JP2009172806A - Laminated body, method of manufacturing the same, and seal member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body where fixing of a rubber substrate with a contacting material, or peeling of a coating layer or the like are hardly caused. <P>SOLUTION: The laminated body 900 comprises a rubber layer 100, as a substrate, having a ground surface 110 keeping one main surface ground with a grinding wheel, and a coating layer 200 formed on the ground surface 110 of the rubber layer 100. The surface roughness of the ground surface 110 is preferably set to be the maximum height of 3.2 μm or more and 6.3 μm or less. The rubber layer 100 is nitrile rubber, nitrile hydroxide rubber, or fluoro-rubber or the like. The coating layer 200 is fluorine resin or molybdenum disulfide or the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminate, a method for producing the laminate, and a seal member using the laminate.

  The fuel gasket is used by being sandwiched between a discharge port of a fuel tank and a cap attached to the discharge port. Since such a fuel gasket needs to be impermeable to fuel, rubber is used as a base material.

  And when removing the cap from the discharge port, when the cap is rotated and slid relative to the discharge port, the rubber base is not slidable enough, so the surface of the rubber base is improved. A coating layer of resin or the like is formed.

  The laminated body which consists of a rubber base material and coating layers, such as resin, which forms such a gasket for fuels, is manufactured as described in patent document 1, for example.

  That is, by coating the surface of the rubber base material with a resin, a laminate composed of the rubber base material and the resin coating layer is obtained.

  However, peeling, cracking, or the like may occur in the coating layer by bending the obtained laminate.

  On the other hand, a laminated body may be formed on a metal plate or the like (metal workpiece). When forming a laminated body in a metal work, it manufactures as shown below.

  That is, first, for example, a metal workpiece having a container shape or the like is prepared, and a vulcanized adhesive is applied to the metal workpiece to perform vulcanization adhesion to the rubber substrate.

  And the laminated body formed in the metal workpiece | work is obtained by coating resin on the surface of a rubber base material.

  However, when vulcanization bonding is performed, the rubber base material is reduced and deformed, while the end portion of the rubber base material is in close contact with the inner side surface of the container (metal workpiece) and is not deformed. If it does so, while the center part of a rubber base material will dent by vulcanization adhesion, both ends of a rubber base material may rise.

  When the main surface of the rubber base material has such a shape, the rubber base material is exposed on the surface because the resin cannot be uniformly coated on the surface of the rubber base material, and the rubber base material and the contact equipment are not fixed. May occur. Further, the adhesive strength between the rubber layer and the coating layer becomes insufficient, and the coating layer may be peeled off. Furthermore, when the fuel gasket is used in a low temperature state or a high temperature state, the possibility of occurrence of adhesion between the rubber layer and the contact material, peeling of the coating layer, or the like increases.

JP 2007-146096 A

  The present invention has been made in view of such problems, and seal members and laminates that are less likely to cause adhesion between a rubber base material and contact equipment, peeling of a coating layer, cracks, wrinkles, and the like. An object of the present invention is to provide a method for manufacturing a laminate.

In order to achieve the above object, the laminate according to the first aspect of the present invention comprises:
A rubber layer as a base material having a grinding surface obtained by grinding one main surface with a grindstone;
And a coating layer formed on the ground surface of the rubber layer.

  The ground surface may be a flat surface.

  The ground surface may have a tapered surface ground with a grindstone at the end of the main surface of the rubber layer.

  Further, the taper angle of the tapered surface may be 5 degrees or more and 15 degrees or less.

  The surface roughness of the ground surface may have a maximum height of 3.2 μm or more and 6.3 μm or less.

  The rubber layer comprises nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), carboxylated nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR), fluorine rubber (FKM), acrylic rubber (ACM · ANM), polyester urethane rubber (AU), polyether urethane rubber (EU), ethylene propylene rubber (EPM / EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), epichlorohydrin rubber (ECO), natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), vinyl methyl silicone rubber (VMQ), fluorinated silicone rubber (FVMQ), polysulfide rubber (T) And nor Formed from rubber containing at least one of Runengomu (NOR), it is also possible.

  The coating layer may contain at least one of fluororesin, silicone resin, molybdenum disulfide, tungsten disulfide, graphite, boron nitride, and boron nitrite.

In order to achieve the above object, a method for manufacturing a laminate according to the second aspect of the present invention includes:
A grinding process of grinding one main surface of the rubber layer with a grindstone to form a ground surface;
And a coating step of forming a coating layer on the ground surface of the rubber layer.

  In the grinding step, the ground surface can be formed as a flat surface.

  In the grinding step, it is also possible to form a tapered surface by grinding an end of one main surface of the rubber layer with a grindstone.

  Further, the taper angle of the tapered surface may be 5 degrees or more and 15 degrees or less.

  In the grinding step, the surface roughness of the ground surface ground by the grindstone may have a maximum height of 3.2 μm or more and 6.3 μm or less.

In order to achieve the above object, a seal member according to a third aspect of the present invention is
A seal member that is sandwiched between a pair of components that slide with respect to the other component and seals these gaps,
As a material of the sealing member, the laminate according to any one of claims 1 to 7, wherein the coating layer is disposed on the one component side, and the rubber layer is disposed on the other component side. It is used.

  In the laminate according to the present invention, adhesion between the rubber base material and the contact material, peeling of the coating layer, cracks, wrinkles, and the like are unlikely to occur.

(Embodiment 1)
[Laminate]
The laminated body 900 which concerns on this embodiment has the rubber layer 100 which has the grinding surface 110, and the coating layer 200, as FIG. 1 shows. The coating layer 200 is formed on the grinding surface 110 of the rubber layer 100. The rubber layer 100 is a base material (rubber base material) of the laminate 900.

  The grinding surface 110 of the rubber layer 100 is formed by grinding the main surface of the rubber layer 100 with a grinding wheel.

  As shown in FIG. 1, the grinding surface 110 has a planar shape as a whole. As shown in FIG. 2, the surface structure of the grinding surface 110 is preferably a waveform formed by a curved surface. This is because if the grinding surface 110 has a zigzag shape formed in a straight line, it may be difficult to form a coating layer uniformly on the grinding surface 110. Moreover, it is because the adhesive strength of the coating layer 200 to the grinding surface 110 may be insufficient.

The surface roughness of the grinding surface 110 is preferably such that the maximum height R _z is 3.2 μm or more and 6.3 μm or less. When the maximum height _Rz is smaller than 3.2 μm, the contact area between the ground surface 110 and the lower surface of the coating layer 200 is decreased, and the adhesive strength of the coating layer 200 to the ground surface 110 may be insufficient. Because there is. On the other hand, if the maximum height R _z is larger than 6.3 μm, the wave of the waveform of the grinding surface 110 is so large that it may be difficult to form the coating layer 200 uniformly on the grinding surface 110. is there.

Here, the maximum height R _z representing the surface roughness means that the waveform curve is sandwiched between two straight lines parallel to the average line R _av , the waveform curve is extracted for the reference length L, and the wave height of the extracted waveform curve is Is the maximum height. The average line R _av is a line indicating the average value of the individual wave heights in the waveform curve. Moreover, the reference length L can select arbitrary length among 0.25 mm, 0.8 mm, 2.5 mm, 8.0 mm, and 25.0 mm.

[Rubber layer]
The thickness of the rubber layer 100 can be variously changed depending on the use of the laminate 900, and can be set to, for example, 1 mm to 10 mm.

  The rubber composition used for the rubber layer 100 is not particularly limited. For example, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), carboxylated nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR) , Fluoro rubber (FKM), Acrylic rubber (ACM / ANM), Polyester urethane rubber (AU), Polyether urethane rubber (EU), Ethylene propylene rubber, Chloroprene rubber (CR), Chlorosulfonated polyethylene rubber (CSM), Epichlorohydrin Rubber (ECO), natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), vinyl methyl silicone rubber (VMQ), fluorinated silicone rubber (FVMQ) It can be formed from rubber containing at least one of polysulfide rubber (T) and norbornene rubber (NOR). The ethylene-propylene rubber is an ethylene-propylene copolymer rubber (EPM or EPR) and an ethylene-propylene-terpolymer obtained by adding a non-conjugated diene as a third component to an ethylene-propylene system. Also included are diene terpolymers (EPDM).

Among these, chloroprene rubber, isoprene rubber, ethylene propylene rubber, butyl rubber, nitrile rubber, and natural rubber are preferable as the rubber composition because of excellent durability and the like.
Fluoro rubber is also preferable because of its excellent heat resistance, oil resistance, and chemical resistance. As the fluororubber, vinylidene fluoride (FKM), tetrafluoroethylene-propylene (FEPM), tetrafluoroethylene-perfluorovinyl ether (FFKM), or the like can be used.

The rubber composition used for the rubber layer 100 can contain a softener (plasticizer). The softener (plasticizer) is blended to impart flexibility to the rubber composition and reduce its hardness, and those having good affinity with the rubber component are preferably used.
Examples of such softeners include paraffinic oils, naphthenic oils, aromatic oils, and the like, and paraffinic oils having excellent affinity for ethylene-propylene-diene terpolymers are particularly preferable. Paraffinic oil is usually a straight-chain or branched hydrocarbon having about 10 to 20 carbon atoms. Among these paraffinic oils, those having a pour point (conforming to JIS K 2269) of −30 ° C. or lower are preferable in order to exert their functions even at low temperatures. In addition, when using oil-extended rubber as a rubber component, the same thing as these softeners can be used as mineral oil.

  The content of the softening agent is 300 to 400 parts by weight per 100 parts by weight of the rubber component of the rubber composition in order to sufficiently impart the flexibility of the rubber composition used for the rubber layer 100. It is preferable that it is a weight part. When the content of the softening agent is less than 300 parts by weight, the hardness of a molded product (rubber molded product) obtained from the rubber composition cannot be lowered to a target level. On the other hand, when the amount exceeds 400 parts by weight, the content of the softening agent becomes excessive, and the excess softening agent may bleed to the surface of the molded product, and there is a possibility that strong adhesiveness is developed there.

Moreover, the rubber composition used for the rubber layer 100 can contain a crosslinking agent (vulcanizing agent). As the crosslinking agent, sulfur, sulfur dichloride, morpholine disulfide, dithiodicaprolactam, ethylenethiourea, m-phenylene dimaleimide, dicumyl peroxide, or the like can be used.
Moreover, an aliphatic or alicyclic peroxide can be mix | blended as a crosslinking agent. Examples of the aliphatic or alicyclic peroxide include 3,3,5-trimethylhexanone peroxide, diisobutyryl peroxide, 1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane. , 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl2,5-di (t-butylperoxy) hexyne-3, n-butyl-4,4-bis (T-Butylperoxy) valerate, di-sec-butylperoxydicarbonate and the like.

  Furthermore, it is possible to contain a crosslinking assistant in addition to the crosslinking agent. Examples of the crosslinking aid include triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,2-polybutadiene, vinyltrimethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- It is possible to blend glycidoxypropyl-tri-methoxysilane and the like.

  Moreover, the rubber composition used for the rubber layer 100 can contain a crosslinking accelerator (vulcanization accelerator). As the crosslinking accelerator (vulcanization accelerator), it is possible to contain thiuram, thiazole, sulfenamide, dithiocarbamate, sulfide, and thiourea compounds. Specifically, dibenzothiazol disulfide, zinc dibutyldithiocarbamate, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, 2-mercaptobenzothiazole, and the like can be used.

  The rubber composition used for the rubber layer 100 can also contain a filler. As the filler, either an inorganic filler or an organic filler can be used.

  Inorganic fillers include metal powders such as aluminum, copper, iron, lead, nickel, silver, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, iron oxide, beryllium oxide, etc. Oxides, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, aluminate hydrate, silicates such as talc, clay, mica, asbestos, bentonite, zeviolite, calcium silicate, montmorillonite, It is possible to use carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite, sulfates such as calcium sulfate sulfate, calcium sulfite sulfate, barium sulfate and calcium sulfite, and also molybdenum disulfide and titanic acid. Potassium, silicon carbide, etc. can also be used.

  Further, as the organic filler, linter, linen, sisal wood powder, silk, leather powder, collagen fiber, viscose, acetate, vinylon, Teflon (registered trademark) powder or the like can be used.

  Further, the rubber composition used for the rubber layer 100 may contain a foaming agent. Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, azo compounds such as azodicarbonamide, benzenesulfonylhydrazide, p, p′-oxybis ( It is possible to contain carbonyl hydrazide compounds such as benzenesulfonyl hydrazide). In particular, sulfonyl hydrazide compounds such as p, p'-oxybis (benzenesulfonyl hydrazide) are preferred. The blending amount of the foaming agent is 0.05 to 25 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the rubber composition.

  Further, the rubber composition used for the rubber layer 100 may contain a processing aid. As processing aids, paraffin waxes, liquid paraffin, fatty acid esters, fatty acid amides and the like can be included. Specific examples include polyethylene wax, polyethylene glycol, fatty acid ester, fatty acid amide, and sub (factis). In addition, commercially available special processing aids (for example, Splendor R-100, Exton K-1, Sun-Aid HP, Yod Plast-P, TE-80 (Technical Processing Co., Ltd.), Actiplast, Aflux 42, Stratol WB212, etc.) Can also be included. These processing aids are used alone or in combination of two or more. The amount of the processing aid is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the rubber composition.

  Further, the rubber composition used for the rubber layer 100 can contain a colorant. Examples of the colorant include inorganic pigments such as titanium oxide, zinc white, lead white, red lead, cuprous oxide, yellow iron oxide, iron black, cadmium yellow, molybdenum red, silver vermilion, yellow lead, chromium oxide, bitumen, and bengara. , Organic pigments such as thioindigo red, phthalocyanine blue, quinacridone red, quinophthalo yellow, condensed azo yellow, ultramarine blue, and the like.

Furthermore, the rubber composition used for the rubber layer 100 can contain a reinforcing material and a flame retardant.
As the reinforcing material, carbon black, silica or the like can be used. As carbon black, furnace black, thermal black, channel black, etc. can be used. As the flame retardant, antimony trioxide, aluminum hydroxide, or the like can be used.

[Coating layer]
Next, the coating layer 200 can be formed of a resin coating layer or a solid lubricating coating layer.

  As the resin for forming the resin coating layer, for example, a fluororesin or a silicone resin can be used.

  As the solid lubricant forming the solid lubricant coating layer, for example, molybdenum disulfide, tungsten disulfide, graphite, boron nitride, boron nitrite and the like can be used.

  Examples of fluororesins include copolymers of ethylene and tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (CTFE), and copolymers of ethylene and chlorotrifluoroethylene (ECTFE). , A copolymer of vinylidene fluoride and tetrafluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene (VDF-HFP), a terpolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene (VDF) -HFP-TFE), polytetrafluoroethylene (PTFE), copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), vinyl fluoride Copolymers den and tetrafluoroethylene, it can be used a copolymer of vinylidene fluoride and hexafluoropropylene. These may be used alone or in combination of two or more. Among these, FEP is preferably used because it has excellent workability and durability.

When a fluororesin is used as the material of the coating layer 200, a filler can be blended for the purpose of improving physical properties. Examples of the filler contained in the fluororesin include, for example, titanium oxide, barium sulfate, calcium carbonate, silica, carbon black, magnesium silicate, aluminum silicate, zinc oxide, alumina, calcium sulfate, aluminum sulfate, calcium hydroxide, Aluminum hydroxide, talc, molybdenum dioxide, whiskers, short fibers, graphite, metal powder, silica sand, pumice powder, slate powder, mica powder, asbestos, glass spheres, and the like can be used.
The blending ratio of the filler is usually set to 30 parts by weight or less, preferably 5 to 20 parts by weight with respect to 100 parts by weight of the fluororesin.

  Moreover, when using a fluororesin as a material of the coating layer 200, it is preferable that a fluororesin provides electroconductivity. This is because, as will be described later, the laminate 900 according to the present embodiment is used as a fuel gasket or the like used by being sandwiched between a discharge port of a fuel tank of gasoline or the like and a cap attached to the discharge port. May be. This is because if static electricity is generated in the laminated body 900, there is a risk of igniting the fuel.

The purpose of imparting conductivity to the fluororesin can be achieved, for example, by blending a fluorocarbon resin with a conductive agent. As the conductive agent, carbon black, fine stainless steel metal fibers, or the like can be used. The blending ratio of the conductive agent is preferably blended in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the fluororesin. This is because when the conductive agent is blended in such a range, the volume low efficiency of the coating layer 200 in the laminate 900 becomes 10 ¹⁰ Ω · cm or less, and it is easy to discharge static electricity to the outside of the laminate 900 and let it escape. Because it becomes.

Molybdenum disulfide is a black solid represented by a composition formula MoS _2. It has a hexagonal layered crystal structure, and each layer has a structure in which both sides of a molybdenum layer are sandwiched between sulfur. While the bond between molybdenum and sulfur is strong, the bond between sulfur is weak, so that each layer slips easily when shearing force is applied. For this reason, since a friction coefficient becomes low and it has slidability, molybdenum disulfide can be used conveniently.

  Moreover, since the silicone resin also has excellent surface slidability, it can be suitably used. Examples of silicone resins include organopolysiloxanes having a methyl group, vinyl group, phenyl group, fluoro group-containing functional group, and the like, specifically, dimethylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, γ- A silicone resin made of an organopolysiloxane such as trifluoropropylmethylpolysiloxane can be used.

  Further, a modified silicone resin can be used as a material used for the coating layer 200. The modified silicone resin cures when the reactive silicon group-containing oligomer forms a siloxane bond. Examples of the reactive silicon group-containing oligomer include an oxyalkylene polymer having a reactive silicon group at the terminal. The reactive silicon group is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond.

  As a curing catalyst for silicone resin or modified silicone resin, organic tin, inorganic tin, titanium catalyst, bismuth catalyst, metal complex, platinum catalyst, basic substance and organic phosphorous oxide are used. Specific examples of organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate, and the like, and reaction products of dibutyltin salts and normal ethyl silicate. Metal complexes include tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, titanate compounds such as ethyl acetyl titanate, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate and cobalt naphthenate, aluminum Examples thereof include metal acetylacetate complexes such as acetylacetate complexes and metal acetylacetonate complexes such as vanadium acetylacetonate complexes.

  The silicone resin or the modified silicone resin can contain a filler. Fillers are formulated for viscosity adjustment, viscosity adjustment, solid content adjustment, etc. Specific examples include inorganic fillers such as calcium carbonate, cinnabar sand, talc, carbon black, titanium oxide, kaolin, and glass for reinforcing cured resins. Examples include reinforcing materials such as fibers, hollow bodies such as shirasu balloons and glass balloons for weight reduction and viscosity adjustment. Among these, calcium carbonate fillers such as heavy calcium carbonate, colloidal calcium carbonate, and surface-treated calcium carbonate are preferable from the viewpoint of miscibility with the resin, stability of the mixed resin, cost, and the like.

  Various stabilizers can be blended in the coating layer 200. As the stabilizer, for example, antioxidants such as phenols, phosphoruss, and sulfurs, and UV absorbers such as hindered amines, benzotriazoles, and benzoates can be contained. As the stabilizer, a phosphoric antioxidant is preferably blended, and the phosphoric antioxidant is used alone or in combination with other antioxidants and / or ultraviolet absorbers.

  Although the thickness of the coating layer 200 can be variously changed according to the use of the laminated body 900, it can be 2 micrometers-100 micrometers, for example. This is because if the thickness is less than 2 μm, a portion that is not covered with the coating layer 200 may occur due to wear of the coating layer 200. On the other hand, if the thickness is larger than 100 μm, the coating layer 200 may be cracked or wrinkled.

  In the laminate 900 according to this embodiment, the main surface of the rubber layer 100 is a ground surface 110 ground with a grindstone, and the coating layer 200 is formed on the ground surface 110. Therefore, the coating layer 200 is firmly bonded to the rubber layer 100 via the grinding surface 110, and the coating layer 200 is difficult to peel off from the rubber layer 100, and the coating layer 200 is less likely to be cracked.

[Method for producing laminate]
Below, the manufacturing method of the laminated body 900 which concerns on this embodiment is demonstrated. In addition, although the manufacturing method of the laminated body 900 demonstrated below is an example which forms the laminated body 900 on a metal workpiece | work, it is a specific example and does not limit the scope of the present invention.

  First, a container-shaped metal workpiece is prepared. As the metal forming the metal workpiece, SPCC, SUS, aluminum, brass, zinc, copper alloy or the like is used.

  Then, a blast process is performed on the metal workpiece. The blasting process is performed by a shot blasting process (a process of causing a particle called a projection material to collide with a metal workpiece). The blasting process is performed to remove burrs from the metal workpiece and to improve the adhesion between the metal workpiece and the rubber layer as described later. Then, the metal workpiece is degreased and cleaned.

  Next, a vulcanized adhesive is applied to the metal workpiece. As the vulcanized adhesive, a chlorinated rubber-based or phenol-based adhesive is suitably used for bonding nitrile rubber (NBR) and metal. In order to bond the ethylene-propylene-diene terpolymer (EPDM) and the metal, a hyperon adhesive is suitably used. A silane-based adhesive is preferably used for bonding the fluororubber (FKM) and the metal.

  After the vulcanized adhesive is applied to the metal workpiece, it is dried at room temperature for about 30 to 60 minutes or at 120 ° C. for several minutes.

  Next, the rubber layer 100 is prepared. For the rubber layer 100, the softening agent (plasticizer), the cross-linking agent (vulcanizing agent), the cross-linking auxiliary agent, the cross-linking accelerator (vulcanization accelerator), the filler, the foaming agent, and the reinforcement described above as necessary. Materials, flame retardants, processing aids, colorants and the like are contained in a predetermined ratio.

  The rubber layer 100 is put into a metal workpiece coated with a vulcanized adhesive, and pressure bonding is performed, whereby the rubber layer 100 and the metal workpiece are vulcanized and bonded.

  Next, one main surface of the rubber layer 100 is ground with a grindstone (grinding step). If the grinding is performed by shot blasting, the finished grinding surface 110 becomes too rough, and it may be difficult to form the coating layer 200 uniformly on the grinding surface 110. Further, if grinding is performed by plasma treatment, the rubber composition forming the rubber layer 100 may be deteriorated. Therefore, grinding of one main surface of the rubber layer 100 is performed with a grindstone. Moreover, since grinding with a grindstone can be performed at normal temperature, there is also an advantage that there is no possibility of deteriorating the rubber composition forming the rubber layer 100.

  In the grinding step, it is preferable that the grinding allowance (grinding volume) is about 30 to 60 μm.

For the grinding operation in the grinding process, as the dresser, for example, a rotary dresser, an imprint dresser, a wheel dresser or the like can be used. The dresser is for flattening (dressing) by eliminating irregularities on the grindstone surface of the grindstone.
As the grinding liquid, for example, an emulsion type, a soluble type or the like can be used.

  After grinding one main surface of the sheet-like rubber layer 100 with a grindstone, degreasing and cleaning are performed with a cleaning liquid. Use alcohol as the cleaning solution.

  After cleaning, the coating layer 200 is formed on the ground surface 110 (coating process). As described above, the coating layer 200 can be formed of a fluororesin, molybdenum disulfide, a silicone resin, or the like.

  The coating layer 200 is formed by applying a fluororesin to the ground surface 110 of the rubber layer 100 or spraying a fluorine latex.

  The coating layer 200 made of molybdenum disulfide is formed by applying a dispersion obtained by dispersing fine powder of molybdenum disulfide in a solvent to the grinding surface 110. Solvents include toluene, xylene, methylene chloride, amyl chloride, butyl stearate, isopropyl acetate, methyl propyl ketone, methyl isobutyl ketone, epichlorohydrin, dioxane, cellosolve acetate, methyl cellosolve, isopropyl alcohol, ethanol, methanol, and fluorocarbon solvents. , And a mixed solvent of these solvents and water can be used.

  Formation of the coating layer 200 with a silicone resin is performed by applying the silicone resin to the grinding surface 110 of the rubber layer 100.

After the coating step, firing is performed (firing step). The firing time varies depending on the firing temperature, but is preferably about 30 to 60 minutes, for example. The firing temperature varies depending on the type of rubber composition used for the rubber layer 100. For example, when the rubber composition is formed of fluoro rubber (FKM), the usable temperature range of fluoro rubber is about −30 to 230 ° C., and therefore the temperature range where baking can be performed is around 250 ° C. desirable. For example, when the rubber composition is formed of hydrogenated nitrile rubber (HNBR), the usable temperature range of hydrogenated nitrile rubber is about −40 to 120 ° C. The vicinity of 160 ° C. is desirable. For example, when the rubber composition is formed of ethylene propylene rubber (EPM / EPDM), the usable temperature range of EPDM is about −40 to 150 ° C., and therefore the temperature range where baking can be performed is 160. The vicinity of ° C is desirable.
By performing baking, the laminated body 900 which concerns on embodiment is obtained.

(Seal member)
The laminate according to this embodiment can be used as the seal member 800. As shown in FIG. 5, the seal member 800 is a ring having a substantially C-shaped cross section. The seal member 800 according to this embodiment is, for example, a gasket that is attached to a fuel cap of an automobile.

  A first lip 510 is formed at the lower end portion of the C shape of the seal member 800, and a second lip 520 is formed at the upper end portion of the C shape. The first lip 510 and the second lip 520 are connected by a connecting portion 530.

  The first lip 510 is pressed against the filler neck 210 at the first seal wall surface 511. The second lip 520 is pressed against the seal holding member 230 by the second seal wall surface 521. A screw-like tank port 220 is provided below the seal holding member 230.

  The seal member 800 is formed with the coating layer 200 on the outside and the rubber layer 100 on the inside. The main surface of the rubber layer 100 is a ground surface 110 ground with a grindstone, and the coating layer 200 is formed on the ground surface 110.

The material forming the rubber layer 100 is not particularly limited. For example, as described above, the rubber layer 100 is formed of nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), fluorine rubber (FKM), acrylic rubber (ACM / ANM), or the like. can do.
Further, as described above, the coating layer 200 can be formed of a fluororesin, molybdenum disulfide, a silicone resin, or the like.

  Since the inside of the seal member 800 is formed of the rubber layer 100, there is no possibility that fuel from the inside of the tank flows out to the outside. And since the outer side of the sealing member 800 is formed with the coating layer 200, the slidability of the part which contact | connects the filler neck 210 and the seal holding member 230 can be improved. Furthermore, since the coating layer 200 is formed on the ground surface 110 of the rubber layer 100, even if the seal member 800 is used in a low temperature region or a high temperature region, the coating layer 200 may be peeled off, cracks, etc. It is unlikely to occur.

(Embodiment 2)
[Laminate]
In the laminate 900 according to the present embodiment, as shown in FIG. 3, the grinding surface 110 has a tapered surface that is ground with a grindstone at the end of the main surface of the rubber layer 100.

  When the laminated body 900 is formed on a metal workpiece, when the metal workpiece and the rubber base material are vulcanized and bonded, the central portion of the rubber base material may be recessed while the both end portions of the rubber base material may be raised. Then, after performing vulcanization adhesion, the edge part of the main surface of a rubber base material is ground with a grindstone. Then, even if both end portions of the rubber base material are raised, the main surface of the rubber base material can be kept flat, so that the coating layer 200 is not easily peeled off or cracks are generated.

  As shown in FIG. 4, the taper angle Θ of the tapered surface is preferably 5 degrees or more and 15 degrees or less. This is because when the taper angle Θ is smaller than 5 degrees, the taper angle may be small and the flatness of the main surface of the rubber base material may not be secured. On the other hand, if the taper angle Θ is greater than 15 degrees, the taper surface may be too angled and the flatness of the taper surface may be lost.

[Method for producing laminate]
Below, the manufacturing method of the laminated body 900 which concerns on this embodiment is demonstrated.
The process up to grinding one main surface of the sheet-like rubber layer 100 with a grindstone is similar to the grinding process according to the first embodiment.

  Next, a tapered surface is formed by grinding an end portion of one main surface of the rubber layer 100 with a grindstone. The taper angle of the tapered surface is preferably 5 degrees or more and 15 degrees or less.

  As the grindstone, for example, a grindstone whose tip is formed of a bell-shaped grinding portion is used. And after making a grindstone incline at a predetermined angle with respect to the perpendicular of a bell-shaped grinding part, a grindstone is made to contact | abut to the edge part of one main surface of the rubber layer 100. FIG. And while rotating a grindstone, it grinds and removes only predetermined depth, and this performs rough finishing grinding of the edge part of one main surface of the rubber layer 100. Next, the grindstone is further brought closer to the end of one main surface of the rubber layer 100 by a slight distance, and is ground and removed by a slight depth, thereby performing finish grinding.

  After grinding one main surface of the sheet-like rubber layer 100 with a grindstone, the coating layer 200 is formed on the grinding surface 110 as in the first embodiment. And baking is performed. Thereby, the laminated body 900 which concerns on Embodiment 2 can be obtained.

(Other embodiments)
In the above-described embodiment, the laminate 900 is used as a seal member. But it is not limited to this, It can use for a roll material, packing, a diaphragm, a valve | bulb, a hose member, etc. In these applications, the rigid insert is indispensable.

  In the embodiment of the method for manufacturing the laminate 900 described above, the laminate 900 is formed on a metal workpiece, but the present invention is not limited to this. It is also possible to form the laminate 900 regardless of the metal workpiece. Even in such a case, since it is firmly bonded to the rubber layer 100 via the ground surface 110, the coating layer 200 is hardly peeled off from the rubber layer 100, and the advantage of the present invention that cracking of the coating layer 200 is hardly generated. Is enjoyed.

  In the embodiment of the manufacturing method of the laminate 900 described above, the metal workpiece has a container shape. However, the metal workpiece is not limited to this, and a metal workpiece having various shapes such as a tubular shape, a flat plate shape, a conical shape, a spherical shape, or the like is used. It is possible.

  The laminated body 900 which concerns on embodiment is not limited to a sheet-like laminated body, The form is not ask | required. For example, a container-shaped laminated body 900 such as a fuel tank or a chemical tank in which a coating layer 200 is formed as an inner layer in contact with gasoline or the like and a rubber layer 100 is formed on the outer peripheral surface of the inner layer is also possible.

  In the above-described embodiment, the grindstone used for grinding is of the same kind with respect to the kind of grindstone, the particle size, the degree of bonding, the binder, and the structure of the grindstone. However, it is not limited to such an embodiment. The grindstone used for grinding may be a grindstone using at least one of different types of grindstones in terms of grain type, particle size, bonding degree, binder and grindstone structure.

  In the above-described embodiment, the coating layer 200 is formed on the ground surface 110 of the rubber layer 100 without using an adhesive. However, the present invention is not limited to such an embodiment, and an adhesive can also be used.

Example 1
[Laminated body 900 according to Example 1]
In the laminate 900 according to Example 1, hydrogenated nitrile rubber (HNBR) was used as the rubber composition forming the rubber layer 100. As HNBR, “ZETPOL” manufactured by Zeon Corporation was used. The thickness of the rubber layer 100 was 2 mm.
Tetrafluoroethylene / hexafluoropropylene copolymer (FEP) was used as the resin forming the coating layer 200.

[Production of Laminate 900 According to Example 1]
First, a container-shaped metal workpiece made of copper was prepared. And the shot blasting process was performed to the metal workpiece. Next, a vulcanized adhesive was applied to the metal workpiece. As the vulcanized adhesive, a top coat “Metallock F-16” / undercoat “Metallock PH-50” manufactured by Toyo Chemical Co., Ltd. was applied. Then, it was dried at 120 ° C. for 10 minutes. And the rubber layer 100 was put in the metal workpiece | work which apply | coated the vulcanization adhesive agent, and pressure bonding was performed. As the rubber composition for forming the rubber layer 100, hydrogenated nitrile rubber (HNBR) was used.
Next, one main surface of the rubber layer 100 was ground with a grindstone. As the grindstone, a grindstone (VRG) manufactured by Noritake Company was used. The dresser used was a rotary dresser.
Thereafter, degreasing and washing were performed with ethyl alcohol, and FEP was coated. And it baked at 160 degreeC. This obtained the laminated body 900 which concerns on Example 1. FIG.

[Low temperature pressurization test]
In an atmosphere of −35 ° C., the laminate 900 according to Example 1 was tested for the presence or absence of cracks and wrinkles during pressing (low temperature pressing test).
In the low-temperature pressurization test, the laminate 900 was allowed to stand, and the coating layer 200 was placed in a −35 ° C. atmosphere in contact with a stainless steel valve seat. A tension was applied to the laminate 900 with a stainless steel valve seat, and the laminate 900 was pressurized until it reached 50N. The pressurization with the stainless steel valve seat was repeated three times, and it was visually confirmed whether cracks or wrinkles occurred on the surface of the coating layer 200.
As a result of the low-temperature pressurization test, no cracks or wrinkles occurred in the laminate 900 according to Example 1.

[High-temperature pressurization test]
Moreover, the presence or absence of the generation | occurrence | production of the crack at the time of pressurization and a wrinkle was tested about the laminated body 900 which concerns on Example 1 in 120 degreeC atmosphere (high temperature pressurization test).
The high temperature pressurization test was performed under the same conditions except that the ambient temperature was changed from -35 ° C to 120 ° C in the low temperature pressurization test.
As a result of the high-temperature pressurization test, no cracks or wrinkles occurred in the laminate 900 according to Example 1.

[Low temperature bending test]
Next, in a −35 ° C. atmosphere, the laminate 900 according to Example 1 was tested for the occurrence of cracks and wrinkles during bending (low temperature bending test).
In the low-temperature bending test, both ends of the laminate 900 were gripped and the central portion of the laminate 900 was bent in an atmosphere of −35 ° C. The folding was performed so that the rubber layer 100 was on the inside and the coating layer 200 was on the outside. The folding was performed until the folded rubber layer 100 reached about 30 degrees. Then, it was visually confirmed whether cracks or wrinkles were generated on the surface of the coating layer 200 (low temperature bending test).
As a result of the low-temperature bending test, no cracks or wrinkles occurred in the laminate 900 according to Example 1.

[High temperature bending test]
Moreover, the presence or absence of the crack at the time of a bending | bending and wrinkles generation | occurrence | production was tested about the laminated body 900 which concerns on Example 1 in 120 degreeC atmosphere (high temperature bending test).
The high temperature bending test was performed under the same conditions except that the ambient temperature was changed from −35 ° C. to 120 ° C. in the low temperature bending test.
As a result of the high temperature bending test, no cracks or wrinkles occurred in the laminate 900 according to Example 1.

[Low temperature restoration test]
Next, about the laminated body 900 which concerns on Example 1, the recovery rate of the elongation when the test piece which gave fixed expansion and was frozen was gradually heated was measured (TR test-JISK6261). The freezing temperature was −70 ° C., and the temperature was raised at a rate of temperature rise of 2 ° C./2 min. And temperature (TR10) when rubber | gum shrink | contracted 10% was measured. As for the laminated body 900 which concerns on Example 1, TR10 was -31 degreeC.
On the other hand, as a comparative example, TR10 was measured for a rubber layer of hydrogenated nitrile rubber (HNBR) having a thickness of 2 mm without the coating layer 200, and it was -31 ° C.
As a result of the low temperature restoration test, no cracks or wrinkles occurred in the laminate 900 according to Example 1.
In addition, it was found that the low temperature restoration test of the laminate 900 according to Example 1 was almost the same as the rubber layer not having the coating layer 200. Thereby, it turned out that the laminated body 900 which concerns on Example 1 has substantially the same rigidity as the rubber layer which does not have the coating layer 200. FIG.

(Example 2)
[Laminated body 900 according to Example 2]
In the laminate 900 according to Example 2, fluororubber (FKM) was used as the rubber composition forming the rubber layer 100. Other than that was the same as the laminate 900 according to Example 1. As the fluoro rubber, DuPont “Viton” was used.

[Production of Laminate 900 According to Example 2]
Example 1 except that a silane-based adhesive is used as a vulcanized adhesive for performing vulcanization adhesion between the metal workpiece and the rubber layer 100, and the firing temperature after forming the coating layer 200 is 250 ° C. It was the same as the manufacturing method concerning.

[Low temperature pressurization test]
In a −35 ° C. atmosphere, the laminate 900 according to Example 2 was tested for occurrence of cracks and wrinkles during pressing (low temperature pressing test). The test was performed in the same manner as in Example 1.
As a result of the low-temperature pressurization test, no cracks or wrinkles occurred in the laminate 900 according to Example 2.

[High-temperature pressurization test]
Moreover, the presence or absence of the generation | occurrence | production of the crack at the time of pressurization and a wrinkle was tested about the laminated body 900 which concerns on Example 2 in 120 degreeC atmosphere (high temperature pressurization test). The test was performed in the same manner as in Example 1.
As a result of the high-temperature pressurization test, no crack or wrinkle occurred in the laminate 900 according to Example 2.

[Low temperature bending test]
Next, in a −35 ° C. atmosphere, the laminate 900 according to Example 2 was tested for the presence or absence of cracks and wrinkles during bending (low temperature bending test). The test was performed in the same manner as in Example 1.
As a result of the low temperature bending test, no cracks or wrinkles occurred in the laminate 900 according to Example 2.

[High temperature bending test]
Moreover, the presence or absence of the generation | occurrence | production of the crack at the time of a bending and a wrinkle was tested about the laminated body 900 which concerns on Example 2 in 120 degreeC atmosphere (high temperature bending test). The test was performed in the same manner as in Example 1.
As a result of the high temperature bending test, no cracks or wrinkles occurred in the laminate 900 according to Example 2.

[Low temperature restoration test]
Next, about the laminated body 900 which concerns on Example 2, the recovery rate of the expansion | extension when a test piece which gave fixed expansion | extension and was frozen was heated up gradually was measured (TR test-JISK6261). The test was performed in the same manner as in Example 1.
It was found that the low temperature restoration test of the laminate 900 according to Example 2 was almost the same as the rubber layer without the coating layer 200.

(Example 3)
[Laminated body 900 according to Example 3]
In the laminate 900 according to Example 3, an ethylene-propylene-diene terpolymer (EPDM) was used as the rubber composition forming the rubber layer 100. Other than that was the same as the laminate 900 according to Example 1. As the EPDM, “Esprein EPDM” manufactured by Sumitomo Chemical Co., Ltd. was used.

[Manufacture of Laminate 900 according to Example 3]
As the vulcanization adhesive for performing vulcanization adhesion between the metal workpiece and the rubber layer 100, a hyperon adhesive was used, and the others were the same as in the manufacturing method according to Example 1.

[Low temperature pressurization test]
In a −35 ° C. atmosphere, the laminate 900 according to Example 3 was tested for occurrence of cracks and wrinkles during pressurization (low temperature pressurization test). The test was performed in the same manner as in Example 1.
As a result of the low-temperature pressurization test, no cracks or wrinkles occurred in the laminate 900 according to Example 3.

[High-temperature pressurization test]
Moreover, the presence or absence of the generation | occurrence | production of the crack at the time of pressurization and a wrinkle was tested about the laminated body 900 which concerns on Example 3 in 120 degreeC atmosphere (high temperature pressurization test). The test was performed in the same manner as in Example 1.
As a result of the high-temperature pressurization test, no cracks or wrinkles occurred in the laminate 900 according to Example 3.

[Low temperature bending test]
Next, in a −35 ° C. atmosphere, the laminate 900 according to Example 3 was tested for the occurrence of cracks and wrinkles during bending (low temperature bending test). The test was performed in the same manner as in Example 1.
As a result of the low temperature bending test, no cracks or wrinkles occurred in the laminate 900 according to Example 3.

[High temperature bending test]
In addition, in a 120 ° C. atmosphere, the laminate 900 according to Example 3 was tested for the presence or absence of cracks and wrinkles during bending (high temperature bending test). The test was performed in the same manner as in Example 1.
As a result of the high temperature bending test, no cracks or wrinkles occurred in the laminate 900 according to Example 3.

[Low temperature restoration test]
Next, about the laminated body 900 which concerns on Example 3, the recovery rate of elongation when the test piece which gave fixed expansion | extension and was frozen was heated up gradually was measured (TR test-JISK6261). The test was performed in the same manner as in Example 1.
It was found that the low-temperature restoration test of the laminate 900 according to Example 3 was almost the same as the rubber layer not having the coating layer 200.

FIG. 3 is a diagram illustrating a cross section of a stacked body according to the first embodiment. It is a figure which expands and demonstrates the grinding surface of the laminated body which concerns on Embodiment 1. FIG. It is a figure explaining the cross section of the laminated body which concerns on Embodiment 2, and is a figure in which the taper part is formed. It is a figure which expands and demonstrates the taper part of the grinding surface of the laminated body which concerns on Embodiment 2. FIG. It is a figure explaining the sealing member using the layered product concerning an embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Rubber layer 110 Grinding surface 200 Coating layer 230 Seal holding member 510 1st lip 511 1st seal wall surface 520 2nd lip 521 2nd seal wall surface 530 Connection part 800 Seal member 900 Laminate

Claims (13)

A rubber layer as a base material having a grinding surface obtained by grinding one main surface with a grindstone;
A coating layer formed on the ground surface of the rubber layer;
A laminate characterized by comprising: The grinding surface is a flat surface,
The laminate according to claim 1. The ground surface has a tapered surface ground with a grindstone at the end of the main surface of the rubber layer.
The laminate according to claim 1. The taper angle of the tapered surface is not less than 5 degrees and not more than 15 degrees.
The laminate according to claim 3. As for the surface roughness of the ground surface, the maximum height is 3.2 μm or more and 6.3 μm or less.
The laminate according to any one of claims 1 to 4, wherein the laminate is any one of the above. The rubber layer is made of nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), carboxylated nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR), fluorine rubber (FKM), acrylic rubber (ACM / ANM) Polyester urethane rubber (AU), polyether urethane rubber (EU), ethylene propylene rubber (EPM / EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), epichlorohydrin rubber (ECO), natural rubber (NR) ), Isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), vinyl methyl silicone rubber (VMQ), fluorinated silicone rubber (FVMQ), polysulfide rubber (T) and norbornene Formed from rubber containing at least one of rubber (NOR),
The laminate according to any one of claims 1 to 5, wherein: The coating layer contains at least one of fluorine resin, silicone resin, molybdenum disulfide, tungsten disulfide, graphite, boron nitride, and boron nitrite.
The laminate according to any one of claims 1 to 6, wherein: A grinding process of grinding one main surface of the rubber layer with a grindstone to form a ground surface;
A coating step of forming a coating layer on the ground surface of the rubber layer;
The manufacturing method of the laminated body characterized by having. In the grinding step, the grinding surface is formed into a flat surface.
The manufacturing method of the laminated body of Claim 8 characterized by the above-mentioned. In the grinding step, further, an end of one main surface of the rubber layer is ground with a grindstone to form a tapered surface.
The manufacturing method of the laminated body of Claim 8 characterized by the above-mentioned. The taper angle of the tapered surface is not less than 5 degrees and not more than 15 degrees.
The manufacturing method of the laminated body of Claim 10 characterized by the above-mentioned. In the grinding step, the surface roughness of the grinding surface ground by the grindstone has a maximum height of 3.2 μm or more and 6.3 μm or less.
The method for manufacturing a laminate according to any one of claims 8 to 11, wherein: A seal member that is sandwiched between a pair of components that slide with respect to the other component and seals these gaps,
As a material of the sealing member, the laminate according to any one of claims 1 to 7, wherein the coating layer is disposed on the one component side, and the rubber layer is disposed on the other component side. Use
The sealing member characterized by the above-mentioned.

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