-22
JPH1121726A (en) * 1997-07-08 1999-01-26 Kuraray Co Ltd Polyvinyl alcohol synthetic fiber and its production
JP2007063383A (en) * 2005-08-31 2007-03-15 Mitsui Chemicals Inc Method for producing (meth)acrylate-modified polyvinyl alcohol
WO2015182567A1 (en) * 2014-05-28 2015-12-03 日本酢ビ・ポバール株式会社 Dispersion stabilizer for suspension polymerization, method for producing vinyl polymer, and vinyl chloride resin

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