WO2015147050A1 - 高飽和ニトリルゴムのラテックスおよび接着剤組成物 - Google Patents
高飽和ニトリルゴムのラテックスおよび接着剤組成物 Download PDFInfo
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- WO2015147050A1 WO2015147050A1 PCT/JP2015/059110 JP2015059110W WO2015147050A1 WO 2015147050 A1 WO2015147050 A1 WO 2015147050A1 JP 2015059110 W JP2015059110 W JP 2015059110W WO 2015147050 A1 WO2015147050 A1 WO 2015147050A1
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- nitrile rubber
- highly saturated
- saturated nitrile
- latex
- weight
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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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
-
- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
Definitions
- the present invention relates to latex of highly saturated nitrile rubber and an adhesive composition containing the latex.
- Rubber and fiber composites are used in many fields such as belts, rubber hoses, and diaphragms.
- belts In the field of 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 a 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 which replaces the processing using a solvent-based rubber paste, is desired.
- Patent Document 1 discloses an adhesive composition containing a carboxyl group-containing highly saturated nitrile rubber latex and a resorcin-formaldehyde resin.
- the fiber base material-highly saturated nitrile rubber composite obtained by bonding the fiber base material to the highly saturated nitrile rubber using this adhesive composition does not necessarily have sufficient wear resistance, and therefore In recent years, it has not been able to sufficiently meet the high performance of the engine room of automobiles.
- An object of the present invention is to provide an adhesive composition capable of forming an adhesive layer excellent in tensile workability and wear resistance, and a latex of a highly saturated nitrile rubber used in the adhesive composition.
- the present inventors have conducted extensive studies on the highly saturated nitrile rubber constituting the latex that is a component of the adhesive composition. As a result, the weight average molecular weight of the soluble component in chloroform was set to 100.
- the above-mentioned object is achieved by controlling the loss tangent tan ⁇ (50 ° C.) at 50 ° C. and the complex torque S * at 100% shear strain at 100 ° C. within a predetermined range while controlling to 1,000,000 or less.
- the present inventors have found that the present invention can be accomplished and have completed the present invention.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is contained in a proportion of 10 to 60% by weight, the iodine value is 120 or less, and the weight average molecular weight of the soluble component in chloroform is 100.
- the loss tangent tan ⁇ (50 ° C.) at 50 ° C. of the film when the volatile content contained in the latex is removed to form a highly saturated nitrile rubber film 150
- the storage elastic modulus G ′ at 100 ° C.
- the highly saturated nitrile rubber latex of the present invention is an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit of 10 to 60% by weight, an acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer. It preferably contains 0.1 to 20% by weight of body units and 20 to 89.9% by weight of diene monomer units and / or ⁇ -olefin monomer units.
- the latex of the highly saturated nitrile rubber of the present invention is obtained by emulsion polymerization of the monomer that forms the highly saturated nitrile rubber, and a molecular weight modifier is added at the start of the emulsion polymerization.
- the adhesive composition formed by containing the latex of the said highly saturated nitrile rubber of this invention is provided.
- the adhesive composition of the present invention preferably further comprises a resorcin-formaldehyde resin, and the content of the resorcin-formaldehyde resin is based on 100 parts by weight of the solid content of the latex of the highly saturated nitrile rubber. More preferably, it is 5 to 30 parts by weight.
- a fiber base material-high saturation nitrile rubber composite obtained by bonding a fiber base material and a highly saturated nitrile rubber with the adhesive composition of the present invention.
- the adhesive composition of the present invention comprising the latex of the highly saturated nitrile rubber of the present invention is excellent in tensile processability (low load necessary for extending to a predetermined magnification) and excellent in wear resistance.
- An adhesive layer can be formed. And by using such an adhesive composition of the present invention as an adhesive, the tensile workability after treating the fiber substrate with the adhesive composition is improved, and the composite has excellent wear resistance. You can get a body.
- the highly saturated nitrile rubber latex of the present invention contains ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units in a proportion of 10 to 60% by weight, an iodine value of 120 or less, and When the highly saturated nitrile rubber having a weight average molecular weight of not more than 100,000 is contained, and the volatile matter contained in the latex is removed to obtain a highly saturated nitrile rubber film, It has specific characteristics to be described later.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit contained in the highly saturated nitrile rubber constituting the latex of the present invention is not particularly limited. However, those having 3 to 18 carbon atoms are preferred, and those having 3 to 9 carbon atoms are particularly preferred. Specific examples thereof include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile and the like, and among them, acrylonitrile is preferable. These ⁇ , ⁇ -ethylenically unsaturated nitrile monomers may be used alone or in combination of two or more.
- the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit in the highly saturated nitrile rubber constituting the latex of the present invention is 10 to 60% by weight, preferably 20 to 50% by weight, more preferably Is 25 to 45% by weight. If the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is too small, the oil resistance of the highly saturated nitrile rubber may be inferior, and conversely if too large, the cold resistance may be lowered.
- the highly saturated nitrile rubber constituting the latex of the present invention includes an acid group-containing ⁇ , ⁇ -ethylene in addition to an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer from the viewpoint of improving adhesiveness and wear resistance. It is preferable to contain a polymerizable unsaturated monomer unit.
- the acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer that forms the acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer unit is composed of an ⁇ , ⁇ -ethylenically unsaturated bond and an acid group in the molecule.
- the acid group is not particularly limited and may be any of a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc., but a carboxyl group is preferred.
- the acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer preferably has 3 to 18 carbon atoms, and particularly preferably has 3 to 9 carbon atoms.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated monomer having a carboxyl group include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid, ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid, and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid.
- acid monoesters there can be mentioned ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid anhydrides that can be converted into compounds having a carboxyl group.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, and cinnamic acid.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid and the like.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester include monomethyl maleate, monoethyl maleate, monobutyl maleate, monocyclohexyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, mono-2-fumarate Examples include hydroxyethyl, monocyclohexyl fumarate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate and the like.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
- ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid is preferable, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 9 carbon atoms is more preferable, acrylic acid and methacrylic acid are further preferable, and methacrylic acid is more preferable. Acid is particularly preferred.
- the content of the acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer unit in the highly saturated nitrile rubber constituting the latex of the present invention is preferably 0.1 to 20% by weight, more preferably 0.5%. -10% by weight, particularly preferably 1-6% by weight.
- the highly saturated nitrile rubber constituting the latex of the present invention preferably further contains a diene monomer unit and / or an ⁇ -olefin monomer unit from the viewpoint of improving adhesiveness due to rubber elasticity. .
- Examples of the diene monomer forming the diene monomer unit include conjugated dienes having 4 or more carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like.
- Non-conjugated dienes having 5 to 12 carbon atoms such as 1,4-pentadiene and 1,4-hexadiene; Of these, conjugated dienes are preferred, and 1,3-butadiene is more preferred.
- the ⁇ -olefin monomer forming the ⁇ -olefin monomer unit is preferably one having 2 to 12 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1- Examples include hexene and 1-octene.
- the content of diene monomer units and / or ⁇ -olefin monomer units in the highly saturated nitrile rubber constituting the latex of the present invention is preferably 20 to 89.9% by weight, more preferably 40 to 79.5. % By weight, particularly preferably 49 to 74% by weight.
- the highly saturated nitrile rubber constituting the latex of the present invention includes an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, an acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer, and a diene and / or ⁇ .
- -It may be a copolymer obtained by further copolymerizing another monomer copolymerizable with olefin.
- the content of other copolymerizable monomer units is preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less in the highly saturated nitrile rubber.
- copolymerizable monomers examples include aromatic vinyl, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester, fluoroolefin, and copolymerizable anti-aging agent.
- fluoroolefin examples include unsaturated fluorine compounds having 2 to 12 carbon atoms. Specific examples thereof include difluoroethylene, tetrafluoroethylene, fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethyl styrene, pentafluorobenzoic acid. Examples include vinyl acid.
- copolymerizable antioxidant 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 Mooney viscosity (ML 1 + 4 , 100 ° C.) of the highly saturated nitrile rubber constituting the latex of the present invention is preferably 10 to 300, more preferably 20 to 250, and particularly preferably 30 to 200. If the Mooney viscosity is too low, the mechanical properties of the composite obtained by bonding with the adhesive composition of the present invention may be reduced. On the other hand, if it is too high, the workability may be deteriorated.
- the iodine value of the highly saturated nitrile rubber constituting the latex of the present invention is 120 or less, preferably 80 or less, more preferably 60 or less, and particularly preferably 30 or less. If the iodine value is too high, when the adhesive layer is used, the heat aging resistance and ozone resistance of the resulting adhesive layer may be reduced.
- the highly saturated nitrile rubber constituting the latex of the present invention has a weight average molecular weight (Mw) of a soluble part in chloroform of 100,000 or less, preferably from 10,000 to 9,0000, more preferably 2, 0000 to 8,0000.
- Mw weight average molecular weight
- the weight average molecular weight of the soluble component in chloroform is obtained, for example, by dissolving a highly saturated nitrile rubber in chloroform and measuring the soluble component of the resulting solution using gel permeation chromatography. Can do.
- the molecular weight distribution (Mw / Mn) of the soluble component in chloroform is not particularly limited, but is preferably 2 to 100, more preferably 2.5 to 50.
- the method for bringing the weight-average molecular weight of the highly-saturated nitrile rubber constituting the latex of the present invention into the above range is not particularly limited.
- the highly saturated nitrile rubber constituting the latex of the present invention is not limited.
- a method of adding a molecular weight modifier in the middle of emulsion polymerization without adding a molecular weight modifier at the start of polymerization can be mentioned.
- the latex of the present invention is a range in which each characteristic of the film in the case where the volatile matter contained in the latex is removed and the highly saturated nitrile rubber constituting the latex of the present invention is used as a film is described below. Is.
- the loss tangent tan ⁇ (50 ° C.) of the film (hereinafter referred to as “film product”) at 50 ° C. ) Is in the range of 0.3 to 0.6, preferably in the range of 0.3 to 0.5.
- the loss tangent tan ⁇ (50 ° C.) at 50 ° C. is an index indicating fluidity, and particularly reflects the influence of low molecular weight components. If the loss tangent tan ⁇ (50 ° C.) is too small, the tensile workability is deteriorated.
- the loss tangent tan ⁇ (50 ° C.) is, for example, a film of highly saturated nitrile rubber having a thickness of 0.1 mm to 0.6 mm by casting the latex of the present invention on a predetermined substrate and drying it. The obtained film can be measured using a dynamic viscoelasticity measuring device.
- the complex torque S * of the film product at 100% shear strain at 100 ° C. is 20 dNm or less, preferably 5 to 19 dNm, particularly preferably 10 to 19 dNm.
- the complex torque S * at 100% shear strain is a torque value when the film is deformed relatively large, and is an index indicating rigidity. If the complex torque S * at the time of 100% shear strain is too large, the resulting adhesive layer will be difficult to deform, and the tensile workability will deteriorate.
- the complex torque S * at the time of 100% shear strain is, for example, a highly saturated nitrile having a thickness of 0.1 mm to 0.7 mm by casting the latex of the present invention on a predetermined substrate and drying it.
- a rubber film can be obtained, and the obtained film can be measured using a dynamic viscoelasticity measuring device under conditions of a dynamic shear strain of 100% and a measurement temperature of 100 ° C.
- the method for setting the loss tangent tan ⁇ (50 ° C.) and the complex torque S * at 100% shear strain in the above range is not particularly limited, but the highly saturated nitrile rubber constituting the latex of the present invention is produced by emulsion polymerization.
- the loss tangent tan ⁇ (50 ° C.) of the film product and the complex torque S * at 100% shear strain are in the above ranges, and also satisfy the following requirements: It is preferable, and, thereby, the tensile workability and wear resistance of the resulting adhesive layer can be further improved.
- the loss tangent tan ⁇ (150 ° C.) at 150 ° C. can be measured in the same manner as the loss tangent tan ⁇ (50 ° C.) at 50 ° C. described above.
- the storage modulus G ′ (100 ° C.) at 100 ° C. of the film product is preferably 200 kPa or less, and more preferably 50 to 150 kPa.
- the storage elastic modulus G ′ (100 ° C.) at 100 ° C. is an index indicating hardness.
- the latex of the present invention is cast on a predetermined substrate and dried to obtain a thickness of 0.
- a highly saturated nitrile rubber film having a thickness of 1 to 0.6 mm can be obtained, and the obtained film can be measured using a dynamic viscoelasticity measuring apparatus.
- the difference ⁇ G ′ G ′ (50 ° C.) ⁇ G between the storage elastic modulus G ′ at 50 ° C. (50 ° C.) and the storage elastic modulus G ′ at 150 ° C. (150 ° C.) in the present invention.
- ' (150 ° C) is preferably 350 kPa or less, more preferably 150 to 310 kPa.
- the storage elastic modulus G ′ (50 ° C.) at 50 ° C. and the storage elastic modulus G ′ (150 ° C.) at 150 ° C. can be measured in the same manner as the storage elastic modulus G ′ (100 ° C.) at 100 ° C. described above. it can.
- the highly saturated nitrile rubber constituting the latex of the present invention can be obtained by copolymerizing the above-mentioned monomers and, if necessary, hydrogenating carbon-carbon double bonds in the resulting copolymer.
- the polymerization method is not particularly limited and may be a known emulsion polymerization method or solution polymerization method. From the viewpoint of industrial productivity, the emulsion polymerization method is preferable. In emulsion polymerization, commonly used polymerization auxiliary materials such as emulsifiers, polymerization initiators, molecular weight regulators and the like can be used.
- nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester; myristic acid, palmitic acid, oleic acid And anionic emulsifiers such as salts of fatty acids such as linolenic acid, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, higher alcohol sulfates, and alkyl sulfosuccinates; sulfoesters of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acid sulfate esters, sulfoalkyl aryl ethers and other copolymerizable emulsifiers.
- the amount of the emulsifier is preferably 0.1 to
- the polymerization initiator is not particularly limited as long as it is a radical initiator, but inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene Hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3, 5, 5 Organic peroxides such as trimethylhexanoyl peroxide and t-butylperoxyisobutyrate; azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, etc.
- inorganic peroxides
- polymerization initiators can be used alone or in combination of two or more.
- an inorganic or organic peroxide is preferable.
- a peroxide is used as the polymerization initiator, it can be used as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite or ferrous sulfate.
- the amount of the polymerization initiator used is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
- a molecular weight modifier is not added at the start of the emulsion polymerization, and after starting the emulsion polymerization, 5 to 60% by weight. It is preferable that a molecular weight modifier is added at the stage when the polymerization conversion rate is reached.
- the weight average molecular weight of the highly saturated nitrile rubber to be soluble in chloroform and the loss tangent are obtained.
- the tan ⁇ (50 ° C.) and the complex torque S * at the time of 100% shear strain can be in the above ranges.
- the highly saturated nitrile rubber latex of the present invention is mixed with an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, an acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer unit, and a diene monomer.
- the emulsion polymerization is started without adding a molecular weight modifier, and then 5 to 60 wt% polymerization conversion It is preferable to add a predetermined amount of a molecular weight regulator, which will be described later, at a stage where the rate is reached, so that emulsion polymerization is continued.
- the timing at which the molecular weight modifier is added midway is preferably the stage where the polymerization conversion is 5 to 60% by weight after the start of emulsion polymerization, and is preferably the stage when 15 to 45% by weight. More preferred.
- the addition method is not particularly limited, and the molecular weight modifier to be added may be added in a lump or may be added in multiple times.
- the molecular weight regulator is preferably added during the emulsion polymerization after the emulsion polymerization is started, and it is preferable not to add the molecular weight regulator at the start of the emulsion polymerization. In some cases, the molecular weight regulator may be substantially not contained. For example, if it is about 10 ppm by weight or less, a compound that acts as a molecular weight regulator may be contained.
- the molecular weight modifier is not particularly limited, but mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, methylene bromide; ⁇ -methylstyrene dimer And sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide. These can be used alone or in combination of two or more.
- the amount of the molecular weight modifier used is preferably 1 to 3 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the monomer used for the polymerization.
- Water is usually used as the emulsion polymerization medium.
- the amount of water is preferably 80 to 500 parts by weight, more preferably 80 to 300 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
- polymerization auxiliary materials such as a stabilizer, a dispersant, a pH adjuster, an oxygen scavenger, and a particle size adjuster can be used as necessary. In using these, neither the kind nor the usage-amount is specifically limited.
- the temperature of emulsion polymerization is preferably 0 to 80 ° C., particularly preferably 0 to 30 ° C.
- the latex of the highly saturated nitrile rubber of the present invention is preferably obtained by subjecting the nitrile rubber latex obtained by emulsion polymerization to a hydrogenation treatment.
- the amount of the conjugated diene monomer unit in the nitrile rubber is small, and therefore the iodine value of the nitrile rubber obtained by emulsion polymerization is not more than the above-described value, it is not always necessary to perform a hydrogenation treatment. Absent.
- the average particle size of the latex thus obtained is preferably 0.01 to 0.5 ⁇ m.
- the solid content concentration of the latex is preferably 60% by weight or less, more preferably 5 to 60% by weight, and particularly preferably 10 to 50% by weight in order to prevent aggregation.
- the hydrogenation may be performed by a known method, such as an oil layer hydrogenation method in which a latex of nitrile rubber obtained by emulsion polymerization is coagulated and then hydrogenated in an oil layer, or an aqueous layer in which latex obtained by polymerization is hydrogenated as it is. Examples thereof include a hydrogenation method, and among these, the aqueous layer hydrogenation method is preferable.
- the aqueous layer hydrogenation method includes an aqueous layer direct hydrogenation method in which hydrogen is supplied by supplying hydrogen to the reaction system in the presence of a hydrogenation catalyst, and hydrogenation by reducing in the presence of an oxidizing agent, a reducing agent and an activator.
- a water layer indirect hydrogenation method to be added, the water layer direct hydrogenation method is more preferable.
- the hydrogenation catalyst used in the water layer direct hydrogenation method is not particularly limited as long as it is a compound that is difficult to decompose with water, and examples thereof include a palladium catalyst.
- the palladium catalyst include palladium salts of carboxylic acids such as formic acid, acetic acid, propionic acid, lauric acid, succinic acid, oleic acid and phthalic acid; palladium chloride, dichloro (cyclooctadiene) palladium, dichloro (norbornadiene) palladium.
- the reaction temperature in the aqueous layer direct hydrogenation method 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 hydrogenation catalyst in the latex is usually removed after completion of the hydrogenation reaction.
- an adsorbent such as activated carbon or ion exchange resin is added to the latex after completion of the hydrogenation reaction and stirred to adsorb the hydrogenation catalyst to the adsorbent.
- a method of filtering or centrifuging can be employed.
- hydrogen peroxide and dimethylglyoxime are added to the latex after completion of the hydrogenation reaction, the pH is adjusted to 8 to 11 and stirring is performed while heating, and the hydrogenation catalyst is precipitated as an insoluble matter in the latex. And can be removed.
- the hydrogenation catalyst may be left in the latex without being removed.
- Adhesive Composition comprises the above-described highly saturated nitrile rubber latex of the present invention.
- the content (solid content) of the highly saturated nitrile rubber in the adhesive composition of the present invention is preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight.
- the adhesive composition of the present invention preferably further contains an adhesive resin in addition to the above-described highly saturated nitrile rubber latex of the present invention.
- an adhesive resin a resorcin-formaldehyde resin, a melamine resin, an epoxy resin and an isocyanate resin can be suitably used. Among them, a resorcin-formaldehyde resin is preferable.
- the resorcin-formaldehyde resin known ones (for example, those disclosed in JP-A-55-142635) can be used.
- the reaction ratio of resorcin to formaldehyde is usually 1: 1 to 1: 5, preferably 1: 1 to 1: 3 in terms of a molar ratio of “resorcin: formaldehyde”.
- the resorcin-formaldehyde resin is preferably 5 to 30 parts by weight, more preferably 8 to 20 parts by weight, based on dry weight, with respect to 100 parts by weight of the solid content of the latex of the highly saturated nitrile rubber of the present invention described above. Used in. When the amount of the resorcin-formaldehyde resin is excessively large, the adhesive layer becomes too hard and the flexibility is impaired, so that the composite obtained using the adhesive composition of the present invention has wear resistance. May decrease.
- the adhesive composition of the present invention can contain a vulcanization aid. By containing a vulcanization aid, the mechanical strength of the composite obtained using the adhesive composition of the present invention can be improved.
- Vulcanization aids include quinone dioximes such as p-quinone dioxime; methacrylic acid esters such as lauryl methacrylate and methyl methacrylate; allyl compounds such as TAC (triallyl cyanurate) and TAIC (triallyl isocyanurate); bis Maleimide, phenylmaleimide, N, Nm-phenylene dimaleimide, 4,4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane
- Maleimide compounds such as bismaleimide, N, N ′-(4-methyl-1,3-phenylene) bis (maleimide); DAF (diallyl fumarate), DAP (diallyl phthalate), diallyl maleate, diallyl sebacate, Triallyl phosphate Allyl esters of polyvalent acids such as: diethylene
- 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.
- 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 highly saturated nitrile rubber contained in the latex constituting the adhesive composition of the present invention is referred to as “adhesive highly saturated nitrile rubber”, and the rubber layer of the fiber substrate-highly saturated nitrile rubber composite.
- the highly saturated nitrile rubber that forms is described as “adherent highly saturated nitrile rubber”.
- the form of the fiber base material-highly saturated nitrile rubber composite is not particularly limited, and the fiber base material and the adherend highly saturated nitrile are formed through the adhesive layer formed using the above-described adhesive composition of the present invention. It is sufficient if the rubber is bonded to each other, but a part of or all of the fiber base material is embedded in the fiber base material and the adherend highly saturated nitrile rubber bonded together or the adherend highly saturated nitrile rubber. Can be exemplified.
- the type of fiber constituting the fiber substrate is not particularly limited, and specific examples thereof include vinylon fiber, polyester fiber, nylon, polyamide fiber such as aramid (aromatic polyamide), PBO fiber, fluorine-based fiber, and glass fiber. , Carbon fiber, cotton, rayon and the like. These are appropriately selected according to the application.
- the shape of the fiber substrate is not particularly limited, and specific examples include staples, filaments, cords, ropes, woven fabrics (canvas, etc.), etc., and the fiber substrate-highly saturated nitrile rubber composite It is appropriately selected according to the application.
- a cord base material can be used as a fiber base material to form a highly saturated nitrile rubber toothed belt with a core wire, and a base cloth-coated high saturation nitrile can be used using a base cloth-like fiber base material such as canvas. It can be a rubber toothed belt.
- the adherend highly saturated nitrile rubber used for the fiber substrate-highly saturated nitrile rubber composite is composed of conjugated diene and ⁇ , ⁇ -ethylenically unsaturated nitrile as essential component monomers. It is a copolymer obtained by copolymerizing a monomer copolymerizable with the polymer and hydrogenating it as necessary. Examples of the copolymerizable monomer include those similar to the above-described adhesive highly saturated nitrile rubber.
- adherend highly saturated nitrile rubber examples include highly saturated butadiene-acrylonitrile copolymer rubber, carboxyl group-containing highly saturated butadiene-acrylonitrile copolymer rubber, highly saturated isoprene-butadiene-acrylonitrile copolymer rubber, highly saturated isoprene-acrylonitrile copolymer rubber.
- Polymerized rubber highly saturated butadiene-methyl acrylate-acrylonitrile copolymer rubber, highly saturated butadiene-acrylic acid-acrylonitrile copolymer rubber, highly saturated butadiene-ethylene-acrylonitrile copolymer rubber, butyl acrylate-ethoxyethyl acrylate-vinyl norbornene -Acrylonitrile copolymer rubber and the like.
- a highly saturated butadiene-acrylonitrile copolymer rubber is preferable from the viewpoint of oil resistance and heat resistance.
- the hydrogenation rate of the adherend highly saturated nitrile rubber is 120 or less, preferably 100 or less, more preferably 80 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 adherend highly saturated nitrile rubber is preferably 10 to 60% by weight, more preferably 12 to 55% by weight, and particularly preferably 15 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 adherend highly saturated nitrile rubber is preferably 10 to 300, more preferably 20 to 250, and particularly preferably 30 to 200. If the Mooney viscosity is too low, the moldability and mechanical properties may be reduced. If it is too high, the moldability may be reduced.
- crosslinking agents such as sulfur, peroxide crosslinking agents, and polyamine crosslinking agents
- reinforcing agents such as carbon black, silica, and short fibers that are usually blended during rubber processing
- a compounding agent such as an accelerator, an anti-aging agent, a plasticizer, a pigment, a tackifier, a processing aid, a scorch inhibitor, and a silane coupling agent can be appropriately added.
- the method for obtaining the fiber base material-highly saturated nitrile rubber composite is not particularly limited.
- the method of mounting and heating and pressurizing this 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 1 to 180 minutes, more preferably 5 to 120 minutes.
- the inner surface of the compressor mold or the surface of the roll is used so that the adherend highly saturated nitrile rubber constituting the fiber substrate-highly saturated nitrile rubber composite has a desired surface shape.
- a fiber base material-highly saturated nitrile rubber-fiber base material 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 fiber bases) and a fiber base-highly saturated nitrile rubber composite. And in combination.
- the fiber base material-highly saturated nitrile rubber-fiber base material composite is prepared by, for example, attaching the adhesive composition of the present invention to a core wire as a fiber base material and a fiber base material as a base fabric. Can be obtained by stacking and heating and pressurizing the fiber base material to which the core wire to which the adhesive has been attached, the adherend highly saturated nitrile rubber and the adhesive composition are attached in this order.
- the fiber base material treated with the adhesive composition of the present invention is excellent in wear resistance and dynamic fatigue resistance. Further, since the adherend highly saturated nitrile rubber is excellent in oil resistance, heat resistance, etc., the fiber base material-highly saturated nitrile rubber composite obtained by using the adhesive composition of the present invention is used as an oil contact member for automobiles.
- the belt is suitable for a belt such as a flat belt, a V belt, a V-ribbed belt, a round belt, a square belt, a toothed belt, and a belt in oil. Further, the fiber base material-highly saturated nitrile rubber composite obtained using 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 using the adhesive composition of the present invention can be used as industrial products such as seals and rubber rolls in addition to the above uses.
- 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 fixed site seals include O-rings and various gaskets.
- Rubber rolls 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. Can be mentioned.
- Weight average molecular weight Mw of chloroform soluble matter A latex of highly saturated nitrile rubber was poured into a glass plate and allowed to stand at 20 ° C. for 72 hours for drying. Then, the film formed by drying is peeled off from the glass plate, and the peeled film is further dried at 60 ° C. under reduced pressure for 24 hours, whereby a highly saturated nitrile rubber film (film-formed product) having a thickness of about 0.3 mm. ) This film was immersed in chloroform and allowed to stand at 25 ° C. for 48 hours to dissolve, passed through a membrane filter (pore size 0.5 ⁇ m), and then measured by gel permeation chromatography under the following conditions.
- a membrane filter pore size 0.5 ⁇ m
- the weight average molecular weight Mw of a chloroform soluble part was calculated
- Mw is standard polystyrene conversion.
- Measuring instrument HLC-8220 (manufactured by Tosoh Corporation) Column: Two brand names “GMH-HR-H” (manufactured by Tosoh Corporation) and one brand name “G3000H-HR” (manufactured by Tosoh Corporation) are connected in series.
- Detector Differential refractometer Eluent: Chloroform Column temperature: 40 ° C
- Loss tangent tan ⁇ , storage elastic modulus G ′ In the same manner as the measurement of the weight average molecular weight and molecular weight distribution described above, a highly saturated nitrile rubber film (filmed product) having a thickness of about 0.3 mm was obtained. Then, using the dynamic viscoelasticity measuring device: trade name “RPA2000” (manufactured by Alpha Technologies Co., Ltd.), the film is cut in accordance with the die shape, and the film is overlapped to be about 5 g. Loss tangent tan ⁇ (50 ° C.) , tan ⁇ (100 ° C.) , tan ⁇ (150 ° C.) at 50 ° C., 100 ° C. and 150 ° C.
- Tensile test of adhesive composition-treated fiber substrate The adhesive composition-treated nylon substrate was cut into a strip shape having a width of 2.5 cm and a length of 10 cm to obtain a test piece. Using a tensile tester, the strip test piece was subjected to a tensile test at a speed of 50 mm / min. In this test, the load at this time was determined by setting the distance between chucks at the start of the test to 4.4 cm and the distance between the chucks to 6.6 cm as 50% strain. The lower this load, the easier the deformation of the fiber substrate treated with the adhesive composition, the easier it is to form a complex fiber-rubber composite, and the better the tensile processability.
- Abrasion Resistance Test of Fiber Substrate-Highly Saturated Nitrile Rubber Composite The abrasion resistance of the fiber base material-highly saturated nitrile rubber composite was tested using a carpet taber abrasion tester. The test conditions were a load of 1 kg, a wear surface temperature of 120 ° C. (infrared lamp irradiation), and a disk rotation speed of 10,000 times. Evaluation criteria were as follows. The higher the numerical value of the evaluation standard, the better the wear resistance. 5: Wear is not recognized or wear is recognized, but it is 25% or less of the surface area of nylon. 4: Wear is recognized in the range of more than 25% and 50% or less of the surface area of the nylon base material.
- Wear is recognized in the range of more than 50% and 75% or less of the surface area of the nylon base material.
- Wear is recognized in the range of more than 75% and 90% or less of the surface area of the nylon base material.
- Abrasion is recognized in the range of more than 90% of the surface area of the nylon base material.
- Example 1 [Production of latex (L1) of highly saturated nitrile rubber (A1)] A reactor was charged with 180 parts of ion-exchanged water, 25 parts of an aqueous sodium dodecylbenzenesulfonate solution having a concentration of 10% by weight, 35 parts of acrylonitrile and 4 parts of methacrylic acid in this order, and the internal gas was replaced with nitrogen three times. 61 parts of 3-butadiene was charged. While maintaining the reactor at 10 ° C., 0.1 part of cumene hydroperoxide (polymerization initiator) was added to start the polymerization reaction, and the polymerization reaction was continued while stirring.
- cumene hydroperoxide polymerization initiator
- the latex of nitrile rubber (X1) and the palladium catalyst are added to the autoclave so that the palladium content relative to the dry weight of the rubber contained in the latex of nitrile rubber (X1) obtained above is 1000 ppm by weight. (1% by weight palladium acetate / acetone solution mixed with equal weight of ion-exchanged water) was added, hydrogenation reaction was carried out for 6 hours at a hydrogen pressure of 3 MPa and a temperature of 50 ° C., and the solid content concentration was adjusted to high saturation. A latex (L1) (solid content concentration of 30% by weight) of nitrile rubber (A1) was obtained.
- the content ratio of each monomer unit in the highly saturated nitrile rubber (A1) was determined by 1 H-NMR measurement. As a result, 34.2% by weight of acrylonitrile unit, 3.3% by weight of methacrylic acid unit, 1,3-butadiene The unit (including the hydrogenated part) was 62.5% by weight. The iodine value was 28. Further, according to the above method, the weight-average molecular weight Mw, the loss tangent tan ⁇ , the storage elastic modulus G ′, and the complex torque S * at 100% shear strain were measured. Then, ⁇ tan ⁇ and ⁇ G ′ were obtained by calculation. The results are shown in Table 1.
- the rubber compound prepared by kneading with a Banbury mixer for 15 minutes with the compounding formulation described in Table 2 was layered on the base fabric 15 cm ⁇ 15 cm pretreated with the adhesive composition obtained above, After spreading to a thickness of 1 mm with a roll, the fiber base material-highly saturated nitrile rubber composite (nylon base material-rubber composite) was pressed with a compressor at a pressure of 0.1 MPa and a temperature of 160 ° C. for 30 minutes. ) The obtained fiber base material-highly saturated nitrile rubber composite was subjected to an abrasion resistance test according to the above method. The results are shown in Table 1.
- Example 2 Except that the temperature of the polymerization reactor was changed from 10 ° C. to 15 ° C., and the addition amount of t-dodecyl mercaptan was changed from 1.5 parts to 1.2 parts when the polymerization conversion reached 20%.
- latex (L2) solid content concentration 30% by weight
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A2) is 33.5% by weight of acrylonitrile unit, 3.5% by weight of methacrylic acid unit, 1,3-butadiene unit (including hydrogenated part) It was 63.0% by weight and the iodine value was 37.
- Table 1 shows the results of each measurement performed in the same manner as in Example 1.
- Example 3 Except that the timing of adding 1.5 parts of t-dodecyl mercaptan was changed from the time when the polymerization conversion was 20% to the time when the polymerization conversion was 40%, the same as in Example 1, 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) is 33.8% by weight of acrylonitrile unit, 3.5% by weight of methacrylic acid unit, and 1,3-butadiene unit (including hydrogenated part).
- the iodine value was 45. Table 1 shows the results of each measurement performed in the same manner as in Example 1.
- Example 4 Except that the temperature of the polymerization reactor was changed from 10 ° C. to 15 ° C., and the addition amount of t-dodecyl mercaptan was changed from 1.5 parts to 1.2 parts when the polymerization conversion reached 20%.
- latex (L4) solid content concentration 30% by weight
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A4) is 34.4% by weight of acrylonitrile unit, 3.2% by weight of methacrylic acid unit, and 1,3-butadiene unit (including hydrogenated part).
- the iodine value was 44. Table 1 shows the results of each measurement performed in the same manner as in Example 1.
- Example 5 A latex (L5) of highly saturated nitrile rubber (A5) was prepared in the same manner as in Example 1 except that the amount of acrylonitrile was changed from 35 parts to 42 parts and the amount of 1,3-butadiene was changed from 61 parts to 54 parts. ) (Solid content concentration 30% by weight).
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A5) is 40.1% by weight of acrylonitrile unit, 3.2% by weight of methacrylic acid unit, 1,3-butadiene unit (including hydrogenated part).
- the iodine value was 31. Table 1 shows the results of each measurement performed in the same manner as in Example 1.
- Comparative Example 1 A reactor is charged with 180 parts of ion-exchanged water, 25 parts of a 10% strength by weight aqueous sodium dodecylbenzenesulfonate solution, 35 parts of acrylonitrile, 4 parts of methacrylic acid, and 0.5 part of t-dodecyl mercaptan (molecular weight regulator) in this order. After replacing the internal gas with nitrogen three times, 61 parts of 1,3-butadiene was charged.
- the latex of nitrile rubber (X6) and the palladium catalyst are added to the autoclave so that the palladium content relative to the dry weight of the rubber contained in the latex of nitrile rubber (X6) obtained above is 1000 ppm by weight. (1% by weight palladium acetate / acetone solution mixed with equal weight of ion-exchanged water) was added, hydrogenation reaction was carried out for 6 hours at a hydrogen pressure of 3 MPa and a temperature of 50 ° C., and the solid content concentration was adjusted to high saturation. A latex (L6) (solid content concentration of 30% by weight) of nitrile rubber (A6) was obtained.
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A6) is 34.1% by weight of acrylonitrile unit, 3.4% by weight of methacrylic acid unit, 1,3-butadiene unit (including hydrogenated part).
- the iodine value was 31. Table 1 shows the results of each measurement performed in the same manner as in Example 1.
- Comparative Example 2 Latex (L7) (solid solid) of highly saturated nitrile rubber (A7) in the same manner as in Comparative Example 1, except that the blending amount of t-dodecyl mercaptan at the start of polymerization was changed from 0.5 part to 0.8 part. A partial concentration of 30% by weight).
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A7) is 34.0% by weight of acrylonitrile unit, 3.3% by weight of methacrylic acid unit, 1,3-butadiene unit (including hydrogenated part). It was 62.7% by weight, and the iodine value was 38.
- Table 1 shows the results of each measurement performed in the same manner as in Example 1.
- Comparative Example 3 Latex (L8) (solid solid) of highly saturated nitrile rubber (A8) in the same manner as in Comparative Example 1, except that the blending amount of t-dodecyl mercaptan at the start of the polymerization was changed from 0.5 part to 1.5 parts. A partial concentration of 30% by weight).
- the content ratio of each monomer unit of the highly saturated nitrile rubber (A8) is 33.7% by weight of acrylonitrile unit, 3.5% by weight of methacrylic acid unit, and 1,3-butadiene unit (including hydrogenated part).
- the iodine value was 47. Table 1 shows the results of each measurement performed in the same manner as in Example 1.
- the adhesive composition of the present invention containing the latex of the predetermined highly saturated nitrile rubber of the present invention is used, the obtained fiber base material is excellent in tensile workability and is obtained.
- the fiber base fabric-highly saturated nitrile rubber composite had excellent wear resistance (Examples 1 to 5).
- the weight average molecular weight of a soluble part in chloroform is more than 100,000, and the loss tangent tan ⁇ (50 ° C.) at 50 ° C. when it is formed into a film is 0.00.
- the complex torque S * at 100 ° C.
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Abstract
Description
本発明の高飽和ニトリルゴムのラテックスにおいて、前記ラテックスに含有される揮発分を除去し、高飽和ニトリルゴムのフィルムとした場合における、該フィルムの100℃における貯蔵弾性率G’(100℃)が200kPa以下であることが好ましい。
本発明の高飽和ニトリルゴムのラテックスにおいて、前記高飽和ニトリルゴムが、α,β-エチレン性不飽和ニトリル単量体単位10~60重量%、酸基含有α,β-エチレン性不飽和単量体単位0.1~20重量%、ならびに、ジエン単量体単位および/またはα-オレフィン単量体単位20~89.9重量%を含有するものであることが好ましい。
また、本発明の高飽和ニトリルゴムのラテックスは、前記高飽和ニトリルゴムを形成する単量体を乳化重合することにより得られたものであり、かつ、乳化重合の開始時には分子量調整剤を添加せず、乳化重合を開始した後、5~60重量%の重合転化率となった段階で、重合に用いる単量体100重量部に対して、1~3重量部の分子量調整剤を添加する工程を経て得られたものであることが好ましい。
本発明の接着剤組成物は、レゾルシン-ホルムアルデヒド樹脂をさらに含有してなることが好ましく、前記レゾルシン-ホルムアルデヒド樹脂の含有量が、前記高飽和ニトリルゴムのラテックスの固形分100重量部に対して、5~30重量部であることが、さらに好ましい。
さらに、本発明によれば、繊維基材と高飽和ニトリルゴムを、上記本発明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が提供される。
本発明の高飽和ニトリルゴムのラテックスは、α,β-エチレン性不飽和ニトリル単量体単位を10~60重量%の割合で含有し、ヨウ素価が120以下、クロロホルムに対する可溶分の重量平均分子量が100,000以下である高飽和ニトリルゴムを含有し、かつ、前記ラテックスに含有される揮発分を除去し、高飽和ニトリルゴムのフィルムとした場合における、該フィルムが後述する特定の特性を備えるものである。
α,β-エチレン性不飽和ジカルボン酸としては、マレイン酸、フマル酸、イタコン酸、シトラコン酸、クロロマレイン酸等が例示される。
α,β-エチレン性不飽和ジカルボン酸モノエステルとしては、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノブチル、マレイン酸モノシクロヘキシル、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノブチル、フマル酸モノ-2-ヒドロキシエチル、フマル酸モノシクロヘキシル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノブチル等が例示される。
α,β-エチレン性不飽和ジカルボン酸無水物としては、無水マレイン酸、無水イタコン酸、無水シトラコン酸等が挙げられる。
これらのなかでも、α,β-エチレン性不飽和モノカルボン酸が好ましく、炭素数3~9のα,β-エチレン性不飽和モノカルボン酸がより好ましく、アクリル酸およびメタクリル酸がさらに好ましく、メタクリル酸が特に好ましい。
α,β-エチレン性不飽和モノカルボン酸エステルとしては、α,β-エチレン性不飽和モノカルボン酸と炭素数1~12の脂肪族アルコールとのエステル体が挙げられ、その具体例としては、(メタ)アクリル酸メチル〔アクリル酸メチルおよび/またはメタクリル酸メチルを意味する。以下、同様。〕、(メタ)アクリル酸ブチル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸トリフルオロエチル、(メタ)アクリル酸テトラフルオロプロピル等が例示される。
フルオロオレフィンとしては、炭素数2~12の不飽和フッ素化合物が挙げられ、その具体例としては、ジフルオロエチレン、テトラフルオロエチレン、フルオロエチルビニルエーテル、フルオロプロピルビニルエーテル、o-トリフルオロメチルスチレン、ペンタフルオロ安息香酸ビニル等が例示される。
パラジウム触媒の具体例としては、ギ酸、酢酸、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パラジウムヨウ素化物;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。
水素添加触媒の使用量は、適宜定めればよいが、水素添加前のニトリルゴムに対し、好ましくは5~10,000重量ppm、より好ましくは10~5,000重量ppmである。
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。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。
なお、水層直接水素添加法においては、水素添加触媒を除去せずにラテックス中に残存させてもよい。
本発明の接着剤組成物は、上述した本発明の高飽和ニトリルゴムのラテックスを含有してなる。
本発明の接着剤組成物における高飽和ニトリルゴムの含有量(固形分量)は、好ましくは5~50重量%、特に好ましくは10~40重量%である。
接着剤樹脂としては、レゾルシン-ホルムアルデヒド樹脂、メラミン樹脂、エポキシ樹脂およびイソシアネート樹脂を好適に使用することができるが、中でもレゾルシン-ホルムアルデヒド樹脂が好ましい。レゾルシン-ホルムアルデヒド樹脂は、公知のもの(たとえば、特開昭55-142635号公報に開示のもの)が使用できる。レゾルシンとホルムアルデヒドとの反応比率は、「レゾルシン:ホルムアルデヒド」のモル比で、通常、1:1~1:5、好ましくは1:1~1:3である。
さらに、本発明の接着剤組成物には、加硫助剤を含有させることができる。加硫助剤を含有させることにより、本発明の接着剤組成物を用いて得られる複合体の機械的強度を向上させることができる。加硫助剤としては、p-キノンジオキシム等のキノンジオキシム;ラウリルメタクリレートやメチルメタクリレート等のメタクリル酸エステル;TAC(トリアリルシアヌレート)、TAIC(トリアリルイソシアヌレート)等のアリル化合物;ビスマレイミド、フェニルマレイミド、N,N-m-フェニレンジマレイミド、4,4'-ジフェニルメタンビスマレイミド、ビスフェノールAジフェニルエーテルビスマレイミド、3,3'-ジメチル-5,5'-ジエチル-4,4'-ジフェニルメタンビスマレイミド、N,N'-(4-メチル-1,3-フェニレン)ビス(マレインイミド)等のマレイミド化合物;DAF(ジアリルフマレート)、DAP(ジアリルフタレート)、ジアリルマレエート、ジアリルセバケート、トリアリルホスフェートなどの多価酸のアリルエステル;ジエチレングリコールビスアリルカーボネート;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のトリアリルエーテル、ペンタエリトリットの部分的アリルエーテルなどのアリルエーテル類;アリル化ノボラック、アリル化レゾール樹脂等のアリル変性樹脂;トリメチロールプロパントリメタクリレートやトリメチロールプロパントリアクリレートなどの、3~5官能のメタクリレート化合物やアクリレート化合物;硫黄;等を挙げることができる。
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、たとえば、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。
なお、以下においては、本発明の接着剤組成物を構成するラテックスに含有される高飽和ニトリルゴムを、「接着剤高飽和ニトリルゴム」とし、繊維基材-高飽和ニトリルゴム複合体のゴム層を形成する高飽和ニトリルゴムを、「被着体高飽和ニトリルゴム」として、説明する。
被着体高飽和ニトリルゴム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12~55重量%、特に好ましくは15~50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、被着体高飽和ニトリルゴムのムーニー粘度(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。ムーニー粘度が低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、高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、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、被着体高飽和ニトリルゴムの加硫及び成形、並びに、繊維基材と被着体高飽和ニトリルゴムとの間の接着を同時に行なうことができる。
なお、この場合においては、繊維基材-高飽和ニトリルゴム複合体を構成する被着体高飽和ニトリルゴムが、所望の表面形状を有するものとなるように、圧縮機の型の内面やロールの表面に、目的とする表面形状を実現する型を形成させておくとよい。
また、本発明の接着剤組成物を用い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を用い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及び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。
高飽和ニトリルゴムの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、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。そして、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。
ガラス板に、高飽和ニトリルゴムのラテックスを流し込み、20℃で72時間静置することで乾燥させた。そして、乾燥により形成された皮膜を、ガラス板から剥がし取り、剥がし取った皮膜を、減圧下60℃で24時間さらに乾燥することにより、厚み約0.3mmの高飽和ニトリルゴムのフィルム(フィルム化物)を得た。このフィルムをクロロホルムに浸漬して25℃で48時間静置することで溶解させ、メンブレンフィルター(孔径0.5μm)を通した後、ゲル・パーミエーション・クロマトグラフィーにより、以下の条件で測定し、クロロホルム可溶分の重量平均分子量Mwを求めた。なお、Mwは標準ポリスチレン換算である。
測定器:HLC-8220(東ソー社製)
カラム:商品名「GMH-HR-H」(東ソー社製)2本と商品名「G3000H-HR」(東ソー社製)1本を直列に接続。
検出器:示差屈折計
溶離液:クロロホルム
カラム温度:40℃
上述した重量平均分子量および分子量分布の測定と同様にして、厚み約0.3mmの高飽和ニトリルゴムのフィルム(フィルム化物)を得た。そして、得られたフィルムに対して、動的粘弾性測定機:商品名「RPA2000」(アルファテクノロジーズ社製)を用いて、ダイ形状に合わせフィルムを切り取り、約5gとなるようフィルムを重ねて測定に供し、動的せん断ひずみ6.98%、周波数1.7Hzで、50℃、100℃、150℃における損失正接tanδ(50℃)、tanδ(100℃)、tanδ(150℃)、および、貯蔵弾性率G’(50℃)、G’(100℃)、G’(150℃)を測定した。
さらに、以下の式において、ΔtanδおよびΔG’を求めた。
Δtanδ=(150℃におけるtanδ(150℃))-(50℃におけるtanδ(50℃))
ΔG’ =(50℃におけるG’(50℃))-(150℃におけるG’(150℃))
上述した重量平均分子量の測定と同様にして、厚み約0.3mmの高飽和ニトリルゴムのフィルム(フィルム化物)を得た。そして、得られたフィルムに対して、動的粘弾性測定機:商品名「RPA2000」(アルファテクノロジーズ社製)を用いて、ダイ形状に合わせフィルムを切り取り、約5gとなるようフィルムを重ねて測定に供し、動的せん断ひずみ100%、周波数1Hz、100℃の条件で、100℃における100%せん断歪み時の複素トルクS*を測定した。
接着剤組成物処理ナイロン基材を幅2.5cm、長さ10cmの短冊型に裁断し、試験片とした。引張試験機を用いて、この短冊型試験片を50mm/分の速度で、引っ張り試験を行った。本試験においては、試験開始時のチャック間距離を4.4cmとし、チャック間距離が6.6cmになるときを50%ひずみとして、この時の荷重を求めた。この荷重が低いほど、接着剤組成物処理繊維基材が変形しやすく、複雑な繊維-ゴム複合体を形成しやすく引張加工性に優れる。
繊維基材-高飽和ニトリルゴム複合体について、カーペット用テーバー摩耗試験機を用いて耐摩耗性を試験した。試験条件は荷重1kg、摩耗表面温度120℃(赤外線ランプ照射)、ディスク回転数1万回の条件で行った。評価の基準は、下記の通りとした。評価基準の数値が高いほど耐摩耗性が優れる。
5 : 摩耗が認められない、または、摩耗が認められるものの、ナイロンの表面積の25%以下である。
4 : ナイロン基材の表面積の25%超、50%以下の範囲に摩耗が認められる。
3 : ナイロン基材の表面積の50%超、75%以下の範囲に摩耗が認められる。
2 : ナイロン基材の表面積の75%超、90%以下の範囲に摩耗が認められる。
1 : ナイロン基材の表面積の90%超の範囲に摩耗が認められる。
〔高飽和ニトリルゴム(A1)のラテックス(L1)の製造〕
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35部、メタクリル酸4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61部を仕込んだ。反応器を10℃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、重合反応を開始させ、攪拌しながら重合反応を継続した。重合転化率が20%となった時点で、t-ドデシルメルカプタン(分子量調整剤)1.5部を添加し、さらに重合反応を継続した。重合転化率が90%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。
結果を表1に示す。
レゾルシン6.5部、ホルムアルデヒド(濃度37%)9.4部、および水酸化ナトリウム(濃度10%)3部を水139.6部に溶解し、25℃で6時間反応させ、レゾルシン-ホルムアルデヒド樹脂液(RF液)を得た。
繊維基材としてのナイロン66からなる基布を、上記にて得られた接着剤組成物(LS1)に浸漬し、引き上げることにより、基布上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。次いで、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110℃で10分間加熱し、次いで、150℃で3分間加熱することで硬化させることにより、接着剤組成物処理繊維基材(接着剤組成物処理ナイロン基材)を得た。そして、得られた接着剤組成物処理繊維基材について、上記方法にしたがって、引張試験を行った。結果を表1に示す。
また、上記とは別に、上記にて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からなる基布を、得られたHAFカーボン混合液に浸漬し、引き上げることにより、基布上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。次いで、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150℃で3分間加熱して、接着剤組成物で前処理した基布を得た。
重合反応器の温度を10℃から15℃に変更し、重合転化率が20%となった時点における、t-ドデシルメルカプタンの添加量を1.5部から1.2部に変更したこと以外は実施例1と同様にして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33.5重量%、メタクリル酸単位3.5重量%、1,3-ブタジエン単位(水素化された部分も含む)63.0重量%であり、ヨウ素価は37であった。また、実施例1と同様にして各測定を行った結果を表1に示す。
t-ドデシルメルカプタン1.5部を添加するタイミングを、重合転化率が20%となった時点から、重合転化率が40%になった時点に変更した以外は、実施例1と同様にして、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33.8重量%、メタクリル酸単位3.5重量%、1,3-ブタジエン単位(水素化された部分も含む)62.7重量%であり、ヨウ素価は45であった。また、実施例1と同様にして各測定を行った結果を表1に示す。
重合反応器の温度を10℃から15℃に変更し、重合転化率が20%となった時点における、t-ドデシルメルカプタンの添加量を1.5部から1.2部に変更したこと以外は実施例1と同様にして高飽和ニトリルゴム(A4)のラテックス(L4)(固形分濃度30重量%)を得た。
高飽和ニトリルゴム(A4)の各単量体単位の含有割合は、アクリロニトリル単位34.4重量%、メタクリル酸単位3.2重量%、1,3-ブタジエン単位(水素化された部分も含む)62.4重量%であり、ヨウ素価は44であった。また、実施例1と同様にして各測定を行った結果を表1に示す。
アクリロニトリルの配合量を35部から42部に、1,3-ブタジエンの配合量を61部から54部に変更した以外は、実施例1と同様にして高飽和ニトリルゴム(A5)のラテックス(L5)(固形分濃度30重量%)を得た。
高飽和ニトリルゴム(A5)の各単量体単位の含有割合は、アクリロニトリル単位40.1重量%、メタクリル酸単位3.2重量%、1,3-ブタジエン単位(水素化された部分も含む)56.7重量%であり、ヨウ素価は31であった。また、実施例1と同様にして各測定を行った結果を表1に示す。
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35部、メタクリル酸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61部を仕込んだ。反応器を10℃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、重合反応を開始させ、攪拌しながら重合反応を継続し、重合転化率が90%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℃で残留単量体を除去し、ニトリルゴム(X6)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(A6)の各単量体単位の含有割合は、アクリロニトリル単位34.1重量%、メタクリル酸単位3.4重量%、1,3-ブタジエン単位(水素化された部分も含む)62.5重量%であり、ヨウ素価は31であった。また、実施例1と同様にして各測定を行った結果を表1に示す。
重合開始時における、t-ドデシルメルカプタンの配合量を0.5部から0.8部に変更した以外は、比較例1と同様にして、高飽和ニトリルゴム(A7)のラテックス(L7)(固形分濃度30重量%)を得た。
高飽和ニトリルゴム(A7)の各単量体単位の含有割合は、アクリロニトリル単位34.0重量%、メタクリル酸単位3.3重量%、1,3-ブタジエン単位(水素化された部分も含む)62.7重量%であり、ヨウ素価は38であった。また、実施例1と同様にして各測定を行った結果を表1に示す。
重合開始時における、t-ドデシルメルカプタンの配合量を0.5部から1.5部に変更した以外は、比較例1と同様にして、高飽和ニトリルゴム(A8)のラテックス(L8)(固形分濃度30重量%)を得た。
高飽和ニトリルゴム(A8)の各単量体単位の含有割合は、アクリロニトリル単位33.7重量%、メタクリル酸単位3.5重量%、1,3-ブタジエン単位(水素化された部分も含む)62.8重量%であり、ヨウ素価は47であった。また、実施例1と同様にして各測定を行った結果を表1に示す。
これに対して、高飽和ニトリルゴムのラテックスとして、クロロホルムに対する可溶分の重量平均分子量が100,000超であり、フィルム化物とした際における、50℃における損失正接tanδ(50℃)が0.3未満であり、100℃における100%せん断歪み時の複素トルクS*が20dNmを超えるものを用いた場合には、得られる繊維基材は50%伸長時の荷重が大きく、引張加工性に劣るものであった(比較例1,2)。
また、高飽和ニトリルゴムのラテックスとして、フィルム化物とした際における、50℃における損失正接tanδ(50℃)が0.6超であるものを用いた場合には、得られる繊維基布-高飽和ニトリルゴム複合体は、耐摩耗性に極めて劣るものであった(比較例3)。
Claims (9)
- α,β-エチレン性不飽和ニトリル単量体単位を10~60重量%の割合で含有し、ヨウ素価が120以下、クロロホルムに対する可溶分の重量平均分子量が100,000以下である高飽和ニトリルゴムのラテックスであって、
前記ラテックスに含有される揮発分を除去し、高飽和ニトリルゴムのフィルムとした場合における、該フィルムの50℃における損失正接tanδ(50℃)が0.3~0.6であり、該フィルムの100℃における100%せん断歪み時の複素トルクS*が、20dNm以下であることを特徴とする高飽和ニトリルゴムのラテックス。 - 前記ラテックスに含有される揮発分を除去し、高飽和ニトリルゴムのフィルムとした場合における、該フィルムの50℃における損失正接tanδ(50℃)と、150℃における損失正接tanδ(150℃)との差Δtanδ=tanδ(150℃)-tanδ(50℃)が0.35以下であることを特徴とする請求項1に記載の高飽和ニトリルゴムのラテックス。
- 前記ラテックスに含有される揮発分を除去し、高飽和ニトリルゴムのフィルムとした場合における、該フィルムの100℃における貯蔵弾性率G’(100℃)が200kPa以下であることを特徴とする請求項1または2に記載の高飽和ニトリルゴムのラテックス。
- 前記高飽和ニトリルゴムが、α,β-エチレン性不飽和ニトリル単量体単位10~60重量%、酸基含有α,β-エチレン性不飽和単量体単位0.1~20重量%、ならびに、ジエン単量体単位および/またはα-オレフィン単量体単位20~89.9重量%を含有するものである請求項1~3のいずれかに記載の高飽和ニトリルゴムのラテックス。
- 前記高飽和ニトリルゴムのラテックスが、前記高飽和ニトリルゴムを形成する単量体を乳化重合することにより得られたものであり、
乳化重合の開始時には分子量調整剤を添加せず、乳化重合を開始した後、5~60重量%の重合転化率となった段階で、重合に用いる単量体100重量部に対して、1~3重量部の分子量調整剤を添加する工程を経て得られたものであることを特徴とする請求項1~4のいずれかに記載の高飽和ニトリルゴムのラテックス。 - 請求項1~5のいずれかに記載の高飽和ニトリルゴムのラテックスを含有してなる接着剤組成物。
- レゾルシン-ホルムアルデヒド樹脂をさらに含有してなる請求項6に記載の接着剤組成物。
- 前記レゾルシン-ホルムアルデヒド樹脂の含有量が、前記高飽和ニトリルゴムのラテックスの固形分100重量部に対して、5~30重量部である請求項7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6~8のいずれか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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EP15769585.9A EP3124512B1 (en) | 2014-03-27 | 2015-03-25 | Highly saturated nitrile rubber latex and adhesive composition |
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CN201580015424.8A CN106164116B (zh) | 2014-03-27 | 2015-03-25 | 高饱和腈橡胶的胶乳及粘接剂组合物 |
US15/127,824 US20170101558A1 (en) | 2014-03-27 | 2015-03-25 | Latex of the highly saturated nitrile rubber and adhesive composition |
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JPWO2019139082A1 (ja) * | 2018-01-12 | 2021-01-28 | 日本ゼオン株式会社 | ラテックス組成物 |
CN114380949A (zh) * | 2020-10-21 | 2022-04-22 | 中国石油天然气股份有限公司 | 丁腈橡胶及其制备方法和应用 |
JP2022538956A (ja) * | 2020-05-26 | 2022-09-07 | エルジー・ケム・リミテッド | カルボン酸変性ニトリル系共重合体ラテックスの製造方法 |
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JP7135287B2 (ja) * | 2017-10-13 | 2022-09-13 | 日本ゼオン株式会社 | 水素化共役ジエン系重合体ラテックスの製造方法 |
US11472908B2 (en) * | 2018-01-12 | 2022-10-18 | Zeon Corporation | Latex composition |
KR102620131B1 (ko) * | 2018-03-12 | 2023-12-29 | 니폰 제온 가부시키가이샤 | 라텍스 및 복합체 |
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EP3666799B1 (en) * | 2018-12-13 | 2022-05-11 | Zeon Corporation | Method for producing hydrogenated conjugated diene polymer latex |
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WO2023043234A1 (ko) * | 2021-09-17 | 2023-03-23 | 주식회사 엘지화학 | 중합체 조성물, 이의 제조방법, 이를 포함하는 딥 성형용 라텍스 조성물 및 성형품 |
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