WO2022030235A1 - Addition-curable silicone rubber composition - Google Patents

Addition-curable silicone rubber composition Download PDF

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Publication number
WO2022030235A1
WO2022030235A1 PCT/JP2021/026907 JP2021026907W WO2022030235A1 WO 2022030235 A1 WO2022030235 A1 WO 2022030235A1 JP 2021026907 W JP2021026907 W JP 2021026907W WO 2022030235 A1 WO2022030235 A1 WO 2022030235A1
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group
silicone rubber
rubber composition
component
alkenyl group
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PCT/JP2021/026907
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French (fr)
Japanese (ja)
Inventor
野歩 加藤
重揮 首藤
幹夫 飯野
毅 橋本
立栄 原
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信越化学工業株式会社
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Priority to JP2022541421A priority Critical patent/JPWO2022030235A1/ja
Publication of WO2022030235A1 publication Critical patent/WO2022030235A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to an addition curable silicone rubber composition.
  • silicone rubber used as an optical waveguide for LED lights and the like is required to have a high hardness (JIS K 6253, durometer type A) of 65 or more.
  • a high hardness JIS K 6253, durometer type A
  • first, primary vulcanization using a mold is performed, and then a high-temperature dryer (orange) is used for the purpose of stabilizing physical properties and removing volatile components in the cured product.
  • Secondary vulcanization is performed using.
  • high-hardness silicone rubber containing no reinforcing silica when the cured product is taken out from the mold after primary molding, it is hard and has low extensibility, so that there is a problem that the cured product is scratched or torn.
  • the present invention has been made to improve the above circumstances, and an object of the present invention is to provide an additive-curable silicone rubber composition which is excellent in removability from a mold and can give a cured product having high transparency. do.
  • the addition curable silicone rubber composition is used.
  • R 1 is a monovalent hydrocarbon group independently selected from an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and has an average of 2.5 in one molecule. It has more than one alkenyl group and is 0 ⁇ a ⁇ 0.7, 0 ⁇ b ⁇ 0.2, 0 ⁇ c ⁇ 0.2, 0 ⁇ d ⁇ 0.7, where 0.8 ⁇ a + d.
  • the ratio of the number of moles of H groups (Si—H group / total alkenyl group) is 1.0 to 1.5, and the torsional vibration type conical die vulcanization tester (B-) described in JIS K 6300-2: 2001.
  • the vulcanization test using method 2 when the 10% curing time at 150 ° C. for 5 minutes is T10 and the 90% curing time is T90, the T90-T10 is 160 seconds or more.
  • the composition is provided.
  • the amount of the alkenyl group of the component (A) is 0.00006 mol / g or less.
  • the amount of the alkenyl group of the component (B) is 0.0006 to 0.001 mol / g.
  • the hardness of the cured product and the elongation at the time of cutting after the primary vulcanization are preferable.
  • the hardness after the primary vulcanization (durometer type A) is as low as 55 or less, the elongation rate at the time of cutting is 300% or more, and the hardness after the secondary vulcanization can be 65 or more.
  • a vulcanized silicone rubber composition can be obtained, which is excellent in ease of removal from a mold and gives a highly transparent cured product.
  • the present inventor has a relatively long chain alkenyl-containing linear organopolysiloxane, a specific alkenyl group-containing silicone resin, and an organohydrogen having a specific structure.
  • siloxane in an appropriate ratio and adjusting the composition so that the difference between the 10% curing time and the 90% curing time in the vulcanization test becomes large, the hardness of the cured product after the primary vulcanization is 55.
  • the elongation at the time of cutting can be set to 300% or more, and further, the hardness can be increased to the desired hardness (for example, 65 or more) by secondary vulcanization, and the silicone rubber composition gives a highly transparent cured product. It was found that a product could be obtained, and the present invention was made.
  • the present invention is an addition curable silicone rubber composition.
  • a linear organopolysiloxane having an average degree of polymerization of 480 or more and containing an alkenyl group bonded to at least two silicon atoms in one molecule.
  • B Silicone resin containing an alkenyl group represented by the following formula (1) (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) ) D (1)
  • R 1 is a monovalent hydrocarbon group independently selected from an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and has an average of 2.5 in one molecule.
  • F is an integer of 0 to 100, e / (e + f) is 40 mol% or more, and the number of silicon atom-bonded hydrogen groups in one molecule is 10 or more).
  • D Addition reaction catalyst: 0.1 to 10 ppm as a platinum group metal (mass equivalent) with respect to the total mass of the composition.
  • the ratio of the number of moles of H groups (Si—H group / total alkenyl group) is 1.0 to 1.5, and the torsional vibration type conical die vulcanization tester (B-) described in JIS K 6300-2: 2001.
  • the T90-T10 is 160 seconds or more. It is a composition.
  • the addition curable silicone rubber composition of the present invention is characterized by containing the following components (A) to (D).
  • the curable silicone rubber composition is preferably liquid.
  • (A) Linear organopolysiloxane containing an alkenyl group
  • the organopolysiloxane (A) component has an alkenyl group bonded to at least two silicon atoms in one molecule and has an average degree of polymerization of 480 or more. It is a linear organopolysiloxane containing an alkenyl group.
  • a component represented by the following general formula (3) can be preferably used.
  • R4 is a monovalent hydrocarbon group selected from the same or different alkyl groups having 1 to 10 carbon atoms and alkenyl groups having 2 to 10 carbon atoms, and g is 500 or more, usually 500 to 10, 000, preferably an integer of 500 to 8,000.
  • Examples of the monovalent hydrocarbon group represented by R4 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group; a vinyl group, an allyl group, a butenyl group and a pentenyl group. Examples thereof include an alkenyl group such as a hexenyl group and a cyclohexenyl group.
  • a methyl group is preferable as R4 , but it is necessary that the molecule contains two or more alkenyl groups.
  • a vinyl group is preferable as the alkenyl group.
  • alkenyl group-containing linear organopolysiloxane examples include both-ended dimethylvinylsiloxy group-blocked dimethylpolysiloxane, both-ended dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, and both-ended trimethylsiloxy group-blocked dimethylsiloxane.
  • Examples thereof include a methylvinylsiloxane copolymer, a double-ended trivinylsiloxy group-blocked dimethylpolysiloxane, and a double-ended trivinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer. These may be used alone or in combination of two or more.
  • the average degree of polymerization of this organopolysiloxane needs to be 480 or more, usually 480 to 10,000, preferably 500 to 8,000. If it is less than 480, the elongation of the rubber after the primary vulcanization will be low.
  • the average degree of polymerization referred to in the present invention refers to a number average degree of polymerization, and refers to an average degree of polymerization using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions. ..
  • the amount of alkenyl groups bonded to silicon atoms (alkenyl group amount) in this organopolysiloxane needs to be 0.00006 mol / g or less, and is usually 0.00006 to 0.000003 mol / g, preferably 0.00006 to 0.000003 mol / g. It is 0.00006 to 0.000006 mol / g, more preferably 0.00006 to 0.00001 mol / g. If it is 0.00006 mol / g or less, the elongation of the rubber after the primary vulcanization does not decrease.
  • the component (A) if it is a linear organopolysiloxane containing an alkenyl group, the molecular structure (for example, the type of the substituent of the triorganosyloxy group at the end of the molecular chain or the diorganosiloxane unit of the main chain) One type or two or more types having different ratios) and degree of polymerization can be used in combination.
  • the alkenyl group-containing silicone resin (B) component is R 1 3 SiO 1/2 unit (M unit), R 1 2 SiO 2/2 unit (D unit), R 1 SiO 3/2 unit (T unit).
  • a silicone resin composed of a constituent unit selected from SiO 4/2 units (Q units), and the silicone resin is represented by the following formula (1).
  • R 1 is a monovalent hydrocarbon group independently selected from an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms.
  • R4 of the above formula (3) can be exemplified, and at least 2.5 Rs, preferably 2.5-5 Rs in one molecule are allowed.
  • 1 is an alkenyl group. If the average number of alkenyl groups in one molecule is less than 2.5, the cured product becomes sticky and difficult to handle.
  • the component (B) is preferably a vinyl group as the alkenyl group from the viewpoint of compatibility with other components, and 80 mol% or more of R1 is preferably a methyl group.
  • a is 0 ⁇ a ⁇ 0.7, preferably 0.3 ⁇ a ⁇ 0.7
  • b is 0 ⁇ b ⁇ 0.2, preferably 0 ⁇ b ⁇ 0.1
  • c is 0 ⁇ c ⁇ 0.2, preferably 0 ⁇ c ⁇ 0.1
  • d is 0 ⁇ d ⁇ 0.7, preferably 0.3 ⁇ d ⁇ 0.7
  • a + b + c + d. 1 is the number.
  • the M unit and the Q unit are indispensable among the above four types of constituent units.
  • the D unit and the T unit may or may not be included.
  • the molar ratio (a / d) between the M unit and the Q unit is 0.5 or more, the compatibility between the component (B) and other components does not deteriorate, and if it is 1.5 or less, the compatibility is not deteriorated. There is no risk that the hardness of the cured product of the additive curable silicone rubber composition will decrease. Therefore, the molar ratio (a / d) of the M unit and the Q unit is preferably in the range of 0.5 to 1.5, and more preferably in the range of 0.7 to 1.2.
  • the alkenyl group content (alkenyl group amount) of the component (B) is preferably 0.0006 to 0.001 mol / g, more preferably 0.0007 to 0.001 mol / g. If the alkenyl group content is 0.0006 mol / g or more, the cured product will not be too hard, and if it is 0.001 mol / g or less, the elongation at the time of cutting after the primary vulcanization will be low. It never ends up.
  • the silicone resin of the component (B) include a copolymer of a vinyldimethylsiloxy group and a Q unit, a polymer of a vinyldimethylsiloxy group / a trimethylsiloxy group and a Q unit, and a vinyldimethylsiloxy group / dimethyl.
  • examples thereof include a copolymer of siloxane and Q unit, a copolymer of trimethylsiloxy group / vinylmethylsiloxane and Q unit, and the like. These may be used alone or in combination of two or more.
  • the organohydrogenpolysiloxane (C) component is a linear organohydrogenpolysiloxane having a hydrogen atom (Si—H group) bonded to a silicon atom, and the Si—H group in the molecule is the above-mentioned. It cross-links with an alkenyl group bonded to a silicon atom such as a component (A) and a component (B) by a hydrosilylation addition reaction, and acts as a curing agent for curing the composition.
  • component (C) a component represented by the following general formula (2) is used.
  • R 2 is an independently alkyl group having 1 to 10 carbon atoms
  • R 3 is independently an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
  • e is an integer of 8 or more.
  • F is an integer of 0 to 100
  • e / (e + f) is 40 mol% or more
  • the number of silicon atom-bonded hydrogen groups in one molecule is 10 or more).
  • examples of the alkyl group having 1 to 10 carbon atoms represented by R 2 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 and a neopentyl group.
  • Hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, etc., and some or all of the hydrogen atoms of these groups are replaced with halogen atoms such as fluorine, bromine, chlorine, cyano group, etc., such as chloromethyl.
  • R 3 includes a hydrogen atom in addition to the one represented by R 2 .
  • e in the formula (2) is an integer of 8 or more, preferably 10 to 200, and more preferably 12 to 100. If e is less than 8, the hardness may be lower than the target (for example, 65 or more) even after secondary vulcanization.
  • f is an integer of 0 to 100, preferably 5 to 80.
  • the molar ratio (ratio) of e units to the total of e units and f units is e / (e + f) of 40 mol% (0.4) or more, preferably 45 mol% (0.45) or more.
  • the upper limit is not particularly limited, but may be, for example, 90 mol% (0.9) or less.
  • the number of silicon atom-bonded hydrogen groups (Si—H groups) in one molecule is 10 or more, preferably 12 or more.
  • linear organohydrogenpolysiloxane of the component (C) include a double-ended trimethylsiloxy group-blocked methylhydrogenpolysiloxane and a double-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer.
  • examples thereof include a terminal dimethylhydrogensiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer. These may be used alone or in combination of two or more.
  • the addition reaction catalyst of the component (D) is not particularly limited as long as it is for a hydrosilylation addition reaction, but platinum black, second platinum chloride, platinum chloride acid, and platinum chloride acid are monovalent. Examples thereof include a reaction product with alcohol, a complex of platinum chloride acid and olefins, a platinum-based catalyst such as platinum bisacetacetate, a palladium-based catalyst, and a rhodium-based catalyst.
  • the addition curable silicone rubber composition of the present invention contains, as other components, a nitrogen-containing compound, an acetylene compound, a phosphorus compound, a nitrile compound, a carboxylate, a tin compound, a mercury compound, and a sulfur compound, if necessary.
  • Hydrosilylation reaction control agents such as, internal mold release agents such as dimethyl silicone oil, adhesive-imparting agents (particularly, alkenyl group, epoxy group, amino group, (meth) acryloxy group, mercapto group and the like are selected in the molecule. It is optionally possible to add at least one functional group and an organic silicon compound such as alkoxysilane that does not contain a Si—H group in the molecule).
  • the blending amount of the component (C) in the addition-curable silicone rubber composition is the ratio of the number of moles of all Si—H groups to the number of moles of all alkenyl groups in the composition (Si—H groups / total alkenyls).
  • the group) is 1.0 to 1.5, and 1.0 to 1.4 is particularly preferable. If it is lower than 1.0, the cured product is strongly sticky, and the rubber becomes low in hardness even after secondary vulcanization. On the other hand, if it is higher than 1.5, the hardness of the cured product after the primary vulcanization becomes too high, and the removability from the mold deteriorates.
  • the blending amount of the component (C) is preferably 7.4 parts by mass or less with respect to 100 parts by mass in total of the component (A) and the component (B). With such a blending amount, the hardness of the cured product after the primary vulcanization and the elongation at the time of cutting become more desirable, and the removal from the mold becomes easier.
  • the blending amount of the component (D), which is an addition reaction catalyst can be a catalytic amount, which is 0.1 to 10 ppm as a platinum group metal (mass equivalent) with respect to the total mass of the composition, and particularly 0.5 to 0.5 to About 10 ppm is preferable. If the blending amount of the component (D) is less than 0.1 ppm, curing will not proceed easily, and if it is more than 10 ppm, the cured product may be colored.
  • An addition curable silicone rubber composition can be prepared by adding the above components (A) to (D) and further, if necessary, other optional components and uniformly mixing them. In this mixing, the addition-curable silicone rubber composition can be prepared.
  • a mixer used for blending general silicone rubber may be used, and examples thereof include a kneader, a gate mixer, a Shinagawa mixer, a pressure mixer, a three-roll, and a two-roll.
  • T90-T10 When the 10% curing time at the time of minute measurement is T10 (seconds) and the 90% curing time is T90 (seconds), T90-T10 needs to be 160 seconds or more, preferably 160 seconds to 260 seconds, and further. It is particularly preferably 170 to 240 seconds. If it is shorter than 160 seconds, the hardness of the cured product after the primary vulcanization is high, and the elongation at the time of cutting becomes low.
  • the addition-curable silicone rubber composition of the present invention is characterized in that the time from 10% curing to 90% curing is sufficiently long (that is, the curing proceeds slowly during this period) at the time of curing. ..
  • the T90 is less than 300 seconds (5 minutes).
  • the molding and curing method of the additive-curable silicone rubber composition is not particularly limited, and a conventional method can be adopted, but as the molding method, a compression molding or an injection molding method is preferably adopted. Further, in order to reduce the roughness of the surface of the cured product and enhance the transparency during molding, a liner having a high flatness may be used for molding.
  • the curing conditions for example, using a mold, the primary temperature is 100 to 180 ° C. for 5 seconds to 30 minutes, preferably 110 to 180 ° C. for 10 seconds to 20 minutes, and particularly 120 to 160 ° C. for 30 seconds to 10 minutes.
  • secondary vulcanization is performed at 80 to 200 ° C., particularly 100 to 200 ° C. for 10 minutes to 24 hours, especially 30 minutes to 10 hours. It is possible to obtain a molded product having a predetermined hardness.
  • the silicone rubber molded product (elastomer) obtained by press curing (primary vulcanization) at 120 ° C./10 minutes has a hardness (durometer) based on JIS K 6253-: 2012. Type A) is 55 or less, the elongation at the time of cutting in the tensile test based on JIS K 6251: 2017 is 300% or more, and post-cure (secondary vulcanization) at 150 ° C. for 1 hour after press curing is performed.
  • the hardness (durometer type A) of the silicone rubber molded body (elastomer) obtained by carrying out the molding is 65 or more, and the 2 mm thick molded body after the post-cure is all with respect to D65 light described in JIS K 7631-1: 1997.
  • the light transmittance is 90% or more, particularly 92% or more, and the haze value of the 2 mm thick molded product after the post-cure is 2% or less in the haze test using D65 light described in JIS K 7136: 2000. It is possible to give a highly hard and highly transparent silicone rubber.
  • the hardness (durometer type A) of the cured product after the primary vulcanization is 55 or less and the elongation at the time of cutting is 300% or more, it can be easily taken out from the mold.
  • the additive-curable silicone rubber composition of the present invention is excellent in the ease of removal from the mold, and after the secondary vulcanization, provides a silicone rubber having high hardness and high transparency, and is used for optics such as LEDs. It can be suitably used as an application.
  • the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
  • the part indicates the mass part.
  • the average degree of polymerization indicates a number average degree of polymerization.
  • Example 1 50 parts of dimethylpolysiloxane (A-1, alkenyl group content: 0.000038mol / g) having an average degree of polymerization of 720 with both ends sealed with a dimethylvinylsiloxy group, and an average of 3. vinyl groups in one molecule.
  • Add 6.2 parts of hydrogen polysiloxane (C-1, hydromethylsiloxane unit / (hydromethylsiloxane unit + dimethylsiloxane unit) 51 mol%) and 0.025 part of ethynylcyclohexanol as a reaction control agent, and add 15 parts. Minute stirring was continued to obtain a silicone rubber mixture.
  • Example 3 55 parts of dimethylpolysiloxane (A-1) according to Example 1, 45 parts of silicone resin (B-1) according to Example 1, and hydrogenpolysiloxane (C-2) according to Example 2 as a cross-linking agent. ) was added in 5.3 parts and 0.025 part of ethynylcyclohexanol as a reaction control agent, and stirring was continued for 15 minutes to obtain a silicone rubber mixture.
  • Example 4 47.5 parts of dimethylpolysiloxane (A-1) according to Example 1, both ends of which are sealed with dimethylvinylsiloxy groups, and dimethylpolysiloxane having an average of 10 vinyl groups on the side chains and an average degree of polymerization of 8000.
  • A-3 alkenyl group content: 0.000020 mol / g
  • B-1 silicone resin
  • Example 1 represented by the following formula (6) as a cross-linking agent.
  • Table 1 shows the blending amounts of each component used in Examples 1 to 4 and Comparative Examples 1 to 4.
  • the curable silicone rubber compositions of Examples 1 to 4 have a low hardness (durometer type A) of 55 or less after primary vulcanization and an elongation rate at cutting of 300% or more. Therefore, the hardness can be 65 or more after the secondary vulcanization, and a highly transparent additive-curable silicone rubber composition can be obtained.
  • Comparative Example 1 using a linear organopolysiloxane having an average degree of polymerization of less than 480, the elongation of the rubber after the primary vulcanization was low, and the mass ratio of the component (A) and the component (B) was ().
  • Comparative Example 3 in which the ratio of the number of moles of all Si—H groups (Si—H groups / total alkenyl groups) to the number of moles of all alkenyl groups in the composition is out of the range of 1.0 to 1.5.
  • Comparative Example 4 in which the hardness of the cured product after the primary smelting was high, the elongation at the time of cutting was low, and the hydromethylsiloxane unit / (hydromethylsiloxane unit + dimethylsiloxane unit) was not 40 mol% or more, after the primary sulfurization. The hardness of the cured product was high, and the elongation during cutting was low.
  • the additive-curable silicone rubber composition of the present invention is an additive-curable silicone rubber composition that is excellent in ease of removal from the mold and can give a highly transparent cured product.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an example, and any of the above-described embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

Abstract

The present invention provides an addition-curable silicone rubber composition which is characterized by containing (A) a linear organopolysiloxane that has an average polymerization degree of 480 or more, while containing at least two alkenyl groups, each of which is bonded to a silicon atom, in each molecule, (B) an alkenyl group-containing silicone resin represented by formula (1), (C) a linear organohydrogen polysiloxane represented by formula (2), and (D) an addition reaction catalyst that is from 0.1 to 10 ppm (in terms of mass) of a platinum group metal relative to the total mass of the composition, said addition-curable silicone rubber composition being also characterized in that the mass ratio of the component (A) to the component (B), namely (A)/(B) is from 40/60 to 60/40. Consequently, the present invention provides an addition-curable silicone rubber composition which enables the achievement of a cured product that exhibits excellent releasability from a mold, while having high transparency.　(1): (R1 3SiO1/2)a(R1 2SiO2/2)b(R1SiO3/2)c(SiO4/2)d　

Description

付加硬化性シリコーンゴム組成物Additive curable silicone rubber composition
　本発明は、付加硬化性シリコーンゴム組成物に関する。 The present invention relates to an addition curable silicone rubber composition.
　ＬＥＤライトや各種液晶モニター画面の耐候性や光導波路の向上等のため、高硬度で高透明なシリコーン系樹脂が注目され、中でもシリカを全く含まず、高透明で、低温でも弾性を損なわず、熱硬化による成形も比較的容易な付加硬化性シリコーンゴム硬化物が採用されるようになった（特許文献１～６）。 High hardness and high transparency silicone resin is attracting attention for improving weather resistance and optical waveguide of LED lights and various liquid crystal monitor screens. Among them, it does not contain silica at all, is highly transparent, and does not impair elasticity even at low temperatures. Additive-curable silicone rubber cured products, which are relatively easy to mold by thermosetting, have come to be adopted (Patent Documents 1 to 6).
　一般的に、ＬＥＤライト等の光導波路として使用されるシリコーンゴムは硬さ（ＪＩＳ　Ｋ　６２５３、デュロメータタイプＡ）が６５以上という高硬度が求められている。このようなシリコーンゴムの成形方法は、まず、金型を用いた一次加硫を行い、次いで物性を安定させたり、硬化物中の揮発成分を除去する目的で、高温の乾燥機（オーブン）を用いて二次加硫を行っている。しかし、補強性シリカを含まない高硬度シリコーンゴムの場合、一次成型後、金型から硬化物を取り出す際、硬く、伸び性が低いため、硬化物にキズや裂けが生じる問題があった。 Generally, silicone rubber used as an optical waveguide for LED lights and the like is required to have a high hardness (JIS K 6253, durometer type A) of 65 or more. In such a silicone rubber molding method, first, primary vulcanization using a mold is performed, and then a high-temperature dryer (orange) is used for the purpose of stabilizing physical properties and removing volatile components in the cured product. Secondary vulcanization is performed using. However, in the case of high-hardness silicone rubber containing no reinforcing silica, when the cured product is taken out from the mold after primary molding, it is hard and has low extensibility, so that there is a problem that the cured product is scratched or torn.
特開２００６－３３５８５７号公報Japanese Unexamined Patent Publication No. 2006-335857 特開２００８－１０１０５６号公報Japanese Unexamined Patent Publication No. 2008-101056 特開２０１０－１７４２３３号公報Japanese Unexamined Patent Publication No. 2010-174233 特開２０１０－１７４２３４号公報Japanese Unexamined Patent Publication No. 2010-174234 ＷＯ２０１６／０９８８８３号WO2016 / 09883 ＷＯ２０１６／０９８８８４号WO2016 / 098844
　本発明は、上記事情を改善するためになされたもので、金型からの取り出し性に優れ、透明性の高い硬化物を与える事のできる付加硬化性シリコーンゴム組成物を提供することを目的とする。 The present invention has been made to improve the above circumstances, and an object of the present invention is to provide an additive-curable silicone rubber composition which is excellent in removability from a mold and can give a cured product having high transparency. do.
　上記課題を解決するために、本発明では、付加硬化性シリコーンゴム組成物であって、
（Ａ）平均重合度が４８０以上で、１分子中に少なくとも２個のケイ素原子と結合したアルケニル基を含有する直鎖状オルガノポリシロキサン、
（Ｂ）下記式（１）で示されるアルケニル基含有シリコーンレジン
　（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ　　　　（１）
（式（１）中、Ｒ１は独立して炭素数１から１０のアルキル基および炭素数２から１０のアルケニル基から選択される１価炭化水素基であり、１分子中に平均２．５個以上のアルケニル基を有し、０＜ａ≦０．７、０≦ｂ≦０．２、０≦ｃ≦０．２、０＜ｄ≦０．７であり、ただし、０．８≦ａ＋ｄ≦１、かつａ＋ｂ＋ｃ＋ｄ＝１となる数である）、
（Ｃ）下記式（２）で示される直鎖状オルガノハイドロジェンポリシロキサン
Figure JPOXMLDOC01-appb-C000002
 （式（２）中、Ｒ２は独立して炭素数１から１０のアルキル基であり、Ｒ３は独立して炭素数１から１０のアルキル基もしくは水素原子であり、ｅが８以上の整数であり、ｆが０～１００の整数であり、ｅ／（ｅ＋ｆ）が４０モル％以上、かつ一分子中のケイ素原子結合水素基の数が１０個以上である）、
（Ｄ）付加反応触媒：組成物の合計質量に対して白金族金属（質量換算）として０．１～１０ｐｐｍ
を含み、前記（Ａ）成分と前記（Ｂ）成分の質量比が（Ａ）／（Ｂ）＝４０／６０～６０／４０であり、組成物中の全アルケニル基のモル数に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）が１．０～１．５であり、ＪＩＳ　Ｋ　６３００－２：２００１に記載のねじり振動式円すいダイ加硫試験機（Ｂ－２法）を用いた加硫試験において、１５０℃、５分測定時の１０％硬化時間をＴ１０、９０％硬化時間をＴ９０としたとき、Ｔ９０－Ｔ１０が１６０秒以上となる付加硬化性シリコーンゴム組成物を提供する。 In order to solve the above problems, in the present invention, the addition curable silicone rubber composition is used.
(A) A linear organopolysiloxane having an average degree of polymerization of 480 or more and containing an alkenyl group bonded to at least two silicon atoms in one molecule.
(B) Silicone resin containing an alkenyl group represented by the following formula (1) (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) ) D (1)
(In the formula (1), R 1 is a monovalent hydrocarbon group independently selected from an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and has an average of 2.5 in one molecule. It has more than one alkenyl group and is 0 <a ≦ 0.7, 0 ≦ b ≦ 0.2, 0 ≦ c ≦ 0.2, 0 <d ≦ 0.7, where 0.8 ≦ a + d. ≤1 and a + b + c + d = 1),
(C) Linear organohydrogenpolysiloxane represented by the following formula (2)
Figure JPOXMLDOC01-appb-C000002
 (In the formula (2), R 2 is an independently alkyl group having 1 to 10 carbon atoms, R 3 is independently an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and e is an integer of 8 or more. , F is an integer of 0 to 100, e / (e + f) is 40 mol% or more, and the number of silicon atom-bonded hydrogen groups in one molecule is 10 or more).
(D) Addition reaction catalyst: 0.1 to 10 ppm as a platinum group metal (mass equivalent) with respect to the total mass of the composition.
The mass ratio of the component (A) to the component (B) is (A) / (B) = 40/60 to 60/40, and the total Si— with respect to the number of moles of the total alkenyl groups in the composition. The ratio of the number of moles of H groups (Si—H group / total alkenyl group) is 1.0 to 1.5, and the torsional vibration type conical die vulcanization tester (B-) described in JIS K 6300-2: 2001. In the vulcanization test using method 2), when the 10% curing time at 150 ° C. for 5 minutes is T10 and the 90% curing time is T90, the T90-T10 is 160 seconds or more. The composition is provided.
　本発明の付加硬化性シリコーンゴム組成物であれば、金型からの取り出し性に優れ、透明性の高い硬化物を与えることができる。 With the addition-curable silicone rubber composition of the present invention, it is possible to provide a cured product having excellent ease of removal from a mold and having high transparency.
　また、前記（Ａ）成分のアルケニル基量が０．００００６ｍｏｌ／ｇ以下であることが好ましい。 Further, it is preferable that the amount of the alkenyl group of the component (A) is 0.00006 mol / g or less.
　このような付加硬化性シリコーンゴム組成物であれば、一次加硫後のゴムの伸びが好ましいものとなる。 With such an addition-curable silicone rubber composition, the elongation of the rubber after the primary vulcanization is preferable.
　また、前記（Ｂ）成分のアルケニル基量が０．０００６～０．００１ｍｏｌ／ｇであることが好ましい。 Further, it is preferable that the amount of the alkenyl group of the component (B) is 0.0006 to 0.001 mol / g.
　このような付加硬化性シリコーンゴム組成物であれば、その硬化物の硬さ及び一次加硫後の切断時伸びが好ましいものとなる。 With such an addition-curable silicone rubber composition, the hardness of the cured product and the elongation at the time of cutting after the primary vulcanization are preferable.
　本発明によれば、一次加硫後の硬さ（デュロメータタイプＡ）が５５以下と低く、切断時伸び率が３００％以上であり、二次加硫後に硬度が６５以上となることが可能であり、金型からの取り出し性に優れ、透明性の高い硬化物を与える付加硬化性シリコーンゴム組成物が得られる。 According to the present invention, the hardness after the primary vulcanization (durometer type A) is as low as 55 or less, the elongation rate at the time of cutting is 300% or more, and the hardness after the secondary vulcanization can be 65 or more. A vulcanized silicone rubber composition can be obtained, which is excellent in ease of removal from a mold and gives a highly transparent cured product.
　上述のように、金型からの取り出し性に優れ、透明性の高い硬化物を与える事のできる付加硬化性シリコーンゴム組成物の開発が求められていた。 As described above, there has been a demand for the development of an additive curable silicone rubber composition that is excellent in ease of removal from the mold and can give a highly transparent cured product.
　本発明者は、上記目的を達成するために鋭意検討を行った結果、比較的長鎖のアルケニル含有直鎖状オルガノポリシロキサンと、特定のアルケニル基含有シリコーンレジンと、特定構造を有するオルガノハイドロジェンシロキサンを適当な比率で使用し、加硫試験における１０％硬化時間と９０％硬化時間との差が大きくなるように調節した組成物とすることで、一次加硫後の硬化物の硬度を５５以下で、切断時伸びを３００％以上とすることができ、さらに、二次加硫によって目的の硬度（例えば６５以上）まで硬度上昇が可能であり、透明性の高い硬化物を与えるシリコーンゴム組成物が得られる事を見出し、本発明をなすに至った。 As a result of diligent studies to achieve the above object, the present inventor has a relatively long chain alkenyl-containing linear organopolysiloxane, a specific alkenyl group-containing silicone resin, and an organohydrogen having a specific structure. By using siloxane in an appropriate ratio and adjusting the composition so that the difference between the 10% curing time and the 90% curing time in the vulcanization test becomes large, the hardness of the cured product after the primary vulcanization is 55. In the following, the elongation at the time of cutting can be set to 300% or more, and further, the hardness can be increased to the desired hardness (for example, 65 or more) by secondary vulcanization, and the silicone rubber composition gives a highly transparent cured product. It was found that a product could be obtained, and the present invention was made.
　上記知見は、各種材料を調査したところ、一次加硫後の硬化物の硬さ（デュロメータタイプＡ）が５５以下かつ切断時伸びが３００％以上であると、金型からの取り出しが容易であることが判明したことから得られたものである。 Based on the above findings, as a result of investigating various materials, if the hardness (durometer type A) of the cured product after primary vulcanization is 55 or less and the elongation at cutting is 300% or more, it is easy to remove it from the mold. It was obtained from the fact that it turned out to be.
　即ち、本発明は、付加硬化性シリコーンゴム組成物であって、
（Ａ）平均重合度が４８０以上で、１分子中に少なくとも２個のケイ素原子と結合したアルケニル基を含有する直鎖状オルガノポリシロキサン、
（Ｂ）下記式（１）で示されるアルケニル基含有シリコーンレジン
　（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ　　　　（１）
（式（１）中、Ｒ１は独立して炭素数１から１０のアルキル基および炭素数２から１０のアルケニル基から選択される１価炭化水素基であり、１分子中に平均２．５個以上のアルケニル基を有し、０＜ａ≦０．７、０≦ｂ≦０．２、０≦ｃ≦０．２、０＜ｄ≦０．７であり、ただし、０．８≦ａ＋ｄ≦１、かつａ＋ｂ＋ｃ＋ｄ＝１となる数である）、
（Ｃ）下記式（２）で示される直鎖状オルガノハイドロジェンポリシロキサン
Figure JPOXMLDOC01-appb-C000003
 （式（２）中、Ｒ２は独立して炭素数１から１０のアルキル基であり、Ｒ３は独立して炭素数１から１０のアルキル基もしくは水素原子であり、ｅが８以上の整数であり、ｆが０～１００の整数であり、ｅ／（ｅ＋ｆ）が４０モル％以上、かつ一分子中のケイ素原子結合水素基の数が１０個以上である）、
（Ｄ）付加反応触媒：組成物の合計質量に対して白金族金属（質量換算）として０．１～１０ｐｐｍ
を含み、前記（Ａ）成分と前記（Ｂ）成分の質量比が（Ａ）／（Ｂ）＝４０／６０～６０／４０であり、組成物中の全アルケニル基のモル数に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）が１．０～１．５であり、ＪＩＳ　Ｋ　６３００－２：２００１に記載のねじり振動式円すいダイ加硫試験機（Ｂ－２法）を用いた加硫試験において、１５０℃、５分測定時の１０％硬化時間をＴ１０、９０％硬化時間をＴ９０としたとき、Ｔ９０－Ｔ１０が１６０秒以上となる付加硬化性シリコーンゴム組成物である。 That is, the present invention is an addition curable silicone rubber composition.
(A) A linear organopolysiloxane having an average degree of polymerization of 480 or more and containing an alkenyl group bonded to at least two silicon atoms in one molecule.
(B) Silicone resin containing an alkenyl group represented by the following formula (1) (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) ) D (1)
(In the formula (1), R 1 is a monovalent hydrocarbon group independently selected from an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and has an average of 2.5 in one molecule. It has more than one alkenyl group and is 0 <a ≦ 0.7, 0 ≦ b ≦ 0.2, 0 ≦ c ≦ 0.2, 0 <d ≦ 0.7, where 0.8 ≦ a + d. ≤1 and a + b + c + d = 1),
(C) Linear organohydrogenpolysiloxane represented by the following formula (2)
Figure JPOXMLDOC01-appb-C000003
 (In the formula (2), R 2 is an independently alkyl group having 1 to 10 carbon atoms, R 3 is independently an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and e is an integer of 8 or more. , F is an integer of 0 to 100, e / (e + f) is 40 mol% or more, and the number of silicon atom-bonded hydrogen groups in one molecule is 10 or more).
(D) Addition reaction catalyst: 0.1 to 10 ppm as a platinum group metal (mass equivalent) with respect to the total mass of the composition.
The mass ratio of the component (A) to the component (B) is (A) / (B) = 40/60 to 60/40, and the total Si— with respect to the number of moles of the total alkenyl groups in the composition. The ratio of the number of moles of H groups (Si—H group / total alkenyl group) is 1.0 to 1.5, and the torsional vibration type conical die vulcanization tester (B-) described in JIS K 6300-2: 2001. In the vulcanization test using method 2), when the 10% curing time at 150 ° C. for 5 minutes is T10 and the 90% curing time is T90, the T90-T10 is 160 seconds or more. It is a composition.
　以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
＜付加硬化性シリコーンゴム組成物＞
　本発明の付加硬化性シリコーンゴム組成物は、下記（Ａ）～（Ｄ）成分を含むことを特徴とする。上記付加硬化性シリコーンゴム組成物は、液状であることが好ましい。 <Additive curable silicone rubber composition>
The addition curable silicone rubber composition of the present invention is characterized by containing the following components (A) to (D). The curable silicone rubber composition is preferably liquid.
（Ａ）アルケニル基を含有する直鎖状オルガノポリシロキサン
　（Ａ）成分であるオルガノポリシロキサンは、１分子中に少なくとも２個のケイ素原子と結合したアルケニル基を有し、平均重合度が４８０以上のアルケニル基含有直鎖状オルガノポリシロキサンである。 (A) Linear organopolysiloxane containing an alkenyl group The organopolysiloxane (A) component has an alkenyl group bonded to at least two silicon atoms in one molecule and has an average degree of polymerization of 480 or more. It is a linear organopolysiloxane containing an alkenyl group.
　この（Ａ）成分として、好適には、下記一般式（３）で示されるものを用いることができる。
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ４は同一又は異種の炭素数１から１０のアルキル基および炭素数２から１０のアルケニル基から選択される１価炭化水素基であり、ｇは５００以上、通常５００～１０，０００、好ましくは５００～８，０００の整数である。） As the component (A), a component represented by the following general formula (3) can be preferably used.
Figure JPOXMLDOC01-appb-C000004
 (In the formula, R4 is a monovalent hydrocarbon group selected from the same or different alkyl groups having 1 to 10 carbon atoms and alkenyl groups having 2 to 10 carbon atoms, and g is 500 or more, usually 500 to 10, 000, preferably an integer of 500 to 8,000.)
　Ｒ４で示される１価炭化水素基としては、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、シクロヘキシル基等のアルキル基；ビニル基、アリル基、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等のアルケニル基が挙げられる。Ｒ４としてはメチル基が好ましいが、分子中にアルケニル基を２個以上含んでいることが必要である。該アルケニル基としてはビニル基が好ましい。 Examples of the monovalent hydrocarbon group represented by R4 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group; a vinyl group, an allyl group, a butenyl group and a pentenyl group. Examples thereof include an alkenyl group such as a hexenyl group and a cyclohexenyl group. A methyl group is preferable as R4 , but it is necessary that the molecule contains two or more alkenyl groups. A vinyl group is preferable as the alkenyl group.
　前記アルケニル基含有直鎖状オルガノポリシロキサンとしては、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、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、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、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、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等が挙げられる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。 Examples of the alkenyl group-containing linear organopolysiloxane include both-ended dimethylvinylsiloxy group-blocked dimethylpolysiloxane, both-ended dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, and both-ended trimethylsiloxy group-blocked dimethylsiloxane. Examples thereof include a methylvinylsiloxane copolymer, a double-ended trivinylsiloxy group-blocked dimethylpolysiloxane, and a double-ended trivinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer. These may be used alone or in combination of two or more.
　このオルガノポリシロキサンの平均重合度は、４８０以上であることが必要であり、通常４８０～１０，０００、好ましくは５００～８，０００である。４８０未満では、一次加硫後のゴムの伸びが低くなってしまう。
　なお、本発明中で言及する平均重合度とは、数平均重合度のことを指し、下記条件で測定したゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレンを標準物質とした平均重合度を指すこととする。
［測定条件］
展開溶媒：トルエン
流量：１ｍＬ／ｍｉｎ
検出器：示差屈折率検出器（ＲＩ）
カラム：ＫＦ－８０５Ｌ×２（Ｓｈｏｄｅｘ社製）
カラム温度：２５℃
試料注入量：３０μＬ（濃度０．２質量％のトルエン溶液） The average degree of polymerization of this organopolysiloxane needs to be 480 or more, usually 480 to 10,000, preferably 500 to 8,000. If it is less than 480, the elongation of the rubber after the primary vulcanization will be low.
The average degree of polymerization referred to in the present invention refers to a number average degree of polymerization, and refers to an average degree of polymerization using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions. ..
[Measurement condition]
Developing solvent: Toluene flow rate: 1 mL / min
Detector: Differential Refractometer Detector (RI)
Column: KF-805L x 2 (manufactured by Shodex)
Column temperature: 25 ° C
Sample injection amount: 30 μL (toluene solution with a concentration of 0.2% by mass)
　また、このオルガノポリシロキサン中のケイ素原子に結合したアルケニル基の量（アルケニル基量）は０．００００６ｍｏｌ／ｇ以下であることが必要であり、通常０．００００６～０．０００００３ｍｏｌ／ｇ、好ましくは０．００００６～０．０００００６ｍｏｌ／ｇ、より好ましくは０．００００６～０．００００１ｍｏｌ／ｇである。０．００００６ｍｏｌ／ｇ以下であれば、一次加硫後のゴムの伸びが低くなってしまうことがない。 Further, the amount of alkenyl groups bonded to silicon atoms (alkenyl group amount) in this organopolysiloxane needs to be 0.00006 mol / g or less, and is usually 0.00006 to 0.000003 mol / g, preferably 0.00006 to 0.000003 mol / g. It is 0.00006 to 0.000006 mol / g, more preferably 0.00006 to 0.00001 mol / g. If it is 0.00006 mol / g or less, the elongation of the rubber after the primary vulcanization does not decrease.
　（Ａ）成分としては、アルケニル基を含有する直鎖状のオルガノポリシロキサンであれば、分子構造（例えば、分子鎖末端のトリオルガノシロキシ基や主鎖のジオルガノシロキサン単位の置換基の種類やそれらの比率）や重合度の異なる１種又は２種以上のものを併用することができる。 As the component (A), if it is a linear organopolysiloxane containing an alkenyl group, the molecular structure (for example, the type of the substituent of the triorganosyloxy group at the end of the molecular chain or the diorganosiloxane unit of the main chain) One type or two or more types having different ratios) and degree of polymerization can be used in combination.
（Ｂ）アルケニル基含有シリコーンレジン
　（Ｂ）成分は、Ｒ１ ３ＳｉＯ１／２単位（Ｍ単位）、Ｒ１ ２ＳｉＯ２／２単位（Ｄ単位）、Ｒ１ＳｉＯ３／２単位（Ｔ単位）及びＳｉＯ４／２単位（Ｑ単位）から選択される構成単位からなるシリコーンレジンであり、該シリコーンレジンは下記式（１）で示されるものである。
　（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ　　　　（１） (B) The alkenyl group-containing silicone resin (B) component is R 1 3 SiO 1/2 unit (M unit), R 1 2 SiO 2/2 unit (D unit), R 1 SiO 3/2 unit (T unit). ) And a silicone resin composed of a constituent unit selected from SiO 4/2 units (Q units), and the silicone resin is represented by the following formula (1).
(R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (1)
　式（１）中、Ｒ１は独立して炭素数１から１０のアルキル基および炭素数２から１０のアルケニル基から選択される１価炭化水素基である。具体例としては、前記式（３）のＲ４で示されたものと同様の基を例示することができ、１分子中の少なくとも平均２．５個、好ましくは２．５～５個のＲ１がアルケニル基である。一分子中のアルケニル基が平均２．５未満の場合、硬化物のべたつきが強く、取り扱いが困難となってしまう。また、（Ｂ）成分は他の成分との相溶性の観点から、アルケニル基としてはビニル基が好ましく、Ｒ１の８０モル％以上がメチル基であることが好ましい。各成分の相溶性が悪化すると、付加硬化性シリコーンゴム組成物の硬化物の透明性が低下するおそれがある。また、ａは、０＜ａ≦０．７、好ましくは０．３＜ａ＜０．７であり、ｂは、０≦ｂ≦０．２、好ましくは０≦ｂ≦０．１であり、ｃは、０≦ｃ≦０．２、好ましくは０≦ｃ≦０．１であり、ｄは、０＜ｄ≦０．７、好ましくは０．３＜ｄ＜０．７であり、かつａ＋ｂ＋ｃ＋ｄ＝１となる数である。 In formula (1), R 1 is a monovalent hydrocarbon group independently selected from an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. As a specific example, the same group as that represented by R4 of the above formula (3) can be exemplified, and at least 2.5 Rs, preferably 2.5-5 Rs in one molecule are allowed. 1 is an alkenyl group. If the average number of alkenyl groups in one molecule is less than 2.5, the cured product becomes sticky and difficult to handle. Further, the component (B) is preferably a vinyl group as the alkenyl group from the viewpoint of compatibility with other components, and 80 mol% or more of R1 is preferably a methyl group. If the compatibility of each component deteriorates, the transparency of the cured product of the additive-curable silicone rubber composition may decrease. Further, a is 0 <a ≦ 0.7, preferably 0.3 <a <0.7, and b is 0 ≦ b ≦ 0.2, preferably 0 ≦ b ≦ 0.1. c is 0 ≦ c ≦ 0.2, preferably 0 ≦ c ≦ 0.1, and d is 0 <d ≦ 0.7, preferably 0.3 <d <0.7, and a + b + c + d. = 1 is the number.
　上記（Ｂ）成分のシリコーンレジン（式（１））において、上記４種の構成単位のうち、Ｍ単位及びＱ単位は必須である。付加硬化性シリコーンゴム組成物の硬化物の硬さを向上させるためには、全構成単位に占めるこの２種の構成単位の割合が８０モル％以上（０．８≦ａ＋ｄ≦１．０）であることが必要であり、好ましくは９０モル％以上（０．９≦ａ＋ｄ≦１．０）、より好ましくは１００モル％（ａ＋ｄ＝１．０）である。なお、Ｄ単位及びＴ単位は含まれていてもよいし、含まれていなくてもよい。Ｍ単位とＱ単位とのモル比（ａ／ｄ）が０．５以上であれば、（Ｂ）成分と他の成分との相溶性が悪化することがなく、１．５以下であれば、付加硬化性シリコーンゴム組成物の硬化物の硬さが低下してしまうおそれがない。したがって、Ｍ単位とＱ単位とのモル比（ａ／ｄ）は０．５～１．５の範囲にあることが好ましく、より好ましくは０．７～１．２の範囲である。 In the silicone resin of the component (B) (formula (1)), the M unit and the Q unit are indispensable among the above four types of constituent units. In order to improve the hardness of the cured product of the addition-curable silicone rubber composition, the ratio of these two types of structural units to all the structural units is 80 mol% or more (0.8 ≦ a + d ≦ 1.0). It is necessary to have, preferably 90 mol% or more (0.9 ≦ a + d ≦ 1.0), and more preferably 100 mol% (a + d = 1.0). The D unit and the T unit may or may not be included. If the molar ratio (a / d) between the M unit and the Q unit is 0.5 or more, the compatibility between the component (B) and other components does not deteriorate, and if it is 1.5 or less, the compatibility is not deteriorated. There is no risk that the hardness of the cured product of the additive curable silicone rubber composition will decrease. Therefore, the molar ratio (a / d) of the M unit and the Q unit is preferably in the range of 0.5 to 1.5, and more preferably in the range of 0.7 to 1.2.
　上記（Ｂ）成分のアルケニル基含有量（アルケニル基量）は０．０００６～０．００１ｍｏｌ／ｇが好ましく、０．０００７～０．００１ｍｏｌ／ｇがより好ましい。アルケニル基含有量が０．０００６ｍｏｌ／ｇ以上であれば硬さの低すぎる硬化物となってしまうことがなく、０．００１ｍｏｌ／ｇ以下であれば一次加硫後の切断時伸びが低くなってしまうことがない。 The alkenyl group content (alkenyl group amount) of the component (B) is preferably 0.0006 to 0.001 mol / g, more preferably 0.0007 to 0.001 mol / g. If the alkenyl group content is 0.0006 mol / g or more, the cured product will not be too hard, and if it is 0.001 mol / g or less, the elongation at the time of cutting after the primary vulcanization will be low. It never ends up.
　この（Ｂ）成分のシリコーンレジンの具体例としては、ビニルジメチルシロキシ基とＱ単位との共重合体、ビニルジメチルシロキシ基・トリメチルシロキシ基とＱ単位との共重合体、ビニルジメチルシロキシ基・ジメチルシロキサンとＱ単位との共重合体、トリメチルシロキシ基・ビニルメチルシロキサンとＱ単位との共重合体等が挙げられる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。 Specific examples of the silicone resin of the component (B) include a copolymer of a vinyldimethylsiloxy group and a Q unit, a polymer of a vinyldimethylsiloxy group / a trimethylsiloxy group and a Q unit, and a vinyldimethylsiloxy group / dimethyl. Examples thereof include a copolymer of siloxane and Q unit, a copolymer of trimethylsiloxy group / vinylmethylsiloxane and Q unit, and the like. These may be used alone or in combination of two or more.
（Ｃ）オルガノハイドロジェンポリシロキサン
　（Ｃ）成分は、ケイ素原子に結合した水素原子（Ｓｉ－Ｈ基）を有する直鎖状オルガノハイドロジェンポリシロキサンであり、分子中のＳｉ－Ｈ基が、前記（Ａ）成分及び（Ｂ）成分等のケイ素原子に結合したアルケニル基とヒドロシリル化付加反応により架橋し、組成物を硬化させるための硬化剤として作用するものである。 (C) The organohydrogenpolysiloxane (C) component is a linear organohydrogenpolysiloxane having a hydrogen atom (Si—H group) bonded to a silicon atom, and the Si—H group in the molecule is the above-mentioned. It cross-links with an alkenyl group bonded to a silicon atom such as a component (A) and a component (B) by a hydrosilylation addition reaction, and acts as a curing agent for curing the composition.
　この（Ｃ）成分として、下記一般式（２）で示されるものを用いる。
Figure JPOXMLDOC01-appb-C000005
 （式（２）中、Ｒ２は独立して炭素数１から１０のアルキル基であり、Ｒ３は独立して炭素数１から１０のアルキル基もしくは水素原子であり、ｅが８以上の整数であり、ｆが０～１００の整数であり、ｅ／（ｅ＋ｆ）が４０モル％以上、かつ一分子中のケイ素原子結合水素基の数が１０個以上である） As the component (C), a component represented by the following general formula (2) is used.
Figure JPOXMLDOC01-appb-C000005
 (In the formula (2), R 2 is an independently alkyl group having 1 to 10 carbon atoms, R 3 is independently an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and e is an integer of 8 or more. , F is an integer of 0 to 100, e / (e + f) is 40 mol% or more, and the number of silicon atom-bonded hydrogen groups in one molecule is 10 or more).
　ここで、Ｒ２で示される炭素数１から１０のアルキル基としては、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、デシル基等や、これらの基の水素原子の一部又は全部をフッ素、臭素、塩素等のハロゲン原子、シアノ基等で置換したもの、例えばクロロメチル基、クロロプロピル基、ブロモエチル基、トリフロロプロピル基、シアノエチル基等が挙げられるが、全てのＲ２の９０モル％以上、特には全てのＲ２基がメチル基であることが好ましい。また、Ｒ３はＲ２で示されるものに加え、水素原子が挙げられる。 Here, examples of the alkyl group having 1 to 10 carbon atoms represented by R 2 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 and a neopentyl group. Hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, etc., and some or all of the hydrogen atoms of these groups are replaced with halogen atoms such as fluorine, bromine, chlorine, cyano group, etc., such as chloromethyl. Examples thereof include a group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group and the like, and it is preferable that 90 mol% or more of all R 2s , particularly all R 2 groups are methyl groups. Further, R 3 includes a hydrogen atom in addition to the one represented by R 2 .
　さらに式（２）中のｅは８以上の整数であり、好ましくは１０～２００、より好ましくは１２～１００である。ｅが８未満の場合、二次加硫後でも硬さが目標（例えば６５以上）よりも低くなってしまう恐れがある。ｆは０～１００の整数であり、５～８０が好ましい。また、ｅ単位とｆ単位の合計に対するｅ単位のモル比（比）はｅ／（ｅ＋ｆ）が４０モル％（０．４）以上であり、４５モル％（０．４５）以上が好ましい。上限値は特に限定されないが、例えば９０モル％（０．９）以下とすることができる。ｅ／（ｅ＋ｆ）が４０モル％未満の場合、一次加硫後の切断時伸びが低く、金型からの取り出し性が悪くなってしまう。また、一分子中のケイ素原子結合水素基（Ｓｉ－Ｈ基）の数が１０個以上であり、１２個以上が好ましい。 Further, e in the formula (2) is an integer of 8 or more, preferably 10 to 200, and more preferably 12 to 100. If e is less than 8, the hardness may be lower than the target (for example, 65 or more) even after secondary vulcanization. f is an integer of 0 to 100, preferably 5 to 80. Further, the molar ratio (ratio) of e units to the total of e units and f units is e / (e + f) of 40 mol% (0.4) or more, preferably 45 mol% (0.45) or more. The upper limit is not particularly limited, but may be, for example, 90 mol% (0.9) or less. When e / (e + f) is less than 40 mol%, the elongation at the time of cutting after the primary vulcanization is low, and the removability from the mold is deteriorated. Further, the number of silicon atom-bonded hydrogen groups (Si—H groups) in one molecule is 10 or more, preferably 12 or more.
　この（Ｃ）成分の直鎖状オルガノハイドロジェンポリシロキサンの具体例としては、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、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、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等が挙げられる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。 Specific examples of the linear organohydrogenpolysiloxane of the component (C) include a double-ended trimethylsiloxy group-blocked methylhydrogenpolysiloxane and a double-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer. Examples thereof include a terminal dimethylhydrogensiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer. These may be used alone or in combination of two or more.
（Ｄ）付加反応触媒
　（Ｄ）成分の付加反応触媒としては、ヒドロシリル化付加反応用のものであれば特に限定されないが、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と１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系触媒、パラジウム系触媒、ロジウム系触媒などが挙げられる。 (D) Addition reaction catalyst The addition reaction catalyst of the component (D) is not particularly limited as long as it is for a hydrosilylation addition reaction, but platinum black, second platinum chloride, platinum chloride acid, and platinum chloride acid are monovalent. Examples thereof include a reaction product with alcohol, a complex of platinum chloride acid and olefins, a platinum-based catalyst such as platinum bisacetacetate, a palladium-based catalyst, and a rhodium-based catalyst.
その他の成分
　本発明の付加硬化性シリコーンゴム組成物には、その他の成分として、必要に応じて、窒素含有化合物やアセチレン化合物、リン化合物、ニトリル化合物、カルボキシレート、錫化合物、水銀化合物、硫黄化合物等のヒドロシリル化反応制御剤、ジメチルシリコーンオイル等の内部離型剤、接着性付与剤（特には、分子中にアルケニル基、エポキシ基、アミノ基、（メタ）アクリロキシ基、メルカプト基等から選ばれる少なくとも１種の官能性基を含有すると共に、分子中にＳｉ－Ｈ基を含有しないアルコキシシラン等の有機ケイ素化合物など）等を配合することが任意に可能である。 Other Ingredients The addition curable silicone rubber composition of the present invention contains, as other components, a nitrogen-containing compound, an acetylene compound, a phosphorus compound, a nitrile compound, a carboxylate, a tin compound, a mercury compound, and a sulfur compound, if necessary. Hydrosilylation reaction control agents such as, internal mold release agents such as dimethyl silicone oil, adhesive-imparting agents (particularly, alkenyl group, epoxy group, amino group, (meth) acryloxy group, mercapto group and the like are selected in the molecule. It is optionally possible to add at least one functional group and an organic silicon compound such as alkoxysilane that does not contain a Si—H group in the molecule).
（Ａ）～（Ｄ）成分の配合量
　付加硬化性シリコーンゴム組成物中の上記（Ａ）成分と（Ｂ）成分の配合量は、（Ａ）成分と（Ｂ）成分の質量比が（Ａ）／（Ｂ）＝４０／６０～６０／４０となる量であり、好ましくは４５／５５～５５／４５である。（Ｂ）成分の割合が６０よりも多いと一次加硫後の硬化物の硬さが高くなり過ぎてしまい、４０よりも少ないと一次加硫後の硬化物の切断時伸びが低くなってしまったり、二次加硫後でも硬さが低くなってしまう。 Blending amount of components (A) to (D) The blending amount of the components (A) and (B) in the additive-curable silicone rubber composition is such that the mass ratio of the components (A) and (B) is (A). ) / (B) = 40/60 to 60/40, preferably 45/55 to 55/45. (B) If the proportion of the component is more than 60, the hardness of the cured product after the primary vulcanization becomes too high, and if it is less than 40, the elongation at cutting of the cured product after the primary vulcanization becomes low. The hardness becomes low even after secondary vulcanization.
　また、上記付加硬化性シリコーンゴム組成物中の（Ｃ）成分の配合量は、組成物中の全アルケニル基のモル数に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）が１．０～１．５であり、特に１．０～１．４が好ましい。１．０よりも低いと硬化物のベタツキが強く、二次加硫後も硬さが低いゴムとなってしまう。一方、１．５よりも高いと一次加硫後の硬化物の硬さが高くなり過ぎてしまい、金型からの取り出し性が悪くなってしまう。 Further, the blending amount of the component (C) in the addition-curable silicone rubber composition is the ratio of the number of moles of all Si—H groups to the number of moles of all alkenyl groups in the composition (Si—H groups / total alkenyls). The group) is 1.0 to 1.5, and 1.0 to 1.4 is particularly preferable. If it is lower than 1.0, the cured product is strongly sticky, and the rubber becomes low in hardness even after secondary vulcanization. On the other hand, if it is higher than 1.5, the hardness of the cured product after the primary vulcanization becomes too high, and the removability from the mold deteriorates.
　更に、（Ｃ）成分の配合量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、７．４質量部以下であることが好ましい。このような配合量であれば、一次加硫後の硬化物の硬さ及び切断時伸びがより望ましいものとなり、金型からの取り出しがより容易になる。 Further, the blending amount of the component (C) is preferably 7.4 parts by mass or less with respect to 100 parts by mass in total of the component (A) and the component (B). With such a blending amount, the hardness of the cured product after the primary vulcanization and the elongation at the time of cutting become more desirable, and the removal from the mold becomes easier.
　付加反応触媒である（Ｄ）成分の配合量は触媒量とすることができ、組成物の合計質量に対し、白金族金属（質量換算）として０．１～１０ｐｐｍであり、特に０．５～１０ｐｐｍ程度が好ましい。（Ｄ）成分の配合量が０．１ｐｐｍより少ないと硬化が進行しにくくなり、１０ｐｐｍより多くとなると硬化物が着色してしまう恐れがある。 The blending amount of the component (D), which is an addition reaction catalyst, can be a catalytic amount, which is 0.1 to 10 ppm as a platinum group metal (mass equivalent) with respect to the total mass of the composition, and particularly 0.5 to 0.5 to About 10 ppm is preferable. If the blending amount of the component (D) is less than 0.1 ppm, curing will not proceed easily, and if it is more than 10 ppm, the cured product may be colored.
＜付加硬化性シリコーンゴム組成物の調製＞
　上記（Ａ）～（Ｄ）成分や、更に必要に応じてその他の任意成分を添加して均一に混合することにより、付加硬化性シリコーンゴム組成物を調製することができるが、この混合においては一般のシリコーンゴム配合に使用される混合機を用いればよく、例えば、ニーダー、ゲートミキサー、品川ミキサー、加圧ミキサー、三本ロール、二本ロール等が挙げられる。 <Preparation of Additive Curable Silicone Rubber Composition>
An addition curable silicone rubber composition can be prepared by adding the above components (A) to (D) and further, if necessary, other optional components and uniformly mixing them. In this mixing, the addition-curable silicone rubber composition can be prepared. A mixer used for blending general silicone rubber may be used, and examples thereof include a kneader, a gate mixer, a Shinagawa mixer, a pressure mixer, a three-roll, and a two-roll.
　上記で得られる付加硬化性シリコーンゴム組成物は、ＪＩＳ　Ｋ　６３００－２：２００１に記載のねじり振動式円すいダイ加硫試験機（Ｂ－２法）を用いた加硫試験において、１５０℃、５分測定時の１０％硬化時間をＴ１０（秒）とし、９０％硬化時間をＴ９０（秒）としたとき、Ｔ９０－Ｔ１０が１６０秒以上である必要があり、１６０秒～２６０秒が好ましく、さらに１７０～２４０秒であることが特に好ましい。１６０秒より短いと一次加硫後の硬化物硬さが高く、切断時伸びが低くなってしまう。 The addition-curable silicone rubber composition obtained above was subjected to a vulcanization test using the torsional vibration type conical die vulcanization tester (B-2 method) described in JIS K 6300-2: 2001 at 150 ° C. and 5 ° C. When the 10% curing time at the time of minute measurement is T10 (seconds) and the 90% curing time is T90 (seconds), T90-T10 needs to be 160 seconds or more, preferably 160 seconds to 260 seconds, and further. It is particularly preferably 170 to 240 seconds. If it is shorter than 160 seconds, the hardness of the cured product after the primary vulcanization is high, and the elongation at the time of cutting becomes low.
　このように、本発明の付加硬化性シリコーンゴム組成物は、その硬化の際に１０％硬化から９０％硬化までの時間が十分長い（即ち、この間の硬化がゆっくり進行する）ことを特徴とする。なお、Ｔ９０は３００秒（５分）未満である。 As described above, the addition-curable silicone rubber composition of the present invention is characterized in that the time from 10% curing to 90% curing is sufficiently long (that is, the curing proceeds slowly during this period) at the time of curing. .. The T90 is less than 300 seconds (5 minutes).
＜付加硬化性シリコーンゴム組成物の成形＞
　上記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、特に限定されず常法を採用し得るが、成形法としては、コンプレッション成形や射出成形法が好適に採用される。また、成形の際に、硬化物表面の粗さを低減させ、透明性を高めるため、平坦度の高いライナーを用いて成形しても構わない。硬化条件としては、例えば、金型を用いて１００～１８０℃で５秒～３０分間、好ましくは１１０～１８０℃で１０秒～２０分間、特に１２０～１６０℃で３０秒～１０分間程度の一次加硫を行い、金型から硬化物を取り出した後、オーブン等により８０～２００℃、特に１００～２００℃にて１０分～２４時間、特に３０分～１０時間の二次加硫を行うことで所定の硬さの成形物を得る事ができる。 <Molding of Additive Curable Silicone Rubber Composition>
The molding and curing method of the additive-curable silicone rubber composition is not particularly limited, and a conventional method can be adopted, but as the molding method, a compression molding or an injection molding method is preferably adopted. Further, in order to reduce the roughness of the surface of the cured product and enhance the transparency during molding, a liner having a high flatness may be used for molding. As the curing conditions, for example, using a mold, the primary temperature is 100 to 180 ° C. for 5 seconds to 30 minutes, preferably 110 to 180 ° C. for 10 seconds to 20 minutes, and particularly 120 to 160 ° C. for 30 seconds to 10 minutes. After vulcanization and taking out the cured product from the mold, secondary vulcanization is performed at 80 to 200 ° C., particularly 100 to 200 ° C. for 10 minutes to 24 hours, especially 30 minutes to 10 hours. It is possible to obtain a molded product having a predetermined hardness.
＜シリコーンゴム成形体＞
　本発明の付加硬化性シリコーンゴム組成物は、１２０℃／１０分のプレスキュア（一次加硫）によって得られるシリコーンゴム成形体（エラストマー）が、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づく硬さ（デュロメータタイプＡ）が５５以下であり、ＪＩＳ　Ｋ　６２５１：２０１７に基づく引張試験での切断時伸びが３００％以上となり、また、プレスキュア後、１５０℃／１時間のポストキュア（二次加硫）を実施して得られるシリコーンゴム成形体（エラストマー）の硬さ（デュロメータタイプＡ）が６５以上となり、上記ポストキュア後の２ｍｍ厚の成形体がＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率が９０％以上、特に９２％以上となり、該ポストキュア後の２ｍｍ厚の成形体がＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ試験において、ヘーズ値が２％以下となる高硬度で高透明なシリコーンゴムを与えることができるものである。一次加硫後の硬化物の硬さ（デュロメータタイプＡ）が５５以下かつ切断時伸びが３００％以上であると、金型からの取り出しが容易になる。 <Silicone rubber molded body>
In the addition curable silicone rubber composition of the present invention, the silicone rubber molded product (elastomer) obtained by press curing (primary vulcanization) at 120 ° C./10 minutes has a hardness (durometer) based on JIS K 6253-: 2012. Type A) is 55 or less, the elongation at the time of cutting in the tensile test based on JIS K 6251: 2017 is 300% or more, and post-cure (secondary vulcanization) at 150 ° C. for 1 hour after press curing is performed. The hardness (durometer type A) of the silicone rubber molded body (elastomer) obtained by carrying out the molding is 65 or more, and the 2 mm thick molded body after the post-cure is all with respect to D65 light described in JIS K 7631-1: 1997. The light transmittance is 90% or more, particularly 92% or more, and the haze value of the 2 mm thick molded product after the post-cure is 2% or less in the haze test using D65 light described in JIS K 7136: 2000. It is possible to give a highly hard and highly transparent silicone rubber. When the hardness (durometer type A) of the cured product after the primary vulcanization is 55 or less and the elongation at the time of cutting is 300% or more, it can be easily taken out from the mold.
　このように、本発明の付加硬化性シリコーンゴム組成物は、金型からの取り出し性に優れ、二次加硫後には高硬度かつ透明性の高いシリコーンゴムを与えるものであり、ＬＥＤ等の光学用途として好適に用いることができる。 As described above, the additive-curable silicone rubber composition of the present invention is excellent in the ease of removal from the mold, and after the secondary vulcanization, provides a silicone rubber having high hardness and high transparency, and is used for optics such as LEDs. It can be suitably used as an application.
　以下、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、数平均重合度を示す。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following example, the part indicates the mass part. Further, the average degree of polymerization indicates a number average degree of polymerization.
［実施例１］
　両末端がジメチルビニルシロキシ基で封鎖された平均重合度が７２０であるジメチルポリシロキサン（Ａ－１、アルケニル基含有量：０．００００３８ｍｏｌ／ｇ）５０部、一分子中にビニル基を平均３．６個有し、数平均分子量が４０００のビニルジメチルシロキシ基・トリメチルシロキシ基とＱ単位との共重合体であるシリコーンレジン（Ｂ－１、アルケニル基含有量：０．０００８９ｍｏｌ／ｇ、構成単位モル比はＭ：Ｄ：Ｔ：Ｑ＝４６：０：０：５４、Ｍ／Ｑ＝０．８５）５０部、架橋剤として下記式（４）で示される、
Figure JPOXMLDOC01-appb-C000006
 ハイドロジェンポリシロキサン（Ｃ－１、ヒドロメチルシロキサン単位／（ヒドロメチルシロキサン単位＋ジメチルシロキサン単位）＝５１ｍｏｌ％）を６．２部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝５０／５０であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．１である。 [Example 1]
50 parts of dimethylpolysiloxane (A-1, alkenyl group content: 0.000038mol / g) having an average degree of polymerization of 720 with both ends sealed with a dimethylvinylsiloxy group, and an average of 3. vinyl groups in one molecule. Silicone resin (B-1, alkenyl group content: 0.00086 mol / g, structural unit mol) which is a copolymer of 6 vinyldimethylsiloxy groups / trimethylsiloxy groups having a number average molecular weight of 4000 and Q units. The ratio is M: D: T: Q = 46: 0: 0: 54, M / Q = 0.85) 50 parts, represented by the following formula (4) as a cross-linking agent.
Figure JPOXMLDOC01-appb-C000006
 Add 6.2 parts of hydrogen polysiloxane (C-1, hydromethylsiloxane unit / (hydromethylsiloxane unit + dimethylsiloxane unit) = 51 mol%) and 0.025 part of ethynylcyclohexanol as a reaction control agent, and add 15 parts. Minute stirring was continued to obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 50/50, and the ratio of the number of moles of all Si—H groups to all alkenyl groups (Si—). H group / total alkenyl group) is 1.1.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
［実施例２］
　両末端がジメチルビニルシロキシ基で封鎖された平均重合度が５００であるジメチルポリシロキサン（Ａ－２、アルケニル基含有量：０．００００５４ｍｏｌ／ｇ）５０部、実施例１に記載のシリコーンレジン（Ｂ－１）５０部、架橋剤として下記式（５）で示される、
Figure JPOXMLDOC01-appb-C000007
 ハイドロジェンポリシロキサン（Ｃ－２、ヒドロメチルシロキサン単位／（ヒドロメチルシロキサン単位＋ジメチルシロキサン単位）＝７３ｍｏｌ％）を４．６部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝５０／５０であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．１である。 [Example 2]
50 parts of dimethylpolysiloxane (A-2, alkenyl group content: 0.000054mol / g) having an average degree of polymerization of 500 in which both ends are sealed with a dimethylvinylsiloxy group, the silicone resin (B) according to Example 1. -1) 50 parts, represented by the following formula (5) as a cross-linking agent,
Figure JPOXMLDOC01-appb-C000007
 Add 4.6 parts of hydrogen polysiloxane (C-2, hydromethylsiloxane unit / (hydromethylsiloxane unit + dimethylsiloxane unit) = 73 mol%) and 0.025 part of ethynylcyclohexanol as a reaction control agent, and add 15 parts. Minute stirring was continued to obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 50/50, and the ratio of the number of moles of all Si—H groups to all alkenyl groups (Si—). H group / total alkenyl group) is 1.1.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
［実施例３］
　実施例１に記載のジメチルポリシロキサン（Ａ－１）５５部、実施例１に記載のシリコーンレジン（Ｂ－１）４５部、架橋剤として実施例２に記載のハイドロジェンポリシロキサン（Ｃ－２）を５．３部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝５５／４５であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．４である。 [Example 3]
55 parts of dimethylpolysiloxane (A-1) according to Example 1, 45 parts of silicone resin (B-1) according to Example 1, and hydrogenpolysiloxane (C-2) according to Example 2 as a cross-linking agent. ) Was added in 5.3 parts and 0.025 part of ethynylcyclohexanol as a reaction control agent, and stirring was continued for 15 minutes to obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 55/45, and the ratio of the number of moles of all Si—H groups to all alkenyl groups (Si—). H group / total alkenyl group) is 1.4.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
［実施例４］
　実施例１に記載のジメチルポリシロキサン（Ａ－１）４７．５部、両末端がジメチルビニルシロキシ基で封鎖され、側鎖にビニル基を平均１０個有する平均重合度が８０００であるジメチルポリシロキサン（Ａ－３、アルケニル基含有量：０．００００２０ｍｏｌ／ｇ）５部、実施例１に記載のシリコーンレジン（Ｂ－１）４７．５部、架橋剤として下記式（６）で示される、
Figure JPOXMLDOC01-appb-C000008
 ハイドロジェンポリシロキサン（Ｃ－３、ヒドロメチルシロキサン単位／（ヒドロメチルシロキサン単位＋ジメチルシロキサン単位）＝５０ｍｏｌ％）を７．３部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝５２．５／４７．５であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．２である。 [Example 4]
47.5 parts of dimethylpolysiloxane (A-1) according to Example 1, both ends of which are sealed with dimethylvinylsiloxy groups, and dimethylpolysiloxane having an average of 10 vinyl groups on the side chains and an average degree of polymerization of 8000. (A-3, alkenyl group content: 0.000020 mol / g) 5 parts, 47.5 parts of the silicone resin (B-1) described in Example 1, represented by the following formula (6) as a cross-linking agent.
Figure JPOXMLDOC01-appb-C000008
 Add 7.3 parts of hydrogen polysiloxane (C-3, hydromethylsiloxane unit / (hydromethylsiloxane unit + dimethylsiloxane unit) = 50 mol%) and 0.025 part of ethynylcyclohexanol as a reaction control agent, and add 15 parts. Minute stirring was continued to obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 52.5 / 47.5, and the number of moles of all Si—H groups with respect to all alkenyl groups is high. The ratio (Si—H group / total alkenyl group) is 1.2.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
［比較例１］
　両末端がジメチルビニルシロキシ基で封鎖された平均重合度が４５０であるジメチルポリシロキサン（Ａ－４、アルケニル基含有量：０．００００６０ｍｏｌ／ｇ）５０部、実施例１に記載のシリコーンレジン（Ｂ－１）５０部、架橋剤として実施例２に記載のハイドロジェンポリシロキサン（Ｃ－２）を４．７部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝５０／５０であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．１である。 [Comparative Example 1]
50 parts of dimethylpolysiloxane (A-4, alkenyl group content: 0.000060 mol / g) having an average degree of polymerization of 450, both ends of which are sealed with a dimethylvinylsiloxy group, the silicone resin (B) according to Example 1. -1) Add 50 parts, 4.7 parts of the hydrogenpolysiloxane (C-2) described in Example 2 as a cross-linking agent, and 0.025 parts of ethynylcyclohexanol as a reaction control agent, and continue stirring for 15 minutes. To obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 50/50, and the ratio of the number of moles of all Si—H groups to all alkenyl groups (Si—). H group / total alkenyl group) is 1.1.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
［比較例２］
　実施例１に記載のジメチルポリシロキサン（Ａ－１）６１部、実施例１に記載のシリコーンレジン（Ｂ－１）３９部、架橋剤として実施例２に記載のハイドロジェンポリシロキサン（Ｃ－２）を４．７部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝６１／３９であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．４である。 [Comparative Example 2]
61 parts of dimethylpolysiloxane (A-1) according to Example 1, 39 parts of silicone resin (B-1) according to Example 1, and hydrogenpolysiloxane (C-2) according to Example 2 as a cross-linking agent. ), And 0.025 part of ethynylcyclohexanol as a reaction control agent was added, and stirring was continued for 15 minutes to obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 61/39, and the ratio of the number of moles of all Si—H groups to all alkenyl groups (Si—). H group / total alkenyl group) is 1.4.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
［比較例３］
　実施例１に記載のジメチルポリシロキサン（Ａ－１）５５部、実施例１に記載のシリコーンレジン（Ｂ－１）４５部、架橋剤として実施例４に記載のハイドロジェンポリシロキサン（Ｃ－３）を９．８部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝５５／４５であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．６である。 [Comparative Example 3]
55 parts of dimethylpolysiloxane (A-1) according to Example 1, 45 parts of silicone resin (B-1) according to Example 1, and hydrogenpolysiloxane (C-3) according to Example 4 as a cross-linking agent. ) Was added in an amount of 9.8 parts and 0.025 part of ethynylcyclohexanol as a reaction control agent, and stirring was continued for 15 minutes to obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 55/45, and the ratio of the number of moles of all Si—H groups to all alkenyl groups (Si—). H group / total alkenyl group) is 1.6.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
［比較例４］
　実施例１に記載のジメチルポリシロキサン（Ａ－１）５０部、実施例１に記載のシリコーンレジン（Ｂ－１）５０部、架橋剤として下記式（７）で示される、
Figure JPOXMLDOC01-appb-C000009
 ハイドロジェンポリシロキサン（Ｃ－４、ヒドロメチルシロキサン単位／（ヒドロメチルシロキサン単位＋ジメチルシロキサン単位）＝３６ｍｏｌ％）を１０．８部、反応制御剤としてエチニルシクロヘキサノール０．０２５部を添加し、１５分撹拌を続けて、シリコーンゴム混合物を得た。
　なお、この混合物において、（Ａ）成分と（Ｂ）成分の質量比は（Ａ）／（Ｂ）＝５０／５０であり、全アルケニル基に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）は１．２である。 [Comparative Example 4]
50 parts of dimethylpolysiloxane (A-1) according to Example 1, 50 parts of silicone resin (B-1) according to Example 1, represented by the following formula (7) as a cross-linking agent.
Figure JPOXMLDOC01-appb-C000009
 Add 10.8 parts of hydrogen polysiloxane (C-4, hydromethylsiloxane unit / (hydromethylsiloxane unit + dimethylsiloxane unit) = 36 mol%) and 0.025 part of ethynylcyclohexanol as a reaction control agent, and add 15 parts. Minute stirring was continued to obtain a silicone rubber mixture.
In this mixture, the mass ratio of the component (A) to the component (B) is (A) / (B) = 50/50, and the ratio of the number of moles of all Si—H groups to all alkenyl groups (Si—). H group / total alkenyl group) is 1.2.
　このシリコーンゴム混合物中に、白金触媒（Ｐｔ濃度１質量％）０．０５部を混合してシリコーンゴム組成物とした。該組成物のＪＩＳ　Ｋ　６３００－２：２００１に基づき、１５０℃、５分測定における硬化性（１０％硬化時間Ｔ１０、及び９０％硬化時間Ｔ９０）をレオメーターＭＤＲ２０００（アルファテクノロジーズ社製）により測定した結果、および１２０℃／１０分のプレスキュア（一次加硫）後に得られた２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果を表２に示した。また、プレスキュア後にオーブン内で１５０℃／１時間のポストキュア（二次加硫）を行った２ｍｍ厚の硬化物について、ＪＩＳ　Ｋ　６２５３－３：２０１２に基づき、デュロメータタイプＡにおける硬さ、及びＪＩＳ　Ｋ　６２５１：２０１７に基づき、切断時伸びを測定した結果、さらに、ＪＩＳ　Ｋ　７３６１－１：１９９７に記載のＤ６５光に対する全光線透過率を測定した結果、および、ＪＩＳ　Ｋ　７１３６：２０００に記載のＤ６５光を用いたヘーズ測定を行った結果を表３に示した。 0.05 parts of a platinum catalyst (Pt concentration 1% by mass) was mixed with this silicone rubber mixture to prepare a silicone rubber composition. Based on JIS K 6300-2: 2001 of the composition, the curability (10% curing time T10 and 90% curing time T90) at 150 ° C. for 5 minutes was measured by a rheometer MDR2000 (manufactured by Alpha Technologies). For the results and the 2 mm thick cured product obtained after press cure (primary vulcanization) at 120 ° C./10 minutes, the hardness in rheometer type A and JIS K 6251: 2017 based on JIS K6253-3:2012. The results of measuring the elongation at the time of cutting are shown in Table 2. In addition, the hardness of the 2 mm thick cured product, which was post-cured (secondary vulcanization) at 150 ° C. for 1 hour after press curing, and the hardness in durometer type A based on JIS K6253-3: 2012, and The result of measuring the elongation at the time of cutting based on JIS K 6251: 2017, the result of measuring the total light transmission rate for D65 light described in JIS K 7631-1: 1997, and the result described in JIS K 7136: 2000. Table 3 shows the results of haze measurement using D65 light.
　実施例１～４、比較例１～４で用いた各成分の配合量を表１に示した。 Table 1 shows the blending amounts of each component used in Examples 1 to 4 and Comparative Examples 1 to 4.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表２、３に示すように、実施例１～４の付加硬化性シリコーンゴム組成物は、一次加硫後の硬さ（デュロメータタイプＡ）が５５以下と低く、切断時伸び率が３００％以上であり、二次加硫後に硬度が６５以上となることが可能であり、透明性の高い付加硬化性シリコーンゴム組成物が得られる。 As shown in Tables 2 and 3, the curable silicone rubber compositions of Examples 1 to 4 have a low hardness (durometer type A) of 55 or less after primary vulcanization and an elongation rate at cutting of 300% or more. Therefore, the hardness can be 65 or more after the secondary vulcanization, and a highly transparent additive-curable silicone rubber composition can be obtained.
　一方、平均重合度が４８０に満たない直鎖状オルガノポリシロキサンを用いた比較例１では、一次加硫後のゴムの伸びが低くなり、（Ａ）成分と（Ｂ）成分の質量比が（Ａ）／（Ｂ）＝４０／６０～６０／４０の範囲外である比較例２では、二次加硫後でも硬さが低くなった。 On the other hand, in Comparative Example 1 using a linear organopolysiloxane having an average degree of polymerization of less than 480, the elongation of the rubber after the primary vulcanization was low, and the mass ratio of the component (A) and the component (B) was (). In Comparative Example 2 in which A) / (B) = 40/60 to 60/40, the hardness was low even after the secondary vulcanization.
　また、組成物中の全アルケニル基のモル数に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）が１．０～１．５の範囲外である比較例３では、一次加硫後の硬化物硬さが高く、切断時伸びが低くなり、ヒドロメチルシロキサン単位／（ヒドロメチルシロキサン単位＋ジメチルシロキサン単位）が４０モル％以上でない比較例４では、一次加硫後の硬化物硬さが高く、切断時伸びが低くなった。 Further, in Comparative Example 3 in which the ratio of the number of moles of all Si—H groups (Si—H groups / total alkenyl groups) to the number of moles of all alkenyl groups in the composition is out of the range of 1.0 to 1.5. In Comparative Example 4, in which the hardness of the cured product after the primary smelting was high, the elongation at the time of cutting was low, and the hydromethylsiloxane unit / (hydromethylsiloxane unit + dimethylsiloxane unit) was not 40 mol% or more, after the primary sulfurization. The hardness of the cured product was high, and the elongation during cutting was low.
　以上のように、本発明の付加硬化性シリコーンゴム組成物であれば、金型からの取り出し性に優れ、透明性の高い硬化物を与える事のできる付加硬化性シリコーンゴム組成物となった。 As described above, the additive-curable silicone rubber composition of the present invention is an additive-curable silicone rubber composition that is excellent in ease of removal from the mold and can give a highly transparent cured product.
　なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any of the above-described embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

Claims (3)

  1. 　付加硬化性シリコーンゴム組成物であって、
    （Ａ）平均重合度が４８０以上で、１分子中に少なくとも２個のケイ素原子と結合したアルケニル基を含有する直鎖状オルガノポリシロキサン、
    （Ｂ）下記式（１）で示されるアルケニル基含有シリコーンレジン
    　（Ｒ１ ３ＳｉＯ１／２）ａ（Ｒ１ ２ＳｉＯ２／２）ｂ（Ｒ１ＳｉＯ３／２）ｃ（ＳｉＯ４／２）ｄ　　　　（１）
    （式（１）中、Ｒ１は独立して炭素数１から１０のアルキル基および炭素数２から１０のアルケニル基から選択される１価炭化水素基であり、１分子中に平均２．５個以上のアルケニル基を有し、０＜ａ≦０．７、０≦ｂ≦０．２、０≦ｃ≦０．２、０＜ｄ≦０．７であり、ただし、０．８≦ａ＋ｄ≦１、かつａ＋ｂ＋ｃ＋ｄ＝１となる数である）、
    （Ｃ）下記式（２）で示される直鎖状オルガノハイドロジェンポリシロキサン
    Figure JPOXMLDOC01-appb-C000001
     （式（２）中、Ｒ２は独立して炭素数１から１０のアルキル基であり、Ｒ３は独立して炭素数１から１０のアルキル基もしくは水素原子であり、ｅが８以上の整数であり、ｆが０～１００の整数であり、ｅ／（ｅ＋ｆ）が４０モル％以上、かつ一分子中のケイ素原子結合水素基の数が１０個以上である）、
    （Ｄ）付加反応触媒：組成物の合計質量に対して白金族金属（質量換算）として０．１～１０ｐｐｍ
    を含み、前記（Ａ）成分と前記（Ｂ）成分の質量比が（Ａ）／（Ｂ）＝４０／６０～６０／４０であり、組成物中の全アルケニル基のモル数に対する全Ｓｉ－Ｈ基のモル数の比（Ｓｉ－Ｈ基／全アルケニル基）が１．０～１．５であり、ＪＩＳ　Ｋ　６３００－２：２００１に記載のねじり振動式円すいダイ加硫試験機（Ｂ－２法）を用いた加硫試験において、１５０℃、５分測定時の１０％硬化時間をＴ１０、９０％硬化時間をＴ９０としたとき、Ｔ９０－Ｔ１０が１６０秒以上となることを特徴とする付加硬化性シリコーンゴム組成物。     Additive-curable silicone rubber composition
    (A) A linear organopolysiloxane having an average degree of polymerization of 480 or more and containing an alkenyl group bonded to at least two silicon atoms in one molecule.
    (B) Silicone resin containing an alkenyl group represented by the following formula (1) (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) ) D (1)
    (In the formula (1), R 1 is a monovalent hydrocarbon group independently selected from an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and has an average of 2.5 in one molecule. It has more than one alkenyl group and is 0 <a ≦ 0.7, 0 ≦ b ≦ 0.2, 0 ≦ c ≦ 0.2, 0 <d ≦ 0.7, where 0.8 ≦ a + d. ≤1 and a + b + c + d = 1),
    (C) Linear organohydrogenpolysiloxane represented by the following formula (2)
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (2), R 2 is an independently alkyl group having 1 to 10 carbon atoms, R 3 is independently an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and e is an integer of 8 or more. , F is an integer of 0 to 100, e / (e + f) is 40 mol% or more, and the number of silicon atom-bonded hydrogen groups in one molecule is 10 or more).
    (D) Addition reaction catalyst: 0.1 to 10 ppm as a platinum group metal (mass equivalent) with respect to the total mass of the composition.
    The mass ratio of the component (A) to the component (B) is (A) / (B) = 40/60 to 60/40, and the total Si— with respect to the number of moles of the total alkenyl groups in the composition. The ratio of the number of moles of H groups (Si—H group / total alkenyl group) is 1.0 to 1.5, and the torsional vibration type conical die vulcanization tester (B-) described in JIS K 6300-2: 2001. In the vulcanization test using the method 2), when the 10% curing time at 150 ° C. for 5 minutes is T10 and the 90% curing time is T90, T90-T10 is 160 seconds or longer. Vulcanizing silicone rubber composition.
  2. 　前記（Ａ）成分のアルケニル基量が０．００００６ｍｏｌ／ｇ以下であることを特徴とする請求項１に記載の付加硬化性シリコーンゴム組成物。 The addition-curable silicone rubber composition according to claim 1, wherein the amount of the alkenyl group of the component (A) is 0.00006 mol / g or less.
  3. 　前記（Ｂ）成分のアルケニル基量が０．０００６～０．００１ｍｏｌ／ｇであることを特徴とする請求項１または２に記載の付加硬化性シリコーンゴム組成物。 The addition-curable silicone rubber composition according to claim 1 or 2, wherein the amount of the alkenyl group of the component (B) is 0.0006 to 0.001 mol / g.
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JPH0753872A (en) * 1993-08-17 1995-02-28 Shin Etsu Chem Co Ltd Curable silicone rubber composition
JPH1160954A (en) * 1997-08-21 1999-03-05 Toshiba Silicone Co Ltd Silicone binder composition
JP2000198930A (en) * 1998-12-28 2000-07-18 Shin Etsu Chem Co Ltd Addition curable silicone composition
JP2005042099A (en) * 2003-07-09 2005-02-17 Shin Etsu Chem Co Ltd Silicone rubber composition, coating protective material for light-emitting semiconductor, and light-emitting semiconductor device
JP2017031368A (en) * 2015-08-05 2017-02-09 信越化学工業株式会社 Additional curable silicone rubber composition and cured product
JP2018048214A (en) * 2016-09-20 2018-03-29 信越化学工業株式会社 Transparent liquid silicone rubber composition
JP2018131482A (en) * 2017-02-13 2018-08-23 信越化学工業株式会社 Addition-curable liquid silicone rubber composition
JP2019189723A (en) * 2018-04-24 2019-10-31 信越化学工業株式会社 High transparent addition curable liquid silicone rubber composition for led lamp, and led lamp

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0753872A (en) * 1993-08-17 1995-02-28 Shin Etsu Chem Co Ltd Curable silicone rubber composition
JPH1160954A (en) * 1997-08-21 1999-03-05 Toshiba Silicone Co Ltd Silicone binder composition
JP2000198930A (en) * 1998-12-28 2000-07-18 Shin Etsu Chem Co Ltd Addition curable silicone composition
JP2005042099A (en) * 2003-07-09 2005-02-17 Shin Etsu Chem Co Ltd Silicone rubber composition, coating protective material for light-emitting semiconductor, and light-emitting semiconductor device
JP2017031368A (en) * 2015-08-05 2017-02-09 信越化学工業株式会社 Additional curable silicone rubber composition and cured product
JP2018048214A (en) * 2016-09-20 2018-03-29 信越化学工業株式会社 Transparent liquid silicone rubber composition
JP2018131482A (en) * 2017-02-13 2018-08-23 信越化学工業株式会社 Addition-curable liquid silicone rubber composition
JP2019189723A (en) * 2018-04-24 2019-10-31 信越化学工業株式会社 High transparent addition curable liquid silicone rubber composition for led lamp, and led lamp

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