JP5226741B2 - Rubber composition and rubber member - Google Patents

Description

  The present invention relates to a rubber composition and a rubber member obtained by crosslinking the rubber composition. Moreover, this invention relates to the rubber member formed by bridge | crosslinking the rubber composition used for a conveyance roller or a sealing member of a flat panel display manufacturing apparatus or a glass manufacturing apparatus.

  A glass substrate used in a flat panel display (FPD) such as a liquid crystal display, a plasma display, and an organic EL display uses a roller conveyance type apparatus that is conveyed by a conveyance roller in and between processes in the manufacturing process. There is a case. For example, in the liquid crystal display manufacturing process, thin film transistors (TFTs) and color filters are formed by repeating processes such as substrate acceptance inspection, cleaning, film formation, exposure, development, etching, resist stripping, and inspection. And between processes, a glass substrate is often conveyed with the apparatus of a roller conveyance system. Also, in the manufacture of plate glass as a raw material for a glass substrate, there are cases where it is transported by a transport roller in processes such as cutting, chamfering, polishing, cleaning, drying, inspection, and movement between processes. For example, the transport roller has a structure in which an O-ring made of rubber is attached to a cylindrical rotating shaft. A glass substrate is placed on the plurality of conveying rollers arranged in a row, and the glass substrate is conveyed by rotating the conveying roller. As an example of equipment provided with the transport roller, Patent Document 1 discloses a cleaning equipment provided with a transport device that transports a glass substrate using a roller to which an O-ring made of rubber is attached.

  In the equipment provided with the transport roller, there is a problem that dust particles adhere to the glass substrate. Causes of the particles include friction with the glass substrate, adhesion of abrasion powder generated by contact with the edge of the glass substrate, transfer of dirt accumulated on the conveyance roller to the glass substrate, and the like. For example, Patent Document 2 has a problem that abrasion powder generated due to damage to the conveyance roller due to contact of the glass substrate edge portion with the conveyance roller, and that the abrasion powder is transferred to the back surface of the substrate. The conveyance roller in the processing area is a cylindrical roller (the roller outer layer is an elastic body such as urethane rubber), and the conveyance roller in the dry area is a disc roller (for example, cast metal or injection molded plastic (for example, polyethylene) As a material that is hard to wear, such as polypropylene), the edge of the substrate is prevented from coming into contact with the transport roller, thereby reducing the damage to the transport roller and reducing the transfer of dirt to the back surface of the substrate. It is disclosed. Patent Document 3 discloses a conveying roller characterized in that the position of the parting line of the O-ring is at a position different from the contact surface with the conveyed object, and that the O-ring is made of a nonmetallic element. According to the transport roller, particles accumulated in the parting line of the O-ring do not adhere to transported objects such as glass substrates and semiconductor wafers, and even if the O-ring wears, metal does not deposit on the surface. It is said that the particles accumulated on the surface and the wear powder of the O-ring do not cause particles of the conveyed product.

  As a rubber member for a transport roller, Patent Document 4 discloses that polyfunctional non-functional per 100 parts by mass of peroxide-crosslinkable fluororubber having a fluorine content of 68% by mass or more as an O-ring considering plasma resistance. A fluororubber composition containing 0.7 to 2.4 parts by mass of a saturated compound and 0.3 to 1.0 part by mass of an organic peroxide is disclosed, and a vulcanized molded product obtained from the fluororubber composition Has good plasma resistance and shows the normal physical property value and compression set value necessary for a seal, and is suitable for use in parts of semiconductor manufacturing equipment and liquid crystal manufacturing equipment, such as seals and transport rollers. It is supposed to be possible.

JP 2004-262626 A JP 2003-124285 A JP 2004-277096 A JP 2008-056739 A

  However, the conveyance rollers disclosed in Patent Documents 1 to 4 have the following problems. That is, in the conveyance rollers of Patent Documents 1 to 4, it is inevitable that the rubber member or the elastic body of the conveyance roller in contact with the glass substrate is worn due to the conveyance of the glass substrate. There is a problem that the abrasion powder adheres to the glass substrate. In addition, the conveyance rollers of Patent Documents 1 to 4 have a problem that resistance to chemicals used in a cleaning process, a wet etching process, and the like in the FPD manufacturing process is not considered. Currently, a rubber member for a transport roller used when transporting a glass substrate from a so-called wet process step or wet process step such as a glass substrate cleaning step or wet etching step in the FPD manufacturing process to the next step is a cleaning liquid or the like. Perfluoroelastomer (FFKM) and special chemical-resistant fluororubber (chemical-resistant FKM) are used in consideration of resistance to chemicals, etc., but the entire FPD manufacturing process including parts that do not come into contact with chemicals In many cases, rubber members for transport rollers made of FFKM or chemical resistant FKM are used. However, since FFKM and chemical-resistant FKM are very expensive, a low-cost rubber member for a conveyance roller is required.

  If the resistance to the chemical is not taken into account, there is a risk that the rubber member may swell or deteriorate due to the chemical. Further, even in applications that do not come into contact with the chemical, if the relaxation of the tensile stress of the rubber member is not taken into account, there is a possibility that a problem that the tightening force of the rubber member is lowered early. When a conveyed product is conveyed by the conveyance roller using the rubber member, any problem occurs, causing the rubber member to idle or wear.

  The present invention pays attention to the above-mentioned problems and has a good chemical resistance in the FPD manufacturing process. When the rubber member is crosslinked and used as a rubber member for a conveying roller of a glass substrate, the rubber member generated by conveying the conveyed item It is an object of the present invention to provide a rubber member in which the wear powder is hardly adhered to the glass substrate.

  Another object of the present invention is to provide a rubber member for a conveyance roller that does not idle for a long period of time.

  The organic peroxide is 0.5 to 3 parts by mass and the polyfunctional unsaturated compound is 1 to 5 parts by mass per 100 parts by mass of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. Hereinafter, the rubber composition is characterized in that the carbon black is 5 parts by mass or more and 60 parts by mass or less and the inorganic compound excluding the carbon black is 1 part by mass or less.

The carbon black may have an average particle diameter of 30 nm to 600 nm and a nitrogen specific surface area of 5 to 80 m ² / g.

  You may use the said rubber composition for a conveyance roller or a seal | sticker of a flat panel display manufacturing apparatus or a glass manufacturing apparatus.

  It is also a rubber member formed by crosslinking the rubber composition.

  According to the present invention, general-purpose fluororubber is used and chemical resistance is good without using expensive fluororubber such as perfluoroelastomer (FFKM) and special chemical-resistant fluororubber (chemical-resistant FKM, etc.). Thus, when used as a rubber member for a conveying roller, a rubber member is provided in which the abrasion powder of the rubber member is extremely less sticky to the conveyed product. Therefore, it can be suitably used for a rubber member used for a conveyance roller or a seal of a flat panel display manufacturing apparatus and a glass manufacturing apparatus.

It is a perspective view of the abrasion test apparatus for testing the adhesiveness of abrasion powder. A test O-ring is inserted into an O-ring holder, (a) a plan view thereof, (b) a cross-sectional front view taken along arrow XX ', and (c) a cross-sectional side view taken along arrow YY'. And (d) is an enlarged view of a groove.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. The rubber composition of the present invention is a polyfunctional unsaturated compound containing 0.5 to 3 parts by mass of organic peroxide per 100 parts by mass of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. Is 1 part by mass or more and 5 parts by mass or less, carbon black is 5 parts by mass or more and 60 parts by mass or less, and the inorganic compound excluding carbon black is 1 part by mass or less.

  In the rubber composition of the present invention, it is preferable to use fluororubber from the viewpoint that chemical resistance is required, and among these, organic from the point that resistance to chemicals used for substrate cleaning in a glass substrate transfer device is extremely excellent. It is more preferable to use fluorine rubber capable of peroxide crosslinking, and when used as a rubber member for a glass substrate transport roller, the abrasion powder generated from the rubber member for the transport roller adheres to the glass substrate being transported. Since it is difficult, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber capable of organic peroxide crosslinking is more preferable. Examples of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber capable of peroxide crosslinking include a reactive halogen group (for example, a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber). And vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber capable of peroxide crosslinking, in which an organic peroxide crosslinking group such as olefin bromide or iodine olefin is introduced.

  The fluorine content in the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber capable of crosslinking the organic peroxide is preferably 67% by mass or more and 72% by mass or less, more preferably 67% by mass or more. It is 71 mass% or less. When the fluorine content is 67% by mass or more and 72% by mass or less, it is preferable because optimum compression set characteristics as a rubber member for sealing can be obtained, and when it is 72% by mass or less, polyfunctionality in the rubber composition is obtained. It is preferable because the dispersion of the unsaturated compound is good, and it is preferably 67% by mass or more and 71% by mass or less because it is easily available commercially.

  The vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber capable of organic peroxide crosslinking suitable for the present invention is, for example, Daiel G-912 (manufactured by Daikin Industries), Daiel G-901 (Daikin). Kogyo), Daiel G-902 (Daikin Kogyo), Daiel G-952 (Daikin Kogyo), Daiel G-9062 (Daikin Kogyo), Daiel G-9074 (Daikin Kogyo), Daiel G-9503 (Daikin Industries), Viton GF-600S (DuPont Elastomer), Technoflon P959 (Solvay Solexis), Technoflon P459 (Solvay Solexis), Technoflon P757 (Solvay Solexis) Or Technoflon P457 (Solvay Solexis) Etc. may be obtained commercially. These vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene-based copolymer rubbers may be used singly or in combination of two or more.

  As the organic peroxide, a known organic peroxide crosslinking agent for rubber can be used. Examples of the organic peroxide include o-methylbenzoyl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxypivalate, t- Butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5- One or more selected from di (t-butylperoxy) -hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane or di-t-butylperoxide Can be used in combination.

  In order to reduce the adhesion of the abrasion powder generated from the rubber member for the conveying roller to the glass substrate and to suitably exhibit the compression set suitable for the rubber member for sealing, the vinylidene fluoride-tetra The blending amount of the organic peroxide is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the fluoroethylene-hexafluoropropylene-based copolymer rubber, and when the blending amount of the organic peroxide is reduced, the wear powder glass Since the amount of adhesion to the substrate tends to increase, 0.7 parts by mass or more is more preferable, and 1.0 part by mass or more is even more preferable. On the other hand, when the amount of the organic peroxide is increased, the crosslinking rate tends to increase, and therefore, there is a possibility that the scorch is generated during molding, which may cause a problem in moldability. In order to obtain, the organic peroxide is preferably 3 parts by mass or less, and preferably 2 parts by mass or less with respect to 100 parts by mass of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. Is more preferable.

  Examples of the polyfunctional unsaturated compound include quinone dioxime (p-quinone dioxime, etc.), methacrylate (triethylene glycol dimethacrylate, methyl methacrylate, trimethylolpropane trimethacrylate, etc.), allyl (diallyl). Phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, etc.), maleimide (maleimide, phenylmaleimide, N, N′-m-phenylenebismaleimide, etc.), maleic anhydride, divinylbenzene, vinyltoluene Or it selects from polyfunctional unsaturated compounds, such as 1, 2- polybutadiene, etc., and can be used 1 type or in combination of 2 or more types.

  The vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber 100 is used in order to reduce the adhesion of wear powder generated from the rubber member to the conveyed product and to obtain a compression set suitable for the seal member. The blending amount of the polyfunctional unsaturated compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to part by mass, in order to more suitably promote the crosslinking reaction by the organic peroxide. More preferably, it is 2.5 parts by mass or more. On the other hand, the polyfunctional unsaturated compound has poor compatibility with the fluororubber, so when blended in a large amount, the polyfunctional unsaturated compound aggregates or polymerizes at the time of molding and a polymer precipitates on the surface of the molded product, resulting in molding failure. In order to obtain suitable moldability, it is preferably 5 parts by mass or less with respect to 100 parts by mass of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. More preferably, it is 4 parts by mass or less.

  When the amount of the organic peroxide and the polyfunctional unsaturated compound is small in the rubber composition of the present invention, the rubber member obtained by crosslinking the rubber composition of the present invention tends to have a large tensile stress relaxation. is there. When the tensile stress relaxation of the rubber member is increased, the elastic force of the rubber member is relaxed when the rubber member is used for a long time as a rubber member for the conveyance roller, and the rotation of the rubber member is caused by the rotation of the axis of the conveyance roller. This is a problem because there is a risk of not following. Therefore, from the viewpoint of suppressing the relaxation of the tensile stress of the rubber member, in the rubber composition of the present invention, the organic peroxide is used with respect to 100 parts by mass of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. The blending amount of the polyfunctional unsaturated compound is required to be 1 part by mass or more.

  When the amount of the organic peroxide and the polyfunctional unsaturated compound is large in the rubber composition of the present invention, there is a problem in moldability such as an increase in defective rate. Therefore, from the viewpoint of good moldability of the rubber member, in the rubber composition of the present invention, the organic peroxide is used with respect to 100 parts by mass of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. It is necessary that the compounding amount of the product is 3 parts by mass or less, and the compounding amount of the polyfunctional unsaturated compound is 5.0 parts by mass or less.

  The carbon black is not particularly limited as long as it is generally used as a rubber compounding agent. Examples of the carbon black include SAF carbon black, ISAF carbon black, HAF carbon black, MAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, furnace black, FT carbon black, MT carbon black, etc. Thermal black, acetylene black, channel black, etc. are mentioned, It can use 1 type or in combination of 2 or more types.

  Carbon blacks suitable for the present invention include, for example, Thermax Floor N990 (MT carbon black, manufactured by Cancarb), Asahi Thermal (FT carbon, manufactured by Asahi Carbon), and Seest GS (SRF carbon black, manufactured by Tokai Carbon). Etc., and Dia Black G (GPF carbon black, manufactured by Mitsubishi Chemical Corporation), etc. can be commercially obtained.

  The carbon black is preferably 5 to 60 parts by mass and more preferably 10 to 50 parts by mass per 100 parts by mass of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. When the carbon black is 5 parts by mass or more, the adhesiveness of the abrasion powder generated from the rubber member to the glass substrate is lowered and can be easily removed without sticking, and the carbon black is 10 parts by mass or more. If so, there is very little adhesion of the abrasion powder generated from the rubber member to the glass substrate. When the carbon black is 60 parts by mass or less, the mixing processability is good, and the rubber composition has an optimum viscosity for processing and molding, so that the occurrence of poor rubber fusion during molding can be suppressed, etc. Good workability and moldability. In addition, the hardness of the rubber member is suitable as a conveying roller and a rubber member for sealing. When the rubber composition having a carbon black content of 50 parts by mass or less is crosslinked and used as a rubber member for a conveyance roller, the hardness becomes extremely optimum as the rubber member for the conveyance roller. Optimum gripping force is obtained and transport efficiency is improved.

  The average particle diameter of the carbon black is preferably 30 to 600 nm, more preferably 50 to 550 nm, from the viewpoint of tensile stress relaxation, compression set, mixing processability and moldability. In addition, the said average particle diameter measured the particle diameter of 1000 carbon black particles selected at random with the transmission electron microscope, and calculated | required the arithmetic average.

The nitrogen specific surface area in JIS K 6217-2 of carbon black, the tensile stress relaxation, compression set, in terms of the mixing processability and moldability, preferably 5~80m ² / g, more preferably 5 to 40 m ² / g.

  The iodine adsorption amount of the carbon black in JIS K 6217-1 is preferably 80 mg / g or less, more preferably 40 mg / g or less, from the viewpoint of relaxation of tensile stress, compression set, mixing processability and moldability. .

Further, DBP absorption amount in JIS K 6217-1 of the carbon black (A method), mixing processability, in terms of moldability, preferably 150 cm ^3/100 g or less, and more preferably not more than 100 cm ^3/100 g.

  Examples of the inorganic compound excluding carbon black include zinc oxide, magnesium oxide, and calcium hydroxide which are acid acceptors, and one or a combination of two or more can be used. In addition, because it is easy to handle, it is made into a powder by impregnating an inorganic compound such as diatomaceous earth, calcium carbonate, or silica with an organic peroxide or polyfunctional unsaturated compound that is a liquid compounding agent (supported product) Can be used. In addition, when a support product is mix | blended with a rubber composition, the inorganic compound component contained in the said support product will be contained in the said rubber composition as an inorganic compound except carbon black.

  When a large amount of the inorganic compound excluding carbon black is blended in the rubber composition of the present invention, a rubber member formed by crosslinking the rubber composition of the present invention is a chemical (for example, phosphoric acid, Nitric acid, acetic acid, mixed acid (such as a mixed solution of phosphoric acid, nitric acid and acetic acid), hydrochloric acid, oxalic acid solution, hydrogen peroxide solution or sodium hypochlorite solution) may swell greatly. When the rubber member swells, the physical properties of the rubber member deteriorate, and when used as a rubber member for a conveyance roller, the contact between the edge of the groove for fixing the rubber member provided on the conveyance roller and the rubber member increases, and This is a problem because the wear of the rubber member for rollers is increased. Therefore, from the point that the chemical resistance effect of the rubber member is sufficiently exerted, the inorganic compound excluding carbon black is added to 100 parts by mass of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. A compounding quantity is 1 mass part or less, Preferably it is 0.5 mass part or less.

  Examples of the rubber composition of the present invention include an anti-aging agent (for example, amine-based, phenol-based, and imidazole-based), a plasticizer (for example, a phthalic acid-based plasticizer (dioctyl phthalate), an adipic acid-based plasticizer ( Dioctyl adipate, etc.), sebacic acid plasticizer (dioctyl sebacate, etc.), trimellitic acid plasticizer (trimellitate, etc.), polymerization plasticizer (eg, polymerization plasticizer such as polyether or polyester)) or processing Additives generally used in the rubber industry such as auxiliaries (eg, stearic acid, palmitic acid, paraffin wax, etc.) can be added as necessary. In addition, the addition amount of each compounding agent can be suitably set as needed as long as the object of the present invention is not impaired.

  The rubber composition of the present invention is kneaded using a conventionally known kneader such as intermix, kneader, Banbury mixer, open roll or twin-screw kneading extruder, and then an injection molding machine, a compression molding machine, and a heating press machine. Alternatively, a rubber member can be obtained by crosslinking and molding into a desired shape using an extruder or the like. In the cross-linking molding, the rubber composition of the present invention performs peroxide cross-linking. Therefore, for example, after performing primary cross-linking at 140 ° C. to 200 ° C. for 2 to 30 minutes, 150 ° C. to 230 ° C. as necessary. It is preferable to carry out under the condition that secondary crosslinking is performed for 24 hours. By applying the secondary cross-linking, the wear powder generated from the rubber member adheres to the glass substrate as the transported object when used as a rubber member for the transport roller as compared with the rubber member only for the primary cross-link. And compression set can be reduced.

  The rubber member obtained in the present invention has a compression set of 40% or less tested under the test conditions of 25% compression and 200 ° C. for 70 hours using a large test piece according to JIS K 6262. Since the hardness measured with an instantaneous value by a Type A durometer based on 6253 is 55 to 90, it can be suitably used as a rubber member for a conveying roller or a seal.

  Further, the rubber member obtained in the present invention has a tensile stress relaxation after 30 minutes measured at an elongation rate of 20% and a test temperature of 40 ° C. in accordance with JIS K 6263, and is 10% or less. It can be used very suitably as a member or a rubber member for sealing.

  The shape of the rubber member of the present invention is not particularly limited, and is a composite formed by combining a ring shape such as an O-ring, a D-ring, a square ring, an X-ring, or a T-ring, a sheet shape, or a metal material or a resin material. Etc. are appropriately selected according to the purpose. The size of the rubber molded product is not particularly limited, and is appropriately selected according to the purpose.

  The rubber member obtained by the present invention is not easily adhered to the glass substrate due to the abrasion powder generated from the rubber member of the transport roller when transporting the glass substrate which is a transported object, and cleaning and etching of the glass substrate. For chemicals used in (for example, phosphoric acid, nitric acid, acetic acid, mixed acid (mixed solution of phosphoric acid, nitric acid and acetic acid, etc.), hydrochloric acid, oxalic acid solution, hydrogen peroxide solution or sodium hypochlorite solution) Since the resistance is extremely excellent, it can be suitably used as a rubber member for a glass substrate transport roller. Even if it is other than a glass substrate conveying roller, it can be suitably used as a rubber member for a conveying roller or the like that requires reduced adhesion of abrasion powder generated from the rubber member to the conveyed product and / or chemical resistance. In addition, since the compression set of the rubber member of the present invention is a value suitable for a seal, it can be applied to a rubber member for a seal of a device requiring chemical resistance such as a wet etching device or a cleaning device. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the material used in the Example etc. is as follows.

As fluoro rubber,
Daiel G-902 (manufactured by Daikin Industries): peroxide-crosslinked vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber, fluorine content of 71% by mass
Daiel G-952 (manufactured by Daikin Industries): peroxide crosslinked vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber, fluorine content 69 mass%
Technofluoron P 757 (manufactured by Solvay Solexis): peroxide-crosslinked vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber, fluorine content 67 mass%
Viton ETP-S (manufactured by DuPont Elastomer): peroxide-crosslinked tetrafluoroethylene-perfluoromethyl vinyl ether-ethylene copolymer rubber, fluorine content 67 mass%
Daiel G-801 (manufactured by Daikin Industries): peroxide-crosslinked vinylidene fluoride-hexafluoropropylene copolymer rubber, fluorine content 66 mass%,
Viton E-60C (manufactured by DuPont Elastomer): polyol-crosslinked vinylidene fluoride-hexafluoropropylene copolymer rubber, fluorine content 66 mass%
Viton B-61J (manufactured by DuPont Elastomer): polyol-crosslinked vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber, fluorine content of 68% by mass

As carbon black,
· Thermax Floform N990 (Cancarb Ltd.): MT carbon black, the average particle diameter of 500 nm, a nitrogen specific surface area of ^9m 2 / g, DBP absorption amount (A ^method) 43cm 3 / 100g
· SEAST G-S (manufactured by Tokai Carbon Co.): SRF carbon black, the average particle diameter of 66 nm, a nitrogen specific surface area of ^27m 2 / g, DBP absorption amount (A ^method) 68cm 3/100 g, iodine adsorption: 26 mg / g

As organic peroxide,
Perhexa 25B (manufactured by NOF Corporation): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (organic peroxide)
・ Lupelox 101XL (manufactured by Arkema Yoshitomi): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (organic peroxide) in calcium carbonate: silica 50 mass%: 50 mass% mixture 45% by weight impregnated powder

As polyfunctional unsaturated compounds,
TAIC (Nippon Kasei Co., Ltd.): triallyl isocyanurate (polyfunctional unsaturated compound)
TAIC M60 (manufactured by Nippon Kasei Co., Ltd.): Powder obtained by impregnating 60% by mass of triallyl isocyanurate (polyfunctional unsaturated compound) in diatomaceous earth.

As an inorganic compound excluding carbon black,
・ Zinc oxide 2 types (manufactured by Sakai Chemical Industry): Zinc oxide (acid acceptor)
・ Kyowa Mag 150 (manufactured by Kyowa Chemical Industry Co., Ltd.): Magnesium oxide (acid acceptor)
・ Caldic 2000 (Omi Chemical Co., Ltd.): Calcium hydroxide (acid acceptor)

  About Examples 1-17, Comparative Example 1, Comparative Example 2, and Comparative Examples 5-9, the rubber and compounding agent of the ratio shown in Tables 1-4 were knead | mixed with the open roll, and the rubber composition was adjusted. Next, the rubber composition was subjected to press crosslinking at 160 ° C. for 10 minutes using a press molding apparatus, and then secondary crosslinked at 200 ° C. for 4 hours to obtain a rubber member. In addition, the unit of the compounding quantity of Tables 1-4 is a mass part.

  In Comparative Examples 10 and 11, rubbers and compounding agents in the proportions shown in Table 5 were kneaded and crosslinked in the same manner as in Example 1 to obtain rubber members. In addition, the unit of the compounding quantity of Table 5 is a mass part.

  Comparative Examples 3 and 4 were carried out in the same manner as in Example 1 except that the rubber composition was press-crosslinked at 170 ° C. for 10 minutes, and then secondary crosslinked at 230 ° C. for 24 hours to obtain a rubber member.

  Of the organic peroxides and polyfunctional unsaturated compounds shown in Table 4, those supported on the carrier (Lupelox 101XL and TAIC M60) are organic peroxides or polyfunctionals in the rubber composition. It is interpreted that the organic unsaturated compound and the carrier (diatomaceous earth, calcium carbonate and silica) are separated and dispersed, and each component (organic peroxide, polyfunctional unsaturated compound and carbon black) is listed in the total amount column of Table 4 The number of parts by mass corresponding to the total blending amount for each inorganic compound) is calculated and shown.

  The rubber members obtained in Examples 1 to 17 and Comparative Examples 1 to 9 were used as samples, and the following (1) to (5) were evaluated, and (6) comprehensive evaluation was performed based on the results. The results are shown in Tables 1-4.

  Using the rubber members obtained in Comparative Examples 10 and 11 as samples, the following (1) to (5) were evaluated, and (6) comprehensive evaluation was performed based on the results. The results are shown in Table 5.

  Moreover, using the rubber members obtained in Examples 1 to 17 and Comparative Examples 5 to 11 as samples, the following (7) is evaluated, and (8) comprehensive evaluation based on the results of (6) and (7) 2 was carried out. The results are shown in Tables 1-5.

(1) Formability 20 G25 size O-rings described in JIS B 2401 were formed and visually checked for appearance, precipitates that appear to be a polymer of a polyfunctional unsaturated compound, molding defects due to scorch, rubber Those in which abnormalities considered to be caused by the blending composition such as poor fusion were confirmed as poor appearance and evaluated according to the following criteria.
○: 1 or less defective appearance of molded product ×: 2 or more defective appearance products

(2) Chemical resistance The volume change rate after immersing three G25 size O-rings described in JIS B 2401 in 150 ml of a test solution at 70 ° C. for 168 hours was determined. The volume change rate was measured according to JIS K 6258 and evaluated according to the following criteria.
○: Volume change rate is 10% or less
×: Volume change rate exceeds 10%

The test solutions used were selected from the seven types shown below as typical chemicals used for glass substrate cleaning and etching.
Nitric acid: 60-61 mass% nitric acid reagent [JIS K 8541] special grade (manufactured by Wako Pure Chemical Industries, Ltd.)
-Acetic acid: Adjusted by adding 100 g of acetic acid reagent [JIS K 8355] special grade (manufactured by Wako Pure Chemical Industries, Ltd.) to 100 ml of distilled water as 50 mass% acetic acid.
・ Phosphoric acid: 85% by mass or more Phosphoric acid reagent [JIS K 9005] Special grade (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Hydrochloric acid: 35 to 37 mass% hydrochloric acid reagent [JIS K 8180] special grade (manufactured by Wako Pure Chemical Industries, Ltd.)
-Hydrogen peroxide solution: 10% by mass hydrogen peroxide solution was prepared by adding 100 ml of about 30% hydrogen peroxide reagent [JIS K 8230] special grade (manufactured by Wako Pure Chemical Industries, Ltd.) to 200 ml of distilled water.
・ Sodium hypochlorite solution: Sodium hypochlorite solution with an effective chlorine concentration of 5% by mass or more for chemical use (Wako Pure Chemical Industries, Ltd.)
-Oxalic acid solution: 5 mass% oxalic acid solution: prepared by adding 98 g or more of oxalic acid reagent (manufactured by Wako Pure Chemical Industries) to 190 ml of distilled water.

(3) Adhesiveness of abrasion powder The adhesion of abrasion powder to the glass plate was confirmed using the abrasion test apparatus shown in FIG. That is, a glass plate 40 (Matsunami Glass Industrial Co., Ltd.) holding a test O-ring 10 of P20 size described in JIS B 2401 with an O-ring holder 20 having a mass of 2.5 N and fixing it to the test O-ring 10 and the movable mount 30. A large slide glass manufactured by the company is pressed by the mass of the O-ring holder 20, and the movable mount 30 with the glass plate 40 fixed by a driving device (not shown) is moved in one direction (arrow) at a speed of 50 times per minute. The glass plate 40 was taken out after 10,000 reciprocations, and the wear powder adhering to the glass plate 40 was visually confirmed and evaluated according to the following criteria.
○: Wear powder is not seen, or wear powder is generated and adhered to the glass surface, but can be easily removed by pouring ethanol using a 100 cc polyethylene washing bottle.
X: Wear powder that is observed in a state where the wear powder extends in the sliding direction of the O-ring and adheres to the glass surface, or that cannot be easily removed even when ethanol is poured using a 100 cc polyethylene washing bottle. It is attached.

  The O-ring holder 20 can be operated by the movable base 30 during the operation of the test apparatus by inserting the O-ring holder 20 into a circular hole provided in the upper part of the holder fixed base 60 fixed to the fixed base 50. The movable base 30 can be freely moved in the direction perpendicular to the operation direction. At this time, the O-ring holder 20 and the holder fixing base 60 are close to each other so that there is no problem in the mobility of the O-ring holder 20 at the O-ring holder insertion portion I. There is no contact at any site.

  Further, as shown in FIG. 2, the O-ring fixing groove of the O-ring holder 20 has a dovetail shape so that the test O-ring 10 does not fall off. The size of the O-ring fixing groove is as follows: O-ring fixing groove center diameter φ = 22.2 mm, O-ring fixing groove opening width d = 2.22 mm, O-ring fixing groove depth h = 1.8 mm, and groove angle θ = 66 .6 °, dovetail groove bottom radius r1 = R0.2, dovetail groove opening edge radius r2 = R0.2.

  Here, the dovetail groove radius r1 = R0.2 is the dovetail groove radius r1 = 0.2 mm, and the dovetail groove opening edge radius r2 = R0.2 is the dovetail groove opening edge radius r2. = 0.2 mm.

(4) Compression set According to JIS K 6262, a large test piece was used and tested under test conditions of 25% compression and 200 ° C. for 70 hours, and evaluated according to the following criteria.
○: Compression set is 40% or less ×: Compression set exceeds 40%

(5) Hardness Based on JIS K 6253, an instantaneous value (a numerical value read at the moment when the pressure plate was brought into contact with the test piece) was measured by a type A durometer and evaluated according to the following criteria. In Tables 1 to 5, the actually measured values and ◯ × evaluation are described.
○: 55-90
X: Less than 55 or more than 90

(6) Comprehensive evaluation It evaluated on the following references | standards from the test result of said (1)-(5).
○: In evaluations (1) to (5), all are ○ ×: In evaluations (1) to (5), there are one or more x

(7) Tensile stress relaxation In accordance with JIS K 6263 tensile stress relaxation test method A, the test piece shape strip No. 1 was stretched by 20% at a test temperature of 40 ° C. and 100 mm / min. Measured and evaluated according to the following criteria. In Tables 1 to 5, the actually measured values and ◯ × evaluation are described.
○: Tensile stress relaxation is 10% or less ×: Tensile stress relaxation exceeds 10%

(8) Overall evaluation 2
From the test results of (6) and (7), the evaluation was made according to the following criteria.
○: In evaluation (6) and (7), both are ○ ×: In evaluation (6) and (7), there is one or more x

  Table 1 evaluates Examples (Examples 1 to 3) and Comparative Examples (Comparative Examples 1 to 4) using fluororubbers having different chemical structures, fluorine contents, or crosslinking methods. Examples 1 to 3 use an organic peroxide cross-linked vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber, and the overall evaluation and the overall evaluation 2 are “◯” judgments. I understood.

  On the other hand, Comparative Example 1 uses a peroxide-crosslinked tetrafluoroethylene-perfluoromethyl vinyl ether-ethylene copolymer rubber, which is an expensive and special chemical-resistant fluororubber that is currently used. Although vinylidene fluoride-hexafluoropropylene copolymer rubber is used, it was found that the wear powder generated from the rubber member easily adheres to the conveyed product.

  Comparative Example 3 and Comparative Example 4 both use polyol-crosslinked fluororubber, but when compared with Examples 1 to 3, the abrasion powder generated from the rubber member tends to stick to the conveyed product, It was found that chemical resistance was also poor.

  Table 2 evaluates Example 1 and Examples (Examples 4 to 8) in which the organic peroxide blending amount and / or the polyfunctional unsaturated compound blending amount of Example 1 are different. In Example 1 and Examples 4 to 8, the organic peroxide compounding amount was 0.5 to 3 parts by mass, or the polyfunctional unsaturated compound compounding amount was 1 to 5% by mass. In the above range, it was confirmed that the overall evaluation and the overall evaluation 2 were “◯”.

  Table 5 evaluates comparative examples (Comparative Examples 10 and 11) in which the organic peroxide blending amount of Example 1 and the blending amount of the polyfunctional unsaturated compound are different. The range of the compounding amounts of the organic peroxide and the polyfunctional unsaturated compound in Comparative Examples 10 and 11 is the range of the examples in Table 2. “The compounding amount of the organic peroxide is 0.5 to 3 parts by mass. Or, if the compounding amount of the polyfunctional unsaturated compound is outside the range of 1% to 5% by mass and below the minimum value in the above range, there is a problem with the adhesiveness of the wear powder, compression set, and relaxation of tensile stress. It has been found that when the value exceeds the maximum value in the above range, there is a problem in formability.

  Table 3 evaluates Example 1 (Example 9 to Example 13) and Comparative Example (Comparative Example 5 and Comparative Example 6) that differ from Example 1 in the amount of carbon black blended in Example 1. In Examples 9 to 13, the compounding amount of carbon black is in the range of 5 parts by mass to 60 parts by mass. In addition, from Example 1 and Example 11, it was found that the overall evaluation and the overall evaluation 2 were “◯” in the same manner regardless of whether the carbon black type was MT carbon or SRF carbon.

  On the other hand, as shown in Comparative Example 5, it was found that when the blending amount of carbon black was 1 part by mass, the adhesion of the abrasion powder generated from the rubber member to the conveyed product became significant. Further, as in Comparative Example 6, when the blending amount of carbon black is 70 parts by mass, the moldability tends to deteriorate and the rubber member tends to become hard. When the rubber member becomes hard, it is predicted that the grip force of the rubber member with respect to the conveyed product is reduced, and therefore, there is a possibility that the conveyance property when the rubber member for the conveyance roller is used is lowered.

  Table 4 shows an example (Examples 14 to 17, Comparative Example 3, Comparative Example 4, and Comparative Example 7 to Comparative Example 9) in which the compounding amount of the inorganic compound excluding the carbon black of Example 1 and Example 1 is different. Is evaluated. In Examples 14 to 17, the compounding amount of the inorganic compound excluding carbon black was 0 to 1 part by mass, and it was found that both were evaluated as “◯” in the comprehensive evaluation and the comprehensive evaluation 2.

  On the other hand, from Comparative Example 3, Comparative Example 4, and Comparative Examples 13 to 15, it was found that the chemical resistance was inferior when the blended amount of the inorganic compound was 1.7 to 9 parts by mass. Note that Comparative Example 3 and Comparative Example 4 both contain polyol-crosslinked fluororubber, but in the case of polyol-crosslinked resin composition, it is necessary to add an acid acceptor which is a kind of inorganic compound excluding carbon black. Yes, it is a formulation formulated with a general compounding amount of acid acceptor.

  From the above results, as in the examples, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber capable of organic peroxide crosslinking, organic peroxide, polyfunctional unsaturated compound and carbon black are included. A rubber composition in which 5 to 60 parts by mass of carbon black and 1 part by mass or less of an inorganic compound excluding carbon black is molded per 100 parts by mass of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. If it is a rubber member, it is confirmed that the adhesion of the abrasion powder generated from the rubber member is reduced, the moldability, transportability and chemical resistance are good, and the compression set is suitable as a sealing material. It was. Therefore, the rubber member is required to have a conveyance roller rubber member and chemical resistance used in a conveyance device where the conveyed product is not wetted by chemicals, a cleaning device or a wet etching device that requires chemical resistance. It was shown to be suitable for a rubber member for sealing.

  From the above results, as in the examples, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber capable of organic peroxide crosslinking, organic peroxide, polyfunctional unsaturated compound, and carbon black A rubber composition containing 5 to 60 parts by mass of carbon black and 1 part by mass or less of an inorganic compound excluding carbon black per 100 parts by mass of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber For molded rubber members, the adhesion of rubber particles generated from the abrasion powder to the conveyed product is reduced, the moldability, transportability and chemical resistance are good, and compression set is suitable as a sealing material. confirmed. Therefore, the rubber member is required to have a conveyance roller rubber member and chemical resistance used in a conveyance device where the conveyed product is not wetted by chemicals, a cleaning device or a wet etching device that requires chemical resistance. It was shown to be suitable for a rubber member for sealing.

10 O-ring for test 20 O-ring holder 30 Workable base 40 Glass plate 50 Fixed base 60 Holder fixed base

Claims (3)

The organic peroxide is 0.5 to 3 parts by mass and the polyfunctional unsaturated compound is 1 to 5 parts by mass per 100 parts by mass of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer rubber. Hereinafter, carbon black is 5 parts by mass or more and 60 parts by mass or less,
And it inorganic compound 1 part by mass der below except carbon black, the flat panel display manufacturing apparatus or a glass manufacturing apparatus is used in the conveyor roller rubber composition characterized Rukoto. ^2. The rubber composition according to claim 1, wherein the carbon black has an average particle diameter of 30 nm to 600 nm and a nitrogen specific surface area of 5 to 80 m ² / g. Rubber member obtained by crosslinking the rubber composition according to claim 1 or 2.

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