WO2014034698A1 - 接着剤組成物 - Google Patents
接着剤組成物 Download PDFInfo
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- WO2014034698A1 WO2014034698A1 PCT/JP2013/072952 JP2013072952W WO2014034698A1 WO 2014034698 A1 WO2014034698 A1 WO 2014034698A1 JP 2013072952 W JP2013072952 W JP 2013072952W WO 2014034698 A1 WO2014034698 A1 WO 2014034698A1
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- weight
- nitrile rubber
- highly saturated
- adhesive composition
- saturated nitrile
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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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/18—Homopolymers or copolymers of nitriles
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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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
- C09J109/04—Latex
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
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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
- C09J115/00—Adhesives based on rubber derivatives
- C09J115/005—Hydrogenated nitrile rubber
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2413/00—Belts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/14—Esters of polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/14—Esters of polycarboxylic acids
- C08F218/16—Esters of polycarboxylic acids with alcohols containing three or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
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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
- C09J113/00—Adhesives based on rubbers containing carboxyl groups
- C09J113/02—Latex
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31924—Including polyene monomers
Definitions
- the present invention relates to an adhesive composition comprising a latex of highly saturated nitrile rubber.
- Rubber and fiber composites are used in many fields such as belts, rubber hoses and diaphragms.
- belts there are timing belts for automobiles, polyribbed belts, wrapped belts, V-belts, and the like, which are usually composed of a composite of a woven fabric base fabric and rubber.
- V-belt the periphery of the belt is protected by a canvas, and in the toothed belt, a covering cloth is laminated on the tooth portion.
- chloroprene rubber and acrylonitrile-butadiene copolymer rubber which are oil-resistant rubbers
- High-saturation nitrile rubber which combines heat resistance and oil resistance, has come to be used because high heat resistance has been required in response to engine room sealing to prevent noise. ing.
- the tooth portion is protected by a nylon base fabric, but in order to increase the adhesive force between the rubber and the base fabric, and to suppress wear due to the meshing between the belt and the gear,
- the base fabric is treated with a solvent-based rubber paste.
- a processing technique using a water-based adhesive is desired in place of the processing using a solvent-based rubber paste.
- Patent Document 1 discloses an adhesive composition containing a carboxyl group-containing highly saturated nitrile rubber latex and a resorcin-formaldehyde resin.
- a carboxyl group-containing highly saturated nitrile rubber latex and a resorcin-formaldehyde resin.
- An object of the present invention is to provide an adhesive composition capable of forming an adhesive layer excellent in mechanical strength, abrasion resistance and water resistance.
- the present inventors use an adhesive composition containing a latex of a highly saturated nitrile rubber having a specific amount of a specific monomer unit and a polyvalent amine compound.
- the inventors have found that the above object can be achieved and have completed the present invention.
- ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit 10 to 55% by weight of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, 25 to 89% by weight of conjugated diene monomer unit, and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid
- a latex of a highly saturated nitrile rubber (A) having a monoester monomer unit of 1 to 20% by weight and an iodine value of 120 or less an adhesive composition containing a polyvalent amine compound (B) Is done.
- A highly saturated nitrile rubber
- B polyvalent amine compound
- the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit is preferably an ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoalkyl ester monomer unit. -Butyl units are more preferred.
- the content ratio of the polyvalent amine compound (B) to 100 parts by weight of the highly saturated nitrile rubber (A) is preferably 0.001 to 100 parts by weight.
- the polyvalent amine compound (B) used in the present invention is preferably polyethyleneimine, and the polyethyleneimine preferably has a weight average molecular weight (Mw) of 100 to 1,000,000.
- a fiber base material-high saturation nitrile rubber composite formed by bonding a fiber base material and a highly saturated nitrile rubber with the above-mentioned adhesive composition.
- an adhesive composition capable of forming an adhesive layer excellent in mechanical strength, abrasion resistance and water resistance is provided.
- the adhesive composition of the present invention comprises 10 to 55% by weight of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, 25 to 89% by weight of conjugated diene monomer unit, and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid. It contains a latex of a highly saturated nitrile rubber (A) having an acid monoester monomer unit of 1 to 20% by weight and an iodine value of 120 or less, and a polyvalent amine compound (B).
- A highly saturated nitrile rubber
- B polyvalent amine compound
- the highly saturated nitrile rubber (A) used in the present invention comprises an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, a conjugated diene monomer, an ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer, and It is a rubber having an iodine value of 120 or less, which is obtained through a step of copolymerizing another monomer copolymerizable with each of the above monomers.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
- acrylonitrile; ⁇ -chloroacrylonitrile, ⁇ -bromoacrylonitrile, etc. ⁇ -halogenoacrylonitrile, ⁇ -alkylacrylonitrile such as methacrylonitrile, and the like Among these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.
- the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is 10 to 55% by weight, preferably 20 to 53% by weight, based on all monomer units constituting the highly saturated nitrile rubber (A). More preferably, it is 25 to 50% by weight. If the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is too small, the resulting cured adhesive layer (the adhesive composition formed after bonding using the adhesive composition of the present invention is cured) The oil resistance of the layer) may be reduced, and conversely if it is too much, the cold resistance may be reduced.
- the conjugated diene monomer is not particularly limited, but a conjugated diene monomer having 4 to 6 carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc. Is preferred, 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is particularly preferred.
- the conjugated diene monomer may be used alone or in combination of two or more.
- the content of the conjugated diene monomer unit is 25 to 89% by weight, preferably 32 to 78% by weight, more preferably 40 to 73%, based on all monomer units constituting the highly saturated nitrile rubber (A). % By weight. If the content of the conjugated diene monomer unit is too small, the flexibility of the resulting cured adhesive layer may be reduced. Conversely, if it is too large, the heat resistance and chemical stability may be impaired. . In addition, content of the said conjugated diene monomer unit is content also including the hydrogenated part, when the below-mentioned copolymer is hydrogenated.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomers include monomethyl maleate, monoethyl maleate, monopropyl maleate, mono n-butyl maleate, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate ⁇ such as mono n-butyl fumarate, monomethyl itaconate, monoethyl itaconate, monopropyl itaconate, mono n-butyl itaconate, monomethyl citraconic acid, monoethyl citraconic acid, monopropyl citraconic acid, mono n-butyl citraconic acid , ⁇ -ethylenically unsaturated dicarboxylic acid monoalkyl ester monomer; monocyclopentyl maleate, monocyclohexyl maleate, monocycloheptyl maleate, monocyclopentyl fumarate, monocyclohexyl fumarate, monofumarate
- ⁇ such as monomethylcyclopentyl maleate, monoethylcyclohexyl maleate, monomethylcyclopentyl fumarate, monoethylcyclohexyl fumarate, monomethylcyclopentyl itaconate, monoethylcyclohexyl itaconate, monomethylcyclopentyl citraconic acid, monoethylcyclohexyl citraconic acid, ⁇ -ethylenically unsaturated dicarboxylic acid monoalkyl cycloalkyl ester monomer; maleic acid mono 2-hydro Xiethyl, mono 3-hydroxypropyl maleate, mono 2-hydroxyethyl fumarate, mono 2-hydroxypropyl fumarate, mono 2-hydroxyethyl itaconic acid, mono 3-hydroxypropyl itaconic acid, mono 2-hydroxyethyl citraconic acid, etc.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monohydroxyalkyl ester monomers ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoesters having an alicyclic structure such as monocyclohexenyl maleate and monocyclohexenyl fumarate Monomers; etc. are mentioned, however, since the effects of the present invention become more remarkable, ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoalkyl ester monomers are preferred, and maleic acid monoalkyl esters are more preferred. Mono n-butyl maleate is particularly preferred .
- the number of carbon atoms in the alkyl group of the alkyl ester is preferably 2-8.
- the content of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit is 1 to 20% by weight, preferably 2 to 15% by weight, more preferably 2%, based on the total monomer units. ⁇ 10% by weight.
- Adhesive composition capable of forming an adhesive layer excellent in mechanical strength, abrasion resistance and water resistance when the content of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit is in the above range. Is easy to obtain.
- the highly saturated nitrile rubber (A) used in the present invention is an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, a conjugated diene monomer, and an ⁇ , ⁇ -ethylenic monomer as long as the effects of the present invention are not impaired.
- the unsaturated dicarboxylic acid monoester monomer and other monomers copolymerizable therewith may be copolymerized.
- Examples of such other monomers include carboxyl group-containing monomers other than ethylene, ⁇ -olefin monomers, aromatic vinyl monomers, and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomers. (Including polyhydric carboxylic acid anhydrides), ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester monomers (not having non-esterified unsubstituted (free) carboxyl groups), fluorine-containing Examples include vinyl monomers and copolymerizable anti-aging agents.
- the ⁇ -olefin monomer preferably has 3 to 12 carbon atoms, and examples thereof include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
- aromatic vinyl monomers examples include styrene, ⁇ -methylstyrene, vinyl pyridine and the like.
- carboxyl group-containing monomers other than ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomers, acrylic acid, methacrylic acid, ethylacrylic acid, crotonic acid, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomers such as cinnamic acid; ⁇ , ⁇ -ethylene such as fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allylmalonic acid, teraconic acid Unsaturated polyvalent carboxylic acids; anhydrides of ⁇ , ⁇ -unsaturated polyvalent carboxylic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride; and the like.
- Examples of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester monomers include, for example, methyl acrylate, ethyl acrylate, acrylic acid (Meth) acrylic acid esters having 1 to 18 carbon atoms such as n-butyl, n-dodecyl acrylate, methyl methacrylate, and ethyl methacrylate (abbreviations for “methacrylic acid esters and acrylic acid esters”; .); (Meth) acrylic acid ester having a C2-C12 alkoxyalkyl group such as methoxymethyl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate; ⁇ -cyanoethyl acrylate, ⁇ -methacrylic acid ⁇ -2 to 1 carbon atoms such as cyanoethyl and ⁇ -cyanobutyl
- Acid esters (meth) acrylic acid esters having a C1-C12 fluoroalkyl group such as trifluoroethyl acrylate and tetrafluoropropyl methacrylate; dimethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl itaconate, etc.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid dialkyl ester and dialkylamino group-containing ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.
- fluorine-containing vinyl monomer examples include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethyl styrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.
- copolymerizable anti-aging agents examples include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4- Anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
- the content of other monomer units is preferably 40% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight or less based on the total monomer units.
- the iodine value of the highly saturated nitrile rubber (A) is 120 or less, preferably 60 or less, particularly preferably 30 or less. If the iodine value of the highly saturated nitrile rubber (A) is too high, the heat resistance and ozone resistance of the resulting cured adhesive layer may be reduced.
- the polymer Mooney viscosity (ML 1 + 4 , 100 ° C.) of the highly saturated nitrile rubber (A) is preferably 15 to 250, more preferably 20 to 200, and particularly preferably 30 to 150. If the polymer Mooney viscosity of the highly saturated nitrile rubber (A) is too low, the mechanical strength of the resulting cured adhesive layer may be reduced. Conversely, if it is too high, the adhesiveness may be reduced.
- the latex of the highly saturated nitrile rubber (A) used in the adhesive composition of the present invention is obtained by copolymerizing the above-mentioned monomer and, if necessary, the resulting copolymer (X) (hereinafter simply referred to as “nitrile rubber”). It is obtained by hydrogenating the carbon-carbon double bond in the medium by a conventionally known method, and further emulsifying if necessary.
- the polymerization method is not particularly limited and may be a known polymerization method, but an emulsion polymerization method is preferable from the viewpoint of industrial productivity.
- Specific methods for hydrogenation include (i) a method of hydrogenating a latex copolymer (X) with gaseous hydrogen, and (ii) a latex copolymer (X).
- a method of adding a hydrogen atom by using a reducing agent such as hydrazine (iii) the latex copolymer (X) is solidified, dried and separated, then dissolved in an organic solvent, and the dissolved copolymer (X And the like, and the method of making it into a latex state by a phase inversion emulsification method, and the like. From the viewpoint of improving productivity, the method (i) is preferable.
- a conventionally known method may be employed as the emulsion polymerization method.
- an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.
- anionic surfactants are preferred, and the amount used is not particularly limited, but from the viewpoint of the adhesive strength of the adhesive composition obtained from this latex, 1 to 10 weights per 100 weight parts of the total monomers. Parts, preferably 2 to 6 parts by weight.
- a polymerization initiator or the like may be usually used.
- the polymerization method is not particularly limited, and any of batch, semi-batch and continuous methods may be used, and the polymerization temperature and pressure are not limited.
- the amount of carbon-carbon double bonds (derived from the conjugated diene monomer unit) in the copolymer (X) is small. Therefore, the iodine value of the nitrile rubber obtained by emulsion polymerization is a desired value. In the following cases, hydrogenation is not necessarily performed.
- the latex of copolymer (X) prepared by emulsion polymerization is diluted by adding water as necessary, and hydrogen is supplied in the presence of a hydrogenation catalyst to carry out the hydrogenation reaction. It is preferred to do so.
- a hydrogenation catalyst will not be specifically limited if it is a compound which is hard to decompose
- Specific examples thereof include palladium salts of carboxylic acids such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid, and phthalic acid; palladium chloride, dichloro (cyclooctadiene) palladium, dichloro (norbornadiene) palladium.
- palladium chlorinated products such as ammonium hexachloropalladium (IV); iodinated products such as palladium iodide; palladium sulfate dihydrate and the like.
- the amount of the hydrogenation catalyst used may be appropriately determined, but is preferably 5 to 6,000 ppm by weight, more preferably 10 to 4,000 ppm by weight with respect to the copolymer (X).
- the reaction temperature of the hydrogenation reaction is preferably 0 to 300 ° C, more preferably 20 to 150 ° C, and particularly preferably 30 to 100 ° C. If the reaction temperature is too low, the reaction rate may decrease. Conversely, if the reaction temperature is too high, side reactions such as hydrogenation of nitrile groups may occur.
- the hydrogen pressure is preferably 0.1 to 30 MPa, more preferably 0.5 to 20 MPa.
- the reaction time is preferably 1 to 15 hours, particularly preferably 2 to 10 hours.
- the average particle size of the latex of the highly saturated nitrile rubber (A) thus obtained is preferably 0.01 to 0.5 ⁇ m. Further, the solid content concentration of the latex is preferably 65% by weight or less, particularly preferably 5 to 60% by weight in order to prevent agglomeration.
- the adhesive composition of the present invention contains a latex of highly saturated nitrile rubber (A).
- the content of the highly saturated nitrile rubber (A) in the adhesive composition of the present invention is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight.
- the adhesive composition of the present invention contains a polyvalent amine compound (B) in addition to the above-described highly saturated nitrile rubber (A).
- the polyvalent amine compound (B) acts as a crosslinking agent for crosslinking the above-described highly saturated nitrile rubber (A).
- the polyvalent amine compound (B) is not particularly limited as long as it is a compound having two or more amino groups or a compound having two or more amino groups at the time of crosslinking.
- Examples of the aliphatic polyvalent amine compound include 2 amino groups (including those in the form of amino groups at the time of crosslinking) such as hexamethylene diamine, hexamethylene diamine carbamate, N, N′-dicinnamylidene-1,6-hexanediamine.
- a high molecular compound having a plurality of amino groups such as polyallylamine, polyethyleneimine, polypropyleneimine, and polybutadieneimine. These may be used alone or in combination.
- aromatic polyamine compound examples include 4,4′-methylenedianiline, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4 ′-(m-phenyl).
- Range isopropylidene) dianiline 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzanilide, 4 4,4'-bis (4-aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine, 1,3,5-benzenetriamine and the like. These may be used alone or in combination.
- hexamethylenediamine carbamate, polyallylamine, and polyethyleneimine are preferable, and polyethyleneimine is particularly preferable because it has a high effect of improving mechanical strength, abrasion resistance, and water resistance when used as an adhesive. preferable.
- Polyallylamine is a polymer containing a unit represented by the following general formula (1).
- R 1 , R 2 and R 3 each independently have a hydrogen atom, a C 1-4 alkyl group which may have a substituent, or a substituent. May be one selected from the group consisting of an aryl group having 6 to 12 carbon atoms and a halogen atom, preferably at least one of R 1 , R 2 and R 3 is a hydrogen atom, , R 1 , R 2 and R 3 are preferably all hydrogen atoms.
- the polyallylamine may be any unit having a unit represented by the above general formula (1), for example, a homopolymer of an allylamine monomer represented by the following general formula (2), or Any of a block polymer or a random polymer of an allylamine monomer represented by the following general formula (2) and a monomer copolymerizable therewith can be used.
- a homopolymer of an allylamine monomer or a block polymer of a monomer copolymerizable with an allylamine monomer is preferable. That is, as polyallylamine, what contains the polymer (block) represented by following General formula (3) is preferable. (In the general formula (2), R 1 , R 2 and R 3 are the same as in the general formula (1).)
- R 1 , R 2 and R 3 are the same as in the general formula (1), and as in the general formula (1), all of R 1 , R 2 and R 3 are Particularly preferred is a hydrogen atom. That is, the polyallylamine is particularly preferably one containing a polymer (block) represented by the following general formula (4).
- n is an integer of 5 to 1000000, preferably 5 to 100,000, more preferably 10 to 10,000, and particularly preferably 15 to 1000.
- the weight average molecular weight (Mw) of polyallylamine is not particularly limited, but is preferably from 300 to 60,000,000 from the viewpoint that the effect of improving mechanical strength, wear resistance and water resistance can be appropriately exhibited. More preferably 300 to 6,000,000, still more preferably 600 to 600,000, and particularly preferably 800 to 60,000.
- the content rate of the unit represented by the general formula (1) is preferably 50% by weight or more, more preferably 70% by weight or more, and the general formula (1)
- the content ratio of the unit represented by is particularly preferably 100% by weight.
- polyallylamine can be obtained by allowing a monomer copolymerizable with an allylamine monomer to coexist with an allylamine monomer represented by the general formula (2), if necessary. -14364, JP-A No. 2001-253905, JP-A No. 2010-47688 and the like.
- allylamine monomers examples include monoallylamine (same as 2-propen-1-amine), 3-methyl-2-propen-1-amine, 3-ethyl-2-propen-1-amine, 3-butyl- 2-propen-1-amine, 3-phenyl-2-propen-1-amine, 3-tolyl-2-propen-1-amine, 3-chloro-2-propen-1-amine, 3-bromo-2- Propene-1-amine, 2-methyl-2-propen-1-amine, 2-ethyl-2-propen-1-amine, 2-butyl-2-propen-1-amine, 2-phenyl-2-propene Examples include 1-amine, 2-tolyl-2-propen-1-amine, 2-chloro-2-propen-1-amine, 2-bromo-2-propen-1-amine, and the like. Even more prominent Since, monoallylamine is preferred.
- Monomers copolymerizable with allylamine monomers include vinylpyrrolidone, ⁇ -methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl methacrylate, methyl vinyl ketone, acrylamide, acrylonitrile, methacrylonitrile, styrene, hydroxyethyl acrylate Acrylic acid, methacrylic acid, vinyl chloride, vinyl isocyanate, methyl vinyl ether, vinyl pyridine, acrolein, methyl acrylate, methyl methacrylate and the like.
- Polyethyleneimine is a polymer obtained by polymerizing ethyleneimine represented by the following formula (5), and is a polymer having a branched structure and a primary to tertiary amino group. It is a polymer having a structure represented by formula (6).
- a, b, and c are each independently 0 or a positive integer. However, at least one of a, b, or c is a positive integer.
- the polyethyleneimine typically has a structure represented by the general formula (6), but in the general formula (6), a nitrogen atom in the branched chain (that is, the number of repeating units). In the form of substituting the nitrogen atom contained in the repeating unit of which is another c, a further branched chain may be formed, and from this another branched chain, a plurality of branched chains may be formed. It may be formed sequentially. That is, the polyethyleneimine may have a number of branched structures.
- the repeating unit having the repeating unit number a and the repeating unit having the repeating unit number b usually have a random arrangement with each other.
- the weight average molecular weight (Mw) of the polyethyleneimine is not particularly limited, but is preferably 100 to 1,000,000 from the viewpoint that the effect of improving mechanical strength, abrasion resistance and water resistance can be appropriately exhibited. More preferably, it is 100 to 100,000, more preferably 150 to 50,000, and particularly preferably 150 to 5,000.
- the content of the polyvalent amine compound (B) in the adhesive composition of the present invention is preferably 0.001 to 100 parts by weight, more preferably 0 with respect to 100 parts by weight of the highly saturated nitrile rubber (A). 0.01 to 80 parts by weight, more preferably 0.1 to 40 parts by weight, and particularly preferably 0.2 to 10 parts by weight.
- the content of a polyvalent amine compound (B) is preferably 0.001 to 100 parts by weight, more preferably 0 with respect to 100 parts by weight of the highly saturated nitrile rubber (A). 0.01 to 80 parts by weight, more preferably 0.1 to 40 parts by weight, and particularly preferably 0.2 to 10 parts by weight.
- Fiber base material-highly saturated nitrile rubber composite The composite obtained by bonding with the adhesive composition of the present invention includes, for example, a fiber base material-highly saturated nitrile rubber composite comprising a fiber base material and a highly saturated nitrile rubber. Can be mentioned. Such a fiber substrate-highly saturated nitrile rubber composite can be usually obtained by bonding a fiber substrate and a highly saturated nitrile rubber with the above-described adhesive composition of the present invention.
- the form of the fiber base material-highly saturated nitrile rubber composite is not particularly limited, but the fiber base material and the highly saturated nitrile rubber are bonded together, or part or all of the fiber base material is embedded in the highly saturated nitrile rubber. The thing etc. can be illustrated.
- the type of fiber constituting the fiber substrate is not particularly limited, and specific examples thereof include polyester fiber, nylon fiber, vinylon fiber, aramid (aromatic polyamide) fiber, glass fiber, cotton, rayon fiber and the like.
- the shape of the fiber substrate is not particularly limited, and specific examples thereof include filaments, staples, cords, ropes, woven fabrics (canvass, etc.), etc., and fiber substrate-highly saturated nitrile rubber composite It is appropriately selected according to the application.
- a cord-shaped fiber base material can be used to make a cored high-saturation nitrile rubber toothed belt, and a base cloth-covered high-saturation nitrile using a base cloth-like fiber base material such as canvas It can be a rubber toothed belt.
- a high-saturation nitrile rubber to be combined with a fiber base material (hereinafter referred to as a high-saturation nitrile rubber (A) constituting the above-mentioned adhesive composition) used for a fiber base material-high-saturation nitrile rubber composite "Highly saturated nitrile rubber (C)”) is composed of conjugated diene and ⁇ , ⁇ -ethylenically unsaturated nitrile as essential component monomers, and optionally copolymerizable monomers. And a copolymer obtained by hydrogenation as necessary.
- “ ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer” used for the synthesis of the highly saturated nitrile rubber (A) constituting the adhesive composition described above The same thing as “the other monomer which can be copolymerized” can be mentioned.
- the “highly saturated nitrile rubber (C)” may be a highly saturated nitrile rubber having the same composition as the “highly saturated nitrile rubber (A)”.
- the highly saturated nitrile rubber (C) include highly saturated butadiene-acrylonitrile copolymer rubber, carboxyl group-containing highly saturated butadiene-acrylonitrile copolymer rubber, highly saturated isoprene-butadiene-acrylonitrile copolymer rubber, and highly saturated isoprene-acrylonitrile.
- Examples thereof include copolymer rubber, highly saturated butadiene-methyl acrylate-acrylonitrile copolymer rubber, highly saturated butadiene-acrylic acid-acrylonitrile copolymer rubber, and highly saturated butadiene-ethylene-acrylonitrile copolymer rubber.
- the highly saturated nitrile rubber (C) for the fiber base material-highly saturated nitrile rubber composite used for automobiles is particularly highly saturated butadiene-acrylonitrile copolymer rubber from the viewpoint of oil resistance and heat resistance. Is preferred.
- the hydrogenation rate of the highly saturated nitrile rubber (C) is 120 or less, preferably 100 or less, more preferably 50 or less in terms of iodine value. If the iodine value is too high, the heat resistance of the resulting fiber substrate-highly saturated nitrile rubber composite may be reduced.
- the content of the acrylonitrile monomer unit in the highly saturated nitrile rubber (C) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and particularly preferably 20 to 50% by weight. If the content of the acrylonitrile monomer unit is too small, the oil resistance of the fiber base material-highly saturated nitrile rubber composite may be inferior, and conversely if too large, the cold resistance may be lowered.
- the Mooney viscosity (ML 1 + 4 , 100 ° C.) of the highly saturated nitrile rubber (C) is preferably 10 to 300, more preferably 20 to 250, and particularly preferably 30 to 200. If the Mooney viscosity is too small, the moldability and mechanical properties may be lowered, and if it is too large, the moldability may be lowered.
- Highly saturated nitrile rubber includes sulfur, peroxide crosslinking agents, polyamine crosslinking agents, and other crosslinking agents, as well as reinforcing agents such as carbon black, silica, and short fibers that are usually blended during rubber processing;
- a compounding agent such as an inhibitor, a plasticizer, a pigment, a tackifier, a processing aid, a scorch inhibitor, and the like can be appropriately added.
- the method for obtaining the fiber base material-highly saturated nitrile rubber composite is not particularly limited.
- the adhesive composition of the present invention is attached to the fiber base material by dipping or the like, and the adhesive composition of the present invention is attached.
- a method of placing the fibrous base material on the highly saturated nitrile rubber (C) and heating and pressurizing it can be shown.
- the pressurization can be performed using a compression (press) molding machine, a metal roll, an injection molding machine or the like.
- the pressurizing pressure is preferably 0.5 to 20 MPa, more preferably 2 to 10 MPa
- the heating temperature is preferably 130 to 300 ° C., more preferably 150 to 250 ° C.
- the operation time is preferably Is 1 to 180 minutes, more preferably 5 to 120 minutes.
- vulcanization and molding of the highly saturated nitrile rubber (C) and adhesion between the fiber substrate and the highly saturated nitrile rubber (C) can be performed simultaneously.
- a mold that realizes a desired surface shape of the high-saturation nitrile rubber (C) of the target fiber substrate-high-saturation nitrile rubber composite is formed. Good.
- a fiber base material-highly saturated nitrile rubber-fiber base composite can be exemplified.
- the fiber base-highly saturated nitrile rubber-fiber base composite is, for example, a fiber base (may be a composite of two or more types of fiber base) and a fiber base-highly saturated nitrile rubber composite. And in combination.
- the core wire as the fiber base material, the highly saturated nitrile rubber (C) and the base fabric as the fiber base material are stacked (At this time, the adhesive composition of the present invention is appropriately attached to the core wire and the base fabric.
- the fiber base material-highly saturated nitrile rubber-fiber base material composite can be obtained by applying pressure while heating.
- the fiber substrate-highly saturated nitrile rubber composite obtained by bonding with the adhesive composition of the present invention is excellent in mechanical strength, wear resistance and water resistance. Therefore, it is suitable for belts such as a flat belt, a V belt, a V-ribbed belt, a round belt, a square belt, and a toothed belt, and is particularly suitable for a belt in oil. Further, the fiber base material-highly saturated nitrile rubber composite obtained by bonding with the adhesive composition of the present invention can be suitably used for hoses, tubes, diaphragms and the like. Examples of the hose include a single tube rubber hose, a multilayer rubber hose, a braided reinforcement hose, and a cloth wound reinforcement hose.
- Examples of the diaphragm include a flat diaphragm and a rolling diaphragm.
- the fiber base material-highly saturated nitrile rubber composite obtained by bonding with the adhesive composition of the present invention can be used as industrial products such as seals and rubber rolls in addition to the above applications.
- Examples of the seal include a moving part seal such as a rotating part, a swinging part, and a reciprocating part, and a fixed part seal.
- Examples of the motion part seal include an oil seal, a piston seal, a mechanical seal, a boot, a dust cover, a diaphragm, and an accumulator.
- Examples of the fixed part seal include an O-ring and various gaskets.
- rolls that are parts of OA equipment such as printing equipment and copying equipment; rolls for fiber processing such as spinning rolls for spinning and drafting rolls for spinning; rolls for iron making such as bridle rolls, snubber rolls, steering rolls, etc.
- OA equipment printing equipment and copying equipment
- rolls for fiber processing such as spinning rolls for spinning and drafting rolls for spinning
- rolls for iron making such as bridle rolls, snubber rolls, steering rolls, etc.
- composition analysis of rubber contained in highly saturated nitrile rubber latex The content ratio of each monomer unit of highly saturated nitrile rubber contained in highly saturated nitrile rubber latex was measured by the following method. First, an excessive amount of methanol is added to the highly saturated nitrile rubber latex, and the precipitated rubber is taken out, further stirred and washed with methanol several times, and dried under reduced pressure at 60 ° C. for 24 hours to obtain a highly saturated nitrile. Got rubber.
- the content ratio of each monomer unit constituting the highly saturated nitrile rubber thus obtained was measured by the following method. That is, the content ratio of mono-n-butyl maleate units and methacrylic acid units was measured by the following method.
- the content ratio of the acrylonitrile unit was calculated by measuring the nitrogen content in the highly saturated nitrile rubber by the Kjeldahl method according to JIS K 6383.
- the content ratio of 1,3-butadiene units (including hydrogenated parts) is determined by adding an excess amount of methanol to the nitrile rubber latex before the hydrogenation reaction, and washing and drying the precipitated rubber.
- the nitrile rubber before the hydrogenation reaction was obtained, and the iodine value (according to JIS K 6235) was measured.
- the content ratio of the n-butyl acrylate unit and the methoxyethyl acrylate unit is the remaining content of the total content of the acrylonitrile unit, 1,3-butadiene unit and mono n-butyl maleate unit determined from the above measured values. Calculated as a quantity.
- Iodine value The iodine value was measured in accordance with JIS K 6235 using a highly saturated nitrile rubber obtained by the same method as in the rubber composition analysis.
- Normal properties (tensile strength, stress, elongation) of cured film of adhesive composition The adhesive composition was poured into a glass mold having a length of 23 cm and a width of 16 cm, dried at 20 ° C. for 96 hours, and then peeled off from the frame to obtain a film having a thickness of 0.5 mm. This film was heat-treated at 170 ° C. for 20 minutes to obtain a cured film of the adhesive composition. Next, the obtained cured film was punched out with a No. 3 dumbbell to produce a test piece. Using this test piece, a tensile test was performed at a tensile speed of 300 mm / min in accordance with JIS K6251. Tensile strength, tensile stress, and elongation were measured.
- a cured film of the adhesive composition was obtained in the same manner as in the evaluation of the normal physical properties.
- the obtained cured film was cut into a size of 3 cm in length and 2 cm in width, and immersed in distilled water at 90 ° C. for 72 hours to measure volume swelling degree ⁇ V before and after water immersion.
- the smaller the absolute value of the volume swelling degree ⁇ V the better the water resistance.
- Abrasion resistance test of a fiber base material- highly saturated nitrile rubber composite The abrasion resistance of a composite of a 15 cm long and 15 cm long nylon base fabric as a fiber base material and a highly saturated nitrile rubber was tested as a taper abrasion tester for carpets. (Product name “Taber Abraser 5150”, manufactured by TALEDYNE TABER) was used for evaluation by rubbing the nylon base fabric side with a disc. The test conditions were a load of 1.0 kg, a wear surface temperature of 130 ° C. (infrared lamp irradiation), and a disk rotation number of 20,000 times (rotation speed: 60 rpm).
- Synthesis example 1 In a reactor, 180 parts of ion-exchanged water, 25 parts of an aqueous solution of sodium dodecylbenzenesulfonate having a concentration of 10% by weight, 37 parts of acrylonitrile, 4 parts of mono-n-butyl maleate, and 0.5 of t-dodecyl mercaptan (molecular weight regulator) Then, after replacing the internal gas with nitrogen three times, 57 parts of 1,3-butadiene was charged. Next, the reactor was kept at 5 ° C., 0.1 part of cumene hydroperoxide (polymerization initiator) was charged, and the polymerization reaction was continued while stirring, and when the polymerization conversion reached 40% and 60%.
- aqueous solution of sodium dodecylbenzenesulfonate having a concentration of 10% by weight 37 parts of acrylonitrile, 4 parts of mono-n-butyl maleate, and 0.5 of t-dodecyl mercap
- the latex of the nitrile rubber (X1) and the latex content of the rubber contained in the latex of the nitrile rubber (X1) obtained above are 1,000 ppm by weight.
- a palladium catalyst (a solution in which 1% by weight palladium acetate / acetone solution and equal weight of ion-exchanged water are mixed) is added, and hydrogenation reaction is performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to adjust the solid content concentration.
- a latex (L1-1) (solid content concentration 30% by weight) of highly saturated nitrile rubber (A1-1) was obtained.
- the content of each monomer unit in the highly saturated nitrile rubber (A1-1) is 35.7% by weight of acrylonitrile units, 5.7% by weight of mono n-butyl maleate units, 1,3-butadiene units (hydrogenated) 58.6% by weight).
- the iodine value was 9.
- Synthesis example 2 In Synthesis Example 1, except that the addition amount of the palladium catalyst was changed so that the palladium content relative to the dry weight of the rubber contained in the latex of the nitrile rubber (X1) during the hydrogenation reaction was 700 ppm by weight.
- a highly saturated nitrile rubber (A1-2) latex (L1-2) solid content concentration of 30% by weight) was obtained.
- the content ratio of each monomer unit in the highly saturated nitrile rubber (A1-2) is 35.7% by weight of acrylonitrile unit, 5.7% by weight of mono n-butyl maleate unit, 1,3-butadiene unit (hydrogenated) 58.6% by weight).
- the iodine value was 30.
- Synthesis example 3 In Synthesis Example 1, except that the addition amount of the palladium catalyst was changed so that the palladium content relative to the dry weight of the rubber contained in the latex of the nitrile rubber (X1) during the hydrogenation reaction was 50 ppm by weight.
- a highly saturated nitrile rubber (A1-3) latex (L1-3) solid content concentration of 30% by weight) was obtained.
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A1-3) is 35.7% by weight of acrylonitrile unit, 5.7% by weight of mono n-butyl maleate unit, 1,3-butadiene unit (hydrogenated) 58.6% by weight).
- the iodine value was 119.
- Synthesis example 4 In a reactor, 180 parts of ion-exchanged water, 25 parts of a 10% strength by weight sodium dodecylbenzenesulfonate aqueous solution, 15 parts of acrylonitrile, 6 parts of mono n-butyl maleate, 39 parts of n-butyl acrylate, and t-dodecyl mercaptan (Molecular weight adjusting agent) 0.5 parts were charged in this order, and the internal gas was replaced with nitrogen three times, and then 40 parts of 1,3-butadiene was charged.
- Molecular weight adjusting agent Molecular weight adjusting agent
- the latex of the nitrile rubber (X2) and the palladium content relative to the dry weight of the rubber contained in the latex of the nitrile rubber (X2) obtained above are A palladium catalyst (a solution in which 1% by weight palladium acetate / acetone solution and equal weight of ion-exchanged water are mixed) is added, and hydrogenation reaction is performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to adjust the solid content concentration.
- a latex (L2) (solid content concentration of 30% by weight) of highly saturated nitrile rubber (A2) was obtained.
- the content of each monomer unit in the highly saturated nitrile rubber (A2) is 15.0% by weight of acrylonitrile units, 5.0% by weight of mono n-butyl maleate units, and 35.0% by weight of n-butyl acrylate units.
- 1,3-butadiene unit (including hydrogenated part) was 45.0% by weight.
- the iodine value was 10.
- Synthesis example 5 In the reactor, 180 parts of ion-exchanged water, 25 parts of a 10% strength by weight sodium dodecylbenzenesulfonate aqueous solution, 20 parts of acrylonitrile, 4.5 parts of mono n-butyl maleate, 35.5 parts of methoxyethyl acrylate, and t -Dodecyl mercaptan (molecular weight modifier) was charged in the order of 0.5 part, and the internal gas was replaced with nitrogen three times, and then 40 parts of 1,3-butadiene was charged.
- the latex of the nitrile rubber (X3) and the palladium content with respect to the dry weight of the rubber contained in the latex of the nitrile rubber (X3) obtained above are 1,000 ppm by weight.
- a palladium catalyst (a solution in which 1% by weight palladium acetate / acetone solution and equal weight of ion-exchanged water are mixed) is added, and hydrogenation reaction is performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to adjust the solid content concentration.
- a latex (L3) (solid content concentration of 30% by weight) of highly saturated nitrile rubber (A3) was obtained.
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A3) was 21.3% by weight of acrylonitrile unit, 5.0% by weight of mono n-butyl maleate unit, 27.1% by weight of methoxyethyl acrylate unit, It was 46.6% by weight of 1,3-butadiene units (including hydrogenated part).
- the iodine value was 10.
- Synthesis Example 6 By adding 10 parts by weight of hexamethylenediamine carbamate (trade name “Diak # 1”, manufactured by DuPont Dow Elastomer Co., Ltd.) as an aliphatic polyvalent amine compound to 90 parts by weight of distilled water, and stirring at room temperature for 1 hour A polyamine aqueous solution (Y1) was obtained.
- hexamethylenediamine carbamate trade name “Diak # 1”, manufactured by DuPont Dow Elastomer Co., Ltd.
- Synthesis example 7 An aqueous solution of polyallylamine as an aliphatic polyvalent amine compound (trade name “polyallylamine PAA-01”, manufactured by Nitto Boseki Co., Ltd., a polymer comprising units represented by the above general formula (4)) in 50 parts by weight of distilled water , 100 parts by weight of a weight average molecular weight (Mw) 1,600, 15% by weight aqueous solution) was added, and the mixture was stirred at room temperature for 1 hour to obtain a polyamine aqueous solution (Y2).
- polyallylamine PAA-01 aliphatic polyvalent amine compound
- Synthesis example 8 Polyethyleneimine (trade name “polyethyleneimine PEI300”, manufactured by Junsei Chemical Co., Ltd., weight average molecular weight (Mw) 300, amine value 21) as an aliphatic polyamine compound is added to 90 parts by weight of distilled water, and room temperature is added. Was stirred for 1 hour to obtain a polyamine aqueous solution (Y3).
- Example 1 Highly saturated nitrile rubber (A1-1) latex (L1-1) obtained in Synthesis Example 1 (solid content concentration 30% by weight) 53.3 parts (in terms of highly saturated nitrile rubber (A1-1) 16 parts) ) 4.2 parts (0.42 parts in terms of hexamethylenediamine carbamate) obtained in Synthesis Example 6 and 30.1 parts distilled water are added, and 1 minute at room temperature. The mixture was stirred to obtain an adhesive composition (LS1). Then, using the obtained adhesive composition (LS1), "normal properties (tensile strength, stress, elongation) of the cured film of the adhesive composition” and “water resistance test of the cured film of the adhesive composition” was evaluated. The results are shown in Table 1.
- Example 2 Instead of latex (L1-1) of highly saturated nitrile rubber (A1-1), latex (L1-2) of highly saturated nitrile rubber (A1-2) obtained in Synthesis Example 2 (solid content concentration: 30% by weight ) was used in the same manner as in Example 1 to obtain an adhesive composition (LS2). And evaluation similar to Example 1 was performed using the obtained adhesive composition (LS2). The results are shown in Table 1.
- Example 3 Instead of the latex (L1-1) of the highly saturated nitrile rubber (A1-1), the latex (L1-3) of the highly saturated nitrile rubber (A1-3) obtained in Synthesis Example 3 (solid content concentration 30% by weight) ) was used in the same manner as in Example 1 to obtain an adhesive composition (LS3) and evaluated in the same manner. The results are shown in Table 1.
- Example 4 Implemented except for using 3.0 parts of the aqueous polyamine solution (Y2) obtained in Synthesis Example 7 (0.3 parts in terms of polyallylamine) instead of 4.2 parts of the aqueous polyamine solution (Y1).
- an adhesive composition (LS4) was obtained and evaluated in the same manner. The results are shown in Table 1.
- Example 5 Implemented except that 5.3 parts of the aqueous polyamine solution (Y3) obtained in Synthesis Example 8 (0.53 parts in terms of polyethyleneimine) was used instead of 4.2 parts of the aqueous polyamine solution (Y1). In the same manner as in Example 1, an adhesive composition (LS5) was obtained and evaluated in the same manner. The results are shown in Table 1.
- Example 6 Instead of latex (L1-1) of highly saturated nitrile rubber (A1-1), latex (L2) (solid content concentration 30% by weight) of highly saturated nitrile rubber (A2) obtained in Synthesis Example 4 was used. Except for the above, an adhesive composition (LS6) was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.
- Example 7 Implemented except for using 3.0 parts of the aqueous polyamine solution (Y2) obtained in Synthesis Example 7 (0.3 parts in terms of polyallylamine) instead of 4.2 parts of the aqueous polyamine solution (Y1).
- an adhesive composition (LS7) was obtained and evaluated in the same manner. The results are shown in Table 1.
- Example 8 Implemented except that 5.3 parts of the aqueous polyamine solution (Y3) obtained in Synthesis Example 8 (0.53 parts in terms of polyethyleneimine) was used instead of 4.2 parts of the aqueous polyamine solution (Y1). In the same manner as in Example 6, an adhesive composition (LS8) was obtained and evaluated in the same manner. The results are shown in Table 1.
- Example 9 instead of the latex (L1-1) of the highly saturated nitrile rubber (A1-1), the latex (L3) (solid content concentration 30% by weight) of the highly saturated nitrile rubber (A3) obtained in Synthesis Example 5 was used. Except for this, an adhesive composition (LS9) was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.
- Example 10 Implemented except for using 3.0 parts of the aqueous polyamine solution (Y2) obtained in Synthesis Example 7 (0.3 parts in terms of polyallylamine) instead of 4.2 parts of the aqueous polyamine solution (Y1).
- an adhesive composition (LS10) was obtained and evaluated in the same manner. The results are shown in Table 1.
- Example 11 Implemented except that 5.3 parts of the aqueous polyamine solution (Y3) obtained in Synthesis Example 8 (0.53 parts in terms of polyethyleneimine) was used instead of 4.2 parts of the aqueous polyamine solution (Y1). In the same manner as in Example 9, an adhesive composition (LS11) was obtained and evaluated in the same manner. The results are shown in Table 1.
- Comparative Example 1 Instead of 4.2 parts of the aqueous polyamine solution (Y1), 24.2 parts of the resorcin-formaldehyde resin liquid (RF1) obtained in Synthesis Example 9 (2.14 parts in terms of resorcin-formaldehyde resin) were used. And except having changed the compounding quantity of distilled water from 30.1 parts to 10.0 parts, it carried out similarly to Example 1, obtained adhesive composition (LC1), and evaluated similarly. The results are shown in Table 1.
- Comparative Example 3 Instead of the latex (L1-1) of the highly saturated nitrile rubber (A1-1), the latex (L3) (solid content concentration 30% by weight) of the highly saturated nitrile rubber (A3) obtained in Synthesis Example 5 was used. Except for the above, an adhesive composition (LC3) was obtained in the same manner as in Comparative Example 1 and evaluated in the same manner. The results are shown in Table 1.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, the conjugated diene monomer unit, and the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit have a specific ratio
- a cured film (corresponding to a cured adhesive layer) obtained from the adhesive composition of the present invention containing a latex of a highly saturated nitrile rubber having an iodine value of 120 or less and a polyvalent amine compound has normal properties (tensile strength). (Stress, Elongation) and water resistance were excellent (Examples 1 to 11).
- Examples 5, 8, and 11 using polyethyleneimine as the polyvalent amine compound (B) had particularly low volume swelling degree ⁇ V and were particularly excellent in water resistance.
- a cured film obtained from an adhesive composition that does not satisfy the requirements of the present invention because a resorcin-formaldehyde resin is used in place of the polyvalent amine compound has normal properties (tensile strength, stress, elongation) and water resistance. (Comparative Examples 1 to 3).
- Example 12 To 400 parts of the adhesive composition (LS1) obtained in Example 1, 40 parts of an aqueous dispersion (25% by weight concentration) of HAF carbon (trade name “Seast 3”, manufactured by Tokai Carbon Co., Ltd.) was added to HAF. After making the carbon mixed solution, a base fabric (woven fabric) made of nylon 66 as a fiber substrate was dipped in the HAF carbon mixed solution and pulled up to apply the adhesive composition to the nylon 66 base fabric. At this time, 20 parts of rubber in the adhesive composition was adhered to 100 parts of nylon 66 base fabric. Next, the base fabric coated with the adhesive composition was heated in an air circulation oven at 180 ° C. for 2 minutes to obtain a base fabric pretreated with the adhesive composition.
- HAF carbon trade name “Seast 3”, manufactured by Tokai Carbon Co., Ltd.
- the sheet A, the sheet B, and the sheet of the crosslinkable highly saturated nitrile rubber composition having a thickness of about 2.5 mm kneaded on a roll C, sheet D, and sheet E were produced.
- seat of a crosslinkable highly saturated nitrile rubber composition is each piled on said pre-processed base fabric (15 cm long, 15 cm wide planar shape), respectively, applying a pressure of 5 MPa with a press machine for 30 minutes at 170 degreeC.
- a composite of a base fabric and a highly saturated nitrile rubber produced using an adhesive composition that does not satisfy the requirements of the present invention because a resorcin-formaldehyde resin is used in place of a polyvalent amine compound has an abrasion resistance.
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Abstract
Description
本発明において、前記高飽和ニトリルゴム(A)100重量部に対する、前記多価アミン化合物(B)の含有割合が、0.001~100重量部であることが好ましい。
本発明で用いる高飽和ニトリルゴム(A)は、α,β-エチレン性不飽和ニトリル単量体、共役ジエン単量体、α,β-エチレン性不飽和ジカルボン酸モノエステル単量体および必要に応じて加えられる、上記各単量体と共重合可能なその他の単量体を共重合する工程を経て得られる、ヨウ素価が120以下のゴムである。
重合方法は、特に限定されず公知の重合法によればよいが、工業的生産性の観点から乳化重合法が好ましい。
重合に使用する乳化剤は、通常、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤等を使用できる。なかでもアニオン性界面活性剤が好ましく、その使用量に特に制限はないが、このラテックスから得られる接着剤組成物の接着力の観点から、全単量体100重量部に対して1~10重量部、好ましくは2~6重量部の範囲である。また、重合開始剤等も通常使用されているものでよい。
また、重合方式も特に限定されず、回分式、半回分式及び連続式のいずれでもよく、重合温度や圧力も制限されない。
なお、共重合体(X)中の炭素-炭素二重結合(共役ジエン単量体単位に由来するもの)の量が少なく、そのため、乳化重合により得られたニトリルゴムのヨウ素価が所望の数値以下である場合には、必ずしも、水素化を行なう必要はない。
その具体例として、パラジウム触媒としては、ギ酸、プロピオン酸、ラウリン酸、コハク酸、オレイン酸、フタル酸等のカルボン酸のパラジウム塩;塩化パラジウム、ジクロロ(シクロオクタジエン)パラジウム、ジクロロ(ノルボルナジエン)パラジウム、ヘキサクロロパラジウム(IV)酸アンモニウム等のパラジウム塩素化物;ヨウ化パラジウム等のヨウ素化物;硫酸パラジウム・二水和物等が挙げられる。
これらの中でもカルボン酸のパラジウム塩、ジクロロ(ノルボルナジエン)パラジウム及びヘキサクロロパラジウム(IV)酸アンモニウムが特に好ましい。
水素化触媒の使用量は、適宜定めればよいが、共重合体(X)に対し、好ましくは5~6,000重量ppm、より好ましくは10~4,000重量ppmである。
反応温度が低すぎると反応速度が低下するおそれがあり、逆に、高すぎるとニトリル基の水素添加等の副反応が起こる可能性がある。
水素圧力は、好ましくは0.1~30MPa、より好ましくは0.5~20MPaである。また、反応時間は、好ましくは1~15時間、特に好ましくは2~10時間である。
本発明の接着剤組成物における高飽和ニトリルゴム(A)の含有量は、好ましくは5~60重量%、特に好ましくは10~50重量%である。
本発明の接着剤組成物は、上述した高飽和ニトリルゴム(A)に加えて、多価アミン化合物(B)を含有する。多価アミン化合物(B)は、上述した高飽和ニトリルゴム(A)を架橋させるための架橋剤として作用する。
また、上記一般式(6)中において、繰返し単位数がaである繰り返し単位と、繰返し単位数がbである繰り返し単位とは、通常、互いにランダムな配列をとっている。
本発明の接着剤組成物で接着して得られる複合体としては、例えば、繊維基材と高飽和ニトリルゴムからなる繊維基材-高飽和ニトリルゴム複合体を挙げることができる。このような繊維基材-高飽和ニトリルゴム複合体は、通常、繊維基材と高飽和ニトリルゴムとを上述した本発明の接着剤組成物で接着することにより得ることができる。
繊維基材-高飽和ニトリルゴム複合体の形態は、特に限定されないが、繊維基材と高飽和ニトリルゴムとを貼り合わせたもの、高飽和ニトリルゴムに繊維基材の一部又は全部を埋め込んだもの等を例示することができる。
繊維基材の形状は特に限定されず、その具体例としては、フィラメント、ステープル、コード状、ロープ状、織布(帆布等)等を挙げることができ、繊維基材-高飽和ニトリルゴム複合体の用途に応じて適宜選定される。例えば、繊維基材としてコード状のものを用いて芯線入りの高飽和ニトリルゴム製歯付きベルトとすることができ、また帆布等の基布状の繊維基材を用いて基布被覆高飽和ニトリルゴム製歯付きベルトとすることができる。
共重合可能な単量体としては、上述した接着剤組成物を構成する高飽和ニトリルゴム(A)の合成に用いられる「α,β-エチレン性不飽和ジカルボン酸モノエステル単量体」や、「共重合可能なその他の単量体」と同様のものを挙げることができる。
なお、「高飽和ニトリルゴム(C)」は、「高飽和ニトリルゴム(A)」と同じ組成の高飽和ニトリルゴムになっていても良い。
これらのうち、特に、自動車用途に用いられる繊維基材-高飽和ニトリルゴム複合体用の高飽和ニトリルゴム(C)としては、耐油性、耐熱性の観点から、高飽和ブタジエン-アクリロニトリル共重合ゴムが好ましい。
高飽和ニトリルゴム(C)のアクリロニトリル単量体単位の含有量は、好ましくは10~60重量%、より好ましくは15~50重量%、特に好ましくは20~50重量%である。アクリロニトリル単量体単位の含有量が少なすぎると繊維基材-高飽和ニトリルゴム複合体の耐油性が劣るおそれがあり、逆に多すぎると耐寒性が低下する可能性がある。
また、高飽和ニトリルゴム(C)のムーニー粘度(ML1+4、100℃)は、好ましくは10~300、より好ましくは20~250、特に好ましくは30~200である。ムーニー粘度が小さすぎると成形加工性や機械的特性が低下するおそれがあり、大きすぎると成形加工性が低下する可能性がある。
加圧は圧縮(プレス)成形機、金属ロール、射出成形機等を用いて行なうことができる。
加圧の圧力は、好ましくは0.5~20MPa、より好ましくは2~10MPaであり、加熱の温度は、好ましくは130~300℃、より好ましくは150~250℃であり、操作時間は、好ましくは1~180分、より好ましくは5~120分である。
この方法により、高飽和ニトリルゴム(C)の加硫及び成形、並びに、繊維基材と高飽和ニトリルゴム(C)との間の接着を同時に行なうことができる。
なお、圧縮機の型の内面やロールの表面には、目的とする繊維基材-高飽和ニトリルゴム複合体の高飽和ニトリルゴム(C)の所望の表面形状を実現する型を形成させておくとよい。
繊維基材-高飽和ニトリルゴム-繊維基材複合体は、例えば、繊維基材(2種以上の繊維基材の複合体であってもよい。)と繊維基材-高飽和ニトリルゴム複合体とを組み合わせてなる。
具体的には、繊維基材としての芯線、高飽和ニトリルゴム(C)および繊維基材としての基布を重ね(このとき、芯線及び基布には、本発明の接着剤組成物を適宜付着させておく)、加熱しながら加圧することにより、繊維基材-高飽和ニトリルゴム-繊維基材複合体を得ることができる。
そのため、平ベルト、Vベルト、Vリブドベルト、丸ベルト、角ベルト、歯付ベルト等のベルト用に好適であり、油中ベルト用に特に適している。
また、本発明の接着剤組成物で接着して得られる繊維基材-高飽和ニトリルゴム複合体は、ホース、チューブ、ダイアフラム等にも好適に使用できる。
ホースとしては、単管ゴムホース、多層ゴムホース、編上式補強ホース、布巻式補強ホース等が挙げられる。ダイアフラムとしては、平形ダイアフラム、転動形ダイアフラム等が挙げられる。
本発明の接着剤組成物で接着して得られる繊維基材-高飽和ニトリルゴム複合体は、上記の用途以外にも、シール、ゴムロール等の工業用製品として用いることができる。シールとしては、回転用、揺動用、往復動等の運動部位シールと固定部位シールが挙げられる。運動部位シールとしては、オイルシール、ピストンシール、メカニカルシール、ブーツ、ダストカバー、ダイアフラム、アキュムレータ等が挙げられる。固定部位シールとしては、Oリング、各種ガスケット等が挙げられる。
ゴムロールとしては、印刷機器、コピー機器等のOA機器の部品であるロール;紡糸用延伸ロール、紡績用ドラフトロール等の繊維加工用ロール;ブライドルロール、スナバロール、ステアリングロール等の製鉄用ロール;等が挙げられる。
また、試験および評価は、下記の方法で行なった。
高飽和ニトリルゴムラテックスに含まれる高飽和ニトリルゴムの各単量体単位の含有割合は、以下の方法により測定した。
まず、高飽和ニトリルゴムラテックスに過剰量のメタノールを添加し、析出したゴムを取り出し、さらにこれを数回メタノールで攪拌、洗浄して、減圧下60℃で24時間乾燥することにより、高飽和ニトリルゴムを得た。このようにして得られた高飽和ニトリルゴムを構成する各単量体単位の含有割合は、以下の方法により測定した。
すなわち、マレイン酸モノn-ブチル単位およびメタクリル酸単位の含有割合は、次の方法により測定した。まず、2mm角の高飽和ニトリルゴム0.2gに、2-ブタノン100mlを加えて16時間攪拌して溶解した後、エタノール20mlおよび水10mlを加え、攪拌しながら水酸化カリウムの0.02N含水エタノール溶液を用いて、室温でチモールフタレインを指示薬とする滴定を行った。次いで、滴定の結果より、高飽和ニトリルゴム100gに対するカルボキシル基のモル数を求め、求めたモル数をマレイン酸モノn-ブチル単位またはメタクリル酸単位の量に換算することにより算出した。
アクリロニトリル単位の含有割合は、JIS K 6383に従い、ケルダール法により、高飽和ニトリルゴム中の窒素含量を測定することにより算出した。
1,3-ブタジエン単位(水素化された部分も含む)の含有割合は、水素添加反応前のニトリルゴムラテックスに上記と同様に過剰量のメタノールを添加し、析出したゴムを洗浄および乾燥することにより水素添加反応前のニトリルゴムを得て、そのヨウ素価(JIS K 6235による)を測定することにより算出した。
さらに、アクリル酸n-ブチル単位およびアクリル酸メトキシエチル単位の含有割合は、上記測定値から求めたアクリロニトリル単位、1,3-ブタジエン単位およびマレイン酸モノn-ブチル単位の合計含有量の残余の含有量として計算で求めた。
ヨウ素価は、上記ゴムの組成分析の場合と同様の方法で得られた高飽和ニトリルゴムを用いて、JIS K 6235に準じて測定した。
縦23cm、横16cmのガラスの型枠内に、接着剤組成物を流し込み、20℃で96時間乾燥させた後、枠から剥がして厚さ0.5mmの膜を得た。この膜を、170℃で20分間熱処理して、接着剤組成物の硬化膜を得た。
次に、得られた硬化膜を、3号形ダンベルで打ち抜いて試験片を作製し、この試験片を用いて、JIS K6251に準じて、300mm/分の引張速度で引張試験を行い、硬化膜の引張強さ、引張応力および伸びを測定した。
上記常態物性の評価と同様にして、接着剤組成物の硬化膜を得た。
得られた硬化膜を縦3cm、横2cmの大きさに切り取り、90℃の蒸留水に72時間浸漬することにより、水浸漬前後の体積膨潤度ΔVを測定した。
なお、体積膨潤度ΔV(単位:%)は、水浸漬前後の硬化膜の体積を測定し、「ΔV=([水浸漬後の体積]-[水浸漬前の体積])/([水浸漬前の体積])×100」に従って算出した。
この体積膨潤度ΔVの絶対値が小さいほど、耐水性が良い。
繊維基材としての縦15cm、横15cmのナイロン基布と高飽和ニトリルゴムとの複合体の耐摩耗性を、カーペット用テーバー摩耗試験機(商品名「Taber Abraser 5150」、TALEDYNE TABER社製)を用い、ナイロン基布側をディスクで擦ることにより評価した。試験条件は荷重1.0kg、摩耗表面温度130℃(赤外線ランプ照射)、ディスク回転回数2万回(回転速度60rpm)で行った。
そして、耐摩耗性は、以下の基準により、ナイロン基布側の摩耗減量を5段階で評価した。
5:ナイロン基布側の表面正常(摩耗減量1%未満)
4:ナイロン基布側が1%以上かつ25%未満摩耗
3:ナイロン基布側が25%以上かつ50%未満摩耗
2:ナイロン基布側が50%以上かつ75%未満摩耗
1:ナイロン基布側が75%以上摩耗
反応器に、イオン交換水180部、濃度10重量%のドデシルベンゼンスルホン酸ナトリウム水溶液25部、アクリロニトリル37部、マレイン酸モノn-ブチル4部、およびt-ドデシルメルカプタン(分子量調整剤)0.5部の順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン57部を仕込んだ。次いで、反応器を5℃に保ち、クメンハイドロパーオキサイド(重合開始剤)0.1部を仕込み、攪拌しながら重合反応を継続し、重合転化率が40%、および60%になった時点で、それぞれ1部のマレイン酸モノn―ブチルを添加し、重合転化率が85%になった時点で、濃度10重量%のハイドロキノン水溶液(重合停止剤)0.1部を加えて重合反応を停止した。次いで、水温60℃で残留単量体を、減圧にして除去し、ニトリルゴム(X1)のラテックス(固形分濃度約30重量%)を得た。
高飽和ニトリルゴム(A1-1)の各単量体単位の含有割合は、アクリロニトリル単位35.7重量%、マレイン酸モノn-ブチル単位5.7重量%、1,3-ブタジエン単位(水素化された部分も含む)58.6重量%であった。また、ヨウ素価は9であった。
合成例1において、水素添加反応を行う際における、ニトリルゴム(X1)のラテックスに含有されるゴムの乾燥重量に対するパラジウム含有量が700重量ppmになるように、パラジウム触媒の添加量を変更した以外は合成例1と同様にして高飽和ニトリルゴム(A1-2)のラテックス(L1-2)(固形分濃度30重量%)を得た。
高飽和ニトリルゴム(A1-2)の各単量体単位の含有割合は、アクリロニトリル単位35.7重量%、マレイン酸モノn-ブチル単位5.7重量%、1,3-ブタジエン単位(水素化された部分も含む)58.6重量%であった。また、ヨウ素価は30であった。
合成例1において、水素添加反応を行う際における、ニトリルゴム(X1)のラテックスに含有されるゴムの乾燥重量に対するパラジウム含有量が50重量ppmになるように、パラジウム触媒の添加量を変更した以外は合成例1と同様にして高飽和ニトリルゴム(A1-3)のラテックス(L1-3)(固形分濃度30重量%)を得た。
高飽和ニトリルゴム(A1-3)の各単量体単位の含有割合は、アクリロニトリル単位35.7重量%、マレイン酸モノn-ブチル単位5.7重量%、1,3-ブタジエン単位(水素化された部分も含む)58.6重量%であった。また、ヨウ素価は119であった。
反応器に、イオン交換水180部、濃度10重量%のドデシルベンゼンスルホン酸ナトリウム水溶液25部、アクリロニトリル15部、マレイン酸モノn-ブチル6部、アクリル酸n-ブチル39部、およびt-ドデシルメルカプタン(分子量調整剤)0.5部の順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン40部を仕込んだ。次いで、反応器を5℃に保ち、クメンハイドロパーオキサイド(重合開始剤)0.1部を仕込み、攪拌しながら重合反応を継続し、重合転化率が85%になった時点で、濃度10重量%のハイドロキノン水溶液(重合停止剤)0.1部を加えて重合反応を停止した。次いで、水温60℃で残留単量体を、減圧にして除去し、ニトリルゴム(X2)のラテックス(固形分濃度約30重量%)を得た。
高飽和ニトリルゴム(A2)の各単量体単位の含有割合は、アクリロニトリル単位15.0重量%、マレイン酸モノn-ブチル単位5.0重量%、アクリル酸n-ブチル単位35.0重量%、1,3-ブタジエン単位(水素化された部分も含む)45.0重量%であった。また、ヨウ素価は10であった。
反応器に、イオン交換水180部、濃度10重量%のドデシルベンゼンスルホン酸ナトリウム水溶液25部、アクリロニトリル20部、マレイン酸モノn-ブチル4.5部、アクリル酸メトキシエチル35.5部、およびt-ドデシルメルカプタン(分子量調整剤)0.5部の順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン40部を仕込んだ。次いで、反応器を5℃に保ち、クメンハイドロパーオキサイド(重合開始剤)0.1部を仕込み、攪拌しながら重合反応を継続し、重合転化率が83%になった時点で、濃度10重量%のハイドロキノン水溶液(重合停止剤)0.1部を加えて重合反応を停止した。次いで、水温60℃で残留単量体を、減圧にして除去し、ニトリルゴム(X3)のラテックス(固形分濃度約30重量%)を得た。
高飽和ニトリルゴム(A3)の各単量体単位の含有割合は、アクリロニトリル単位21.3重量%、マレイン酸モノn-ブチル単位5.0重量%、アクリル酸メトキシエチル単位27.1重量%、1,3-ブタジエン単位(水素化された部分も含む)46.6重量%であった。また、ヨウ素価は10であった。
蒸留水90重量部に、脂肪族多価アミン化合物としてのヘキサメチレンジアミンカルバメート(商品名「Diak#1」、デュポン・ダウ・エラストマー社製)10重量部を加え、室温で1時間攪拌することにより、多価アミン水溶液(Y1)を得た。
蒸留水50重量部に、脂肪族多価アミン化合物としてのポリアリルアミンの水溶液(商品名「ポリアリルアミンPAA-01」、日東紡績社製、上記一般式(4)で表される単位からなる重合体、重量平均分子量(Mw)1,600、15重量%水溶液)100重量部を加え、室温で1時間攪拌することにより、多価アミン水溶液(Y2)を得た。
蒸留水90重量部に、脂肪族多価アミン化合物としてのポリエチレンイミン(商品名「ポリエチレンイミンPEI300」、純正化学社製、重量平均分子量(Mw)300、アミン価21)10重量部を加え、室温で1時間攪拌することにより、多価アミン水溶液(Y3)を得た。
レゾルシン11部、ホルマリン(37重量%濃度)8.1部、水酸化ナトリウム(10重量%濃度)3部を蒸留水194部に溶解し、室温で20時間攪拌し、レゾルシン-ホルムアルデヒド樹脂液(RF1)を得た。
合成例1で得られた高飽和ニトリルゴム(A1-1)のラテックス(L1-1)(固形分濃度30重量%)53.3部(高飽和ニトリルゴム(A1-1)換算で、16部)に、合成例6で得られた多価アミン水溶液(Y1)4.2部(ヘキサメチレンジアミンカルバメート換算で、0.42部)、および蒸留水30.1部を添加し、室温で1分間攪拌し、接着剤組成物(LS1)を得た。
そして、得られた接着剤組成物(LS1)を用い、「接着剤組成物の硬化膜の常態物性(引張強さ、応力、伸び)」および「接着剤組成物の硬化膜の耐水性試験」の評価を行った。結果を表1に示す。
高飽和ニトリルゴム(A1-1)のラテックス(L1-1)に代えて、合成例2で得られた高飽和ニトリルゴム(A1-2)のラテックス(L1-2)(固形分濃度30重量%)を用いた以外は実施例1と同様にして、接着剤組成物(LS2)を得た。そして、得られた接着剤組成物(LS2)を用い、実施例1と同様の評価を行った。結果を表1に示す。
高飽和ニトリルゴム(A1-1)のラテックス(L1-1)に代えて、合成例3で得られた高飽和ニトリルゴム(A1-3)のラテックス(L1-3)(固形分濃度30重量%)を用いた以外は実施例1と同様にして、接着剤組成物(LS3)を得て、同様に評価を行った。結果を表1に示す。
多価アミン水溶液(Y1)4.2部に代えて、合成例7で得られた多価アミン水溶液(Y2)3.0部(ポリアリルアミン換算で、0.3部)を用いた以外は実施例1と同様にして、接着剤組成物(LS4)を得て、同様に評価を行った。結果を表1に示す。
多価アミン水溶液(Y1)4.2部に代えて、合成例8で得られた多価アミン水溶液(Y3)5.3部(ポリエチレンイミン換算で、0.53部)を用いた以外は実施例1と同様にして、接着剤組成物(LS5)を得て、同様に評価を行った。結果を表1に示す。
高飽和ニトリルゴム(A1-1)のラテックス(L1-1)に代えて、合成例4で得られた高飽和ニトリルゴム(A2)のラテックス(L2)(固形分濃度30重量%)を用いた以外は実施例1と同様にして、接着剤組成物(LS6)を得て、同様に評価を行った。結果を表1に示す。
多価アミン水溶液(Y1)4.2部に代えて、合成例7で得られた多価アミン水溶液(Y2)3.0部(ポリアリルアミン換算で、0.3部)を用いた以外は実施例6と同様にして、接着剤組成物(LS7)を得て、同様に評価を行った。結果を表1に示す。
多価アミン水溶液(Y1)4.2部に代えて、合成例8で得られた多価アミン水溶液(Y3)5.3部(ポリエチレンイミン換算で、0.53部)を用いた以外は実施例6と同様にして、接着剤組成物(LS8)を得て、同様に評価を行った。結果を表1に示す。
高飽和ニトリルゴム(A1-1)のラテックス(L1-1)に代えて、合成例5で得られた高飽和ニトリルゴム(A3)のラテックス(L3)(固形分濃度30重量%)を用いた以外は実施例1と同様にして、接着剤組成物(LS9)を得て、同様に評価を行った。結果を表1に示す。
多価アミン水溶液(Y1)4.2部に代えて、合成例7で得られた多価アミン水溶液(Y2)3.0部(ポリアリルアミン換算で、0.3部)を用いた以外は実施例9と同様にして、接着剤組成物(LS10)を得て、同様に評価を行った。結果を表1に示す。
多価アミン水溶液(Y1)4.2部に代えて、合成例8で得られた多価アミン水溶液(Y3)5.3部(ポリエチレンイミン換算で、0.53部)を用いた以外は実施例9と同様にして、接着剤組成物(LS11)を得て、同様に評価を行った。結果を表1に示す。
多価アミン水溶液(Y1)4.2部に代えて、合成例9で得られたレゾルシン-ホルムアルデヒド樹脂液(RF1)24.2部(レゾルシン-ホルムアルデヒド樹脂換算で、2.14部)を用い、かつ、蒸留水の配合量を30.1部から10.0部に変更した以外は、実施例1と同様にして、接着剤組成物(LC1)を得て、同様に評価を行った。結果を表1に示す。
高飽和ニトリルゴム(A1-1)のラテックス(L1-1)に代えて、合成例4で得られた高飽和ニトリルゴム(A2)のラテックス(L2)(固形分濃度30重量%)を用いた以外は比較例1と同様にして、接着剤組成物(LC2)を得て、同様に評価を行った。結果を表1に示す。
高飽和ニトリルゴム(A1-1)のラテックス(L1-1)に代えて、合成例5で得られた高飽和ニトリルゴム(A3)のラテックス(L3)(固形分濃度30重量%)を用いた以外は比較例1と同様にして、接着剤組成物(LC3)を得て、同様に評価を行った。結果を表1に示す。
一方、多価アミン化合物の代わりに、レゾルシン-ホルムアルデヒド樹脂を用いたために本発明の要件を満たさない接着剤組成物から得られる硬化膜は、常態物性(引張強さ、応力、伸び)および耐水性に劣る結果となった(比較例1~3)。
実施例1で得られた接着剤組成物(LS1)400部に、HAFカーボン(商品名「シースト3」、東海カーボン社製)の水分散体(25重量%濃度)40部を添加してHAFカーボン混合液とした後、繊維基材としてのナイロン66からなる基布(織布)を該HAFカーボン混合液に浸漬し、引き上げることによりナイロン66の基布に接着剤組成物を塗布した。この際、ナイロン66の基布100部に対して、接着剤組成物中のゴムが20部付着するようにした。
次に接着剤組成物を塗布した基布を、空気循環式オーブンにて180℃で2分間加熱して、接着剤組成物で前処理した基布を得た。
また、表2に記載の配合例A、B、C、D及びEに従い、ロール上で混練し、約2.5mmの厚さの架橋性高飽和ニトリルゴム組成物のシートA、シートB、シートC、シートD及びシートEを作製した。
そして、架橋性高飽和ニトリルゴム組成物のシートを、上記の前処理した基布(縦15cm、横15cmの平面状)にそれぞれ重ね、プレス機で5MPaの圧力をかけながら、170℃で30分間保持して架橋し、繊維基材としてのナイロン66からなる基布と、高飽和ニトリルゴムの複合体を得た(シートAから得られる複合体、シートBから得られる複合体、シートCから得られる複合体、シートDから得られる複合体及びシートEから得られる複合体)。
そして、得られた複合体について、「繊維基材-高飽和ニトリルゴム複合体の耐摩耗性試験」を行った。結果を表3に示す。
接着剤組成物(LS1)に代えて、実施例4~11で得られた接着剤組成物(LS4)~(LS11)(実施例13~20)、および比較例1~3で得られた接着剤組成物(LC1)~(LC3)(比較例4~6)をそれぞれ用いた以外は、実施例12と同様にして複合体を得た。
そして、得られた複合体について、「繊維基材-高飽和ニトリルゴム複合体の耐摩耗性試験」を行った。結果を表3に示す。
一方、多価アミン化合物の代わりに、レゾルシン-ホルムアルデヒド樹脂を用いたために本発明の要件を満たさない接着剤組成物を用いて作製した、基布と高飽和ニトリルゴムの複合体は、耐摩耗性に劣る結果となった(比較例4~6)。
Claims (7)
- α,β-エチレン性不飽和ニトリル単量体単位10~55重量%、共役ジエン単量体単位25~89重量%、およびα,β-エチレン性不飽和ジカルボン酸モノエステル単量体単位1~20重量%を有し、ヨウ素価が120以下である高飽和ニトリルゴム(A)のラテックス、ならびに、
多価アミン化合物(B)を含有する接着剤組成物。 - 前記α,β-エチレン性不飽和ジカルボン酸モノエステル単量体単位が、α,β-エチレン性不飽和ジカルボン酸モノアルキルエステル単量体単位である請求項1に記載の接着剤組成物。
- 前記α,β-エチレン性不飽和ジカルボン酸モノアルキルエステル単量体単位が、マレイン酸モノn-ブチル単位である請求項2に記載の接着剤組成物。
- 前記高飽和ニトリルゴム(A)100重量部に対する、前記多価アミン化合物(B)の含有割合が、0.001~100重量部である請求項1~3のいずれかに記載の接着剤組成物。
- 前記多価アミン化合物(B)が、ポリエチレンイミンである請求項1~4のいずれか1項に記載の接着剤組成物。
- 前記ポリエチレンイミンの重量平均分子量(Mw)が、100~1,000,000である請求項5に記載の接着剤組成物。
- 繊維基材と高飽和ニトリルゴムを、請求項1~6のいずれか1項に記載の接着剤組成物で接着してなる繊維基材-高飽和ニトリルゴム複合体。
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- 2013-08-28 WO PCT/JP2013/072952 patent/WO2014034698A1/ja active Application Filing
- 2013-08-28 EP EP13832375.3A patent/EP2891694B1/en active Active
- 2013-08-28 JP JP2014533036A patent/JP6090326B2/ja active Active
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CN107109193B (zh) * | 2014-12-26 | 2020-10-16 | 日本瑞翁株式会社 | 摩擦材料用胶乳及摩擦材料 |
KR20180011459A (ko) * | 2015-05-26 | 2018-02-01 | 니폰 제온 가부시키가이샤 | 니트릴기 함유 고포화 공중합체 고무 |
US20180127530A1 (en) * | 2015-05-26 | 2018-05-10 | Zeon Corporation | Nitrile group-containing highly saturated copolymer rubber |
US20180134831A1 (en) * | 2015-05-26 | 2018-05-17 | Zeon Corporation | Nitrile group-containing highly saturated copolymer rubber |
US10752717B2 (en) * | 2015-05-26 | 2020-08-25 | Zeon Corporation | Nitrile group-containing highly saturated copolymer rubber |
US11091577B2 (en) * | 2015-05-26 | 2021-08-17 | Zeon Corporation | Nitrile group-containing highly saturated copolymer rubber |
KR102500517B1 (ko) | 2015-05-26 | 2023-02-15 | 니폰 제온 가부시키가이샤 | 니트릴기 함유 고포화 공중합체 고무 |
JP2022545702A (ja) * | 2019-08-30 | 2022-10-28 | ランクセス・ドイチュランド・ゲーエムベーハー | アミン架橋性ゴムと、ポリエチレンイミンとを含む混合物 |
JP7335423B2 (ja) | 2019-08-30 | 2023-08-29 | ランクセス・ドイチュランド・ゲーエムベーハー | アミン架橋性ゴムと、ポリエチレンイミンとを含む混合物 |
WO2022210392A1 (ja) * | 2021-03-31 | 2022-10-06 | 日本ゼオン株式会社 | ゴム積層体およびホース |
Also Published As
Publication number | Publication date |
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KR20150051996A (ko) | 2015-05-13 |
CN104520399A (zh) | 2015-04-15 |
EP2891694B1 (en) | 2018-06-06 |
US10336918B2 (en) | 2019-07-02 |
US20150225618A1 (en) | 2015-08-13 |
JP6090326B2 (ja) | 2017-03-08 |
CN104520399B (zh) | 2017-11-10 |
ES2680580T3 (es) | 2018-09-10 |
JPWO2014034698A1 (ja) | 2016-08-08 |
EP2891694A4 (en) | 2016-04-13 |
EP2891694A1 (en) | 2015-07-08 |
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