WO2018092490A1 - Addition-curable liquid silicone rubber composition for automobile oil filter sealing member, and automobile oil filter sealing member - Google Patents

Addition-curable liquid silicone rubber composition for automobile oil filter sealing member, and automobile oil filter sealing member Download PDF

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Publication number
WO2018092490A1
WO2018092490A1 PCT/JP2017/037534 JP2017037534W WO2018092490A1 WO 2018092490 A1 WO2018092490 A1 WO 2018092490A1 JP 2017037534 W JP2017037534 W JP 2017037534W WO 2018092490 A1 WO2018092490 A1 WO 2018092490A1
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silicone rubber
group
oil filter
rubber composition
component
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PCT/JP2017/037534
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French (fr)
Japanese (ja)
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諒 芦田
首藤　重揮
英典 水嶋
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信越化学工業株式会社
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Priority to JP2018551528A priority Critical patent/JP6696586B2/en
Publication of WO2018092490A1 publication Critical patent/WO2018092490A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention relates to an addition-curable liquid silicone rubber composition for an automobile oil filter seal member and an automobile oil filter seal member.
  • the addition-curable silicone rubber composition contains an organopolysiloxane containing an aliphatic unsaturated group such as an alkenyl group, and is cured (crosslinked) by a hydrosilylation reaction to give a cured silicone rubber.
  • the silicone rubber cured product thus obtained is excellent in heat resistance, cold resistance and electrical insulation, and has a low compression set. Therefore, rocker cover gaskets for vehicles including automobiles, ships, airplanes, etc., oil packings, head covers Used for gaskets such as gaskets, cylinder liner packing, valve system seals, oil filters and sealing.
  • silicone rubber cured products are used as oil-resistant parts such as gaskets, packings, and sealants that are used in environments where they are temporarily or constantly in contact with oils such as automotive engine oils and lubricating oils such as ATF, they are long at high temperatures. When used for a long time, there are problems such as cracking, softening and deterioration, and loss of rubber elasticity.
  • Patent Document 1 proposes a method of introducing a 3,3,3-trifluoropropyl group into an organopolysiloxane as a base polymer.
  • the silicone rubber obtained by this method is expensive and can only be used for limited applications.
  • Patent Document 2 a method for dealing with the breaking of the siloxane bond by increasing the crosslinking density has been proposed in Japanese Patent Application Laid-Open No. 9-012890 (Patent Document 2).
  • Patent Document 2 Increasing the hardness will increase the hardness of the cured silicone rubber, resulting in a sudden loss of rubber properties.
  • Patent Document 3 there is also a problem that the hardness of the silicone cured product decreases with time and the durability is insufficient only by increasing the crosslinking density.
  • Patent Document 3 proposes a method for improving oil resistance by using a diarylpolysiloxane having both ends blocked with dimethylvinylsiloxy groups as a base polymer. This method has a problem that the rubber properties of the resulting silicone rubber are poor.
  • the present invention has been made in view of the above circumstances, and even when the oil such as lubricating oil based on mineral oil such as engine oil and ATF is contacted at high temperature for a long time, the deterioration of the rubber physical property is small and the rubber physical property is improved.
  • An oil-resistant addition-curable liquid silicone rubber composition for automobile oil filter seal members that provides excellent silicone rubber, and an automobile that can be suitably used as an O-ring, packing, gasket, sealing material, etc. made of a cured product of the composition
  • An object of the present invention is to provide an oil filter seal member.
  • the present inventors have made the following components (A) to (E) as essential components, thereby providing lubrication based on mineral oils such as engine oil and ATF. Even if it is in contact with oil such as oil for a long time at a high temperature, the occurrence of cracks, softening deterioration, loss of rubber elasticity, etc. is suppressed, and the rubber physical properties are not significantly reduced and the rubber properties are good.
  • the present inventors have found that an oil-resistant addition-curable liquid silicone rubber composition for automobile oil filter seal members that gives a silicone rubber can be obtained on a regular basis.
  • the present invention provides the following addition curable silicone rubber composition for automobile oil filter seal members and automobile oil filter seal members.
  • A Organopolysiloxane liquid at 25 ° C. containing alkenyl groups bonded to two or more silicon atoms in one molecule: 100 parts by mass
  • B Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: The number of hydrogen atoms bonded to silicon atoms contained in one molecule of this component is
  • C Reinforcing silica fine powder having a specific surface area of 50 m 2 / g or more in the BET method: 0.1 to 100 parts by mass,
  • D platinum group metal catalyst as hydrosilylation catalyst: effective amount
  • E Fine silicate mineral powder: 20 to 100 parts by mass, Addition-curing liquid silicone rubber composition for automobile oil filter seal members.
  • a combination of specific amounts of the above components (A) to (E) allows contact with oil such as engine oil and lubricating oil based on mineral oil such as ATF for a long time at high temperature.
  • Oil-resistant automotive oil filter that can suppress the occurrence of cracks, softening deterioration, loss of rubber elasticity, etc., and can provide a silicone rubber having good rubber properties with little deterioration in rubber properties.
  • An addition curable liquid silicone rubber composition for a seal member and an automobile oil filter seal member can be provided.
  • the viscosity is a value measured with a rotational viscometer at 25 ° C. according to the method described in JIS K 7117-1: 1999.
  • Component (A) is an organopolysiloxane that is liquid at 25 ° C. and contains an alkenyl group bonded to two or more silicon atoms in one molecule.
  • Examples of the molecular structure of the component (A) include linear, cyclic, and branched chains.
  • the main chain is basically composed of repeating diorganosiloxane units, and both ends of the molecular chain are trivalent.
  • a linear diorganopolysiloxane blocked with an organosiloxy group is preferred. Note that it is preferable not to include a three-dimensional network (resin-like) structure.
  • the position of the silicon atom to which the alkenyl group is bonded in the organopolysiloxane molecule is at the end of the molecular chain (ie, Either a triorganosiloxy group) and a molecular chain (that is, a difunctional diorganosiloxane unit or a trifunctional monoorganosilsesquioxane unit located at the non-terminal end of the molecular chain) may be used.
  • the component (A) is particularly preferably a linear diorganopolysiloxane containing alkenyl groups bonded to silicon atoms at both ends of the molecular chain.
  • Examples of the alkenyl group bonded to the silicon atom in the component (A) usually include those having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, a heptenyl group, and the like, and a vinyl group is particularly preferable.
  • the content of the alkenyl group bonded to the silicon atom in the component (A) is preferably 0.001 to 10 mol%, particularly 0.01 to 10 mol% with respect to the entire monovalent hydrocarbon group bonded to the silicon atom. It is preferably about 5 mol%.
  • Examples of the monovalent organic group bonded to the silicon atom other than the alkenyl group as the component (A) include, for example, the same or different monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably about 1 to 10 carbon atoms. Is mentioned.
  • Specific examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and a heptyl group; a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • Aryl groups such as benzyl groups, phenethyl groups and the like, and 90 mol% or more is preferably a methyl group.
  • the viscosity of component (A) at 25 ° C. is preferably in the range of 100 to 500,000 mPa ⁇ s, particularly preferably in the range of 300 to 100,000 mPa ⁇ s. When the viscosity is within this range, the workability of the resulting composition is good, and the mechanical properties of the resulting cured silicone rubber are good.
  • organopolysiloxane of component (A) include: a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of a molecular chain, a trimethylsiloxy group-capped methylvinylpolysiloxane with a molecular chain at both ends, and a trimethylsiloxy group with both ends of a molecular chain.
  • silane-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer dimethylvinylsiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, dimethylvinylsiloxy group-blocked methylvinylpolysiloxane at both ends of the molecular chain, dimethylvinyl at both ends of the molecular chain
  • Component (B) The organohydrogenpolysiloxane of component (B) acts as a crosslinking agent (curing agent) by hydrosilylation addition reaction with the alkenyl group in component (A) and has at least two silicon atoms in one molecule. It is necessary to have a hydrogen atom bonded to (hydrosilyl group represented by SiH), and the molecule substantially does not contain a hydroxyl group bonded to a silicon atom (that is, a silanol group).
  • the (B) component organohydrogenpolysiloxane may be used alone or in combination of two or more.
  • organohydrogenpolysiloxane those represented by the following average composition formula (1) can be used.
  • R 1 is the same or different from each other, and is a monovalent hydrocarbon group bonded to a silicon atom, preferably having 1 to 10 carbon atoms, excluding an aliphatic unsaturated bond such as an alkenyl group
  • Examples of the unsubstituted or substituted monovalent hydrocarbon group in R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, and a hexyl group.
  • Alkyl groups such as cyclohexyl group, octyl group, nonyl group, decyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, etc. It is done.
  • the monovalent hydrocarbon group for R 1 is preferably an alkyl group or an aryl group, and more preferably a methyl group.
  • A is 0.7 to 2.1
  • b is 0.001 to 1.0
  • a + b is a positive number satisfying 0.8 to 3.0.
  • a is 1.0 to 1.0.
  • 2.0 and b are positive numbers satisfying 0.01 to 1.0 and a + b satisfying 1.5 to 2.5.
  • At least 2 (usually 2 to 200), preferably 3 or more (for example, 3 to 100), more preferably 4 to 50 SiH groups in one molecule are molecular chain ends, It may be located in the middle of the molecular chain, or may be located in both of them.
  • the molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is
  • the viscosity is usually 2 to 300, preferably 3 to 150, more preferably 4 to 100, and the viscosity at 25 ° C. is usually 0.1 to 1,000 mPa ⁇ s, preferably 0.5 to 500 mPa.
  • the degree of polymerization can be determined, for example, as the number average degree of polymerization (number average molecular weight) in terms of polystyrene in GPC (gel permeation chromatography) analysis using toluene as a developing solvent.
  • organohydrogenpolysiloxane of component (B) examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris (hydrogendimethylsiloxy).
  • the blending amount of component (B) is 1 to 10 moles (or individual) of silicon atom-bonded hydrogen atoms in component (B) with respect to 1 mole (or individual) of silicon-bonded alkenyl groups in component (A), The amount is preferably in the range of 1 to 5 moles (or pieces).
  • the silicon atom-bonded hydrogen atom in the component (B) is less than 1 mole relative to 1 mole of the silicon atom-bonded alkenyl group in the component (A), the composition may not be cured sufficiently, and this is 10 moles. If it exceeds 1, the heat resistance of the resulting cured silicone rubber is extremely deteriorated.
  • the reinforcing silica fine powder of component (C) is used as a rubber reinforcing agent, and has a specific surface area of 50 m 2 / g or more by the BET method.
  • precipitated silica (wet silica), fumed silica (dry silica), calcined silica, etc., having a specific surface area by the BET method of 50 to 400 m 2 / g, particularly 100 to 350 m 2 / g, are preferably used to improve rubber strength. From the viewpoint of improvement, fumed silica is preferable.
  • the reinforcing silica fine powder may be a silica fine powder whose surface has been hydrophobized with a surface treatment agent to be described later.
  • these silica fine powders may be in a powder state and have been subjected to a surface hydrophobization treatment directly with a surface treatment agent, or may be a silicone oil (for example, an alkenyl group-containing organopolysiloxane of component (A) above).
  • a surface treatment agent may be added at the time of kneading with (siloxane) to make the surface hydrophobic.
  • the untreated silica fine powder and the surface treatment agent are placed in a mechanical kneading apparatus or fluidized bed sealed at normal pressure, and at room temperature or heat treatment (heating) in the presence of an inert gas as necessary.
  • the lower part) can be mixed.
  • a surface treatment may be promoted by using a catalyst (hydrolysis accelerator or the like).
  • the surface-treated silica fine powder can be produced by drying.
  • the compounding amount of the surface treatment agent may be an amount calculated from the coating area of the surface treatment agent, and is usually 1 to 50 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass of untreated silica fine powder.
  • the amount can be 40 parts by mass, more preferably 10 to 30 parts by mass.
  • the surface treatment agent include silazanes such as hexamethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyl Trimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) silane, trimethylchlorosilane, dimethyldichlorosilane, divinyl Silane coupling agents such as dimethoxysilane, chloropropyltrimethoxysilane, trimethylsilanol and hydroxypentamethyldisiloxane, polymethylsiloxane, organohydrogen Organosilicon compounds such
  • the compounding amount of the component (C) is 0.1 to 100 parts by mass, preferably 5 to 60 parts by mass, and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the component (A).
  • the blending amount of component (C) is less than 0.1 parts by mass, a sufficient reinforcing effect cannot be obtained, and when it exceeds 100 parts by mass, the silicone rubber composition becomes highly viscous and handling operability is deteriorated.
  • [(D) component] As the platinum group metal catalyst of component (D), platinum black, chloroplatinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, platinum bisacetate Examples include platinum group metal catalysts such as acetate.
  • the compounding amount of the platinum group metal catalyst can be a catalytic amount.
  • the platinum group metal in terms of mass
  • the platinum group metal is 0.5 to 1 with respect to the total mass of the components (A) to (E). 1,000 ppm, particularly about 1 to 500 ppm. If the amount added is too small, the curability may be lowered, and if the amount added is too large, the heat resistance may deteriorate.
  • the silicate mineral fine powder of component (E) used in the present invention acts as an oil resistance improver.
  • the fine silicate mineral powder preferably has a median diameter of 0.1 to 30 ⁇ m, more preferably 0.3 to 20 ⁇ m, as measured by a laser diffraction method. When the median diameter is larger than 30 ⁇ m, the physical properties of the silicone rubber composition may be lowered. When the median diameter is smaller than 0.1 ⁇ m, the viscosity of the silicone rubber composition becomes high, and molding may be difficult.
  • the silicate mineral fine powder of component (E) preferably has a whiteness of 80% or more, more preferably 85% or more in the Hunter method measured according to JIS Z 8722: 2009. .
  • the whiteness is lower than 80%, the proportion of impurities contained in the silicate mineral is large, which may cause deterioration of physical properties of the silicone rubber composition.
  • the fine silicate mineral powder of component (E) preferably has an oil absorption of 20 to 80 ml / 100 g, more preferably 30 to 60 ml / 100 g, measured according to JIS K 5101-13-1: 2004. More preferably. If the oil absorption is lower than 20 ml / 100 g, a sufficient oil resistance improvement effect may not be obtained, and if it is higher than 80 ml / 100 g, the viscosity of the silicone rubber composition may increase and workability may deteriorate.
  • Such fine silicate mineral powders include fine silicate minerals such as nesosilicate minerals, solosilicate minerals, cyclosilicate minerals, inosilicate minerals, phyllosilicate minerals, and tectosilicate minerals.
  • Pyrosilicates selected from clay minerals such as mica such as muscovite, biotite, phlogopite, kaolinite (kaolin), montmorillonite (acid clay, activated clay), sericite, talc, zeolite. Minerals are preferably used.
  • talc chemical formula: Mg 3 Si 4 O 10 (OH) 2
  • kaolinite kaolin
  • Al 4 Si 4 O 10 (OH) 8 is preferable.
  • such fine silicate mineral powders can be used singly or in combination of two or more if the median diameter, whiteness and oil absorption are within the above ranges.
  • the silicate mineral fine powder may be a surface-untreated one, but a silicate mineral fine powder that has been surface-treated with a surface treatment agent described later can also be used.
  • the untreated silicate mineral fine powder and the surface treatment agent are placed in a mechanical kneading apparatus or fluidized bed sealed at normal pressure, and if necessary, In the presence of an active gas, mixing can be performed at room temperature (25 ° C.) or heat treatment (under heating). In some cases, the surface treatment may be accelerated using water or a catalyst (hydrolysis accelerator or the like). After the kneading, the surface-treated silicate mineral fine powder can be produced by drying.
  • the compounding amount of the surface treatment agent may be more than the amount calculated from the coating area of the surface treatment agent, and usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the untreated fine silicate mineral powder. Preferably, the amount can be 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass.
  • the surface treatment agent include silazanes such as hexamethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyl Trimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) silane, trimethylchlorosilane, dimethyldichlorosilane, divinyl Silane coupling agents such as dimethoxysilane, chloropropyltrimethoxysilane, trimethylsilanol and hydroxypentamethyldisiloxane, polymethylsiloxane, organohydrogen Organosilicon compounds such
  • the compounding amount of the component (E) is 20 to 100 parts by mass, preferably 20 to 90 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the component (A).
  • the blending amount of the component (E) is less than 20 parts by mass, a sufficient oil resistance improvement effect cannot be obtained, and when it is more than 100 parts by mass, the silicone rubber composition becomes highly viscous and handling operability is improved. Deteriorate.
  • Non-reinforcing fillers As fillers other than the components (C) and (E), for example, crystalline silica (for example, quartz powder having a BET specific surface area of less than 50 m 2 / g), hollow filler made of organic resin , Polymethylsilsesquioxane fine particles (so-called silicone resin powder), fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, zinc carbonate, layered mica, carbon black, diatomaceous earth Fillers such as glass fibers; fillers obtained by subjecting these fillers to surface hydrophobic treatment with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, low molecular weight siloxane compounds, silicone rubber powders, and silicones Resin powder etc. are mentioned.
  • the blending amount can be 0 to 100 parts by weight, particularly 0 to 50 parts by weight, per 100 parts by weight of component (A).
  • an organopolysiloxane containing one silicon-bonded hydrogen atom in one molecule and no other functional group, one silicon-bonded alkenyl group in one molecule An organopolysiloxane containing no other functional groups, a non-functional organopolysiloxane containing no silicon-bonded hydrogen atoms, silicon-bonded alkenyl groups, or other functional groups (so-called dimethyl silicone oil), An organic solvent, an anti-creep hardening agent, a plasticizer, a thixotropic agent, a pigment, a dye, an antifungal agent and the like can be blended.
  • the addition-curable silicone rubber composition As a method for molding and curing the addition-curable silicone rubber composition, a conventional method can be adopted. However, as a molding method, an optimum method selected from injection molding, transfer molding, injection molding, compression molding and the like is selected. Is possible.
  • the composition can be cured by heating at 80 to 230 ° C., preferably 100 to 180 ° C. The heating time is preferably about 30 seconds to 3 hours, particularly preferably about 1 minute to 1 hour. Further, secondary vulcanization (post-cure) may be performed at 40 to 230 ° C. for about 10 minutes to 24 hours as required.
  • Oil-resistant silicone rubber The cured product of the composition of the present invention thus obtained has a small decrease in rubber properties even when contacted for a long time at high temperature with oils such as engine oils and lubricating oils based on mineral oils such as ATF. Excellent silicone rubber. Therefore, the oil-resistant silicone rubber can be used under conditions of temporary or constant contact with oil for a long time at high temperature, and is suitable for automotive oil filter seal members such as O-rings, packings, gaskets, and sealing materials. Can be used.
  • an average degree of polymerization shows the number average degree of polymerization of polystyrene conversion in the gel permeation chromatography (GPC) analysis which used toluene as the developing solvent.
  • both ends of the molecular chain are blocked with vinyldimethylsiloxy groups, 24 parts of dimethylpolysiloxane (A1) having a viscosity at 25 ° C. of 30,000 mPa ⁇ s, and the bifunctionality constituting the main chain Dimethyl-vinyl having a viscosity of 700 mPa ⁇ s at 25 ° C. containing 5 mol% of vinylmethylsiloxane units and 95 mol% of dimethylsiloxane units and having both ends of the molecular chain blocked with trimethylsiloxy groups. 5 parts of methylpolysiloxane (A2) was added and mixed until uniform to obtain a base compound (I).
  • Example 1 128 parts of the base compound (I) prepared in Preparation Example 1, 46 parts of dimethylpolysiloxane (A1) having both molecular chain ends blocked with vinyldimethylsiloxy groups and a viscosity at 25 ° C.
  • Table 1 shows the results of measuring the oil resistance by measuring the hardness, elongation at break, and tensile strength of the sheet after being immersed in test oil at 150 ° C. for 70 hours in accordance with JIS K 6258: 2010. It was. Note that the test oil specified in JIS K 6258: 2010 is a test lubricant No. IRM-901 (Nihon Sun Oil Co., Ltd.) corresponding to 1 oil was used.
  • Example 2 The talc of Example 1 has a median diameter of 7.0 ⁇ m, a whiteness of 95.0%, and an oil absorption of 35 ml / 100 g (trade name MICRO ACE K-1 manufactured by Nippon Talc Co., Ltd.). Table 1 shows the results of preparing a silicone rubber composition with the same formulation, producing a sheet under the same conditions as in Example 1, and evaluating the initial physical properties and oil resistance, except that the same mass part was replaced. Indicated.
  • Example 3 The talc of Example 1 was replaced with kaolinite (manufactured by BASF: trade name ASP-170) having the same median diameter of 0.4 ⁇ m, whiteness of 96%, and oil absorption of 45 ml / 100 g with the same parts by mass.
  • Table 1 shows the results of preparing a silicone rubber composition with the same formulation, producing a sheet under the same conditions as in Example 1, and evaluating the initial physical properties and oil resistance.
  • Example 1 All except that talc of Example 1 was not added, a silicone rubber composition was prepared with the same formulation, a sheet was produced under the same conditions as in Example 1, and the initial physical properties and oil resistance were evaluated. Are shown in Table 1.
  • compositions (Examples) that satisfy the conditions of the present invention have good initial physical properties, and the decrease in rubber physical properties after the oil resistance test is small, while the oil resistance is excellent. Since the composition (comparative example) which does not satisfy the conditions of the present invention has a large decrease in rubber physical properties after the oil resistance test, it was insufficient as a sealing material, and it was confirmed that the composition was inferior in oil resistance.

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Abstract

Provided is an addition-curable liquid silicone rubber composition for an automobile oil filter sealing member. This addition-curable liquid silicone rubber composition for an automobile oil filter sealing member contains: (A) 100 parts by mass of an organopolysiloxane which contains alkenyl groups bonded to two or more silicon atoms in one molecule and is a liquid at 25°C; (B) an organohydrogen polysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule, wherein the amount of the organohydrogen polysiloxane is such that the number of hydrogen atoms bonded to silicon atoms contained in one molecule of the organohydrogen polysiloxane with respect to the total number of the alkenyl groups bonded to silicon atoms in component (A) is 1-10 hydrogen atoms per 1 alkenyl group; (C) 0.1-100 parts by mass of reinforcing silica fine powder having a specific surface area of 50 m2/g or more as measured by the BET method; (D) an effective amount of a platinum-group metal-based catalyst as a catalyst for a hydrosilylation reaction; and (E) 20-100 parts by mass of silicate mineral fine powder.

Description

自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物及び自動車オイルフィルターシール部材Addition-curable liquid silicone rubber composition for automobile oil filter seal member and automobile oil filter seal member
　本発明は、自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物及び自動車オイルフィルターシール部材に関する。 The present invention relates to an addition-curable liquid silicone rubber composition for an automobile oil filter seal member and an automobile oil filter seal member.
　付加硬化型シリコーンゴム組成物は、アルケニル基等の脂肪族不飽和基を含有するオルガノポリシロキサンを含み、ヒドロシリル化反応によって硬化（架橋）してシリコーンゴム硬化物を与える。このようにして得られるシリコーンゴム硬化物は、耐熱性、耐寒性、電気絶縁性に優れ、低い圧縮永久歪を有するため、自動車を含む車両、船舶、飛行機等のロッカーカバーガスケット、オイルパッキン、ヘッドカバーガスケット、シリンダーライナーパッキン、バルブシステムシール、オイルフィルター、シーリング等のガスケット用途などに用いられている。 The addition-curable silicone rubber composition contains an organopolysiloxane containing an aliphatic unsaturated group such as an alkenyl group, and is cured (crosslinked) by a hydrosilylation reaction to give a cured silicone rubber. The silicone rubber cured product thus obtained is excellent in heat resistance, cold resistance and electrical insulation, and has a low compression set. Therefore, rocker cover gaskets for vehicles including automobiles, ships, airplanes, etc., oil packings, head covers Used for gaskets such as gaskets, cylinder liner packing, valve system seals, oil filters and sealing.
　しかしながら、シリコーンゴム硬化物を自動車のエンジンオイルやＡＴＦ等の潤滑油などのオイルと一時的或いは常時接触する環境で用いられるガスケット、パッキン、シール材などの耐油部品として使用する場合、高温下で長時間使用されると亀裂が発生したり、軟化劣化し、ゴム弾性を失ったりするなどの問題が発生している。 However, when silicone rubber cured products are used as oil-resistant parts such as gaskets, packings, and sealants that are used in environments where they are temporarily or constantly in contact with oils such as automotive engine oils and lubricating oils such as ATF, they are long at high temperatures. When used for a long time, there are problems such as cracking, softening and deterioration, and loss of rubber elasticity.
　このような欠点を改良する方法として、特開平６－１０７９５２号公報（特許文献１）では、ベースポリマーであるオルガノポリシロキサンに３，３，３－トリフルオロプロピル基を導入する方法が提案されているが、この方法で得られたシリコーンゴムは、コストが高く、限られた用途にしか使用できない。 As a method for improving such a defect, Japanese Patent Laid-Open No. 6-107952 (Patent Document 1) proposes a method of introducing a 3,3,3-trifluoropropyl group into an organopolysiloxane as a base polymer. However, the silicone rubber obtained by this method is expensive and can only be used for limited applications.
　また、シロキサン結合が切断されることに対しては、架橋密度の増加により対処する方法が特開平９－０１２８９０号公報（特許文献２）で提案されているが、単純に官能基を増やし架橋密度を高めるとシリコーンゴム硬化物の硬度が上がり、ゴム物性が急激に失われてしまうことになる。また、架橋密度を高めるのみでは、時間とともにシリコーン硬化物の硬度が下がり、耐久性に乏しいという問題もある。 In addition, a method for dealing with the breaking of the siloxane bond by increasing the crosslinking density has been proposed in Japanese Patent Application Laid-Open No. 9-012890 (Patent Document 2). Increasing the hardness will increase the hardness of the cured silicone rubber, resulting in a sudden loss of rubber properties. Moreover, there is also a problem that the hardness of the silicone cured product decreases with time and the durability is insufficient only by increasing the crosslinking density.
　また、特開２０１１－２５６２５３号公報（特許文献３）では、両末端がジメチルビニルシロキシ基で封鎖されたジアリールポリシロキサンをベースポリマーにすることで耐油性を向上させる方法が提案されているが、この方法では、得られるシリコーンゴムのゴム物性が悪いという問題がある。 Japanese Patent Application Laid-Open No. 2011-256253 (Patent Document 3) proposes a method for improving oil resistance by using a diarylpolysiloxane having both ends blocked with dimethylvinylsiloxy groups as a base polymer. This method has a problem that the rubber properties of the resulting silicone rubber are poor.
　従って、自動車オイルフィルターシール部材用に耐油性に優れたシリコーンゴムを与えるシリコーンゴム組成物の開発が望まれている。 Therefore, it is desired to develop a silicone rubber composition that provides a silicone rubber excellent in oil resistance for automobile oil filter seal members.
特開平６－１０７９５２号公報Japanese Patent Laid-Open No. 6-107952 特開平９－０１２８９０号公報Japanese Patent Laid-Open No. 9-012890 特開２０１１－２５６２５３号公報JP 2011-256253 A
　本発明は、上記事情に鑑みなされたもので、エンジンオイル、ＡＴＦ等の鉱物油をベースとした潤滑油等の油と高温下で長時間接触してもゴム物性の低下が小さく、ゴム物性に優れたシリコーンゴムを与える耐油性の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物、及び該組成物の硬化物からなるＯ－リング、パッキン、ガスケット、シール材等として好適に使用できる自動車オイルフィルターシール部材を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and even when the oil such as lubricating oil based on mineral oil such as engine oil and ATF is contacted at high temperature for a long time, the deterioration of the rubber physical property is small and the rubber physical property is improved. An oil-resistant addition-curable liquid silicone rubber composition for automobile oil filter seal members that provides excellent silicone rubber, and an automobile that can be suitably used as an O-ring, packing, gasket, sealing material, etc. made of a cured product of the composition An object of the present invention is to provide an oil filter seal member.
　本発明者らは、上記目的を達成するべく鋭意検討を行った結果、後述する（Ａ）～（Ｅ）成分を必須成分とすることで、エンジンオイル、ＡＴＦなどの鉱物油をベースとした潤滑油等の油と高温下で長時間接触していても亀裂の発生、軟化劣化、ゴム弾性を失うなどの問題が発生することが抑制され、ゴム物性の低下が小さく、且つ良好なゴム物性を有するシリコーンゴムを与える耐油性の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物が定常的に得られることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have made the following components (A) to (E) as essential components, thereby providing lubrication based on mineral oils such as engine oil and ATF. Even if it is in contact with oil such as oil for a long time at a high temperature, the occurrence of cracks, softening deterioration, loss of rubber elasticity, etc. is suppressed, and the rubber physical properties are not significantly reduced and the rubber properties are good. The present inventors have found that an oil-resistant addition-curable liquid silicone rubber composition for automobile oil filter seal members that gives a silicone rubber can be obtained on a regular basis.
　従って、本発明は、下記に示す自動車オイルフィルターシール部材用付加硬化型シリコーンゴム組成物及び自動車オイルフィルターシール部材を提供する。
〔１〕
　（Ａ）１分子中に２個以上のケイ素原子に結合したアルケニル基を含有する２５℃で液状のオルガノポリシロキサン：１００質量部、
（Ｂ）１分子中に少なくとも２個のケイ素原子に結合した水素原子を含有するオルガノハイドロジェンポリシロキサン：本成分の１分子中に含まれるケイ素原子に結合した水素原子の数が、（Ａ）成分中のケイ素原子結合アルケニル基の合計１個当たり、１～１０個となる量、
（Ｃ）ＢＥＴ法における比表面積が５０ｍ2／ｇ以上である補強性シリカ微粉末：０．１～１００質量部、
（Ｄ）ヒドロシリル化反応用触媒としての白金族金属系触媒：有効量、
（Ｅ）ケイ酸塩鉱物微粉末：２０～１００質量部、
を含有する自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。
〔２〕
　（Ｅ）成分のレーザー回折法によるメジアン径が０．１～３０μｍである〔１〕に記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。
〔３〕
　（Ｅ）成分のＪＩＳ　Ｚ　８７２２：２００９に準じて測定したハンター法における白色度が８０％以上である〔１〕又は〔２〕に記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。
〔４〕
　（Ｅ）成分のＪＩＳ　Ｋ　５１０１－１３－１：２００４に準じて測定した吸油量が２０～８０ｍｌ／１００ｇである〔１〕～〔３〕のいずれかに記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。
〔５〕
　（Ｅ）成分が、タルク、カオリナイト、又はカオリンである〔１〕～〔４〕のいずれかに記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。
〔６〕
　〔１〕～〔５〕のいずれかに記載のシリコーンゴム組成物の硬化物からなる自動車オイルフィルターシール部材。 Accordingly, the present invention provides the following addition curable silicone rubber composition for automobile oil filter seal members and automobile oil filter seal members.
[1]
(A) Organopolysiloxane liquid at 25 ° C. containing alkenyl groups bonded to two or more silicon atoms in one molecule: 100 parts by mass
(B) Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: The number of hydrogen atoms bonded to silicon atoms contained in one molecule of this component is (A) An amount of 1 to 10 per total of silicon-bonded alkenyl groups in the component,
(C) Reinforcing silica fine powder having a specific surface area of 50 m 2 / g or more in the BET method: 0.1 to 100 parts by mass,
(D) platinum group metal catalyst as hydrosilylation catalyst: effective amount,
(E) Fine silicate mineral powder: 20 to 100 parts by mass,
Addition-curing liquid silicone rubber composition for automobile oil filter seal members.
[2]
The addition curable liquid silicone rubber composition for automotive oil filter seal members according to [1], wherein the median diameter of component (E) by laser diffraction method is 0.1 to 30 μm.
[3]
Addition-curing liquid silicone rubber composition for automobile oil filter seal members according to [1] or [2], wherein the whiteness in the Hunter method measured according to JIS Z 8722: 2009 of component (E) is 80% or more .
[4]
Addition curing for automobile oil filter seal members according to any one of [1] to [3], wherein the oil absorption measured according to JIS K 5101-13-1: 2004 of component (E) is 20 to 80 ml / 100 g Type liquid silicone rubber composition.
[5]
(E) The addition-curable liquid silicone rubber composition for automobile oil filter seal members according to any one of [1] to [4], wherein the component is talc, kaolinite, or kaolin.
[6]
An automobile oil filter seal member comprising a cured product of the silicone rubber composition according to any one of [1] to [5].
　本発明によれば、上記（Ａ）～（Ｅ）成分の特定量の組み合わせにより、エンジンオイル、ＡＴＦ等の鉱物油をベースとした潤滑油等の油と高温下で長時間接触していても亀裂の発生、軟化劣化、ゴム弾性を失うなどの問題が発生することが抑制され、ゴム物性の低下が小さく、且つ良好なゴム物性を有するシリコーンゴムを与えることが可能な耐油性の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物及び自動車オイルフィルターシール部材を提供することができる。 According to the present invention, a combination of specific amounts of the above components (A) to (E) allows contact with oil such as engine oil and lubricating oil based on mineral oil such as ATF for a long time at high temperature. Oil-resistant automotive oil filter that can suppress the occurrence of cracks, softening deterioration, loss of rubber elasticity, etc., and can provide a silicone rubber having good rubber properties with little deterioration in rubber properties. An addition curable liquid silicone rubber composition for a seal member and an automobile oil filter seal member can be provided.
　以下、本発明につき更に詳しく説明する。なお、本明細書中において、粘度は、２５℃においてＪＩＳ　Ｋ　７１１７－１：１９９９に記載の方法で回転粘度計により測定した値である。 Hereinafter, the present invention will be described in more detail. In the present specification, the viscosity is a value measured with a rotational viscometer at 25 ° C. according to the method described in JIS K 7117-1: 1999.
［（Ａ）成分］
　（Ａ）成分は、１分子中に２個以上のケイ素原子に結合したアルケニル基を含有する２５℃で液状のオルガノポリシロキサンである。
　（Ａ）成分の分子構造としては、例えば、直鎖状、環状、分岐鎖状等のものが挙げられるが、主鎖が基本的にジオルガノシロキサン単位の繰り返しからなり、分子鎖両末端がトリオルガノシロキシ基で封鎖された直鎖状のジオルガノポリシロキサンが好ましい。なお、三次元網状（樹脂状）構造は含まないことが好ましい。また、（Ａ）成分のオルガノポリシロキサンの分子構造が直鎖状又は分岐鎖状である場合、該オルガノポリシロキサンの分子中においてアルケニル基が結合するケイ素原子の位置は、分子鎖末端（即ち、トリオルガノシロキシ基）及び分子鎖途中（即ち、分子鎖非末端に位置する２官能性のジオルガノシロキサン単位又は３官能性のモノオルガノシルセスキオキサン単位）のどちらか一方でも両方でもよい。（Ａ）成分として、特に好ましくは、少なくとも分子鎖両末端のケイ素原子に結合したアルケニル基を含有する直鎖状のジオルガノポリシロキサンである。 [(A) component]
Component (A) is an organopolysiloxane that is liquid at 25 ° C. and contains an alkenyl group bonded to two or more silicon atoms in one molecule.
Examples of the molecular structure of the component (A) include linear, cyclic, and branched chains. The main chain is basically composed of repeating diorganosiloxane units, and both ends of the molecular chain are trivalent. A linear diorganopolysiloxane blocked with an organosiloxy group is preferred. Note that it is preferable not to include a three-dimensional network (resin-like) structure. In addition, when the molecular structure of the organopolysiloxane of component (A) is linear or branched, the position of the silicon atom to which the alkenyl group is bonded in the organopolysiloxane molecule is at the end of the molecular chain (ie, Either a triorganosiloxy group) and a molecular chain (that is, a difunctional diorganosiloxane unit or a trifunctional monoorganosilsesquioxane unit located at the non-terminal end of the molecular chain) may be used. The component (A) is particularly preferably a linear diorganopolysiloxane containing alkenyl groups bonded to silicon atoms at both ends of the molecular chain.
　（Ａ）成分中のケイ素原子に結合したアルケニル基としては、例えば、通常、炭素数２～８、好ましくは炭素数２～４のものが挙げられる。その具体例としては、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、シクロヘキセニル基、ヘプテニル基等が挙げられ、特にビニル基であることが好ましい。 Examples of the alkenyl group bonded to the silicon atom in the component (A) usually include those having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, a heptenyl group, and the like, and a vinyl group is particularly preferable.
　（Ａ）成分中のケイ素原子に結合したアルケニル基の含有量は、ケイ素原子に結合した１価炭化水素基全体に対して０．００１～１０モル％であることが好ましく、特に０．０１～５モル％程度であることが好ましい。 The content of the alkenyl group bonded to the silicon atom in the component (A) is preferably 0.001 to 10 mol%, particularly 0.01 to 10 mol% with respect to the entire monovalent hydrocarbon group bonded to the silicon atom. It is preferably about 5 mol%.
　（Ａ）成分のアルケニル基以外のケイ素原子に結合する１価の有機基としては、例えば、互いに同一又は異種の、炭素数１～１２、好ましくは炭素数１～１０程度の１価炭化水素基が挙げられる。１価炭化水素基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基等のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基などが挙げられるが、９０モル％以上がメチル基であることが好ましい。 Examples of the monovalent organic group bonded to the silicon atom other than the alkenyl group as the component (A) include, for example, the same or different monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably about 1 to 10 carbon atoms. Is mentioned. Specific examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and a heptyl group; a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Aryl groups such as benzyl groups, phenethyl groups and the like, and 90 mol% or more is preferably a methyl group.
　（Ａ）成分の２５℃における粘度は、１００～５００，０００ｍＰａ・ｓの範囲内であることが好ましく、特に３００～１００，０００ｍＰａ・ｓの範囲内であることが好ましい。該粘度がこの範囲内にあると、得られる組成物の取り扱い作業性が良好であり、また、得られるシリコーンゴム硬化物の機械的特性が良好である。 The viscosity of component (A) at 25 ° C. is preferably in the range of 100 to 500,000 mPa · s, particularly preferably in the range of 300 to 100,000 mPa · s. When the viscosity is within this range, the workability of the resulting composition is good, and the mechanical properties of the resulting cured silicone rubber are good.
　（Ａ）成分のオルガノポリシロキサンの具体例としては、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジビニルメチルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジビニルメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端トリビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、及びこれらのオルガノポリシロキサンの２種以上からなる混合物が挙げられる。 Specific examples of the organopolysiloxane of component (A) include: a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of a molecular chain, a trimethylsiloxy group-capped methylvinylpolysiloxane with a molecular chain at both ends, and a trimethylsiloxy group with both ends of a molecular chain. Siloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, dimethylvinylsiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, dimethylvinylsiloxy group-blocked methylvinylpolysiloxane at both ends of the molecular chain, dimethylvinyl at both ends of the molecular chain Siloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecule Divinylmethylsiloxy group-blocked dimethylpolysiloxane at both ends, molecular chain both ends divinylmethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trivinylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends trivinylsiloxy Examples thereof include a blocked dimethylsiloxane / methylvinylsiloxane copolymer, and a mixture of two or more of these organopolysiloxanes.
［（Ｂ）成分］
　（Ｂ）成分のオルガノハイドロジェンポリシロキサンは、（Ａ）成分中のアルケニル基とヒドロシリル化付加反応し、架橋剤（硬化剤）として作用するものであり、１分子中に少なくとも２個のケイ素原子に結合した水素原子（ＳｉＨで表されるヒドロシリル基）を有する必要があり、また実質的に分子中にケイ素原子に結合した水酸基（即ち、シラノール基）を含有しないものである。（Ｂ）成分のオルガノハイドロジェンポリシロキサンは、１種単独で用いても２種以上を併用してもよい。 [Component (B)]
The organohydrogenpolysiloxane of component (B) acts as a crosslinking agent (curing agent) by hydrosilylation addition reaction with the alkenyl group in component (A) and has at least two silicon atoms in one molecule. It is necessary to have a hydrogen atom bonded to (hydrosilyl group represented by SiH), and the molecule substantially does not contain a hydroxyl group bonded to a silicon atom (that is, a silanol group). The (B) component organohydrogenpolysiloxane may be used alone or in combination of two or more.
　このオルガノハイドロジェンポリシロキサンとしては、下記平均組成式（１）で示されるものを用いることができる。
　　Ｒ1 aＨbＳｉＯ(4-a-b)/2　　　　　（１） As this organohydrogenpolysiloxane, those represented by the following average composition formula (1) can be used.
R 1 a H b SiO (4-ab) / 2 (1)
　上記式（１）中、Ｒ1は互いに同一又は異種の、アルケニル基等の脂肪族不飽和結合を除く、好ましくは炭素数１～１０の、ケイ素原子に結合した１価炭化水素基であり、このＲ1における非置換もしくは置換の１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基等が挙げられる。Ｒ1の１価炭化水素基としては、好ましくはアルキル基、アリール基であり、より好ましくはメチル基である。また、ａは０．７～２．１、ｂは０．００１～１．０で、かつａ＋ｂが０．８～３．０を満足する正数であり、好ましくは、ａは１．０～２．０、ｂは０．０１～１．０、ａ＋ｂが１．５～２．５を満足する正数である。 In the above formula (1), R 1 is the same or different from each other, and is a monovalent hydrocarbon group bonded to a silicon atom, preferably having 1 to 10 carbon atoms, excluding an aliphatic unsaturated bond such as an alkenyl group, Examples of the unsubstituted or substituted monovalent hydrocarbon group in R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, and a hexyl group. , Alkyl groups such as cyclohexyl group, octyl group, nonyl group, decyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, etc. It is done. The monovalent hydrocarbon group for R 1 is preferably an alkyl group or an aryl group, and more preferably a methyl group. A is 0.7 to 2.1, b is 0.001 to 1.0, and a + b is a positive number satisfying 0.8 to 3.0. Preferably, a is 1.0 to 1.0. 2.0 and b are positive numbers satisfying 0.01 to 1.0 and a + b satisfying 1.5 to 2.5.
　ここで、１分子中に少なくとも２個（通常、２～２００個）、好ましくは３個以上（例えば、３～１００個）、より好ましくは４～５０個含有するＳｉＨ基は、分子鎖末端、分子鎖途中のいずれに位置していてもよく、またこの両方に位置するものであってもよい。また、このオルガノハイドロジェンポリシロキサンの分子構造は、直鎖状、環状、分岐鎖状、三次元網状構造のいずれであってもよいが、１分子中のケイ素原子の数（又は重合度）は、通常２～３００個、好ましくは３～１５０個、より好ましくは４～１００個のものが望ましく、２５℃における粘度が、通常０．１～１，０００ｍＰａ・ｓ、好ましくは０．５～５００ｍＰａ・ｓの、２５℃で液状のものが使用される。なお、重合度は、例えば、トルエンを展開溶媒としてＧＰＣ（ゲルパーミエーションクロマトグラフィ）分析におけるポリスチレン換算の数平均重合度（数平均分子量）として求めることができる。 Here, at least 2 (usually 2 to 200), preferably 3 or more (for example, 3 to 100), more preferably 4 to 50 SiH groups in one molecule are molecular chain ends, It may be located in the middle of the molecular chain, or may be located in both of them. The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is The viscosity is usually 2 to 300, preferably 3 to 150, more preferably 4 to 100, and the viscosity at 25 ° C. is usually 0.1 to 1,000 mPa · s, preferably 0.5 to 500 mPa. -S liquid at 25 ° C is used. The degree of polymerization can be determined, for example, as the number average degree of polymerization (number average molecular weight) in terms of polystyrene in GPC (gel permeation chromatography) analysis using toluene as a developing solvent.
　このような（Ｂ）成分のオルガノハイドロジェンポリシロキサンとしては、１，１，３，３－テトラメチルジシロキサン、１，３，５，７－テトラメチルシクロテトラシロキサン、トリス（ハイドロジェンジメチルシロキシ）メチルシラン、トリス（ハイドロジェンジメチルシロキシ）フェニルシラン、メチルハイドロジェンシクロポリシロキサン、メチルハイドロジェンシロキサン・ジメチルシロキサン環状共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルフェニルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジフェニルポリシロキサンや、これらの各例示化合物において、メチル基の一部又は全部がエチル基、プロピル基等の他のアルキル基で置換されたもの、式：Ｒ2 3ＳｉＯ1/2（式中のＲ2はアルケニル基以外の１価炭化水素基であり、前記Ｒ1と同様の基である。）で示されるシロキサン単位と式：Ｒ2 2ＨＳｉＯ1/2で示されるシロキサン単位と式：ＳｉＯ4/2で示されるシロキサン単位からなるオルガノシロキサン共重合体、式：Ｒ2 2ＨＳｉＯ1/2で示されるシロキサン単位と式：ＳｉＯ4/2で示されるシロキサン単位からなるオルガノシロキサン共重合体、式：Ｒ2ＨＳｉＯ2/2で示されるシロキサン単位と式：Ｒ2ＳｉＯ3/2で示されるシロキサン単位もしくは式：ＨＳｉＯ3/2で示されるシロキサン単位からなるオルガノシロキサン共重合体、及びこれらのオルガノポリシロキサンの２種以上からなる混合物が挙げられる。 Examples of the organohydrogenpolysiloxane of component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris (hydrogendimethylsiloxy). Methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both-end trimethyl Siloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain Molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpoly Siloxane, dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends of molecular chain dimethylhydrogensiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer, dimethylhydrogen, both ends of molecular chain Siloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, molecule And both ends endcapped with dimethyl hydrogen siloxy group diphenyl polysiloxane, in each of these exemplified compounds, those in which a part of the methyl group or entirely substituted with an ethyl group, other alkyl groups such as propyl group, the formula: R 2 3 A siloxane unit represented by SiO 1/2 (wherein R 2 is a monovalent hydrocarbon group other than an alkenyl group and is the same group as R 1 above) and a formula: R 2 2 HSiO 1/2 Organosiloxane copolymer comprising a siloxane unit shown and a siloxane unit represented by the formula: SiO 4/2 , a siloxane unit represented by a formula: R 2 2 HSiO 1/2 and a siloxane unit represented by a formula: SiO 4/2 organosiloxane copolymers consisting of the formula: siloxane units represented by the formula R 2 HSiO 2/2: siloxane units or of the formula represented by R 2 SiO 3/2: white represented by HSiO 3/2 Organosiloxane copolymers consisting of acid units, and mixtures of two or more of these organopolysiloxanes.
　（Ｂ）成分の配合量は、（Ａ）成分中のケイ素原子結合アルケニル基１モル（又は個）に対して（Ｂ）成分中のケイ素原子結合水素原子が１～１０モル（又は個）、好ましくは１～５モル（又は個）の範囲内となる量である。（Ａ）成分中のケイ素原子結合アルケニル基１モルに対して（Ｂ）成分中のケイ素原子結合水素原子が１モル未満であると、組成物は十分に硬化しないことがあり、またこれが１０モルを超えると、得られるシリコーンゴム硬化物の耐熱性が極端に悪化する。 The blending amount of component (B) is 1 to 10 moles (or individual) of silicon atom-bonded hydrogen atoms in component (B) with respect to 1 mole (or individual) of silicon-bonded alkenyl groups in component (A), The amount is preferably in the range of 1 to 5 moles (or pieces). When the silicon atom-bonded hydrogen atom in the component (B) is less than 1 mole relative to 1 mole of the silicon atom-bonded alkenyl group in the component (A), the composition may not be cured sufficiently, and this is 10 moles. If it exceeds 1, the heat resistance of the resulting cured silicone rubber is extremely deteriorated.
［（Ｃ）成分］
　（Ｃ）成分の補強性シリカ微粉末は、ゴムの補強剤として使用されるもので、ＢＥＴ法による比表面積が５０ｍ2／ｇ以上のものが用いられる。特にＢＥＴ法による比表面積が５０～４００ｍ2／ｇ、とりわけ１００～３５０ｍ2／ｇの、沈澱シリカ（湿式シリカ）、ヒュームドシリカ（乾式シリカ）、焼成シリカ等が好適に使用され、ゴム強度を向上することからヒュームドシリカが好適である。また、上記補強性シリカ微粉末は、後述する表面処理剤で、表面が疎水化処理されたシリカ微粉末であってもよい。その場合、これらのシリカ微粉末は、予め粉体の状態で、表面処理剤により直接、表面疎水化処理されたものでもよいし、シリコーンオイル（例えば、上記（Ａ）成分のアルケニル基含有オルガノポリシロキサン）との混練時に表面処理剤を添加して、表面疎水化処理したものでもよい。 [Component (C)]
The reinforcing silica fine powder of component (C) is used as a rubber reinforcing agent, and has a specific surface area of 50 m 2 / g or more by the BET method. In particular, precipitated silica (wet silica), fumed silica (dry silica), calcined silica, etc., having a specific surface area by the BET method of 50 to 400 m 2 / g, particularly 100 to 350 m 2 / g, are preferably used to improve rubber strength. From the viewpoint of improvement, fumed silica is preferable. Further, the reinforcing silica fine powder may be a silica fine powder whose surface has been hydrophobized with a surface treatment agent to be described later. In that case, these silica fine powders may be in a powder state and have been subjected to a surface hydrophobization treatment directly with a surface treatment agent, or may be a silicone oil (for example, an alkenyl group-containing organopolysiloxane of component (A) above). A surface treatment agent may be added at the time of kneading with (siloxane) to make the surface hydrophobic.
　表面処理方法としては、例えば、常圧で密閉された機械混練装置又は流動層に上記未処理のシリカ微粉末と表面処理剤を入れ、必要に応じて不活性ガス存在下において室温あるいは熱処理（加熱下）にて混合処理することができる。場合により、触媒（加水分解促進剤等）を使用して表面処理を促進してもよい。混練後、乾燥することにより表面処理シリカ微粉末を製造し得る。表面処理剤の配合量は、その表面処理剤の被覆面積から計算される量以上であればよく、通常、未処理のシリカ微粉末１００質量部に対し、１～５０質量部、好ましくは５～４０質量部、より好ましくは１０～３０質量部とすることができる。 As the surface treatment method, for example, the untreated silica fine powder and the surface treatment agent are placed in a mechanical kneading apparatus or fluidized bed sealed at normal pressure, and at room temperature or heat treatment (heating) in the presence of an inert gas as necessary. The lower part) can be mixed. In some cases, a surface treatment may be promoted by using a catalyst (hydrolysis accelerator or the like). After kneading, the surface-treated silica fine powder can be produced by drying. The compounding amount of the surface treatment agent may be an amount calculated from the coating area of the surface treatment agent, and is usually 1 to 50 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass of untreated silica fine powder. The amount can be 40 parts by mass, more preferably 10 to 30 parts by mass.
　表面処理剤としては、具体的には、へキサメチルジシラザン、１，１，３，３，５，５－ヘキサメチルシクロトリシラザン等のシラザン類、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、ビニルトリス（メトキシエトキシ）シラン、トリメチルクロロシラン、ジメチルジクロロシラン、ジビニルジメトキシシラン、クロロプロピルトリメトキシシラン、トリメチルシラノール及びヒドロキシペンタメチルジシロキサン等のシランカップリング剤、ポリメチルシロキサン、オルガノハイドロジェンポリシロキサン等の有機ケイ素化合物が挙げられ、これらで表面処理し、疎水性シリカ微粉末として用いる。処理剤としては、特にシラン系カップリング剤又はシラザン類が好ましい。 Specific examples of the surface treatment agent include silazanes such as hexamethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyl Trimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) silane, trimethylchlorosilane, dimethyldichlorosilane, divinyl Silane coupling agents such as dimethoxysilane, chloropropyltrimethoxysilane, trimethylsilanol and hydroxypentamethyldisiloxane, polymethylsiloxane, organohydrogen Organosilicon compounds such as polysiloxane and the like, which in a surface treatment, is used as the hydrophobic silica fine powder. As the treating agent, silane coupling agents or silazanes are particularly preferable.
　（Ｃ）成分の配合量は、（Ａ）成分１００質量部に対して、０．１～１００質量部、好ましくは５～６０質量部、より好ましくは１０～６０質量部である。（Ｃ）成分の配合量が、０．１質量部より少ないと十分な補強効果が得られず、また１００質量部を超えるとシリコーンゴム組成物が高粘度になり、取扱い作業性が悪くなる。 The compounding amount of the component (C) is 0.1 to 100 parts by mass, preferably 5 to 60 parts by mass, and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of component (C) is less than 0.1 parts by mass, a sufficient reinforcing effect cannot be obtained, and when it exceeds 100 parts by mass, the silicone rubber composition becomes highly viscous and handling operability is deteriorated.
［（Ｄ）成分］
　（Ｄ）成分の白金族金属系触媒としては、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金族金属系触媒が挙げられる。なお、この白金族金属系触媒の配合量は触媒量とすることができ、通常、白金族金属（質量換算）として、（Ａ）～（Ｅ）成分の合計質量に対し、０．５～１，０００ｐｐｍ、特に１～５００ｐｐｍ程度である。添加量が少なすぎると硬化性の低下を起こし、添加量が多すぎると耐熱性が悪化することがある。 [(D) component]
As the platinum group metal catalyst of component (D), platinum black, chloroplatinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, platinum bisacetate Examples include platinum group metal catalysts such as acetate. The compounding amount of the platinum group metal catalyst can be a catalytic amount. Usually, the platinum group metal (in terms of mass) is 0.5 to 1 with respect to the total mass of the components (A) to (E). 1,000 ppm, particularly about 1 to 500 ppm. If the amount added is too small, the curability may be lowered, and if the amount added is too large, the heat resistance may deteriorate.
［（Ｅ）成分］
　本発明に用いられる（Ｅ）成分のケイ酸塩鉱物微粉末は、耐油性向上剤として作用する。かかるケイ酸塩鉱物微粉末は、レーザー回折法によるメジアン径が０．１～３０μｍであることが好ましく、さらに０．３～２０μｍであることがより好ましい。メジアン径が３０μｍより大きいとシリコーンゴム組成物の物性低下を引き起こすことがあり、また０．１μｍより小さいとシリコーンゴム組成物の粘度が高くなり、成形が困難となることがある。 [(E) component]
The silicate mineral fine powder of component (E) used in the present invention acts as an oil resistance improver. The fine silicate mineral powder preferably has a median diameter of 0.1 to 30 μm, more preferably 0.3 to 20 μm, as measured by a laser diffraction method. When the median diameter is larger than 30 μm, the physical properties of the silicone rubber composition may be lowered. When the median diameter is smaller than 0.1 μm, the viscosity of the silicone rubber composition becomes high, and molding may be difficult.
　また、（Ｅ）成分のケイ酸塩鉱物微粉末は、ＪＩＳ　Ｚ　８７２２：２００９に準じて測定したハンター法における白色度が８０％以上であることが好ましく、さらに８５％以上であることがより好ましい。白色度が８０％よりも低いとケイ酸塩鉱物に含まれる不純物の割合が大きく、シリコーンゴム組成物の物性低下を引き起こすことがある。 In addition, the silicate mineral fine powder of component (E) preferably has a whiteness of 80% or more, more preferably 85% or more in the Hunter method measured according to JIS Z 8722: 2009. . When the whiteness is lower than 80%, the proportion of impurities contained in the silicate mineral is large, which may cause deterioration of physical properties of the silicone rubber composition.
　また、（Ｅ）成分のケイ酸塩鉱物微粉末は、ＪＩＳ　Ｋ　５１０１－１３－１：２００４に準じて測定した吸油量が２０～８０ｍｌ／１００ｇであることが好ましく、さらに３０～６０ｍｌ／１００ｇであることがより好ましい。吸油量が２０ｍｌ／１００ｇより低いと十分な耐油性向上効果が得られないことがあり、また８０ｍｌ／１００ｇより高いとシリコーンゴム組成物の粘度が高くなり作業性が悪化することがある。 The fine silicate mineral powder of component (E) preferably has an oil absorption of 20 to 80 ml / 100 g, more preferably 30 to 60 ml / 100 g, measured according to JIS K 5101-13-1: 2004. More preferably. If the oil absorption is lower than 20 ml / 100 g, a sufficient oil resistance improvement effect may not be obtained, and if it is higher than 80 ml / 100 g, the viscosity of the silicone rubber composition may increase and workability may deteriorate.
　このようなケイ酸塩鉱物微粉末としては、ネソケイ酸塩鉱物、ソロケイ酸塩鉱物、サイクロケイ酸塩鉱物、イノケイ酸塩鉱物、フィロケイ酸塩鉱物、テクトケイ酸塩鉱物などのケイ酸塩鉱物の微粉末が挙げられ、中でも白雲母、黒雲母、金雲母などの雲母類やカオリナイト（カオリン）、モンモリロナイト（酸性白土、活性白土）、セリサイト、タルク、ゼオライトなどの粘土鉱物から選ばれるフィロケイ酸塩鉱物が好ましく用いられる。特には、タルク（化学式：Ｍｇ3Ｓｉ4Ｏ10（ＯＨ）2）又はカオリナイト（カオリン）（化学式：Ａｌ4Ｓｉ4Ｏ10（ＯＨ）8）であることが好ましい。 Such fine silicate mineral powders include fine silicate minerals such as nesosilicate minerals, solosilicate minerals, cyclosilicate minerals, inosilicate minerals, phyllosilicate minerals, and tectosilicate minerals. Pyrosilicates selected from clay minerals such as mica such as muscovite, biotite, phlogopite, kaolinite (kaolin), montmorillonite (acid clay, activated clay), sericite, talc, zeolite. Minerals are preferably used. In particular, talc (chemical formula: Mg 3 Si 4 O 10 (OH) 2 ) or kaolinite (kaolin) (chemical formula: Al 4 Si 4 O 10 (OH) 8 ) is preferable.
　本発明において、このようなケイ酸塩鉱物微粉末は、メジアン径、白色度及び吸油量が上記範囲内であれば、１種又は２種以上を併用して用いることができる。 In the present invention, such fine silicate mineral powders can be used singly or in combination of two or more if the median diameter, whiteness and oil absorption are within the above ranges.
　本発明において、上記ケイ酸塩鉱物微粉末には、表面未処理のものを用いることもできるが、後述する表面処理剤で、表面処理されたケイ酸塩鉱物微粉末を用いることもできる。 In the present invention, the silicate mineral fine powder may be a surface-untreated one, but a silicate mineral fine powder that has been surface-treated with a surface treatment agent described later can also be used.
　ケイ酸塩鉱物微粉末の表面処理方法としては、例えば、常圧で密閉された機械混練装置又は流動層に上記未処理のケイ酸塩鉱物微粉末と表面処理剤を入れ、必要に応じて不活性ガス存在下において室温（２５℃）あるいは熱処理（加熱下）にて混合処理することができる。場合により、水又は触媒（加水分解促進剤等）を使用して表面処理を促進してもよい。混練後、乾燥することにより表面処理ケイ酸塩鉱物微粉末を製造し得る。表面処理剤の配合量は、その表面処理剤の被覆面積から計算される量以上であればよく、通常、未処理のケイ酸塩鉱物微粉末１００質量部に対し、０．１～２０質量部、好ましくは０．１～１５質量部、より好ましくは０．１～１０質量部とすることができる。 As a surface treatment method of the silicate mineral fine powder, for example, the untreated silicate mineral fine powder and the surface treatment agent are placed in a mechanical kneading apparatus or fluidized bed sealed at normal pressure, and if necessary, In the presence of an active gas, mixing can be performed at room temperature (25 ° C.) or heat treatment (under heating). In some cases, the surface treatment may be accelerated using water or a catalyst (hydrolysis accelerator or the like). After the kneading, the surface-treated silicate mineral fine powder can be produced by drying. The compounding amount of the surface treatment agent may be more than the amount calculated from the coating area of the surface treatment agent, and usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the untreated fine silicate mineral powder. Preferably, the amount can be 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass.
　表面処理剤としては、具体的には、へキサメチルジシラザン、１，１，３，３，５，５－ヘキサメチルシクロトリシラザン等のシラザン類、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、ビニルトリス（メトキシエトキシ）シラン、トリメチルクロロシラン、ジメチルジクロロシラン、ジビニルジメトキシシラン、クロロプロピルトリメトキシシラン、トリメチルシラノール及びヒドロキシペンタメチルジシロキサン等のシランカップリング剤、ポリメチルシロキサン、オルガノハイドロジェンポリシロキサン等の有機ケイ素化合物が挙げられる。 Specific examples of the surface treatment agent include silazanes such as hexamethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyl Trimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) silane, trimethylchlorosilane, dimethyldichlorosilane, divinyl Silane coupling agents such as dimethoxysilane, chloropropyltrimethoxysilane, trimethylsilanol and hydroxypentamethyldisiloxane, polymethylsiloxane, organohydrogen Organosilicon compounds such as Li siloxanes.
　（Ｅ）成分の配合量は、（Ａ）成分１００質量部に対して２０～１００質量部、好ましくは２０～９０質量部、より好ましくは２０～８０質量部である。（Ｅ）成分の配合量が、２０質量部よりも少ないと十分な耐油性向上の効果が得られず、また１００質量部よりも多いとシリコーンゴム組成物が高粘度になり、取扱い作業性が悪くなる。 The compounding amount of the component (E) is 20 to 100 parts by mass, preferably 20 to 90 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of the component (E) is less than 20 parts by mass, a sufficient oil resistance improvement effect cannot be obtained, and when it is more than 100 parts by mass, the silicone rubber composition becomes highly viscous and handling operability is improved. Deteriorate.
［その他の成分］
　本発明にかかる組成物には、前記（Ａ）～（Ｅ）成分以外にも、本発明の目的を損なわない範囲で、その他の任意の成分を配合することができる。その具体例としては、以下のものが挙げられる。その他の成分は、１種単独で用いても２種以上を併用してもよい。 [Other ingredients]
In addition to the components (A) to (E), other optional components can be blended in the composition according to the present invention as long as the object of the present invention is not impaired. Specific examples thereof include the following. Other components may be used alone or in combination of two or more.
・非補強性充填剤
　（Ｃ）成分及び（Ｅ）成分以外の充填剤としては、例えば、結晶性シリカ（例えば、ＢＥＴ法比表面積が５０ｍ2／ｇ未満の石英粉）、有機樹脂製中空フィラー、ポリメチルシルセスキオキサン微粒子（いわゆるシリコーンレジンパウダー）、ヒュームド二酸化チタン、酸化マグネシウム、酸化亜鉛、酸化鉄、水酸化アルミニウム、炭酸マグネシウム、炭酸カルシウム、炭酸亜鉛、層状マイカ、カーボンブラック、ケイ藻土、ガラス繊維等の充填剤；これらの充填剤をオルガノアルコキシシラン化合物、オルガノクロロシラン化合物、オルガノシラザン化合物、低分子量シロキサン化合物等の有機ケイ素化合物により表面疎水化処理した充填剤、シリコーンゴムパウダー、及びシリコーンレジンパウダーなどが挙げられる。その配合量としては、（Ａ）成分１００質量部に対し、０～１００質量部、特に０～５０質量部とすることができる。 Non-reinforcing fillers As fillers other than the components (C) and (E), for example, crystalline silica (for example, quartz powder having a BET specific surface area of less than 50 m 2 / g), hollow filler made of organic resin , Polymethylsilsesquioxane fine particles (so-called silicone resin powder), fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, zinc carbonate, layered mica, carbon black, diatomaceous earth Fillers such as glass fibers; fillers obtained by subjecting these fillers to surface hydrophobic treatment with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, low molecular weight siloxane compounds, silicone rubber powders, and silicones Resin powder etc. are mentioned. The blending amount can be 0 to 100 parts by weight, particularly 0 to 50 parts by weight, per 100 parts by weight of component (A).
・その他の成分
　その他にも、例えば、１分子中に１個のケイ素原子結合水素原子を含有し、他の官能性基を含有しないオルガノポリシロキサン、１分子中に１個のケイ素原子結合アルケニル基を含有し、他の官能性基を含有しないオルガノポリシロキサン、ケイ素原子結合水素原子もケイ素原子結合アルケニル基も他の官能性基も含有しない無官能性のオルガノポリシロキサン（いわゆるジメチルシリコーンオイル）、有機溶剤、クリープハードニング防止剤、可塑剤、チキソ性付与剤、顔料、染料、防かび剤などを配合することができる。 Other components In addition, for example, an organopolysiloxane containing one silicon-bonded hydrogen atom in one molecule and no other functional group, one silicon-bonded alkenyl group in one molecule An organopolysiloxane containing no other functional groups, a non-functional organopolysiloxane containing no silicon-bonded hydrogen atoms, silicon-bonded alkenyl groups, or other functional groups (so-called dimethyl silicone oil), An organic solvent, an anti-creep hardening agent, a plasticizer, a thixotropic agent, a pigment, a dye, an antifungal agent and the like can be blended.
　この付加硬化性シリコーンゴム組成物の成形、硬化方法としては、常法を採用し得るが、成形法として、射出成形、トランスファー成形、注入成形、圧縮成形等から目的にあった最適な手段を選択することが可能である。
　硬化条件としては、８０～２３０℃、好ましくは１００～１８０℃で加熱することにより該組成物を硬化させることができる。加熱時間は、３０秒～３時間程度、特に１分～１時間程度が好ましい。更に、必要に応じて任意に、４０～２３０℃で１０分～２４時間程度の二次加硫（ポストキュア）を行ってもよい。 As a method for molding and curing the addition-curable silicone rubber composition, a conventional method can be adopted. However, as a molding method, an optimum method selected from injection molding, transfer molding, injection molding, compression molding and the like is selected. Is possible.
As the curing conditions, the composition can be cured by heating at 80 to 230 ° C., preferably 100 to 180 ° C. The heating time is preferably about 30 seconds to 3 hours, particularly preferably about 1 minute to 1 hour. Further, secondary vulcanization (post-cure) may be performed at 40 to 230 ° C. for about 10 minutes to 24 hours as required.
［耐油性シリコーンゴム］
　こうして得られる本発明組成物の硬化物は、エンジンオイル、ＡＴＦなどの鉱物油をベースとした潤滑油等の油と高温下で長時間接触してもゴム物性の低下が小さく、且つゴム物性に優れたシリコーンゴムとなる。従って、該耐油性シリコーンゴムは、高温下で長時間にわたりオイルと一時的あるいは常時接触する条件でも使用することができ、Ｏ－リング、パッキン、ガスケット、シール材等の自動車オイルフィルターシール部材に好適に用いることができる。 [Oil-resistant silicone rubber]
The cured product of the composition of the present invention thus obtained has a small decrease in rubber properties even when contacted for a long time at high temperature with oils such as engine oils and lubricating oils based on mineral oils such as ATF. Excellent silicone rubber. Therefore, the oil-resistant silicone rubber can be used under conditions of temporary or constant contact with oil for a long time at high temperature, and is suitable for automotive oil filter seal members such as O-rings, packings, gaskets, and sealing materials. Can be used.
　以下、調製例及び実施例と比較例により本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、下記例で部は質量部を示す。また、平均重合度は、トルエンを展開溶媒としたゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析におけるポリスチレン換算の数平均重合度を示す。 Hereinafter, the present invention will be described in detail with reference to Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, a part shows a mass part by the following example. Moreover, an average degree of polymerization shows the number average degree of polymerization of polystyrene conversion in the gel permeation chromatography (GPC) analysis which used toluene as the developing solvent.
［調製例１］
　分子鎖両末端がビニルジメチルシロキシ基で封鎖され、２５℃での粘度が３０，０００ｍＰａ・ｓのジメチルポリシロキサン（Ａ１）６０部、ヘキサメチルジシラザン８部、水２部、比表面積がＢＥＴ法で３００ｍ2／ｇであるシリカ微粉末（Ｃ）（Ａｅｒｏｓｉｌ　３００、日本アエロジル社製）４０部をニーダー中に投入し、室温にて１時間混合した。その後温度を１５０℃に昇温し、引き続き２時間混合した。この後、室温まで降温して分子鎖両末端がビニルジメチルシロキシ基で封鎖され、２５℃での粘度が３０，０００ｍＰａ・ｓのジメチルポリシロキサン（Ａ１）２４部、主鎖を構成する２官能性ジオルガノシロキサン単位のうちビニルメチルシロキサン単位を５モル％、ジメチルシロキサン単位を９５モル％含有し、分子鎖両末端がトリメチルシロキシ基で封鎖された２５℃での粘度が７００ｍＰａ・ｓのジメチル－ビニルメチルポリシロキサン（Ａ２）５部を添加して均一になるまで混合し、ベースコンパウンド（Ｉ）を得た。 [Preparation Example 1]
Both ends of the molecular chain are blocked with vinyldimethylsiloxy groups, 60 parts of dimethylpolysiloxane (A1) having a viscosity of 30,000 mPa · s at 25 ° C., 8 parts of hexamethyldisilazane, 2 parts of water, specific surface area is BET method 40 parts of silica fine powder (C) (Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.) of 300 m 2 / g was put into a kneader and mixed at room temperature for 1 hour. Thereafter, the temperature was raised to 150 ° C., followed by mixing for 2 hours. Thereafter, the temperature is lowered to room temperature, both ends of the molecular chain are blocked with vinyldimethylsiloxy groups, 24 parts of dimethylpolysiloxane (A1) having a viscosity at 25 ° C. of 30,000 mPa · s, and the bifunctionality constituting the main chain Dimethyl-vinyl having a viscosity of 700 mPa · s at 25 ° C. containing 5 mol% of vinylmethylsiloxane units and 95 mol% of dimethylsiloxane units and having both ends of the molecular chain blocked with trimethylsiloxy groups. 5 parts of methylpolysiloxane (A2) was added and mixed until uniform to obtain a base compound (I).
［実施例１］
　調製例１で調製したベースコンパウンド（Ｉ）を１２８部に、分子鎖両末端がビニルジメチルシロキシ基で封鎖され、２５℃での粘度が３０，０００ｍＰａ・ｓのジメチルポリシロキサン（Ａ１）４６部、架橋剤として分子鎖両末端がトリメチルシロキシ基で封鎖され、側鎖にＳｉＨ基を有するメチルハイドロジェンポリシロキサン（Ｂ１）（平均重合度４０、ＳｉＨ基量０．００７３ｍｏｌ／ｇの分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体）１．７５部、両末端がジメチルハイドロジェンシロキシ基で封鎖され、ケイ素原子に直接結合する酸素原子、水素原子以外の、ケイ素原子に結合する１価炭化水素基の全てがメチル基であるオルガノハイドロジェンポリシロキサン（Ｂ２）（平均重合度２０、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、ＳｉＨ基量０．００１４ｍｏｌ／ｇ）１．７５部（ＳｉＨ基／ビニル基＝１．８ｍｏｌ／ｍｏｌ）、メジアン径が５．２μｍであり、白色度が９５．９％であり、吸油量が４０ｍｌ／１００ｇであるタルク（日本タルク株式会社製：商品名ＭＩＣＲＯ　ＡＣＥ　Ｐ－３）を５０部（Ｅ）、及び反応制御剤としてエチニルシクロヘキサノール０．０６部を添加し、１５分撹拌した。次いで白金と１，３－ジビニル－１，１，３，３－テトラメチルジシロキサンの錯体のトルエン溶液（Ｄ）（白金原子１質量％）０．１０部を添加し、１５分間撹拌して均一なシリコーンゴム組成物を調製し、１２０℃、１０分でプレスキュアーした後に、１５０℃の乾燥機で１時間のポストキュアをすることで、１３０ｍｍ×１７０ｍｍ×２．２ｍｍの硬化物シートを作製し、このシートについてＪＩＳ　Ｋ　６２４９：２００３に従って、硬さ、切断時伸び、引張強さの測定を行い、初期物性を評価した結果を表１に示した。また、ＪＩＳ　Ｋ　６２５８：２０１０に準拠し、試験油に１５０℃×７０時間浸漬後のシートについて、硬さ、切断時伸び、引張強さを測定し、耐油性を評価した結果を表１に示した。なお、試験油にはＪＩＳ　Ｋ　６２５８：２０１０で規定された、試験用潤滑油Ｎｏ．１油に相当するＩＲＭ－９０１（日本サン石油株式会社製）を使用した。 [Example 1]
128 parts of the base compound (I) prepared in Preparation Example 1, 46 parts of dimethylpolysiloxane (A1) having both molecular chain ends blocked with vinyldimethylsiloxy groups and a viscosity at 25 ° C. of 30,000 mPa · s, Methyl hydrogen polysiloxane (B1) having both ends of a molecular chain blocked with trimethylsiloxy groups as cross-linking agents and having SiH groups in the side chain (average molecular degree 40, SiH group amount 0.0073 mol / g molecular chain both ends trimethyl Siloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer) 1.75 parts, both ends blocked with dimethylhydrogensiloxy groups, bonded to silicon atoms other than oxygen and hydrogen atoms directly bonded to silicon atoms Organohydrogenpolysiloxane in which all monovalent hydrocarbon groups are methyl groups (B2 (Average polymerization degree 20, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, SiH group amount 0.0014 mol / g) 1.75 parts (SiH group / vinyl group = 1.8 mol / mol), median diameter is 50 parts (E) of talc (trade name: MICRO ACE P-3, manufactured by Nippon Talc Co., Ltd.) having 5.2 μm, whiteness of 95.9% and oil absorption of 40 ml / 100 g, and reaction control 0.06 part of ethynylcyclohexanol was added as an agent and stirred for 15 minutes. Next, 0.10 parts of a toluene solution (D) of a complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (D) (platinum atom 1% by mass) was added and stirred for 15 minutes to be uniform. A silicone rubber composition was prepared, press cured at 120 ° C. for 10 minutes, and then cured for 1 hour with a dryer at 150 ° C. to produce a cured sheet of 130 mm × 170 mm × 2.2 mm. The sheet was measured for hardness, elongation at break and tensile strength according to JIS K 6249: 2003, and the results of evaluating the initial physical properties are shown in Table 1. Table 1 shows the results of measuring the oil resistance by measuring the hardness, elongation at break, and tensile strength of the sheet after being immersed in test oil at 150 ° C. for 70 hours in accordance with JIS K 6258: 2010. It was. Note that the test oil specified in JIS K 6258: 2010 is a test lubricant No. IRM-901 (Nihon Sun Oil Co., Ltd.) corresponding to 1 oil was used.
［実施例２］
　実施例１のタルクをメジアン径が７．０μｍであり、白色度が９５．０％であり、吸油量が３５ｍｌ／１００ｇであるタルク（日本タルク株式会社製：商品名ＭＩＣＲＯ　ＡＣＥ　Ｋ－１）に同質量部で置き換えたこと以外は全て、同一処方にて、シリコーンゴム組成物を調製し、実施例１と同様の条件でシートを作製し、初期物性、耐油性を評価した結果を表１に示した。 [Example 2]
The talc of Example 1 has a median diameter of 7.0 μm, a whiteness of 95.0%, and an oil absorption of 35 ml / 100 g (trade name MICRO ACE K-1 manufactured by Nippon Talc Co., Ltd.). Table 1 shows the results of preparing a silicone rubber composition with the same formulation, producing a sheet under the same conditions as in Example 1, and evaluating the initial physical properties and oil resistance, except that the same mass part was replaced. Indicated.
［実施例３］
　実施例１のタルクをメジアン径が０．４μｍであり、白色度が９６％であり、吸油量が４５ｍｌ／１００ｇであるカオリナイト（ＢＡＳＦ社製：商品名　ＡＳＰ－１７０）に同質量部で置き換えたこと以外は全て、同一処方にて、シリコーンゴム組成物を調製し、実施例１と同様の条件でシートを作製し、初期物性、耐油性を評価した結果を表１に示した。 [Example 3]
The talc of Example 1 was replaced with kaolinite (manufactured by BASF: trade name ASP-170) having the same median diameter of 0.4 μm, whiteness of 96%, and oil absorption of 45 ml / 100 g with the same parts by mass. Table 1 shows the results of preparing a silicone rubber composition with the same formulation, producing a sheet under the same conditions as in Example 1, and evaluating the initial physical properties and oil resistance.
［比較例１］
　実施例１のタルクを添加しなかったこと以外は全て、同一処方にて、シリコーンゴム組成物を調製し、実施例１と同様の条件でシートを作製し、初期物性、耐油性を評価した結果を表１に示した。 [Comparative Example 1]
All except that talc of Example 1 was not added, a silicone rubber composition was prepared with the same formulation, a sheet was produced under the same conditions as in Example 1, and the initial physical properties and oil resistance were evaluated. Are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の結果より、本発明の条件を満たす組成物（実施例）は良好な初期物性を有し、且つ耐油試験後のゴム物性の低下が小さく、耐油性に優れているのに対して、本発明の条件を満たさない組成物（比較例）は耐油試験後のゴム物性の低下が大きいため、シール材としては不十分なものであり、耐油性に劣ることが確認された。 From the results shown in Table 1, compositions (Examples) that satisfy the conditions of the present invention have good initial physical properties, and the decrease in rubber physical properties after the oil resistance test is small, while the oil resistance is excellent. Since the composition (comparative example) which does not satisfy the conditions of the present invention has a large decrease in rubber physical properties after the oil resistance test, it was insufficient as a sealing material, and it was confirmed that the composition was inferior in oil resistance.

Claims (6)

  1. 　（Ａ）１分子中に２個以上のケイ素原子に結合したアルケニル基を含有する２５℃で液状のオルガノポリシロキサン：１００質量部、
    （Ｂ）１分子中に少なくとも２個のケイ素原子に結合した水素原子を含有するオルガノハイドロジェンポリシロキサン：本成分の１分子中に含まれるケイ素原子に結合した水素原子の数が、（Ａ）成分中のケイ素原子結合アルケニル基の合計１個当たり、１～１０個となる量、
    （Ｃ）ＢＥＴ法における比表面積が５０ｍ2／ｇ以上である補強性シリカ微粉末：０．１～１００質量部、
    （Ｄ）ヒドロシリル化反応用触媒としての白金族金属系触媒：有効量、
    （Ｅ）ケイ酸塩鉱物微粉末：２０～１００質量部、
    を含有する自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。     (A) Organopolysiloxane liquid at 25 ° C. containing alkenyl groups bonded to two or more silicon atoms in one molecule: 100 parts by mass
    (B) Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: The number of hydrogen atoms bonded to silicon atoms contained in one molecule of this component is (A) An amount of 1 to 10 per total of silicon-bonded alkenyl groups in the component,
    (C) Reinforcing silica fine powder having a specific surface area of 50 m 2 / g or more in the BET method: 0.1 to 100 parts by mass,
    (D) platinum group metal catalyst as hydrosilylation catalyst: effective amount,
    (E) Fine silicate mineral powder: 20 to 100 parts by mass,
    Addition-curing liquid silicone rubber composition for automobile oil filter seal members.
  2. 　（Ｅ）成分のレーザー回折法によるメジアン径が０．１～３０μｍである請求項１に記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。 2. The addition-curable liquid silicone rubber composition for automobile oil filter seal members according to claim 1, wherein the median diameter of component (E) by laser diffraction method is 0.1 to 30 μm.
  3. 　（Ｅ）成分のＪＩＳ　Ｚ　８７２２：２００９に準じて測定したハンター法における白色度が８０％以上である請求項１又は２に記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。 The addition curing type liquid silicone rubber composition for automobile oil filter seal members according to claim 1 or 2, wherein the whiteness in the Hunter method measured in accordance with JIS Z 8722: 2009 of the component (E) is 80% or more.
  4. 　（Ｅ）成分のＪＩＳ　Ｋ　５１０１－１３－１：２００４に準じて測定した吸油量が２０～８０ｍｌ／１００ｇである請求項１～３のいずれか１項に記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。 The addition curing for an automobile oil filter seal member according to any one of claims 1 to 3, wherein the oil absorption measured according to JIS K 5101-13-1: 2004 of component (E) is 20 to 80 ml / 100 g. Type liquid silicone rubber composition.
  5. 　（Ｅ）成分が、タルク、カオリナイト、又はカオリンである請求項１～４のいずれか１項に記載の自動車オイルフィルターシール部材用付加硬化型液状シリコーンゴム組成物。 The addition-curable liquid silicone rubber composition for automobile oil filter seal members according to any one of claims 1 to 4, wherein the component (E) is talc, kaolinite, or kaolin.
  6. 　請求項１～５のいずれか１項に記載のシリコーンゴム組成物の硬化物からなる自動車オイルフィルターシール部材。 An automobile oil filter seal member comprising a cured product of the silicone rubber composition according to any one of claims 1 to 5.
PCT/JP2017/037534 2016-11-17 2017-10-17 Addition-curable liquid silicone rubber composition for automobile oil filter sealing member, and automobile oil filter sealing member WO2018092490A1 (en)

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JPH055064A (en) * 1991-06-27 1993-01-14 Toray Dow Corning Silicone Co Ltd Silicone rubber composition for gasket
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