WO1999025784A1 - Adhesif, composite comprenant un caoutchouc et une toile, et courroie crantee - Google Patents

Adhesif, composite comprenant un caoutchouc et une toile, et courroie crantee Download PDF

Info

Publication number
WO1999025784A1
WO1999025784A1 PCT/JP1998/005089 JP9805089W WO9925784A1 WO 1999025784 A1 WO1999025784 A1 WO 1999025784A1 JP 9805089 W JP9805089 W JP 9805089W WO 9925784 A1 WO9925784 A1 WO 9925784A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
canvas
weight
rubber
copolymer rubber
Prior art date
Application number
PCT/JP1998/005089
Other languages
English (en)
Japanese (ja)
Inventor
Shigehiro Isshiki
Masami Sato
Masanori Hirayama
Osamu Mori
Yutaka Ozawa
Satoshi Takeuchi
Original Assignee
Nippon Zeon Co., Ltd.
Unitta Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co., Ltd., Unitta Company filed Critical Nippon Zeon Co., Ltd.
Publication of WO1999025784A1 publication Critical patent/WO1999025784A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • 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
    • 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
    • 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
    • B32B2433/00—Closed loop articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof

Definitions

  • the present invention relates to an adhesive, a composite in which a nitrile group-containing highly saturated copolymer rubber and canvas are adhered with the adhesive, and a toothed belt comprising the composite.
  • Toothed belts such as toothed belts for automobiles, polyribbed belts, wrapped belts, and V-belts are composed of a composite of woven canvas and rubber.
  • chloroprene rubber (C R) and acrylonitrile-butadiene copolymer rubber (NBR), which are mainly oil-resistant rubbers, have been used.
  • C R chloroprene rubber
  • NBR acrylonitrile-butadiene copolymer rubber
  • the toothed belt for automobiles has been The rubber used has been lacking in heat resistance. Therefore, the use of nitrile group-containing highly saturated copolymer rubber having both heat resistance and oil resistance has been proposed (Japanese Patent Publication No. 2-36767).
  • This adhesive has no problem of environmental pollution, and has excellent adhesion to nitrile group-containing highly saturated copolymer rubber, and the toothed belt manufactured using this adhesive has excellent performance.
  • a toothed belt with better wear resistance and water resistance has been required.
  • An object of the present invention is to provide an adhesive capable of adhering a nitrile group-containing highly saturated copolymer rubber to canvas without using an organic solvent, and a nitrile group-containing highly saturated copolymer rubber using the adhesive.
  • An object of the present invention is to provide a composite having excellent abrasion resistance and water resistance bonded to a canvas, and a toothed belt made of such a composite having excellent abrasion resistance and water resistance.
  • the present inventors have conducted intensive studies and found that the use of an adhesive obtained by blending a resorcinol-formaldehyde resin with a so-called self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex having an appropriate amount of a gel component, They have found that a toothed note can be obtained, and have completed the present invention.
  • a resorcinol-formaldehyde resin is blended with a self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex having a methylethyl ketone insoluble content of 75 to 90% by weight or less.
  • the present invention provides a composite of a rubber and a cloth obtained by bonding a nitrile group-containing highly saturated copolymer rubber and a canvas with the adhesive, and a toothed belt made of the composite.
  • the latex is a latex of a copolymer rubber of a conjugated diene monomer, an unsaturated nitrile monomer, an ethylenically unsaturated carboxylic acid monomer, and an ethylenic self-crosslinking monomer.
  • the proportion of the constituent monomers of the copolymer constituting the self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex is usually 30 to 85% by weight of a conjugated diene monomer unit and an unsaturated nitrile monomer. From 10 to 50% by weight, preferably from 25 to 40% by weight, from 1 to 10% by weight, preferably from 2 to 8% by weight, of ethylenically unsaturated carboxylic acid monomer units, and The ethylenic self-crosslinking monomer unit is 0.3 to 10% by weight, preferably 0.5 to 8% by weight.
  • the use of a copolymer latex having such a constituent monomer ratio improves the balance between the abrasion resistance and adhesion of the composite and the toothed belt and the flexibility of the composite and the toothed belt.
  • the content of the carboxyl group is preferably at least 0.01 ephr, more preferably at least 0.02 ephr, particularly preferably at least 0.02 ephr. Preferably it is at least 0.3 ephr.
  • Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and isoprene.
  • Examples of the unsaturated nitrile monomer unit include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile and the like, and usually acrylonitrile is used.
  • Examples of the ethylenically unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, and maleic acid.
  • Ethylenic self-crosslinking monomers include ⁇ -methylol (meth) acrylamide, ⁇ , ⁇ -dimethylol (meth) acrylamide, (meth) acrylamide, and ⁇ -methoxymethyl (meth) acrylamide , ⁇ Examples include 1-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, ⁇ '-methylenebisacrylamide, etc., and the composite and toothed belt have excellent wear resistance. Thus, ⁇ -methylol (meth) acrylamide is preferred.
  • copolymerizable monomers can be used in addition to these monomers as long as the effects obtained by the present invention are not impaired.
  • copolymerizable monomers include styrene, ⁇ -methylstyrene, vinylpyridine and the like, and their fluorine-substituted products ⁇ —trifluoromethylstyrene, ⁇ —trifluoromethylstyrene, pentafluoro Vinyl aromatic monomers such as vinyl benzoate, difluoroethylene and tetrafluoroethylene; non-conjugated diene monomers such as vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene; Fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether, fluoropropyl vinyl ether, trifluoromethylvinyl ether, trifluoroethyl vinyl ether, perfluoropropyl ether, and perfluorohexavinyl
  • the insoluble portion of methyl ethyl ketone as a gel component is 75% by weight or more, preferably 80% by weight or more, more preferably 82% by weight or more. % By weight and 90% by weight or less. If the methylethyl ketone insoluble content is too small, the abrasion resistance is insufficient, and if it is too large, the adhesion to the nitrile group-containing highly saturated copolymer rubber deteriorates.
  • the self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex is usually obtained by an emulsion polymerization method.
  • the emulsion polymerization method is not particularly limited, and may be any of a conventionally known method, a batch system, a semi-batch system, and a continuous system.
  • the pressure is not limited.
  • the polymerization initiator, the molecular weight regulator and the like are not particularly limited. For example, inorganic peroxides such as potassium persulfate and ammonium persulfate and / or organic peroxides such as cumperoxide can be used as the polymerization initiator.
  • the molecular weight regulator may be used in an amount necessary to control the gel content of the self-crosslinkable carboxyl group-containing unsaturated nitrile rubber of the present invention, and has, for example, a mercapto group such as t-decyl mercaptan. Hydrocarbon compounds can be used.
  • the emulsifier is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used. Since the polymer rubber latex has an excellent balance between mechanical stability and chemical stability, as an emulsifier, polyoxyethylene phenyl phosphate or polyoxyethylene alkyl as anionic surfactant is used. Preferred are phosphoric acid ester salts and the like.
  • the amount of the emulsifier used is not particularly limited, but from the viewpoint of the emulsifying effect, the water resistance of the composite or the toothed belt, and the adhesiveness between the nitrile group-containing highly saturated copolymer rubber as an adhesive and the canvas.
  • the total amount of the monomers is preferably 100 parts by weight, and the emulsifier is preferably used in an amount of 1 to 10 parts by weight, more preferably 2 to 6 parts by weight.
  • the average particle size of the latex is not limited, and the particle size obtained is controlled by the amount of the emulsifier to be used and the like, and a particle having an appropriate particle size may be used according to the intended use.
  • the average particle size of the polymer rubber latex of the present invention is preferably 0.08 to 0.2 // m for ordinary use, and the average particle size is 0.2 to 0.2 / m by a seed polymerization method or the like. It can be used well even if it is enlarged up to 3.
  • the resorcinol-formaldehyde resin used in the present invention is not particularly limited ⁇ For example, it is described in Japanese Patent Application Laid-Open No. 55-142,635. These include resorcinol obtained by dissolving resorcinol and an aqueous solution of formaldehyde in water, and reacting with an alkali metal hydroxide such as sodium hydroxide or hydroxide catalyzed by a catalyst, and oxalic acid and hydrochloric acid. There is a novolak type obtained by reacting such acidic compounds as a catalyst, and either type can be used in the present invention.
  • novolak resin examples include Sumikanol 700 (manufactured by Sumitomo Chemical Co., Ltd.) and Adha-RF (manufactured by Hodogaya Chemical Co., Ltd.).
  • the novolak resin is added to water to which a small amount of sodium hydroxide solution is added, and used as an aqueous solution.
  • an aqueous formaldehyde solution may be added as necessary.
  • the molar ratio to the compound is preferably 1: 1 to 1: 3, more preferably 1: 1.2 to 1: 2, in terms of a molar ratio.
  • the adhesive of the present invention comprises a self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex and a resorcin-formaldehyde resin as main components.
  • the adhesive of the present invention is usually a self-crosslinkable carboxyl from the viewpoint of the water resistance of the composite or the toothed belt, and the adhesiveness between the nitrile group-containing highly saturated copolymer rubber and the canvas as the adhesive.
  • Resorcin-formaldehyde resin is dry weighted to 100 parts by weight of solids of unsaturated nitrile rubber latex containing group. The amount is preferably 5 to 30 parts by weight, more preferably 7 to 15 parts by weight.
  • a cross-linking agent such as zinc oxide, zinc peroxide, and sulfur, a cross-linking accelerator, an antioxidant, and an aqueous dispersion of carbon black may be added as long as the effects of the present invention are not impaired.
  • the amount of carbon black used depends on the solid content of the self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex from the viewpoint of the adhesion between the nitrile group-containing highly saturated copolymer rubber and the canvas and the abrasion of the canvas.
  • the amount is 5 to 20 parts by weight, preferably 7 to 15 parts by weight, based on 100 parts by weight.
  • the particle size of the carbon black is preferably from 0.02 to 0.04 // m, and the grade is preferably one of the ISAF, HAF, and FEF grades.
  • the adhesive of the present invention includes a styrene-butadiene copolymer rubber latex, a modified styrene-butadiene copolymer rubber latex, an acrylonitrile-lilubutadiene copolymer rubber latex, and a modified acryloyl as long as the effects of the present invention are not impaired.
  • Nitrile butadiene copolymer rubber latex, hydrogenated acrylonitrile-butadiene rubber latex, black-mouthed prene rubber latex, chlorosulfonated polyethylene latex, acrylic latex, or natural rubber latex may be added.
  • the composite of the present invention uses the above adhesive comprising a nitrile group-containing highly saturated copolymer rubber and a canvas, and a self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex and a resorcinol-formaldehyde resin. They are bonded together.
  • the canvas is made of cotton, vinylon, rayon, nylon, polyester, aramide, etc. These are selected according to the required properties; You.
  • a sulfuric acid relative viscosity of 2.45 to 2.53, a tensile strength of 5 gram nodenier or more, and a single fiber diameter of 6 denier or less are required.
  • a woven-like canvas composed of nylon 66 yarn for industrial materials.
  • the nitrile group-containing highly saturated copolymer rubber used in the present invention comprises: (a) at least an unsaturated nitrile monomer and a conjugated diene monomer or a copolymer thereof. (B) a rubber obtained by treating a copolymer rubber obtained by copolymerizing an unsaturated monomer with an unsaturated monomer, and (b) at least an unsaturated nitrile monomer and an ⁇ -olefin And (c) non-conjugated with at least an unsaturated nitrile monomer and (c) at least one unsaturated nitrile monomer.
  • an unsaturated rubber obtained by hydrogenating a nitrile group-containing copolymer rubber containing a large amount of unsaturated bonds derived from a conjugated diene monomer is used.
  • the iodine value is 120 or less, preferably 80 or less, more preferably 15 or less, and 0 or more.
  • Examples of the unsaturated nitrile-based monomer include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and the like, with acrylonitrile being preferred.
  • Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, and 1,3-pentadiene, and preferred is 1,3-butadiene.
  • the ⁇ _ orffine preferably has 2 to 12 carbon atoms. Examples include ethylene, propylene, butene-11, 4-methylpentene-11, hexene-1 and octene-11.
  • non-conjugated diene monomer examples include allene, 1,2-butadiene, 3-methyl-1,2-butadiene, and 1,5-hexadiene.
  • the copolymerizable monomer is not particularly limited.For example, in the production of the above-mentioned self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latetus, as a copolymerizable monomer or an ethylenic self-crosslinkable monomer, What was illustrated can be used. In the copolymerization, each monomer need not be limited to one kind of monomer, and two or more kinds may be used for copolymerization.
  • the content of unsaturated nitrile units in the nitrile group-containing highly saturated copolymer rubber is preferably at least 10% by weight, more preferably at least 15% by weight, preferably at most 50% by weight, more preferably at most 40% by weight. % By weight or less.
  • Specific examples of these nitrile group-containing highly saturated copolymer rubbers include Zetpo 1 10 10.Zetpol 1020.Zetpol 2000, Zetol 2000 L.Zetpol 2010, manufactured by Zeon Corporation, which is a commercially available product. Zetpol 2010H, Zetpol 2020, Zetpol 2020L, etc.
  • the nitrile group-containing highly saturated copolymer rubber used in the present invention is usually used by blending carbon black, a plasticizer, a crosslinking agent and the like.
  • the crosslinking agent is not particularly limited, and a sulfur-based crosslinking agent or an organic peroxide crosslinking agent can be used.
  • the shape of the nitrile group-containing highly saturated copolymer rubber is not particularly limited, and may be formed into a shape suitable for the purpose.
  • the composite of the present invention is obtained by laminating a nitrile group-containing highly saturated copolymer rubber and canvas with the adhesive of the present invention.
  • the manufacturing method is particularly limited However, in general, the canvas to which the adhesive is adhered is bonded to the bonded part of the nitrile group-containing highly saturated copolymer rubber, and the adhesive is crosslinked between the adhesive and the nitrile group-containing highly saturated copolymer rubber. Adhere.
  • the method of attaching the adhesive of the present invention to canvas is not particularly limited, and a method using an aqueous solution or aqueous dispersion of an adhesive composed of resorcinol-formaldehyde resin and latex is employed as in the case of general tire cord. it can.
  • the canvas may be immersed in an aqueous adhesive solution or aqueous dispersion whose concentration is preferably adjusted to have a viscosity of 10 to 20 cpm, and then dried to remove water.
  • the drying conditions are not particularly limited, and a temperature of 100 to 180 ° C. and a time of about 0.5 to 10 minutes are usually employed.
  • the fiber prior to immersion of the fiber, it is preliminarily immersed in an isocyanate compound solution or an aqueous solution of an isocyanate compound, an epoxy compound solution, an aqueous dispersion of an epoxy compound, etc., and dried. Adhesion can be enhanced by adhering the individual epoxy to the fibers.
  • the drying temperature in this case may be a temperature and time sufficient for the isocyanate compound and the epoxy compound to adhere to the fibers and to dry a solvent such as water, and may be several tens of seconds at 120 to 200 ° C. ⁇ A few minutes.
  • the amount of these compounds attached to the fiber is preferably 0.05 to 1.0% by weight based on the weight of the canvas.
  • the amount of these compounds attached to the fiber can be adjusted by adjusting the concentration of the solution or aqueous dispersion, adjusting the immersion time, and repeating the immersion.
  • the isocyanate compound is not particularly limited, and examples thereof include diphenylmethane diisocyanate, tolylene diisocyanate, trifluoromethane isocyanate, and polymethylene polyphenyl isocyanate. Examples thereof include a phenol block and a ketone oxime block.
  • the epoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether.
  • the amount of the adhesive applied to the canvas is not particularly limited, but from the viewpoint of the adhesion between the rubber and the canvas and the abrasion resistance of the canvas, the amount of the adhesive is preferably 10% by weight or more, based on the weight of the canvas, and 20% by weight. % Or more is more preferable. Further, from the viewpoint of the mechanical properties and flexibility of the canvas, the amount of adhesion is preferably less than 50% by weight, more preferably less than 30% by weight, based on the weight of the canvas. The amount of adhesion can be adjusted by adjusting the immersion time or repeating immersion.
  • the respective bonded portions are usually bonded and heated.
  • the conditions of the heat treatment are not particularly limited, and the time and temperature are sufficient to fix the adhered adhesive and the condensation reaction of the self-crosslinking monomer (for example, a reforming reaction of N-methylol group). Is performed under conditions such that Usually, it is performed at about 130 to 230 ° C. for several tens of seconds to several minutes.
  • the self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex of the present invention is blended with a resorcinol-formaldehyde resin to impart excellent abrasion resistance and adhesion to fibers treated with the adhesive. Can be done.
  • the composite of nylon canvas and rubber of the present invention is particularly suitable as a treating agent for canvas such as toothed belts for automobiles because the composite has excellent abrasion properties even after a long-term belt running test.
  • FIG. 1 is a partial sectional view of a toothed belt which is a composite of the present invention
  • FIG. 2 is an explanatory view of a toothed belt running test device.
  • a polyester cord, a glass fiber cord, an aramide fiber cord, or the like is generally used as the cord 4 together with the canvas.
  • Glass fiber cords and aramide fiber cords are preferred.
  • E glass (alkali-free glass) or high-strength glass fiber cord is generally used.
  • a cord formed by bundling several hundred glass fiber filaments having a wire diameter of 7 to 10 ⁇ m is immersed in an aqueous solution of resorcinol-formaldehyde resin, and the water is evaporated to cause the resorcinol-formaldehyde resin to adhere to the resin. It is common to use several bundles and twists.
  • the core wire used in the present invention was treated with a latex of vinyl pyridine-styrene butadiene terpolymer rubber in order to enhance the adhesiveness with the nitrile group-containing highly saturated copolymer rubber. Thereafter, a core wire is coated with an overcoating agent such as an adhesive obtained by dissolving a mixture of an organic diisocyanate compound and a chlorosulfonated polyethylene rubber in a xylene solvent, as exemplified in JP-A-63-1355564. Is coated.
  • the cord is generally provided so as to be sandwiched between the canvas and the nitrile group-containing highly saturated copolymer rubber.
  • the adhesive of the present invention is applied to a dedicated molding drum. After laminating the canvas 2, the cord 4, and the nitrile group-containing highly saturated copolymer rubber 1 in this order, they are crosslinked by heating and pressing in a vulcanizing kettle. At this time, the rubber flows so as to extend the canvas 2, and the belt tooth form is vulcanized. After vulcanization is completed, the mold is removed and the belt is cut to obtain a toothed belt.
  • the crosslinking temperature is between 140 and 180 ° C and the crosslinking time is between 15 and 50 minutes.
  • a pressure-resistant bottle with an internal volume of 1 liter was charged with 150 parts by weight of water, 3.5 parts by weight of potassium salt of polyoxyethylene phenyl phosphate adjusted to pH 5.5, and 35.0 parts of acrylonitrile. Parts by weight, 3.5 parts by weight of methacrylic acid, 1.0 part by weight of N-methylol methacrylamide, and 0.2 part by weight of t-decyl mercaptan as a molecular weight modifier were added in this order. After purging with nitrogen, 60.5 parts by weight of butadiene were injected.
  • a self-crosslinkable unsaturated acrylonitrile-butadiene copolymer rubber latex A-2 to A-5 was obtained by the same operation except that the amount of the molecular weight modifier was changed as described in Table 1. Was.
  • the gel content was measured as follows: 100 g of 45% by weight latex was coagulated with 1 liter of methanol, followed by vacuum drying overnight at 60 ° C and drying. The rubber was precisely weighed in a 100-mesh basket made of wire mesh with 0.3 grams, immersed in 100 ml of methylethyl ketone, and air-dried with a wire. Each was dried under vacuum at 60 ° C overnight, and the dry weight was precisely weighed to measure the insoluble content (gel content) remaining in the basket without being dissolved.
  • the nitrile group-containing highly saturated copolymer rubber and the compounding agent were kneaded on a roll, and a nitrile group-containing highly saturated copolymer rubber having a thickness of about 2.5 mm was not added. A sulfur sheet was created.
  • the abrasion property of the Nymouth-treated canvas was evaluated using a Taber abrasion tester for carpet.
  • the test conditions were a load of 1 kg, a wear surface temperature of 120 ° C (irradiation with an infrared lamp), and a disk rotation of 10,000 times.
  • the abrasion resistance was evaluated based on the following criteria, and the degree of abrasion of the treating agent (adhesive composition) was evaluated on a 10-point scale.
  • nylon cloth with the adhesive and the nitrile group-containing highly saturated copolymer rubber molded article (a) prepared according to the formulation shown in Table 2 were overlapped and crosslinked in the same manner as described above.
  • a 5 cm square peel adhesion test piece was prepared.
  • the peel test specimen was immersed in boiling water for 3 hours to obtain a water-resistant adhesive test specimen.
  • the adhesive strength was measured for the initial adhesive strength and the water resistant adhesive strength at an exfoliation speed of 50 mm / min using an instrument-type tensilon.
  • Nyltyl group-containing highly saturated copolymer rubber molded product 2 obtained with the formulation shown in Table 2, nylon canvas 5 with adhesive and glass fiber cord 4 (E glass filament, filament diameter approx. 9 ⁇ m, strand 15,000 ⁇ -no-pound, priming strand 3, priming 2.0 times per inch ⁇ Z direction, 1 ply twisted yarn 1 2.0 times per inch ⁇ Fired in the S direction.Hereinafter referred to as core wire S. Similarly, the bottom twist is 2.0 times per inch. * In the S direction, 1 bottom twisted yarn is combined. Yarn is twisted 2.0 times per inch. Twisted in the Z direction (hereinafter referred to as “core Z”), and a canvas with adhesive applied to a special forming drum is arranged as shown below.
  • core Z Twisted in the Z direction
  • a toothed belt 11 And 13 In a 100 ° C environment surrounded by a case 14 made of heat insulating material and a cover 15 made of heat insulating material as shown in Fig. 2, a toothed belt 11 And 13), run the belt at 600 rpm for 1 minute, measure the initial abrasion time of the belt tooth root cloth from the start of running, and evaluate the performance of the toothed belt based on the time did.
  • the results of the peeling test, abrasion test and belt running test are shown in Table 1 above.
  • Example 8 As latex, A-2 was used in Example 8 and A-4 was used in Example 9, and instead of the nitrile group-containing highly saturated copolymer rubber molded article (a), a latex prepared according to the compounding recipe shown in Table 2 was used. The same procedure as in Example 1 was conducted except that the temperature of the vulcanization was changed from 150 ° C. to 160 ° C. using the molded article (b) of a highly saturated copolymer rubber containing a trill group. Test specimens and belts were prepared and their properties were measured. The results are shown in Table 1.
  • a self-crosslinking force containing a self-crosslinkable monomer having a methylethylketone insoluble content of 75 to 90% by weight or less was used.
  • Nain canvas treated with an adhesive composition containing tass and resorcinol-formaldehyde resin as main components is also excellent in abrasion by a Taber abrasion tester for carpet and initial abrasion in belt running. You can see that.
  • a self-crosslinkable carboxyl group-containing unsaturated nitrile rubber latex containing a predetermined amount of both a self-crosslinkable monomer and a hydroxyl group and a resorcinol-formaldehyde resin were used.
  • the abrasion property of the napkin canvas and the occurrence of initial abrasion in a belt running test have a self-crosslinkable monomer or a carboxyl group.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention porte sur un adhésif comprenant un latex-d'élastomère caoutchouc insaturé, carboxylé, autoréticulable, ayant une teneur en matières insolubles à base de méthyléthylcétone comprise entre 75 % et 90 % en poids et contenant une colle résorcine-formol. Selon cette invention, on prépare un matériau composite en liant un caoutchouc copolymère de nitrile hautement insaturé et une toile au moyen de l'adhésif précité, ce matériau composite étant utile pour fabriquer une courroie crantée présentant une excellente résistance à l'usure et à l'eau.
PCT/JP1998/005089 1997-11-13 1998-11-12 Adhesif, composite comprenant un caoutchouc et une toile, et courroie crantee WO1999025784A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9329588A JPH11140404A (ja) 1997-11-13 1997-11-13 接着剤、ゴムと帆布との複合体、および歯付ベルト
JP9/329588 1997-11-13

Publications (1)

Publication Number Publication Date
WO1999025784A1 true WO1999025784A1 (fr) 1999-05-27

Family

ID=18223037

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/005089 WO1999025784A1 (fr) 1997-11-13 1998-11-12 Adhesif, composite comprenant un caoutchouc et une toile, et courroie crantee

Country Status (2)

Country Link
JP (1) JPH11140404A (fr)
WO (1) WO1999025784A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4273682B2 (ja) * 2001-08-29 2009-06-03 日本ゼオン株式会社 繊維部材、および繊維とゴムとの複合体
ITTO20070874A1 (it) * 2007-12-03 2009-06-04 Bridgestone Corp Mescola adesiva a base acquosa per la produzione di pneumatici
JP5591724B2 (ja) * 2011-01-21 2014-09-17 日本ゼオン株式会社 ゴム補強用コード及びそれを用いたゴム製品
WO2015147050A1 (fr) * 2014-03-27 2015-10-01 日本ゼオン株式会社 Latex de caoutchouc de nitrile fortement saturé et composition adhésive
JP6750670B2 (ja) * 2016-03-31 2020-09-02 日本ゼオン株式会社 補強ゴムの評価方法
CN113930199B (zh) * 2021-11-12 2024-02-20 航天特种材料及工艺技术研究所 一种增韧型酚醛胶粘剂及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06286015A (ja) * 1993-03-30 1994-10-11 Nippon Zeon Co Ltd ゴムと繊維との接着剤組成物及びゴムと繊維との複合体
JPH08100160A (ja) * 1994-09-28 1996-04-16 Nippon Zeon Co Ltd 接着剤組成物及びゴムと繊維との複合体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06286015A (ja) * 1993-03-30 1994-10-11 Nippon Zeon Co Ltd ゴムと繊維との接着剤組成物及びゴムと繊維との複合体
JPH08100160A (ja) * 1994-09-28 1996-04-16 Nippon Zeon Co Ltd 接着剤組成物及びゴムと繊維との複合体

Also Published As

Publication number Publication date
JPH11140404A (ja) 1999-05-25

Similar Documents

Publication Publication Date Title
JP3601550B2 (ja) 接着剤組成物およびゴムと繊維との複合体
JP3601544B2 (ja) 接着剤組成物及びゴムと繊維との複合体
CA3003879C (fr) Traitement adhesif pour fibre de renfort polymere et produits renforces
JPH0243767B2 (fr)
CN106164116B (zh) 高饱和腈橡胶的胶乳及粘接剂组合物
JP3496292B2 (ja) ニトリル基含有高飽和共重合体ゴムと繊維との複合体
KR960001365B1 (ko) 고무 및 섬유의 접착제
WO2005098123A1 (fr) Composition pour revetement de corde, corde pour le renfort de caoutchouc fabrique a partir de cette composition, et produit de caoutchouc fabrique a partir de cette corde
JP2004250709A (ja) ゴム組成物、その製造方法並びにそれらから得られる加硫された複合材料
JPS61207442A (ja) ゴム配合物と繊維との接着方法
JP3266976B2 (ja) ゴムと繊維との接着剤組成物及びゴムと繊維との複合体
WO1999025784A1 (fr) Adhesif, composite comprenant un caoutchouc et une toile, et courroie crantee
JP3754132B2 (ja) ゴム補強用繊維処理剤、補強用繊維、およびゴム補強物
JP4354791B2 (ja) ゴム製品の補強用繊維
JP3513938B2 (ja) ニトリル基含有高飽和共重合体ゴムの水性エマルジョンおよびその接着剤組成物
KR960006169B1 (ko) 섬유-고무 복합체의 제조방법
JP2005009010A (ja) ゴム製品の補強用繊維
JP2627554B2 (ja) ポリエステル繊維の処理方法及びポリエステル繊維とニトリル基含有高飽和共重合体ゴムとの接着方法
JP4499338B2 (ja) ラテックス、接着処理液、繊維部材および繊維部材と加硫ゴム部材との複合部材
WO2003076710A1 (fr) Agent de traitement pour fibre de verre de renforcement de caoutchouc, cable de renforcement de caoutchouc produit avec celui-ci et produit de caoutchouc
JP4522279B2 (ja) ガラス繊維被覆用塗布液およびそれを用いたゴム補強用ガラス繊維
JP2667555B2 (ja) 接着剤組成物
JP4837817B2 (ja) ゴム組成物と繊維材料との複合体、及びその製造方法
JPH09296378A (ja) ゴム部品の補強用心線及びその製造方法
JP5151730B2 (ja) ゴム補強用ガラス繊維およびそれを用いた伝動ベルト

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: KR

122 Ep: pct application non-entry in european phase