WO2020217805A1 - Silicone rubber composition for molding and silicone rubber mold - Google Patents
Silicone rubber composition for molding and silicone rubber mold Download PDFInfo
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- WO2020217805A1 WO2020217805A1 PCT/JP2020/012573 JP2020012573W WO2020217805A1 WO 2020217805 A1 WO2020217805 A1 WO 2020217805A1 JP 2020012573 W JP2020012573 W JP 2020012573W WO 2020217805 A1 WO2020217805 A1 WO 2020217805A1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Definitions
- the present invention relates to a silicone rubber composition for molding and a silicone rubber mold, and more specifically, to an addition-curing silicone rubber composition for molding and a silicone molding base (so-called female mold) obtained by curing the silicone rubber composition. ..
- silicone rubber has been widely used in various fields by taking advantage of its excellent heat resistance, cold resistance, electrical characteristics, etc., and has been used as a silicone rubber mold (mother mold) due to its good releasability. ing.
- silicone rubber mold mother mold
- the addition reaction type liquid silicone rubber composition has come to be widely used as a molding material using the silicone rubber composition from the viewpoint of good quality.
- the addition reaction type silicone rubber composition has preferable molding properties as a molding material, but it may be difficult to release the mold due to a more complicated shape or a reverse gradient, especially for a glass master.
- various studies have been made on a method of adding a mold release component to the silicone rubber composition to improve the mold release property.
- a method of blending non-reactive silicone oil Patent Document 1
- a method of blending a water-in-oil emulsion using dimethyl silicone oil as an oil layer Patent Document 2
- a phenyl group-containing dimethyl silicone oil bleed component a method of blending non-reactive silicone oil (Patent Document 1), a method of blending a water-in-oil emulsion using dimethyl silicone oil as an oil layer, and a phenyl group-containing dimethyl silicone oil bleed component.
- Patent Documents 3 to 5 A method of blending a composition, a higher fatty acid or a higher fatty acid metal salt, a dimethyl silicone oil having an alkoxysilane group at the molecular terminal
- Patent Document 6 a method of blending water
- Patent Document 7 a method of blending wax.
- JP-A-58-225152 Japanese Unexamined Patent Publication No. 2001-098153 JP-A-2002-188008 Japanese Patent No. 2686903 Japanese Patent No. 53199005 Japanese Unexamined Patent Publication No. 9-143372 Japanese Unexamined Patent Publication No. 2004-107373
- the present invention has been made in view of the above circumstances, and uses a silicone rubber composition for molding that provides a silicone rubber mold that is excellent in releasability to a glass master and can be used repeatedly, and the silicone rubber mold. It is an object of the present invention to provide a method for producing a duplicated epoxy resin product.
- the present inventors have found that the structure of the organohydrogenpolysiloxane greatly contributes to the releasability from the glass master in the liquid addition-curable silicone rubber composition.
- the structure of the organohydrogenpolysiloxane greatly contributes to the releasability from the glass master in the liquid addition-curable silicone rubber composition.
- it has excellent mechanical strength, releasability from a glass master, releasability from molded products such as epoxy resin, and advanced releasability such as complicated and reverse gradient.
- the present invention has been completed by finding that it can be a silicone rubber molding material suitable for molding materials that require properties.
- Linear or cyclic organohydrogenpolysiloxane represented by: The number of hydrogen atoms bonded to the silicon atom in the component (B) per alkenyl group bonded to the silicon atom in the component (A) is 0.
- a silicone rubber composition for molding which comprises an amount of 5 to 5.0 pieces and (C) a hydrosilylation reaction catalyst.
- Molding agent for glass which comprises 1 or 2 silicone rubber composition for molding, 4. Silicone rubber mold made by curing 1 or 2 silicone rubber composition for molding, 5.
- a method for producing an epoxy resin replica which comprises using the silicone rubber mold of No. 4.
- the silicone rubber mold obtained by curing the silicone rubber composition for molding of the present invention has excellent mold releasability with respect to a glass master and mold releasability from a molded product such as an epoxy resin, thus improving productivity. Can be made to.
- the silicone rubber composition for molding has fluidity in an uncured state, and is brought into contact with the entire surface or a part of the surface of the prototype by a method such as casting or coating.
- the releasability is a term that includes not only the releasability of the cured mold (mother mold) from the prototype but also the releasability of the duplicated product from the obtained mold (mother mold). Use.
- the silicone rubber composition for molding according to the present invention contains the following components (A) to (C).
- (A) Organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule
- (B) The following average unit formula (1) (R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
- R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u.
- Component (A) is an organopolysiloxane having at least two, preferably 2 to 10, and more preferably 2 to 5 alkenyl groups bonded to silicon atoms in one molecule. If less than two, the composition will be insufficiently cured.
- the upper limit is not particularly limited, but 10 or less is preferable from the viewpoint of preventing the cured product from becoming brittle.
- the alkenyl group bonded to the silicon atom is not particularly limited and may be linear, branched or cyclic, but has 2 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups.
- the alkenyl group may be present at either or both of the end of the molecular chain and the non-end of the molecular chain (that is, the side chain of the molecular chain), but is preferably present at least at both ends of the molecular chain.
- the organic group bonded to a silicon atom other than the alkenyl group is not particularly limited as long as it does not have an addition-reactive carbon-carbon unsaturated bond, and is linear, branched, or cyclic.
- a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, a monovalent hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a monovalent hydrocarbon group having 1 to 5 carbon atoms is preferable. Even more preferable.
- linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and n-hexyl groups; cyclic alkyl groups such as cyclohexyl groups; phenyl and trill groups.
- aryl groups examples thereof include aralkyl groups such as benzyl and phenylethyl groups.
- a part or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as F, Cl and Br, cyano groups and the like, and specific examples of such groups include.
- Halogen-substituted hydrocarbon groups such as 3,3,3-trifluoropropyl group; cyano-substituted hydrocarbon groups such as 2-cyanoethyl group and the like can be mentioned. Of these, a methyl group is preferable.
- Examples of the component (A) include organopolysiloxane represented by the following average composition formula (2).
- R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond
- R 3 independently represents an alkenyl group.
- C is 1.9 to 2.1
- d is 0.005 to 1.0
- c + d is a number satisfying 1.95 to 3.0.
- Examples of the monovalent hydrocarbon group of R 2 include the same groups as those exemplified above as the organic group bonded to the silicon atom other than the alkenyl group, but the methyl group is preferable.
- Examples of the alkenyl group of R 3 include the same groups as those exemplified above as the alkenyl group bonded to the silicon atom, but a vinyl group is preferable.
- the number of c is preferably 1.95 to 2.0
- the number of d is preferably 0.01 to 0.5
- the number of c + d is preferably 1.96 to 2.5.
- Examples of the component (A) represented by the average composition formula (2) include, but are not limited to, organopolysiloxanes represented by the following formulas (3) to (9).
- Vi means a vinyl group (the same applies hereinafter).
- R 2 has
- e, f, and g are integers of 0 or more.
- e is preferably an integer satisfying 10 ⁇ e ⁇ 10,000, and more preferably an integer satisfying 50 ⁇ e ⁇ 2,000.
- f and g are preferably integers satisfying 10 ⁇ f + g ⁇ 10,000 and 0 ⁇ f / (f + g) ⁇ 0.2, and more preferably an integer satisfying 50 ⁇ f + g ⁇ 2,000.
- h is an integer of 2 or more, an integer satisfying 2 ⁇ h, 10 ⁇ f + g ⁇ 10,000, and 0 ⁇ h / (g + h) ⁇ 0.2 is preferable, and 50 ⁇ g + h ⁇ 2,000. Integers that satisfy are more preferred.
- the viscosity of the component (A) at 25 ° C. is preferably 1 to 100,000 mPa ⁇ s, more preferably 5 to 10,000 mPa ⁇ s. When the viscosity is in this range, the fluidity is high and the workability is excellent.
- the viscosity in the present invention is a measured value using a rotational viscometer.
- the component (A) may be used alone or in combination of two or more.
- Component (B) is an organohydrogenpolysiloxane represented by the following average formula (1), and acts as a cross-linking agent by hydrosilylating with the alkenyl group in the component (A).
- R 1 3 SiO 1/2 s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u
- R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ⁇ t, 5 ⁇ t + u ⁇ 800, and 0.1 ⁇ t / (t + u) ⁇ 0.4.
- the monovalent hydrocarbon group of R 1 may be the same as the group exemplified in R 2 of the component (A), but is preferably a methyl group.
- s is 0 or 2
- component (B) is a linear or cyclic organohydrogenpolysiloxane, and s is preferably 2, i.e. a linear structure.
- t and u are numbers that satisfy 2 ⁇ t, 5 ⁇ t + u ⁇ 800, and 0.1 ⁇ t / (t + u) ⁇ 0.4, but t is preferably a number from 2 to 300. More preferably, it is a number of 3 to 200. Further, t / (t + u) is preferably in the range of 0.14 to 0.25.
- the viscosity of the component (B) at 25 ° C. is not particularly limited, but is preferably 1 to 3,000 mPa ⁇ s because the workability of the composition and the mechanical properties of the cured product are more excellent. More preferably, 5 to 200 mPa ⁇ s.
- organohydrogenpolysiloxane of the component (B) examples include both-terminal trimethylsiloxy group-blocking methylhydrogenpolysiloxane, both-terminal trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, and both-terminal trimethylsiloxy group-blocking methylhydro.
- the number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.5 to 5.0 per alkenyl group bonded to the silicon atom in the component (A).
- the amount is preferably 0.7 to 3.0 pieces. If the number is less than 0.5, the cross-linking becomes insufficient, and as a result, the silicone rubber mold obtained by curing the composition becomes sticky, and the releasability to the master and the replica is lowered. If the number exceeds 5.0, foaming due to the generation of hydrogen gas is likely to occur during curing, the replication accuracy is lowered due to the unevenness of the surface of the silicone rubber mold, and the rubber strength is lowered due to the generation of voids inside the cured product.
- the component (B) may be used alone or in combination of two or more.
- Component (C) is a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction between the alkenyl group in the component (A) and the SiH group in the component (B).
- a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction between the alkenyl group in the component (A) and the SiH group in the component (B).
- Specific examples thereof include platinum (including platinum black), rhodium, palladium and other platinum group metals alone; H 2 PtCl 4 ⁇ nH 2 O, H 2 PtCl 6 ⁇ nH 2 O, NaHPtCl 6 ⁇ nH 2 O, KH PtCl.
- n is Platinum chloride, chloroplatinic acid and chloroplatinate such as (0 to 6, preferably 0 or 6); alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972).
- Complex of chloroplatinic acid and olefin see US Pat. Nos.
- Platinum black palladium Platinum group metals such as, supported on a carrier such as alumina, silica, carbon; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, platinum chloride acid or platinum chloride salt Examples thereof include platinum group metal-based catalysts such as a complex with a vinyl group-containing siloxane.
- the component (C) may be used alone or in combination of two or more.
- the blending amount of the component (C) is not limited as long as it promotes the curing (hydrosilylation reaction) of the composition, and the metal atoms in the component are added to the total mass of each component of the composition.
- the amount in the range of 0.1 to 1,000 ppm in terms of mass is preferable, the range of 1 to 500 ppm is more preferable, and the range of 3 to 100 ppm is even more preferable. Within this range, the reaction rate of the addition reaction becomes appropriate, and a cured product having high strength can be obtained.
- Silica may be added as the component (D) to the silicone rubber composition for molding of the present invention in order to improve physical strength such as hardness and tensile strength.
- Examples of silica include fumed silica, crystalline silica (quartz powder), precipitated silica, silica whose surface is hydrophobized, and the like, and these may be used alone or in combination of two or more. ..
- silica as hydrophilic silica, Aerosil 130, 200, 300 (manufactured by Nippon Aerosil Co., Ltd.), Cabosil MS-5, MS-7 (manufactured by Cabot), Rheorosil QS-102,103 ((() Fumed silica such as Tokuyama Co., Ltd .; Precipitated silica such as Tokseal US-F (manufactured by Tokuyama Co., Ltd.) and Nippon Silica LP (manufactured by Nippon Silica Industry Co., Ltd.) can be mentioned as hydrophobic silica.
- Fumed silica such as Aerosil R-812, R-812S, R-972, R-974 (manufactured by Nippon Aerosil Co., Ltd.), Rheorosil MT-10 (manufactured by Tokuyama Co., Ltd.); Nippon Silica SS series (Nippon Silica Industry (Nippon Silica Industry) Precipitated silica (manufactured by Tatsumori Co., Ltd.), crystalline silica such as Crystallite (manufactured by Tatsumori Co., Ltd.), MIN-U-SIL (manufactured by US Silka Company), Imisil (manufactured by Illinois Mineral), etc. Can be mentioned.
- silicas may be used as they are, but those which have been surface-hydrophobicized in advance with a surface treatment agent may be used, or the silica surface may be hydrophobized by adding a surface treatment agent when kneading the component (A). It is preferable to use it.
- the surface treatment agent include alkylalkoxysilane, alkylhydroxysilane, alkylchlorosilane, alkylsilazane, silane coupling agent, low molecular weight polysiloxane, titanate treatment agent, fatty acid ester and the like, and alkyldisilazane is more preferable. Is hexamethyldisilazane.
- the amount of the surface treatment agent used is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 2 to 30 parts by mass with respect to 100 parts by mass of silica.
- the amount of the surface treatment agent used is within the above range, the surface treatment agent or its decomposition products do not remain in the composition, fluidity can be obtained, and the increase in viscosity with time can be suppressed.
- the component (D) preferably has a specific surface area of 50 to 400 m 2 / g by the BET method, particularly 100 to 350 m 2 / g. Within such a range, sufficient rubber strength can be obtained.
- the amount added is preferably 5 to 100 parts by mass, preferably 20 to 50 parts by mass, based on 100 parts by mass of the component (A) from the viewpoint of handleability of the composition and mechanical strength of the cured product. Parts by mass are more preferred.
- the silicone rubber composition for molding of the present invention contains hydrosilyls so as not to cause thickening or gelation when the composition is prepared or before heat curing such as when molding.
- the reaction control agent (E) may be added for the purpose of controlling the reactivity of the chemical reaction catalyst.
- Specific examples of the reaction control agent include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, and 1-ethynyl.
- the amount added is preferably 0.01 to 2.0 parts by mass, preferably 0.01 to 0.1 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). More preferred. Within such a range, the effect of reaction control is fully exhibited.
- the silicone rubber composition for molding of the present invention contains other components exemplified below as long as the object of the present invention is not impaired. You may.
- Other components include conductive agents such as iron oxide, carbon black, conductive zinc oxide, and metal powder; heat resistant agents such as titanium oxide and cerium oxide; internal mold release agents such as dimethyl silicone oil; adhesive imparting agents; thixo. Examples include sex-imparting agents.
- the silicone rubber composition for molding of the present invention contains the above-mentioned components (A) to (C), components (D) and (E) used as necessary, and other components such as a kneader and a planetary mixer. It can be prepared by mixing by the known method used.
- the silicone rubber composition for molding of the present invention comprises a first agent consisting of a component (A), a component (C) and, if necessary, other components, and a component (A), a component (B) and, if necessary.
- a second agent composed of other components may be prepared separately, and a two-agent type composition may be prepared in which the first agent and the second agent are mixed before use.
- curing condition of the silicone rubber composition for molding of the present invention for example, curing proceeds even at room temperature (5 to 35 ° C.), but curing can be accelerated by heating, and when it is desired to improve mass productivity. This method is effective. In the case of heat curing, it is preferable to cure at 70 to 200 ° C. for 30 seconds to 60 minutes, particularly at 90 to 120 ° C. for 1 minute to 30 minutes.
- Examples 1 to 4, Comparative Examples 1 to 3 The following components were mixed at the compounding ratio (parts by mass) shown in Table 1 to prepare a silicone rubber composition. Specifically, first, 85 parts by mass of the component (A), 30 parts by mass of the component (D), 5 parts by mass of hexamethyldisilazane, and 2 parts by mass of water are mixed at 25 ° C. for 30 minutes using a kneader, and then brought to 150 ° C. The temperature was raised, stirring was continued for 4 hours, and after cooling to 25 ° C., the component (C) was added to the silicone rubber base obtained by mixing 15 parts by mass of the component (A), and 25 using a planetary mixer. After stirring and mixing at ° C. for 15 minutes, the component (B) was added, stirred and mixed at 25 ° C. for 15 minutes using a planetary mixer, and defoamed under reduced pressure at 25 ° C. for 30 minutes to obtain a silicone rubber composition. ..
- (B) Ingredient: (B-1) Organohydrogenpolysiloxane represented by the following average structural formula (content of silicon atom-bonded hydrogen atom 0.0018 mol / g) (In the formula, the sequence of siloxane units is random or block.)
- (C) component (C-1) Dimethylsiloxane solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 1.0% by mass)
- thermosetting epoxy resin 5 (trade name:) was formed in the gap 4A of the silicone mold 4 produced by the same procedure as above and peeled from the glass master 1.
- NM102A / B manufactured by Pernox
- the work of taking out the produced epoxy resin replica 6 from the silicone mold 4 was repeated, and the number of times that the resin did not adhere to the silicone mold 4 and could be easily taken out was confirmed.
- the cured product obtained from the molding silicone composition of the present invention prepared in Examples 1 to 3 has excellent mold releasability with respect to the glassy master and the epoxy resin, and is a replica of the epoxy resin. It can be seen that the number of times is good. On the other hand, in Comparative Examples 1 to 3 in which the component (B) of the present invention is not used, it is difficult to peel off from the glass and the epoxy resin, the number of duplications of the epoxy resin is small, and it is found that the epoxy resin is not suitable for molding.
Abstract
A composition containing (A) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule, (B) an organohydrogenpolysiloxane represented by average formula (1) (R1
3SiO1/2) s [R1
1(H)SiO2/2] t (R1
2SiO2/2) u (1) (R1 each independently represent a substituted or unsubstituted monovalent hydrocarbon group free of addition reactive carbon-carbon unsaturated bonds, s is 0 or 2, and t and u represent numbers that satisfy 2≦t, 5≦t+u≦800, and 0.1≦t/(t+u) ≦0.4.) in an amount such that the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.5-5.0 per alkenyl group bonded to a silicon atom in component (A), and (C) a hydrosilylation reaction catalyst gives a silicon rubber mold having excellent releasability from a glass master that can be used repeatedly.
Description
本発明は、型取り用シリコーンゴム組成物およびシリコーンゴム型に関し、さらに詳述すると、付加硬化型の型取り用シリコーンゴム組成物およびこれが硬化してなるシリコーン型取り母型（いわゆるメス型）に関する。
The present invention relates to a silicone rubber composition for molding and a silicone rubber mold, and more specifically, to an addition-curing silicone rubber composition for molding and a silicone molding base (so-called female mold) obtained by curing the silicone rubber composition. ..
従来、シリコーンゴムは、その優れた耐熱性、耐寒性、電気特性などを生かして、様々な分野で広く利用されており、その離型性の良さから、シリコーンゴム型（母型）として用いられている。
特に、電子機器、事務機、家庭電器、自動車部品などの分野では、商品開発段階や商品見本作製などの際に用いるプロトタイプ成形において、費用や所要期間の改善に効果的であることや、作業性が良好であることなどの点から、シリコーンゴム組成物を用いた型取り材料として付加反応型の液状シリコーンゴム組成物が多用されるようになってきた。 Conventionally, silicone rubber has been widely used in various fields by taking advantage of its excellent heat resistance, cold resistance, electrical characteristics, etc., and has been used as a silicone rubber mold (mother mold) due to its good releasability. ing.
In particular, in the fields of electronic devices, office machines, home appliances, automobile parts, etc., it is effective in improving costs and required time in prototype molding used at the product development stage and product sample production, and workability. The addition reaction type liquid silicone rubber composition has come to be widely used as a molding material using the silicone rubber composition from the viewpoint of good quality.
特に、電子機器、事務機、家庭電器、自動車部品などの分野では、商品開発段階や商品見本作製などの際に用いるプロトタイプ成形において、費用や所要期間の改善に効果的であることや、作業性が良好であることなどの点から、シリコーンゴム組成物を用いた型取り材料として付加反応型の液状シリコーンゴム組成物が多用されるようになってきた。 Conventionally, silicone rubber has been widely used in various fields by taking advantage of its excellent heat resistance, cold resistance, electrical characteristics, etc., and has been used as a silicone rubber mold (mother mold) due to its good releasability. ing.
In particular, in the fields of electronic devices, office machines, home appliances, automobile parts, etc., it is effective in improving costs and required time in prototype molding used at the product development stage and product sample production, and workability. The addition reaction type liquid silicone rubber composition has come to be widely used as a molding material using the silicone rubber composition from the viewpoint of good quality.
付加反応型のシリコーンゴム組成物は、型取り材料として好ましい成形特性を有するが、より複雑な形状や逆勾配で、とりわけ、ガラス製のマスタに対しては離型が困難になる場合がある。
このような問題を解決するために、シリコーンゴム組成物に離型成分を添加し、離型性を向上する手法について様々な検討がなされている。
例えば、非反応性シリコーンオイルを配合する方法（特許文献１）、ジメチルシリコーンオイルを油層とした油中水型エマルジョンを配合する方法（特許文献２）、フェニル基含有ジメチルシリコーンオイルブリード成分を配合する組成物、高級脂肪酸または高級脂肪酸金属塩、分子末端にアルコキシシラン基を有するジメチルシリコーンオイルを配合する方法（特許文献３～５）、水を配合する方法（特許文献６）、ワックスを配合する方法（特許文献７）などが報告されている。
しかし、これらの手法では、シリコーンゴムの架橋に関与しない離型剤を配合するため、シリコーンゴム型の透明性や機械的強度の低下を招き易く、添加した離型剤が滲出して複製品が汚損するため用途によっては適しておらず、また、繰り返し使用による離型剤の枯渇に伴って離型性が悪化するという問題もあった。 The addition reaction type silicone rubber composition has preferable molding properties as a molding material, but it may be difficult to release the mold due to a more complicated shape or a reverse gradient, especially for a glass master.
In order to solve such a problem, various studies have been made on a method of adding a mold release component to the silicone rubber composition to improve the mold release property.
For example, a method of blending non-reactive silicone oil (Patent Document 1), a method of blending a water-in-oil emulsion using dimethyl silicone oil as an oil layer (Patent Document 2), and a phenyl group-containing dimethyl silicone oil bleed component. A method of blending a composition, a higher fatty acid or a higher fatty acid metal salt, a dimethyl silicone oil having an alkoxysilane group at the molecular terminal (Patent Documents 3 to 5), a method of blending water (Patent Document 6), a method of blending wax. (Patent Document 7) and the like have been reported.
However, in these methods, since a mold release agent that is not involved in the cross-linking of the silicone rubber is blended, the transparency and mechanical strength of the silicone rubber mold are likely to decrease, and the added mold release agent exudes to produce a duplicate product. It is not suitable for some applications because it is soiled, and there is also a problem that the releasability deteriorates due to the depletion of the releasing agent due to repeated use.
このような問題を解決するために、シリコーンゴム組成物に離型成分を添加し、離型性を向上する手法について様々な検討がなされている。
例えば、非反応性シリコーンオイルを配合する方法（特許文献１）、ジメチルシリコーンオイルを油層とした油中水型エマルジョンを配合する方法（特許文献２）、フェニル基含有ジメチルシリコーンオイルブリード成分を配合する組成物、高級脂肪酸または高級脂肪酸金属塩、分子末端にアルコキシシラン基を有するジメチルシリコーンオイルを配合する方法（特許文献３～５）、水を配合する方法（特許文献６）、ワックスを配合する方法（特許文献７）などが報告されている。
しかし、これらの手法では、シリコーンゴムの架橋に関与しない離型剤を配合するため、シリコーンゴム型の透明性や機械的強度の低下を招き易く、添加した離型剤が滲出して複製品が汚損するため用途によっては適しておらず、また、繰り返し使用による離型剤の枯渇に伴って離型性が悪化するという問題もあった。 The addition reaction type silicone rubber composition has preferable molding properties as a molding material, but it may be difficult to release the mold due to a more complicated shape or a reverse gradient, especially for a glass master.
In order to solve such a problem, various studies have been made on a method of adding a mold release component to the silicone rubber composition to improve the mold release property.
For example, a method of blending non-reactive silicone oil (Patent Document 1), a method of blending a water-in-oil emulsion using dimethyl silicone oil as an oil layer (Patent Document 2), and a phenyl group-containing dimethyl silicone oil bleed component. A method of blending a composition, a higher fatty acid or a higher fatty acid metal salt, a dimethyl silicone oil having an alkoxysilane group at the molecular terminal (Patent Documents 3 to 5), a method of blending water (Patent Document 6), a method of blending wax. (Patent Document 7) and the like have been reported.
However, in these methods, since a mold release agent that is not involved in the cross-linking of the silicone rubber is blended, the transparency and mechanical strength of the silicone rubber mold are likely to decrease, and the added mold release agent exudes to produce a duplicate product. It is not suitable for some applications because it is soiled, and there is also a problem that the releasability deteriorates due to the depletion of the releasing agent due to repeated use.
本発明は、上記事情に鑑みてなされたものであって、ガラス製マスタに対する離型性に優れ、繰り返し使用可能なシリコーンゴム型を与える型取り用シリコーンゴム組成物、およびこのシリコーンゴム型を使用したエポキシ樹脂複製品の製造方法を提供することを目的とする。
The present invention has been made in view of the above circumstances, and uses a silicone rubber composition for molding that provides a silicone rubber mold that is excellent in releasability to a glass master and can be used repeatedly, and the silicone rubber mold. It is an object of the present invention to provide a method for producing a duplicated epoxy resin product.
本発明者らは、上記課題を解決すべく鋭意検討した結果、液状付加硬化型シリコーンゴム組成物において、オルガノハイドロジェンポリシロキサンの構造がガラス製マスタからの離型性に大きく寄与していることを突き止め、その構造を適正に選択することで機械的強度、およびガラス製マスタからの離型性やエポキシ樹脂などの成形品からの離型性に優れ、複雑かつ逆勾配など、高度な離型性を要する型取り材に適したシリコーンゴム型取り材料となり得ることを見出し、本発明を完成させた。
As a result of diligent studies to solve the above problems, the present inventors have found that the structure of the organohydrogenpolysiloxane greatly contributes to the releasability from the glass master in the liquid addition-curable silicone rubber composition. By locating and properly selecting the structure, it has excellent mechanical strength, releasability from a glass master, releasability from molded products such as epoxy resin, and advanced releasability such as complicated and reverse gradient. The present invention has been completed by finding that it can be a silicone rubber molding material suitable for molding materials that require properties.
すなわち、本発明は、
１． （Ａ）ケイ素原子と結合したアルケニル基を１分子中に少なくとも２個有するオルガノポリシロキサン：１００質量部、
（Ｂ）下記平均式（１）
（Ｒ1 3ＳｉＯ1/2）s［Ｒ1 1（Ｈ）ＳｉＯ2/2］t（Ｒ1 2ＳｉＯ2/2）u （１）
（式中、Ｒ1は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、ｓは、０または２であり、ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数を表す。）
で表される直鎖状または環状のオルガノハイドロジェンポリシロキサン：（Ａ）成分中のケイ素原子と結合したアルケニル基１個あたりの（Ｂ）成分中のケイ素原子と結合した水素原子の数が０．５～５．０個となる量、および
（Ｃ）ヒドロシリル化反応触媒
を含有することを特徴とする型取り用シリコーンゴム組成物、
２． （Ｄ）シリカを、（Ａ）成分１００質量部に対して５～１００質量部含有する１の型取り用シリコーンゴム組成物、
３． １または２の型取り用シリコーンゴム組成物からなるガラス用型取り剤、
４． １または２の型取り用シリコーンゴム組成物を硬化させてなるシリコーンゴム型、
５． ４のシリコーンゴム型を用いることを特徴とするエポキシ樹脂製複製品の製造方法
を提供する。 That is, the present invention
1. 1. (A) Organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule: 100 parts by mass,
(B) The following average formula (1)
(R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4.
Linear or cyclic organohydrogenpolysiloxane represented by: The number of hydrogen atoms bonded to the silicon atom in the component (B) per alkenyl group bonded to the silicon atom in the component (A) is 0. A silicone rubber composition for molding, which comprises an amount of 5 to 5.0 pieces and (C) a hydrosilylation reaction catalyst.
2. (D) Silicone rubber composition for molding 1 containing silica in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the component (A).
3. 3. Molding agent for glass, which comprises 1 or 2 silicone rubber composition for molding,
4. Silicone rubber mold made by curing 1 or 2 silicone rubber composition for molding,
5. Provided is a method for producing an epoxy resin replica, which comprises using the silicone rubber mold of No. 4.
１． （Ａ）ケイ素原子と結合したアルケニル基を１分子中に少なくとも２個有するオルガノポリシロキサン：１００質量部、
（Ｂ）下記平均式（１）
（Ｒ1 3ＳｉＯ1/2）s［Ｒ1 1（Ｈ）ＳｉＯ2/2］t（Ｒ1 2ＳｉＯ2/2）u （１）
（式中、Ｒ1は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、ｓは、０または２であり、ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数を表す。）
で表される直鎖状または環状のオルガノハイドロジェンポリシロキサン：（Ａ）成分中のケイ素原子と結合したアルケニル基１個あたりの（Ｂ）成分中のケイ素原子と結合した水素原子の数が０．５～５．０個となる量、および
（Ｃ）ヒドロシリル化反応触媒
を含有することを特徴とする型取り用シリコーンゴム組成物、
２． （Ｄ）シリカを、（Ａ）成分１００質量部に対して５～１００質量部含有する１の型取り用シリコーンゴム組成物、
３． １または２の型取り用シリコーンゴム組成物からなるガラス用型取り剤、
４． １または２の型取り用シリコーンゴム組成物を硬化させてなるシリコーンゴム型、
５． ４のシリコーンゴム型を用いることを特徴とするエポキシ樹脂製複製品の製造方法
を提供する。 That is, the present invention
1. 1. (A) Organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule: 100 parts by mass,
(B) The following average formula (1)
(R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4.
Linear or cyclic organohydrogenpolysiloxane represented by: The number of hydrogen atoms bonded to the silicon atom in the component (B) per alkenyl group bonded to the silicon atom in the component (A) is 0. A silicone rubber composition for molding, which comprises an amount of 5 to 5.0 pieces and (C) a hydrosilylation reaction catalyst.
2. (D) Silicone rubber composition for molding 1 containing silica in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the component (A).
3. 3. Molding agent for glass, which comprises 1 or 2 silicone rubber composition for molding,
4. Silicone rubber mold made by curing 1 or 2 silicone rubber composition for molding,
5. Provided is a method for producing an epoxy resin replica, which comprises using the silicone rubber mold of No. 4.
本発明の型取り用シリコーンゴム組成物を硬化して得られるシリコーンゴム型は、ガラス製マスタに対する離型性およびエポキシ樹脂などの成形品からの離型性に優れているため、生産性を向上させることができる。
The silicone rubber mold obtained by curing the silicone rubber composition for molding of the present invention has excellent mold releasability with respect to a glass master and mold releasability from a molded product such as an epoxy resin, thus improving productivity. Can be made to.
以下、本発明について具体的に説明する。
なお、本発明において、型取り用シリコーンゴム組成物とは、未硬化状態で流動性を有し、原型の全表面または一部の表面に、注型または塗布のような方法で接触させ、その状態で硬化させて樹脂などによる複製に供する型（型取り用の母型）を形成する未硬化状態の（液状）の組成物をいう。
また、本発明において、離型性とは、硬化した型（母型）の原型からの離型性のみでなく、得られた型（母型）からの複製品の離型性を含める用語として用いる。 Hereinafter, the present invention will be specifically described.
In the present invention, the silicone rubber composition for molding has fluidity in an uncured state, and is brought into contact with the entire surface or a part of the surface of the prototype by a method such as casting or coating. An uncured (liquid) composition that is cured in a state to form a mold (mother mold for molding) that is used for duplication with a resin or the like.
Further, in the present invention, the releasability is a term that includes not only the releasability of the cured mold (mother mold) from the prototype but also the releasability of the duplicated product from the obtained mold (mother mold). Use.
なお、本発明において、型取り用シリコーンゴム組成物とは、未硬化状態で流動性を有し、原型の全表面または一部の表面に、注型または塗布のような方法で接触させ、その状態で硬化させて樹脂などによる複製に供する型（型取り用の母型）を形成する未硬化状態の（液状）の組成物をいう。
また、本発明において、離型性とは、硬化した型（母型）の原型からの離型性のみでなく、得られた型（母型）からの複製品の離型性を含める用語として用いる。 Hereinafter, the present invention will be specifically described.
In the present invention, the silicone rubber composition for molding has fluidity in an uncured state, and is brought into contact with the entire surface or a part of the surface of the prototype by a method such as casting or coating. An uncured (liquid) composition that is cured in a state to form a mold (mother mold for molding) that is used for duplication with a resin or the like.
Further, in the present invention, the releasability is a term that includes not only the releasability of the cured mold (mother mold) from the prototype but also the releasability of the duplicated product from the obtained mold (mother mold). Use.
本発明に係る型取り用シリコーンゴム組成物は、下記（Ａ）～（Ｃ）成分を含有するものである。
（Ａ）ケイ素原子と結合したアルケニル基を１分子中に少なくとも２個有するオルガノポリシロキサン
（Ｂ）下記平均単位式（１）
（Ｒ1 3ＳｉＯ1/2）s［Ｒ1 1（Ｈ）ＳｉＯ2/2］t（Ｒ1 2ＳｉＯ2/2）u （１）
（式中、Ｒ1は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、ｓは、０または２であり、ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数を表す。）
で表される直鎖状または環状のオルガノハイドロジェンポリシロキサン
（Ｃ）ヒドロシリル化反応触媒 The silicone rubber composition for molding according to the present invention contains the following components (A) to (C).
(A) Organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule (B) The following average unit formula (1)
(R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4.
Linear or cyclic organohydrogenpolysiloxane (C) hydrosilylation reaction catalyst represented by
（Ａ）ケイ素原子と結合したアルケニル基を１分子中に少なくとも２個有するオルガノポリシロキサン
（Ｂ）下記平均単位式（１）
（Ｒ1 3ＳｉＯ1/2）s［Ｒ1 1（Ｈ）ＳｉＯ2/2］t（Ｒ1 2ＳｉＯ2/2）u （１）
（式中、Ｒ1は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、ｓは、０または２であり、ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数を表す。）
で表される直鎖状または環状のオルガノハイドロジェンポリシロキサン
（Ｃ）ヒドロシリル化反応触媒 The silicone rubber composition for molding according to the present invention contains the following components (A) to (C).
(A) Organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule (B) The following average unit formula (1)
(R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4.
Linear or cyclic organohydrogenpolysiloxane (C) hydrosilylation reaction catalyst represented by
［１］（Ａ）成分
（Ａ）成分は、ケイ素原子と結合したアルケニル基を１分子中に少なくとも２個、好ましくは２～１０個、より好ましくは２～５個有するオルガノポリシロキサンである。２個未満では組成物の硬化が不十分になる。また、上限は特に制限されないが、硬化物が脆くなることを防ぐという点から、１０個以下が好ましい。
ケイ素原子に結合したアルケニル基としては、特に限定されるものではなく、直鎖、分岐、環状のいずれでもよいが、ビニル、アリル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル基等の炭素原子数２～８のものが好ましく、炭素原子数２～４のものがより好ましく、ビニル基がより一層好ましい。
このアルケニル基は、分子鎖末端および分子鎖非末端（即ち、分子鎖側鎖）のいずれかまたは両方に存在してもよいが、少なくとも分子鎖両末端に存在することが好ましい。 [1] Component (A) The component (A) is an organopolysiloxane having at least two, preferably 2 to 10, and more preferably 2 to 5 alkenyl groups bonded to silicon atoms in one molecule. If less than two, the composition will be insufficiently cured. The upper limit is not particularly limited, but 10 or less is preferable from the viewpoint of preventing the cured product from becoming brittle.
The alkenyl group bonded to the silicon atom is not particularly limited and may be linear, branched or cyclic, but has 2 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups. It is preferably from 8 to 8, more preferably from 2 to 4 carbon atoms, and even more preferably from a vinyl group.
The alkenyl group may be present at either or both of the end of the molecular chain and the non-end of the molecular chain (that is, the side chain of the molecular chain), but is preferably present at least at both ends of the molecular chain.
（Ａ）成分は、ケイ素原子と結合したアルケニル基を１分子中に少なくとも２個、好ましくは２～１０個、より好ましくは２～５個有するオルガノポリシロキサンである。２個未満では組成物の硬化が不十分になる。また、上限は特に制限されないが、硬化物が脆くなることを防ぐという点から、１０個以下が好ましい。
ケイ素原子に結合したアルケニル基としては、特に限定されるものではなく、直鎖、分岐、環状のいずれでもよいが、ビニル、アリル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル基等の炭素原子数２～８のものが好ましく、炭素原子数２～４のものがより好ましく、ビニル基がより一層好ましい。
このアルケニル基は、分子鎖末端および分子鎖非末端（即ち、分子鎖側鎖）のいずれかまたは両方に存在してもよいが、少なくとも分子鎖両末端に存在することが好ましい。 [1] Component (A) The component (A) is an organopolysiloxane having at least two, preferably 2 to 10, and more preferably 2 to 5 alkenyl groups bonded to silicon atoms in one molecule. If less than two, the composition will be insufficiently cured. The upper limit is not particularly limited, but 10 or less is preferable from the viewpoint of preventing the cured product from becoming brittle.
The alkenyl group bonded to the silicon atom is not particularly limited and may be linear, branched or cyclic, but has 2 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups. It is preferably from 8 to 8, more preferably from 2 to 4 carbon atoms, and even more preferably from a vinyl group.
The alkenyl group may be present at either or both of the end of the molecular chain and the non-end of the molecular chain (that is, the side chain of the molecular chain), but is preferably present at least at both ends of the molecular chain.
（Ａ）成分のオルガノポリシロキサンにおいて、アルケニル基以外のケイ素原子に結合した有機基は、付加反応性炭素－炭素不飽和結合を有しないものであれば特に限定はなく、直鎖、分岐、環状のいずれでもよいが、炭素原子数１～２０の１価炭化水素基が好ましく、炭素原子数１～１０の１価炭化水素基がより好ましく、炭素原子数１～５の１価炭化水素基がより一層好ましい。
その具体例としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、ｔｅｒｔ－ブチル、ｎ－ヘキシル基等の直鎖または分岐のアルキル基；シクロヘキシル基等の環状アルキル基；フェニル、トリル基等のアリール基；ベンジル、フェニルエチル基等のアラルキル基などが挙げられる。
また、これらの１価炭化水素基の水素原子の一部または全部は、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子、シアノ基等で置換されていてもよく、そのような基の具体例としては、３，３，３－トリフルオロプロピル基等のハロゲン置換炭化水素基；２－シアノエチル基等のシアノ置換炭化水素基等が挙げられる。
これらの中でもメチル基が好ましい。 In the organopolysiloxane of the component (A), the organic group bonded to a silicon atom other than the alkenyl group is not particularly limited as long as it does not have an addition-reactive carbon-carbon unsaturated bond, and is linear, branched, or cyclic. However, a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, a monovalent hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a monovalent hydrocarbon group having 1 to 5 carbon atoms is preferable. Even more preferable.
Specific examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and n-hexyl groups; cyclic alkyl groups such as cyclohexyl groups; phenyl and trill groups. And other aryl groups; examples thereof include aralkyl groups such as benzyl and phenylethyl groups.
Further, a part or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as F, Cl and Br, cyano groups and the like, and specific examples of such groups include. Halogen-substituted hydrocarbon groups such as 3,3,3-trifluoropropyl group; cyano-substituted hydrocarbon groups such as 2-cyanoethyl group and the like can be mentioned.
Of these, a methyl group is preferable.
その具体例としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、ｔｅｒｔ－ブチル、ｎ－ヘキシル基等の直鎖または分岐のアルキル基；シクロヘキシル基等の環状アルキル基；フェニル、トリル基等のアリール基；ベンジル、フェニルエチル基等のアラルキル基などが挙げられる。
また、これらの１価炭化水素基の水素原子の一部または全部は、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子、シアノ基等で置換されていてもよく、そのような基の具体例としては、３，３，３－トリフルオロプロピル基等のハロゲン置換炭化水素基；２－シアノエチル基等のシアノ置換炭化水素基等が挙げられる。
これらの中でもメチル基が好ましい。 In the organopolysiloxane of the component (A), the organic group bonded to a silicon atom other than the alkenyl group is not particularly limited as long as it does not have an addition-reactive carbon-carbon unsaturated bond, and is linear, branched, or cyclic. However, a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, a monovalent hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a monovalent hydrocarbon group having 1 to 5 carbon atoms is preferable. Even more preferable.
Specific examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and n-hexyl groups; cyclic alkyl groups such as cyclohexyl groups; phenyl and trill groups. And other aryl groups; examples thereof include aralkyl groups such as benzyl and phenylethyl groups.
Further, a part or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as F, Cl and Br, cyano groups and the like, and specific examples of such groups include. Halogen-substituted hydrocarbon groups such as 3,3,3-trifluoropropyl group; cyano-substituted hydrocarbon groups such as 2-cyanoethyl group and the like can be mentioned.
Of these, a methyl group is preferable.
（Ａ）成分としては、例えば、下記平均組成式（２）で表されるオルガノポリシロキサンが挙げられる。
Ｒ2 cＲ3 dＳｉＯ(4-c-d)/2 （２）
（式中、Ｒ2は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、Ｒ3は、それぞれ独立してアルケニル基を表し、ｃは１．９～２．１、ｄは０．００５～１．０、かつ、ｃ＋ｄは１．９５～３．０を満たす数である。） Examples of the component (A) include organopolysiloxane represented by the following average composition formula (2).
R 2 c R 3 d SiO (4-cd) / 2 (2)
(In the formula, R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, and R 3 independently represents an alkenyl group. , C is 1.9 to 2.1, d is 0.005 to 1.0, and c + d is a number satisfying 1.95 to 3.0.)
Ｒ2 cＲ3 dＳｉＯ(4-c-d)/2 （２）
（式中、Ｒ2は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、Ｒ3は、それぞれ独立してアルケニル基を表し、ｃは１．９～２．１、ｄは０．００５～１．０、かつ、ｃ＋ｄは１．９５～３．０を満たす数である。） Examples of the component (A) include organopolysiloxane represented by the following average composition formula (2).
R 2 c R 3 d SiO (4-cd) / 2 (2)
(In the formula, R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, and R 3 independently represents an alkenyl group. , C is 1.9 to 2.1, d is 0.005 to 1.0, and c + d is a number satisfying 1.95 to 3.0.)
Ｒ2の１価炭化水素基としては、アルケニル基以外のケイ素原子に結合した有機基として上で例示した基と同様のものが挙げられるが、メチル基が好ましい。
Ｒ3のアルケニル基としては、ケイ素原子に結合したアルケニル基として上で例示した基と同様のものが挙げられるが、ビニル基が好ましい。
ｃは１．９５～２．０の数が好ましく、ｄは０．０１～０．５の数が好ましく、ｃ＋ｄは１．９６～２．５を満たすことが好ましい。 Examples of the monovalent hydrocarbon group of R 2 include the same groups as those exemplified above as the organic group bonded to the silicon atom other than the alkenyl group, but the methyl group is preferable.
Examples of the alkenyl group of R 3 include the same groups as those exemplified above as the alkenyl group bonded to the silicon atom, but a vinyl group is preferable.
The number of c is preferably 1.95 to 2.0, the number of d is preferably 0.01 to 0.5, and the number of c + d is preferably 1.96 to 2.5.
Ｒ3のアルケニル基としては、ケイ素原子に結合したアルケニル基として上で例示した基と同様のものが挙げられるが、ビニル基が好ましい。
ｃは１．９５～２．０の数が好ましく、ｄは０．０１～０．５の数が好ましく、ｃ＋ｄは１．９６～２．５を満たすことが好ましい。 Examples of the monovalent hydrocarbon group of R 2 include the same groups as those exemplified above as the organic group bonded to the silicon atom other than the alkenyl group, but the methyl group is preferable.
Examples of the alkenyl group of R 3 include the same groups as those exemplified above as the alkenyl group bonded to the silicon atom, but a vinyl group is preferable.
The number of c is preferably 1.95 to 2.0, the number of d is preferably 0.01 to 0.5, and the number of c + d is preferably 1.96 to 2.5.
平均組成式（２）で表される（Ａ）成分としては、例えば、下記式（３）～（９）で表されるオルガノポリシロキサン等が挙げられるが、これらに限定されるものではない。
ＶｉＲ2 2ＳｉＯ（Ｒ2 2ＳｉＯ）eＳｉＲ2 2Ｖｉ （３）
ＶｉＲ2 2ＳｉＯ（Ｒ2ＶｉＳｉＯ）f（Ｒ2 2ＳｉＯ）gＳｉＲ2 2Ｖｉ （４）
Ｖｉ2Ｒ2ＳｉＯ（Ｒ2 2ＳｉＯ）eＳｉＲ2Ｖｉ2 （５）
Ｖｉ3ＳｉＯ（Ｒ2 2ＳｉＯ）eＳｉＶｉ3 （６）
Ｖｉ2Ｒ2ＳｉＯ（Ｒ2ＶｉＳｉＯ）f（Ｒ2 2ＳｉＯ）gＳｉＲ2Ｖｉ2 （７）
Ｖｉ3ＳｉＯ（Ｒ2ＶｉＳｉＯ）f（Ｒ2 2ＳｉＯ）gＳｉＶｉ3 （８）
Ｒ2 3ＳｉＯ（Ｒ2ＶｉＳｉＯ）h（Ｒ2 2ＳｉＯ）gＳｉＲ2 3 （９）
（式中、Ｖｉは、ビニル基を意味する（以下同様）。Ｒ2は、上記と同じ意味を表す。） Examples of the component (A) represented by the average composition formula (2) include, but are not limited to, organopolysiloxanes represented by the following formulas (3) to (9).
ViR 2 2 SiO (R 2 2 SiO) e SiR 2 2 Vi (3)
ViR 2 2 SiO (R 2 ViSiO) f (R 2 2 SiO) g SiR 2 2 Vi (4)
Vi 2 R 2 SiO (R 2 2 SiO) e SiR 2 Vi 2 (5)
Vi 3 SiO (R 2 2 SiO) e SiVi 3 (6)
Vi 2 R 2 SiO (R 2 ViSiO) f (R 2 2 SiO) g SiR 2 Vi 2 (7)
Vi 3 SiO (R 2 ViSiO) f (R 2 2 SiO) g SiVi 3 (8)
R 2 3 SiO (R 2 ViSiO) h (R 2 2 SiO) g SiR 2 3 (9)
(In the formula, Vi means a vinyl group (the same applies hereinafter). R 2 has the same meaning as above.)
ＶｉＲ2 2ＳｉＯ（Ｒ2 2ＳｉＯ）eＳｉＲ2 2Ｖｉ （３）
ＶｉＲ2 2ＳｉＯ（Ｒ2ＶｉＳｉＯ）f（Ｒ2 2ＳｉＯ）gＳｉＲ2 2Ｖｉ （４）
Ｖｉ2Ｒ2ＳｉＯ（Ｒ2 2ＳｉＯ）eＳｉＲ2Ｖｉ2 （５）
Ｖｉ3ＳｉＯ（Ｒ2 2ＳｉＯ）eＳｉＶｉ3 （６）
Ｖｉ2Ｒ2ＳｉＯ（Ｒ2ＶｉＳｉＯ）f（Ｒ2 2ＳｉＯ）gＳｉＲ2Ｖｉ2 （７）
Ｖｉ3ＳｉＯ（Ｒ2ＶｉＳｉＯ）f（Ｒ2 2ＳｉＯ）gＳｉＶｉ3 （８）
Ｒ2 3ＳｉＯ（Ｒ2ＶｉＳｉＯ）h（Ｒ2 2ＳｉＯ）gＳｉＲ2 3 （９）
（式中、Ｖｉは、ビニル基を意味する（以下同様）。Ｒ2は、上記と同じ意味を表す。） Examples of the component (A) represented by the average composition formula (2) include, but are not limited to, organopolysiloxanes represented by the following formulas (3) to (9).
ViR 2 2 SiO (R 2 2 SiO) e SiR 2 2 Vi (3)
ViR 2 2 SiO (R 2 ViSiO) f (R 2 2 SiO) g SiR 2 2 Vi (4)
Vi 2 R 2 SiO (R 2 2 SiO) e SiR 2 Vi 2 (5)
Vi 3 SiO (R 2 2 SiO) e SiVi 3 (6)
Vi 2 R 2 SiO (R 2 ViSiO) f (R 2 2 SiO) g SiR 2 Vi 2 (7)
Vi 3 SiO (R 2 ViSiO) f (R 2 2 SiO) g SiVi 3 (8)
R 2 3 SiO (R 2 ViSiO) h (R 2 2 SiO) g SiR 2 3 (9)
(In the formula, Vi means a vinyl group (the same applies hereinafter). R 2 has the same meaning as above.)
上記各式において、ｅ、ｆ、ｇは０以上の整数である。
特に、ｅは、１０≦ｅ≦１０，０００を満たす整数が好ましく、５０≦ｅ≦２，０００を満たす整数がより好ましい。
また、ｆおよびｇは、１０≦ｆ＋ｇ≦１０，０００、かつ、０≦ｆ／（ｆ＋ｇ）≦０．２を満たす整数が好ましく、５０≦ｆ＋ｇ≦２，０００を満たす整数がより好ましい。
ｈは、２以上の整数であるが、２≦ｈ、１０≦ｆ＋ｇ≦１０，０００、かつ、０≦ｈ／（ｇ＋ｈ）≦０．２を満たす整数が好ましく、５０≦ｇ＋ｈ≦２，０００を満たす整数がより好ましい。 In each of the above equations, e, f, and g are integers of 0 or more.
In particular, e is preferably an integer satisfying 10 ≦ e ≦ 10,000, and more preferably an integer satisfying 50 ≦ e ≦ 2,000.
Further, f and g are preferably integers satisfying 10 ≦ f + g ≦ 10,000 and 0 ≦ f / (f + g) ≦ 0.2, and more preferably an integer satisfying 50 ≦ f + g ≦ 2,000.
Although h is an integer of 2 or more, an integer satisfying 2 ≦ h, 10 ≦ f + g ≦ 10,000, and 0 ≦ h / (g + h) ≦ 0.2 is preferable, and 50 ≦ g + h ≦ 2,000. Integers that satisfy are more preferred.
特に、ｅは、１０≦ｅ≦１０，０００を満たす整数が好ましく、５０≦ｅ≦２，０００を満たす整数がより好ましい。
また、ｆおよびｇは、１０≦ｆ＋ｇ≦１０，０００、かつ、０≦ｆ／（ｆ＋ｇ）≦０．２を満たす整数が好ましく、５０≦ｆ＋ｇ≦２，０００を満たす整数がより好ましい。
ｈは、２以上の整数であるが、２≦ｈ、１０≦ｆ＋ｇ≦１０，０００、かつ、０≦ｈ／（ｇ＋ｈ）≦０．２を満たす整数が好ましく、５０≦ｇ＋ｈ≦２，０００を満たす整数がより好ましい。 In each of the above equations, e, f, and g are integers of 0 or more.
In particular, e is preferably an integer satisfying 10 ≦ e ≦ 10,000, and more preferably an integer satisfying 50 ≦ e ≦ 2,000.
Further, f and g are preferably integers satisfying 10 ≦ f + g ≦ 10,000 and 0 ≦ f / (f + g) ≦ 0.2, and more preferably an integer satisfying 50 ≦ f + g ≦ 2,000.
Although h is an integer of 2 or more, an integer satisfying 2 ≦ h, 10 ≦ f + g ≦ 10,000, and 0 ≦ h / (g + h) ≦ 0.2 is preferable, and 50 ≦ g + h ≦ 2,000. Integers that satisfy are more preferred.
（Ａ）成分の２５℃における粘度は１～１００，０００ｍＰａ・ｓが好ましく、５～１０，０００ｍＰａ・ｓがより好ましい。粘度がこの範囲であれば、流動性が高く作業性に優れる。本発明における粘度は回転粘度計を用いた測定値である。
なお、（Ａ）成分は、１種単独で用いても２種以上を併用してもよい。 The viscosity of the component (A) at 25 ° C. is preferably 1 to 100,000 mPa · s, more preferably 5 to 10,000 mPa · s. When the viscosity is in this range, the fluidity is high and the workability is excellent. The viscosity in the present invention is a measured value using a rotational viscometer.
The component (A) may be used alone or in combination of two or more.
なお、（Ａ）成分は、１種単独で用いても２種以上を併用してもよい。 The viscosity of the component (A) at 25 ° C. is preferably 1 to 100,000 mPa · s, more preferably 5 to 10,000 mPa · s. When the viscosity is in this range, the fluidity is high and the workability is excellent. The viscosity in the present invention is a measured value using a rotational viscometer.
The component (A) may be used alone or in combination of two or more.
［２］（Ｂ）成分
（Ｂ）成分は、下記平均式（１）で表されるオルガノハイドロジェンポリシロキサンであり、（Ａ）成分中のアルケニル基とヒドロシリル化反応することにより架橋剤として作用する。
（Ｒ1 3ＳｉＯ1/2）s［Ｒ1 1（Ｈ）ＳｉＯ2/2］t（Ｒ1 2ＳｉＯ2/2）u （１）
（式中、Ｒ1は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、ｓは、０または２であり、ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数を表す。） [2] Component (B) The component (B) is an organohydrogenpolysiloxane represented by the following average formula (1), and acts as a cross-linking agent by hydrosilylating with the alkenyl group in the component (A). To do.
(R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4.
（Ｂ）成分は、下記平均式（１）で表されるオルガノハイドロジェンポリシロキサンであり、（Ａ）成分中のアルケニル基とヒドロシリル化反応することにより架橋剤として作用する。
（Ｒ1 3ＳｉＯ1/2）s［Ｒ1 1（Ｈ）ＳｉＯ2/2］t（Ｒ1 2ＳｉＯ2/2）u （１）
（式中、Ｒ1は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、ｓは、０または２であり、ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数を表す。） [2] Component (B) The component (B) is an organohydrogenpolysiloxane represented by the following average formula (1), and acts as a cross-linking agent by hydrosilylating with the alkenyl group in the component (A). To do.
(R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4.
Ｒ1の１価炭化水素基は、（Ａ）成分のＲ2で例示した基と同様のものが挙げられるが、好ましくはメチル基である。
ｓは、０または２であり、即ち、（Ｂ）成分は直鎖状または環状のオルガノハイドロジェンポリシロキサンであって、ｓは好ましくは２、即ち、直鎖状の構造である。
ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数であるが、ｔは、好ましくは２～３００の数であり、より好ましくは３～２００の数である。また、ｔ／（ｔ＋ｕ）は０．１４～０．２５の範囲が好ましい。 The monovalent hydrocarbon group of R 1 may be the same as the group exemplified in R 2 of the component (A), but is preferably a methyl group.
s is 0 or 2, i.e. component (B) is a linear or cyclic organohydrogenpolysiloxane, and s is preferably 2, i.e. a linear structure.
t and u are numbers that satisfy 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4, but t is preferably a number from 2 to 300. More preferably, it is a number of 3 to 200. Further, t / (t + u) is preferably in the range of 0.14 to 0.25.
ｓは、０または２であり、即ち、（Ｂ）成分は直鎖状または環状のオルガノハイドロジェンポリシロキサンであって、ｓは好ましくは２、即ち、直鎖状の構造である。
ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数であるが、ｔは、好ましくは２～３００の数であり、より好ましくは３～２００の数である。また、ｔ／（ｔ＋ｕ）は０．１４～０．２５の範囲が好ましい。 The monovalent hydrocarbon group of R 1 may be the same as the group exemplified in R 2 of the component (A), but is preferably a methyl group.
s is 0 or 2, i.e. component (B) is a linear or cyclic organohydrogenpolysiloxane, and s is preferably 2, i.e. a linear structure.
t and u are numbers that satisfy 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4, but t is preferably a number from 2 to 300. More preferably, it is a number of 3 to 200. Further, t / (t + u) is preferably in the range of 0.14 to 0.25.
（Ｂ）成分の２５℃での粘度は、特に限定されるものではないが、組成物の作業性や硬化物の力学特性がより優れたものとなるため、１～３，０００ｍＰａ・ｓが好ましく、５～２００ｍＰａ・ｓがより好ましい。
The viscosity of the component (B) at 25 ° C. is not particularly limited, but is preferably 1 to 3,000 mPa · s because the workability of the composition and the mechanical properties of the cured product are more excellent. More preferably, 5 to 200 mPa · s.
（Ｂ）成分のオルガノハイドロジェンポリシロキサンとしては、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、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、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シロキサン・ジフェニルシロキサン・ジメチ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メチルハイドロジェンシロキサン・メチルフェニルシロキサン・ジメチルシロキサン共重合体、ジメチルシロキサン・メチルハイドロジェンシロキサン環状共重合体等、これらのオルガノポリシロキサンの２種以上からなる混合物等が挙げられる。
より具体的には、下記式で表されるオルガノハイドロジェンポリシロキサン等が挙げられる。なお、式中、Ｍｅは、メチル基を意味する（以下同様）。 Examples of the organohydrogenpolysiloxane of the component (B) include both-terminal trimethylsiloxy group-blocking methylhydrogenpolysiloxane, both-terminal trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, and both-terminal trimethylsiloxy group-blocking methylhydro. Gensiloxane / diphenylsiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, Examples thereof include a mixture of two or more of these organopolysiloxanes, such as a dimethylsiloxane / methylhydrogensiloxane cyclic copolymer.
More specifically, an organohydrogenpolysiloxane represented by the following formula can be mentioned. In the formula, Me means a methyl group (the same applies hereinafter).
より具体的には、下記式で表されるオルガノハイドロジェンポリシロキサン等が挙げられる。なお、式中、Ｍｅは、メチル基を意味する（以下同様）。 Examples of the organohydrogenpolysiloxane of the component (B) include both-terminal trimethylsiloxy group-blocking methylhydrogenpolysiloxane, both-terminal trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, and both-terminal trimethylsiloxy group-blocking methylhydro. Gensiloxane / diphenylsiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, Examples thereof include a mixture of two or more of these organopolysiloxanes, such as a dimethylsiloxane / methylhydrogensiloxane cyclic copolymer.
More specifically, an organohydrogenpolysiloxane represented by the following formula can be mentioned. In the formula, Me means a methyl group (the same applies hereinafter).
（Ｂ）成分の配合量は、（Ａ）成分中のケイ素原子と結合したアルケニル基１個あたりの（Ｂ）成分中のケイ素原子と結合した水素原子の数が０．５～５．０個となる量であり、好ましくは０．７～３．０個となる量である。０．５個未満の場合は架橋が不十分なものとなる結果、組成物を硬化して得られるシリコーンゴム型が粘着性を帯び、マスタおよび複製品に対する離型性が低下する。５．０個を超える場合、硬化の際に水素ガスの発生による発泡が起こりやすく、シリコーンゴム型の表面の凹凸により複製精度が低下し、硬化物内部の空隙の発生によりゴム強度が低下する。
なお、（Ｂ）成分は、１種単独で用いても２種以上を併用してもよい。 As for the blending amount of the component (B), the number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.5 to 5.0 per alkenyl group bonded to the silicon atom in the component (A). The amount is preferably 0.7 to 3.0 pieces. If the number is less than 0.5, the cross-linking becomes insufficient, and as a result, the silicone rubber mold obtained by curing the composition becomes sticky, and the releasability to the master and the replica is lowered. If the number exceeds 5.0, foaming due to the generation of hydrogen gas is likely to occur during curing, the replication accuracy is lowered due to the unevenness of the surface of the silicone rubber mold, and the rubber strength is lowered due to the generation of voids inside the cured product.
The component (B) may be used alone or in combination of two or more.
なお、（Ｂ）成分は、１種単独で用いても２種以上を併用してもよい。 As for the blending amount of the component (B), the number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.5 to 5.0 per alkenyl group bonded to the silicon atom in the component (A). The amount is preferably 0.7 to 3.0 pieces. If the number is less than 0.5, the cross-linking becomes insufficient, and as a result, the silicone rubber mold obtained by curing the composition becomes sticky, and the releasability to the master and the replica is lowered. If the number exceeds 5.0, foaming due to the generation of hydrogen gas is likely to occur during curing, the replication accuracy is lowered due to the unevenness of the surface of the silicone rubber mold, and the rubber strength is lowered due to the generation of voids inside the cured product.
The component (B) may be used alone or in combination of two or more.
［３］（Ｃ）成分
（Ｃ）成分は、（Ａ）成分中のアルケニル基と（Ｂ）成分中のＳｉＨ基とのヒドロシリル化反応を促進するためのヒドロシリル化反応触媒である。
その具体例としては、白金（白金黒を含む）、ロジウム、パラジウム等の白金族金属単体；Ｈ2ＰｔＣｌ4・ｎＨ2Ｏ、Ｈ2ＰｔＣｌ6・ｎＨ2Ｏ、ＮａＨＰｔＣｌ6・ｎＨ2Ｏ、ＫＨＰｔＣｌ6・ｎＨ2Ｏ、Ｎａ2ＰｔＣｌ6・ｎＨ2Ｏ、Ｋ2ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ2、Ｎａ2ＨＰｔＣｌ4・ｎＨ2Ｏ（但し、式中、ｎは０～６の整数であり、好ましくは０または６である。）等の塩化白金、塩化白金酸および塩化白金酸塩；アルコール変性塩化白金酸（米国特許第３，２２０，９７２号明細書参照）；塩化白金酸とオレフィンとの錯体（米国特許第３，１５９，６０１号明細書、同第３，１５９，６６２号明細書、同第３，７７５，４５２号明細書参照）；白金黒、パラジウム等の白金族金属をアルミナ、シリカ、カーボン等の担体に担持させたもの；ロジウム－オレフィン錯体；クロロトリス（トリフェニルフォスフィン）ロジウム（ウィルキンソン触媒）；塩化白金、塩化白金酸または塩化白金酸塩とビニル基含有シロキサンとの錯体などの白金族金属系触媒が挙げられる。
なお、（Ｃ）成分は、１種単独で用いても、２種以上を組み合わせて用いてもよい。 [3] Component (C) Component (C) is a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction between the alkenyl group in the component (A) and the SiH group in the component (B).
Specific examples thereof include platinum (including platinum black), rhodium, palladium and other platinum group metals alone; H 2 PtCl 4 · nH 2 O, H 2 PtCl 6 · nH 2 O, NaHPtCl 6 · nH 2 O, KH PtCl. 6・ nH 2 O, Na 2 PtCl 6・ nH 2 O, K 2 PtCl 4・ nH 2 O, PtCl 4・ nH 2 O, PtCl 2 , Na 2 HPtCl 4・ nH 2 O (However, in the formula, n is Platinum chloride, chloroplatinic acid and chloroplatinate such as (0 to 6, preferably 0 or 6); alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972). Complex of chloroplatinic acid and olefin (see US Pat. Nos. 3,159,601, 3,159,662, 3,775,452); Platinum black, palladium Platinum group metals such as, supported on a carrier such as alumina, silica, carbon; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, platinum chloride acid or platinum chloride salt Examples thereof include platinum group metal-based catalysts such as a complex with a vinyl group-containing siloxane.
The component (C) may be used alone or in combination of two or more.
（Ｃ）成分は、（Ａ）成分中のアルケニル基と（Ｂ）成分中のＳｉＨ基とのヒドロシリル化反応を促進するためのヒドロシリル化反応触媒である。
その具体例としては、白金（白金黒を含む）、ロジウム、パラジウム等の白金族金属単体；Ｈ2ＰｔＣｌ4・ｎＨ2Ｏ、Ｈ2ＰｔＣｌ6・ｎＨ2Ｏ、ＮａＨＰｔＣｌ6・ｎＨ2Ｏ、ＫＨＰｔＣｌ6・ｎＨ2Ｏ、Ｎａ2ＰｔＣｌ6・ｎＨ2Ｏ、Ｋ2ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ2、Ｎａ2ＨＰｔＣｌ4・ｎＨ2Ｏ（但し、式中、ｎは０～６の整数であり、好ましくは０または６である。）等の塩化白金、塩化白金酸および塩化白金酸塩；アルコール変性塩化白金酸（米国特許第３，２２０，９７２号明細書参照）；塩化白金酸とオレフィンとの錯体（米国特許第３，１５９，６０１号明細書、同第３，１５９，６６２号明細書、同第３，７７５，４５２号明細書参照）；白金黒、パラジウム等の白金族金属をアルミナ、シリカ、カーボン等の担体に担持させたもの；ロジウム－オレフィン錯体；クロロトリス（トリフェニルフォスフィン）ロジウム（ウィルキンソン触媒）；塩化白金、塩化白金酸または塩化白金酸塩とビニル基含有シロキサンとの錯体などの白金族金属系触媒が挙げられる。
なお、（Ｃ）成分は、１種単独で用いても、２種以上を組み合わせて用いてもよい。 [3] Component (C) Component (C) is a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction between the alkenyl group in the component (A) and the SiH group in the component (B).
Specific examples thereof include platinum (including platinum black), rhodium, palladium and other platinum group metals alone; H 2 PtCl 4 · nH 2 O, H 2 PtCl 6 · nH 2 O, NaHPtCl 6 · nH 2 O, KH PtCl. 6・ nH 2 O, Na 2 PtCl 6・ nH 2 O, K 2 PtCl 4・ nH 2 O, PtCl 4・ nH 2 O, PtCl 2 , Na 2 HPtCl 4・ nH 2 O (However, in the formula, n is Platinum chloride, chloroplatinic acid and chloroplatinate such as (0 to 6, preferably 0 or 6); alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972). Complex of chloroplatinic acid and olefin (see US Pat. Nos. 3,159,601, 3,159,662, 3,775,452); Platinum black, palladium Platinum group metals such as, supported on a carrier such as alumina, silica, carbon; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, platinum chloride acid or platinum chloride salt Examples thereof include platinum group metal-based catalysts such as a complex with a vinyl group-containing siloxane.
The component (C) may be used alone or in combination of two or more.
（Ｃ）成分の配合量は、組成物の硬化（ヒドロシリル化反応）を促進する量であれば限定されず、本組成物の各成分の質量の合計に対して、本成分中の金属原子が質量換算で０．１～１，０００ｐｐｍの範囲となる量が好ましく、１～５００ｐｐｍの範囲がより好ましく、３～１００ｐｐｍの範囲がより一層好ましい。この範囲であれば、付加反応の反応速度が適切なものとなり、高い強度を有する硬化物を得ることができる。
The blending amount of the component (C) is not limited as long as it promotes the curing (hydrosilylation reaction) of the composition, and the metal atoms in the component are added to the total mass of each component of the composition. The amount in the range of 0.1 to 1,000 ppm in terms of mass is preferable, the range of 1 to 500 ppm is more preferable, and the range of 3 to 100 ppm is even more preferable. Within this range, the reaction rate of the addition reaction becomes appropriate, and a cured product having high strength can be obtained.
［４］（Ｄ）成分
本発明の型取り用シリコーンゴム組成物には、硬度および引張り強さなどの物理的強度の向上のため、（Ｄ）成分としてシリカを添加してもよい。
シリカとしては、例えば、ヒュームドシリカ、結晶性シリカ（石英粉）、沈降性シリカ、これらの表面を疎水化処理したシリカ等が挙げられ、これらは１種単独でも２種以上を組み合わせてもよい。 [4] Component (D) Silica may be added as the component (D) to the silicone rubber composition for molding of the present invention in order to improve physical strength such as hardness and tensile strength.
Examples of silica include fumed silica, crystalline silica (quartz powder), precipitated silica, silica whose surface is hydrophobized, and the like, and these may be used alone or in combination of two or more. ..
本発明の型取り用シリコーンゴム組成物には、硬度および引張り強さなどの物理的強度の向上のため、（Ｄ）成分としてシリカを添加してもよい。
シリカとしては、例えば、ヒュームドシリカ、結晶性シリカ（石英粉）、沈降性シリカ、これらの表面を疎水化処理したシリカ等が挙げられ、これらは１種単独でも２種以上を組み合わせてもよい。 [4] Component (D) Silica may be added as the component (D) to the silicone rubber composition for molding of the present invention in order to improve physical strength such as hardness and tensile strength.
Examples of silica include fumed silica, crystalline silica (quartz powder), precipitated silica, silica whose surface is hydrophobized, and the like, and these may be used alone or in combination of two or more. ..
このようなシリカとしては、親水性のシリカとして、Ａｅｒｏｓｉｌ １３０、２００、３００（日本アエロジル（株）製）、Ｃａｂｏｓｉｌ ＭＳ－５，ＭＳ－７（Ｃａｂｏｔ社製），Ｒｈｅｏｒｏｓｉｌ ＱＳ－１０２，１０３（（株）トクヤマ製）等のヒュームドシリカ；トクシールＵＳ－Ｆ（（株）トクヤマ製）、Ｎｉｐｓｉｌ ＬＰ（日本シリカ工業（株）製）等の沈降性シリカ等が挙げられ、疎水性のシリカとして、Ａｅｒｏｓｉｌ Ｒ－８１２，Ｒ－８１２Ｓ，Ｒ－９７２，Ｒ－９７４（日本アエロジル（株）製）、Ｒｈｅｏｒｏｓｉｌ ＭＴ－１０（（株）トクヤマ製）等のヒュームドシリカ；Ｎｉｐｓｉｌ ＳＳシリーズ（日本シリカ工業（株）製）等の沈降性シリカ；クリスタライト（（株）龍森製）、ＭＩＮ－Ｕ－ＳＩＬ（Ｕ．Ｓ．Ｓｉｌｉｃａ Ｃｏｍｐａｎｙ社製）、Ｉｍｉｓｉｌ（Ｉｌｌｉｎｏｉｓ Ｍｉｎｅｒａｌ社製）等の結晶性シリカ等が挙げられる。
As such silica, as hydrophilic silica, Aerosil 130, 200, 300 (manufactured by Nippon Aerosil Co., Ltd.), Cabosil MS-5, MS-7 (manufactured by Cabot), Rheorosil QS-102,103 ((() Fumed silica such as Tokuyama Co., Ltd .; Precipitated silica such as Tokseal US-F (manufactured by Tokuyama Co., Ltd.) and Nippon Silica LP (manufactured by Nippon Silica Industry Co., Ltd.) can be mentioned as hydrophobic silica. Fumed silica such as Aerosil R-812, R-812S, R-972, R-974 (manufactured by Nippon Aerosil Co., Ltd.), Rheorosil MT-10 (manufactured by Tokuyama Co., Ltd.); Nippon Silica SS series (Nippon Silica Industry (Nippon Silica Industry) Precipitated silica (manufactured by Tatsumori Co., Ltd.), crystalline silica such as Crystallite (manufactured by Tatsumori Co., Ltd.), MIN-U-SIL (manufactured by US Silka Company), Imisil (manufactured by Illinois Mineral), etc. Can be mentioned.
これらのシリカはそのまま用いても構わないが、表面処理剤で予め表面疎水化処理したものを使用したり、（Ａ）成分の混練時に表面処理剤を添加してシリカ表面を疎水化処理して使用したりすることが好ましい。表面処理剤としては、アルキルアルコキシシラン、アルキルヒドロキシシラン、アルキルクロロシラン、アルキルシラザン、シランカップリング剤、低分子ポリシロキサン、チタネート系処理剤、脂肪酸エステル等が挙げられ、好ましくはアルキルジシラザン、より好ましくはヘキサメチルジシラザンである。これらの表面処理剤は１種単独で用いても、２種以上を同時にまたは異なるタイミングで用いても構わない。
表面処理剤の使用量は、シリカ１００質量部に対して、好ましくは０．５～５０質量部、より好ましくは１～４０質量部、より一層好ましくは２～３０質量部である。表面処理剤の使用量が上記範囲内であると、組成物中に表面処理剤またはその分解物が残らず、流動性が得られ、経時で粘度が上昇することを抑制できる。 These silicas may be used as they are, but those which have been surface-hydrophobicized in advance with a surface treatment agent may be used, or the silica surface may be hydrophobized by adding a surface treatment agent when kneading the component (A). It is preferable to use it. Examples of the surface treatment agent include alkylalkoxysilane, alkylhydroxysilane, alkylchlorosilane, alkylsilazane, silane coupling agent, low molecular weight polysiloxane, titanate treatment agent, fatty acid ester and the like, and alkyldisilazane is more preferable. Is hexamethyldisilazane. These surface treatment agents may be used alone or in combination of two or more at the same time or at different timings.
The amount of the surface treatment agent used is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 2 to 30 parts by mass with respect to 100 parts by mass of silica. When the amount of the surface treatment agent used is within the above range, the surface treatment agent or its decomposition products do not remain in the composition, fluidity can be obtained, and the increase in viscosity with time can be suppressed.
表面処理剤の使用量は、シリカ１００質量部に対して、好ましくは０．５～５０質量部、より好ましくは１～４０質量部、より一層好ましくは２～３０質量部である。表面処理剤の使用量が上記範囲内であると、組成物中に表面処理剤またはその分解物が残らず、流動性が得られ、経時で粘度が上昇することを抑制できる。 These silicas may be used as they are, but those which have been surface-hydrophobicized in advance with a surface treatment agent may be used, or the silica surface may be hydrophobized by adding a surface treatment agent when kneading the component (A). It is preferable to use it. Examples of the surface treatment agent include alkylalkoxysilane, alkylhydroxysilane, alkylchlorosilane, alkylsilazane, silane coupling agent, low molecular weight polysiloxane, titanate treatment agent, fatty acid ester and the like, and alkyldisilazane is more preferable. Is hexamethyldisilazane. These surface treatment agents may be used alone or in combination of two or more at the same time or at different timings.
The amount of the surface treatment agent used is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 2 to 30 parts by mass with respect to 100 parts by mass of silica. When the amount of the surface treatment agent used is within the above range, the surface treatment agent or its decomposition products do not remain in the composition, fluidity can be obtained, and the increase in viscosity with time can be suppressed.
また、（Ｄ）成分は、ＢＥＴ法による比表面積が５０～４００ｍ2／ｇ、特に１００～３５０ｍ2／ｇのものが好ましい。このような範囲であれば十分なゴム強度が得られる。
The component (D) preferably has a specific surface area of 50 to 400 m 2 / g by the BET method, particularly 100 to 350 m 2 / g. Within such a range, sufficient rubber strength can be obtained.
（Ｄ）成分を用いる場合、その添加量は、組成物の取り扱い性および硬化物の機械的強度の点から、（Ａ）成分１００質量部に対して５～１００質量部が好ましく、２０～５０質量部がより好ましい。
When the component (D) is used, the amount added is preferably 5 to 100 parts by mass, preferably 20 to 50 parts by mass, based on 100 parts by mass of the component (A) from the viewpoint of handleability of the composition and mechanical strength of the cured product. Parts by mass are more preferred.
［５］（Ｅ）成分
本発明の型取り用シリコーンゴム組成物には、組成物を調製する際や、型取りの際などの加熱硬化前に、増粘やゲル化を起こさないようにヒドロシリル化反応触媒の反応性を制御する目的で、必要に応じて（Ｅ）反応制御剤を添加してもよい。
反応制御剤の具体例としては、３－メチル－１－ブチン－３－オール、３－メチル－１－ペンチン－３－オール、３，５－ジメチル－１－ヘキシン－３－オール、１－エチニルシクロヘキサノール、エチニルメチルデシルカルビノール、３－メチル－３－トリメチルシロキシ－１－ブチン、３－メチル－３－トリメチルシロキシ－１－ペンチン、３，５－ジメチル－３－トリメチルシロキシ－１－ヘキシン、１－エチニル－１－トリメチルシロキシシクロヘキサン、ビス（２，２－ジメチル－３－ブチノキシ）ジメチルシラン、１，３，５，７－テトラメチル－１，３，５，７－テトラビニルシクロテトラシロキサン、１，１，３，３－テトラメチル－１，３－ジビニルジシロキサン等が挙げられ、これらは１種単独で用いても、２種以上を組み合わせて用いてもよい。
これらの中でも、１－エチニルシクロヘキサノール、エチニルメチルデシルカルビノール、３－メチル－１－ブチン－３－オールが好ましい。 [5] (E) Ingredients The silicone rubber composition for molding of the present invention contains hydrosilyls so as not to cause thickening or gelation when the composition is prepared or before heat curing such as when molding. If necessary, the reaction control agent (E) may be added for the purpose of controlling the reactivity of the chemical reaction catalyst.
Specific examples of the reaction control agent include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, and 1-ethynyl. Cyclohexanol, ethynylmethyldecylcarbinol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, which may be used alone or in combination of two or more.
Among these, 1-ethynylcyclohexanol, ethynylmethyldecylcarbinol, and 3-methyl-1-butyne-3-ol are preferable.
本発明の型取り用シリコーンゴム組成物には、組成物を調製する際や、型取りの際などの加熱硬化前に、増粘やゲル化を起こさないようにヒドロシリル化反応触媒の反応性を制御する目的で、必要に応じて（Ｅ）反応制御剤を添加してもよい。
反応制御剤の具体例としては、３－メチル－１－ブチン－３－オール、３－メチル－１－ペンチン－３－オール、３，５－ジメチル－１－ヘキシン－３－オール、１－エチニルシクロヘキサノール、エチニルメチルデシルカルビノール、３－メチル－３－トリメチルシロキシ－１－ブチン、３－メチル－３－トリメチルシロキシ－１－ペンチン、３，５－ジメチル－３－トリメチルシロキシ－１－ヘキシン、１－エチニル－１－トリメチルシロキシシクロヘキサン、ビス（２，２－ジメチル－３－ブチノキシ）ジメチルシラン、１，３，５，７－テトラメチル－１，３，５，７－テトラビニルシクロテトラシロキサン、１，１，３，３－テトラメチル－１，３－ジビニルジシロキサン等が挙げられ、これらは１種単独で用いても、２種以上を組み合わせて用いてもよい。
これらの中でも、１－エチニルシクロヘキサノール、エチニルメチルデシルカルビノール、３－メチル－１－ブチン－３－オールが好ましい。 [5] (E) Ingredients The silicone rubber composition for molding of the present invention contains hydrosilyls so as not to cause thickening or gelation when the composition is prepared or before heat curing such as when molding. If necessary, the reaction control agent (E) may be added for the purpose of controlling the reactivity of the chemical reaction catalyst.
Specific examples of the reaction control agent include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, and 1-ethynyl. Cyclohexanol, ethynylmethyldecylcarbinol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, which may be used alone or in combination of two or more.
Among these, 1-ethynylcyclohexanol, ethynylmethyldecylcarbinol, and 3-methyl-1-butyne-3-ol are preferable.
（Ｅ）成分を用いる場合、その添加量は、（Ａ）成分および（Ｂ）成分の合計１００質量部に対して０．０１～２．０質量部が好ましく、０．０１～０．１質量部がより好ましい。このような範囲であれば反応制御の効果が十分発揮される。
When the component (E) is used, the amount added is preferably 0.01 to 2.0 parts by mass, preferably 0.01 to 0.1 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). More preferred. Within such a range, the effect of reaction control is fully exhibited.
［６］その他の成分
本発明の型取り用シリコーンゴム組成物には、上記（Ａ）～（Ｅ）成分以外にも、本発明の目的を損なわない限り、以下に例示するその他の成分を配合してもよい。
その他の成分としては、酸化鉄、カーボンブラック、導電性亜鉛華、金属粉等の導電剤；酸化チタン、酸化セリウム等の耐熱剤；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；チクソ性付与剤等が挙げられる。 [6] Other Ingredients In addition to the above components (A) to (E), the silicone rubber composition for molding of the present invention contains other components exemplified below as long as the object of the present invention is not impaired. You may.
Other components include conductive agents such as iron oxide, carbon black, conductive zinc oxide, and metal powder; heat resistant agents such as titanium oxide and cerium oxide; internal mold release agents such as dimethyl silicone oil; adhesive imparting agents; thixo. Examples include sex-imparting agents.
本発明の型取り用シリコーンゴム組成物には、上記（Ａ）～（Ｅ）成分以外にも、本発明の目的を損なわない限り、以下に例示するその他の成分を配合してもよい。
その他の成分としては、酸化鉄、カーボンブラック、導電性亜鉛華、金属粉等の導電剤；酸化チタン、酸化セリウム等の耐熱剤；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；チクソ性付与剤等が挙げられる。 [6] Other Ingredients In addition to the above components (A) to (E), the silicone rubber composition for molding of the present invention contains other components exemplified below as long as the object of the present invention is not impaired. You may.
Other components include conductive agents such as iron oxide, carbon black, conductive zinc oxide, and metal powder; heat resistant agents such as titanium oxide and cerium oxide; internal mold release agents such as dimethyl silicone oil; adhesive imparting agents; thixo. Examples include sex-imparting agents.
本発明の型取り用シリコーンゴム組成物は、上記の（Ａ）～（Ｃ）成分、必要に応じて用いられる（Ｄ）および（Ｅ）成分、並びにその他の成分をニーダー、プラネタリーミキサー等を用いた公知の方法で混合して調製することができる。
本発明の型取り用シリコーンゴム組成物は、（Ａ）成分、（Ｃ）成分および必要に応じてその他の成分からなる第一剤と、（Ａ）成分、（Ｂ）成分および必要に応じてその他の成分からなる第二剤を別々に調製し、使用前に第一剤と第二剤を混合する二剤型の組成物としてもよい。なお、第一剤および第二剤で共通に使用される成分があってもよい。組成物をこのような二剤型とすることにより、さらに保存安定性が確保できる。 The silicone rubber composition for molding of the present invention contains the above-mentioned components (A) to (C), components (D) and (E) used as necessary, and other components such as a kneader and a planetary mixer. It can be prepared by mixing by the known method used.
The silicone rubber composition for molding of the present invention comprises a first agent consisting of a component (A), a component (C) and, if necessary, other components, and a component (A), a component (B) and, if necessary. A second agent composed of other components may be prepared separately, and a two-agent type composition may be prepared in which the first agent and the second agent are mixed before use. In addition, there may be a component commonly used in the first agent and the second agent. By making the composition into such a two-dosage form, storage stability can be further ensured.
本発明の型取り用シリコーンゴム組成物は、（Ａ）成分、（Ｃ）成分および必要に応じてその他の成分からなる第一剤と、（Ａ）成分、（Ｂ）成分および必要に応じてその他の成分からなる第二剤を別々に調製し、使用前に第一剤と第二剤を混合する二剤型の組成物としてもよい。なお、第一剤および第二剤で共通に使用される成分があってもよい。組成物をこのような二剤型とすることにより、さらに保存安定性が確保できる。 The silicone rubber composition for molding of the present invention contains the above-mentioned components (A) to (C), components (D) and (E) used as necessary, and other components such as a kneader and a planetary mixer. It can be prepared by mixing by the known method used.
The silicone rubber composition for molding of the present invention comprises a first agent consisting of a component (A), a component (C) and, if necessary, other components, and a component (A), a component (B) and, if necessary. A second agent composed of other components may be prepared separately, and a two-agent type composition may be prepared in which the first agent and the second agent are mixed before use. In addition, there may be a component commonly used in the first agent and the second agent. By making the composition into such a two-dosage form, storage stability can be further ensured.
また、本発明の型取り用シリコーンゴム組成物の硬化条件としては、例えば常温（５～３５℃）でも硬化が進行するが、加熱により硬化促進させることもでき、量産性を向上させたい場合には、この手法が有効である。
加熱硬化させる場合、７０～２００℃で３０秒～６０分間、特に９０～１２０℃で１分～３０分間の条件で硬化させることが好ましい。 Further, as a curing condition of the silicone rubber composition for molding of the present invention, for example, curing proceeds even at room temperature (5 to 35 ° C.), but curing can be accelerated by heating, and when it is desired to improve mass productivity. This method is effective.
In the case of heat curing, it is preferable to cure at 70 to 200 ° C. for 30 seconds to 60 minutes, particularly at 90 to 120 ° C. for 1 minute to 30 minutes.
加熱硬化させる場合、７０～２００℃で３０秒～６０分間、特に９０～１２０℃で１分～３０分間の条件で硬化させることが好ましい。 Further, as a curing condition of the silicone rubber composition for molding of the present invention, for example, curing proceeds even at room temperature (5 to 35 ° C.), but curing can be accelerated by heating, and when it is desired to improve mass productivity. This method is effective.
In the case of heat curing, it is preferable to cure at 70 to 200 ° C. for 30 seconds to 60 minutes, particularly at 90 to 120 ° C. for 1 minute to 30 minutes.
以下、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
［実施例１～４，比較例１～３］
下記成分を表１に示される配合比（質量部）で混合し、シリコーンゴム組成物を調製した。具体的には、まず（Ａ）成分８５質量部、（Ｄ）成分３０質量部、ヘキサメチルジシラザン５質量部、水２質量部を２５℃でニーダーを用いて３０分混合後、１５０℃に昇温し、４時間撹拌を続け、２５℃に冷却した後に（Ａ）成分１５質量部を混合して得られたシリコーンゴムベースに、（Ｃ）成分を添加し、プラネタリーミキサーを用いて２５℃で１５分間撹拌混合後、（Ｂ）成分を添加し、プラネタリーミキサーを用いて２５℃で１５分間撹拌混合を行い、さらに２５℃で３０分間減圧脱泡し、シリコーンゴム組成物を得た。 [Examples 1 to 4, Comparative Examples 1 to 3]
The following components were mixed at the compounding ratio (parts by mass) shown in Table 1 to prepare a silicone rubber composition. Specifically, first, 85 parts by mass of the component (A), 30 parts by mass of the component (D), 5 parts by mass of hexamethyldisilazane, and 2 parts by mass of water are mixed at 25 ° C. for 30 minutes using a kneader, and then brought to 150 ° C. The temperature was raised, stirring was continued for 4 hours, and after cooling to 25 ° C., the component (C) was added to the silicone rubber base obtained by mixing 15 parts by mass of the component (A), and 25 using a planetary mixer. After stirring and mixing at ° C. for 15 minutes, the component (B) was added, stirred and mixed at 25 ° C. for 15 minutes using a planetary mixer, and defoamed under reduced pressure at 25 ° C. for 30 minutes to obtain a silicone rubber composition. ..
下記成分を表１に示される配合比（質量部）で混合し、シリコーンゴム組成物を調製した。具体的には、まず（Ａ）成分８５質量部、（Ｄ）成分３０質量部、ヘキサメチルジシラザン５質量部、水２質量部を２５℃でニーダーを用いて３０分混合後、１５０℃に昇温し、４時間撹拌を続け、２５℃に冷却した後に（Ａ）成分１５質量部を混合して得られたシリコーンゴムベースに、（Ｃ）成分を添加し、プラネタリーミキサーを用いて２５℃で１５分間撹拌混合後、（Ｂ）成分を添加し、プラネタリーミキサーを用いて２５℃で１５分間撹拌混合を行い、さらに２５℃で３０分間減圧脱泡し、シリコーンゴム組成物を得た。 [Examples 1 to 4, Comparative Examples 1 to 3]
The following components were mixed at the compounding ratio (parts by mass) shown in Table 1 to prepare a silicone rubber composition. Specifically, first, 85 parts by mass of the component (A), 30 parts by mass of the component (D), 5 parts by mass of hexamethyldisilazane, and 2 parts by mass of water are mixed at 25 ° C. for 30 minutes using a kneader, and then brought to 150 ° C. The temperature was raised, stirring was continued for 4 hours, and after cooling to 25 ° C., the component (C) was added to the silicone rubber base obtained by mixing 15 parts by mass of the component (A), and 25 using a planetary mixer. After stirring and mixing at ° C. for 15 minutes, the component (B) was added, stirred and mixed at 25 ° C. for 15 minutes using a planetary mixer, and defoamed under reduced pressure at 25 ° C. for 30 minutes to obtain a silicone rubber composition. ..
（Ａ）成分：
（Ａ－１）両末端がジメチルビニルシロキシ基で封鎖され、２５℃における粘度が５，０００ｍＰａ・ｓであるジメチルポリシロキサン（ビニル基含有量０．００６ｍｏｌ／１００ｇ） (A) Ingredient:
(A-1) Didimethylpolysiloxane (vinyl group content 0.006 mol / 100 g) having both ends sealed with a dimethylvinylsiloxy group and a viscosity at 25 ° C. of 5,000 mPa · s.
（Ａ－１）両末端がジメチルビニルシロキシ基で封鎖され、２５℃における粘度が５，０００ｍＰａ・ｓであるジメチルポリシロキサン（ビニル基含有量０．００６ｍｏｌ／１００ｇ） (A) Ingredient:
(A-1) Didimethylpolysiloxane (vinyl group content 0.006 mol / 100 g) having both ends sealed with a dimethylvinylsiloxy group and a viscosity at 25 ° C. of 5,000 mPa · s.
（Ｂ）成分：
（Ｂ－１）下記平均構造式で表されるオルガノハイドロジェンポリシロキサン（ケイ素原子結合水素原子の含有量＝０．００１８ｍｏｌ／ｇ）
（式中、シロキサン単位の配列はランダムまたはブロックである。）
(B) Ingredient:
(B-1) Organohydrogenpolysiloxane represented by the following average structural formula (content of silicon atom-bonded hydrogen atom = 0.0018 mol / g)
(In the formula, the sequence of siloxane units is random or block.)
（Ｂ－１）下記平均構造式で表されるオルガノハイドロジェンポリシロキサン（ケイ素原子結合水素原子の含有量＝０．００１８ｍｏｌ／ｇ）
(B-1) Organohydrogenpolysiloxane represented by the following average structural formula (content of silicon atom-bonded hydrogen atom = 0.0018 mol / g)
（Ｂ－２）下記平均構造式で表されるオルガノハイドロジェンポリシロキサン（ケイ素原子結合水素原子の含有量＝０．００３４ｍｏｌ／ｇ）
（式中、シロキサン単位の配列はランダムまたはブロックである。）
(B-2) Organohydrogenpolysiloxane represented by the following average structural formula (content of silicon atom-bonded hydrogen atom = 0.0034 mol / g)
(In the formula, the sequence of siloxane units is random or block.)
（Ｂ－３）下記平均構造式で表されるオルガノハイドロジェンポリシロキサン（ケイ素原子結合水素原子の含有量＝０．００２１ｍｏｌ／ｇ）
（式中、シロキサン単位の配列はランダムまたはブロックである。）
(B-3) Organohydrogenpolysiloxane represented by the following average structural formula (content of silicon atom-bonded hydrogen atom = 0.0021 mol / g)
(In the formula, the sequence of siloxane units is random or block.)
（Ｂ－４）下記平均構造式で表されるオルガノハイドロジェンポリシロキサン（比較成分）
（式中、シロキサン単位の配列はランダムまたはブロックである。）
(B-4) Organohydrogenpolysiloxane represented by the following average structural formula (comparative component)
(In the formula, the sequence of siloxane units is random or block.)
（Ｂ－５）下記平均構造式で表されるオルガノハイドロジェンポリシロキサン（比較成分：ケイ素原子結合水素原子の含有量＝０．００４２ｍｏｌ／ｇ）
（式中、シロキサン単位の配列はランダムまたはブロックである。）
(B-5) Organohydrogenpolysiloxane represented by the following average structural formula (comparative component: content of silicon atom-bonded hydrogen atom = 0.0042 mol / g)
(In the formula, the sequence of siloxane units is random or block.)
（Ｂ－６）下記平均構造式で表されるオルガノハイドロジェンポリシロキサン（比較成分：ケイ素原子結合水素原子の含有量＝０．０００８８ｍｏｌ／ｇ）
（式中、シロキサン単位の配列はランダムまたはブロックである。）
(B-6) Organohydrogenpolysiloxane represented by the following average structural formula (comparative component: content of silicon atom-bonded hydrogen atom = 0.00088 mol / g)
(In the formula, the sequence of siloxane units is random or block.)
（Ｃ）成分：
（Ｃ－１）白金１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のジメチルシロキサン溶液（白金含有量１．０質量％） (C) component:
(C-1) Dimethylsiloxane solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 1.0% by mass)
（Ｃ－１）白金１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のジメチルシロキサン溶液（白金含有量１．０質量％） (C) component:
(C-1) Dimethylsiloxane solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 1.0% by mass)
（Ｄ）成分：
（Ｄ－１）フュームドシリカ（日本アエロジル（株）製、アエロジル３００、ＢＥＴ比表面積３００ｍ2／ｇ） Ingredient (D):
(D-1) Fumed silica (manufactured by Nippon Aerosil Co., Ltd., Aerosil 300, BET specific surface area 300 m 2 / g)
（Ｄ－１）フュームドシリカ（日本アエロジル（株）製、アエロジル３００、ＢＥＴ比表面積３００ｍ2／ｇ） Ingredient (D):
(D-1) Fumed silica (manufactured by Nippon Aerosil Co., Ltd., Aerosil 300, BET specific surface area 300 m 2 / g)
（Ｅ）成分：
（Ｅ－１）エチニルシクロヘキサノール (E) Ingredient:
(E-1) Ethynylcyclohexanol
（Ｅ－１）エチニルシクロヘキサノール (E) Ingredient:
(E-1) Ethynylcyclohexanol
得られた組成物を用い、下記の各特性を評価した。結果を表２に示す。
［離型性］
図１（Ａ）～（Ｃ）に示されるように、実施例１～３および比較例１～３で調製した型取り用シリコーンゴム組成物３を、逆勾配のガラス製マスタ１を置いた枠２の内部に流し込み、１００℃、５０分の硬化条件にて硬化してシリコーンゴム型４を作製した。シリコーンゴム型４がガラス製マスタ１から手で容易に剥離できるか否か、および剥離したシリコーンゴム型４の表面を目視にて観察することにより、シリコーンゴム型４の離型性を評価した。
シリコーンゴム型４がガラス製マスタから容易に剥離することができ、かつ、シリコーンゴム型４の表面が平滑であって表面の状態が良好であるものを○と表示し、シリコーンゴム型４の一部が凝集破壊してガラス製マスタ１に付着しているものを×と表示した。
［エポキシ樹脂複製回数］
図２（Ａ）～（Ｃ）に示されるように、上記と同様の手順で作製し、ガラス製マスタ１から剥離したシリコーン型４の空隙部４Ａに、熱硬化性エポキシ樹脂５（商品名：ＮＭ１０２Ａ／Ｂ、ペルノックス社製）を流し込み１００℃×６０分で硬化させてエポキシ樹脂複製品６を作製した。作製したエポキシ樹脂複製品６をシリコーン型４から取り出す作業を繰り返し、シリコーン型４への樹脂の付着が無く容易に取り出し可能な回数を確認した。 Using the obtained composition, each of the following characteristics was evaluated. The results are shown in Table 2.
[Releasability]
As shown in FIGS. 1 (A) to 1 (C), a frame in which a reverse-gradient glass master 1 is placed on the molding silicone rubber composition 3 prepared in Examples 1 to 3 and Comparative Examples 1 to 3. It was poured into the inside of No. 2 and cured under curing conditions of 100 ° C. for 50 minutes to prepare a silicone rubber mold 4. The releasability of the silicone rubber mold 4 was evaluated by visually observing whether or not the silicone rubber mold 4 could be easily peeled off from the glass master 1 and the surface of the peeled silicone rubber mold 4.
When the silicone rubber mold 4 can be easily peeled off from the glass master and the surface of the silicone rubber mold 4 is smooth and the surface condition is good, a circle is displayed, and one of the silicone rubber molds 4 Those in which the parts were coagulated and broken and adhered to the glass master 1 were marked with x.
[Epoxy resin replication count]
As shown in FIGS. 2 (A) to 2 (C), the thermosetting epoxy resin 5 (trade name:) was formed in thegap 4A of the silicone mold 4 produced by the same procedure as above and peeled from the glass master 1. NM102A / B (manufactured by Pernox) was poured and cured at 100 ° C. for 60 minutes to prepare an epoxy resin replica 6. The work of taking out the produced epoxy resin replica 6 from the silicone mold 4 was repeated, and the number of times that the resin did not adhere to the silicone mold 4 and could be easily taken out was confirmed.
［離型性］
図１（Ａ）～（Ｃ）に示されるように、実施例１～３および比較例１～３で調製した型取り用シリコーンゴム組成物３を、逆勾配のガラス製マスタ１を置いた枠２の内部に流し込み、１００℃、５０分の硬化条件にて硬化してシリコーンゴム型４を作製した。シリコーンゴム型４がガラス製マスタ１から手で容易に剥離できるか否か、および剥離したシリコーンゴム型４の表面を目視にて観察することにより、シリコーンゴム型４の離型性を評価した。
シリコーンゴム型４がガラス製マスタから容易に剥離することができ、かつ、シリコーンゴム型４の表面が平滑であって表面の状態が良好であるものを○と表示し、シリコーンゴム型４の一部が凝集破壊してガラス製マスタ１に付着しているものを×と表示した。
［エポキシ樹脂複製回数］
図２（Ａ）～（Ｃ）に示されるように、上記と同様の手順で作製し、ガラス製マスタ１から剥離したシリコーン型４の空隙部４Ａに、熱硬化性エポキシ樹脂５（商品名：ＮＭ１０２Ａ／Ｂ、ペルノックス社製）を流し込み１００℃×６０分で硬化させてエポキシ樹脂複製品６を作製した。作製したエポキシ樹脂複製品６をシリコーン型４から取り出す作業を繰り返し、シリコーン型４への樹脂の付着が無く容易に取り出し可能な回数を確認した。 Using the obtained composition, each of the following characteristics was evaluated. The results are shown in Table 2.
[Releasability]
As shown in FIGS. 1 (A) to 1 (C), a frame in which a reverse-gradient glass master 1 is placed on the molding silicone rubber composition 3 prepared in Examples 1 to 3 and Comparative Examples 1 to 3. It was poured into the inside of No. 2 and cured under curing conditions of 100 ° C. for 50 minutes to prepare a silicone rubber mold 4. The releasability of the silicone rubber mold 4 was evaluated by visually observing whether or not the silicone rubber mold 4 could be easily peeled off from the glass master 1 and the surface of the peeled silicone rubber mold 4.
When the silicone rubber mold 4 can be easily peeled off from the glass master and the surface of the silicone rubber mold 4 is smooth and the surface condition is good, a circle is displayed, and one of the silicone rubber molds 4 Those in which the parts were coagulated and broken and adhered to the glass master 1 were marked with x.
[Epoxy resin replication count]
As shown in FIGS. 2 (A) to 2 (C), the thermosetting epoxy resin 5 (trade name:) was formed in the
表２に示されるように、実施例１～３で調製した本発明の型取り用シリコーン組成物から得られた硬化物は、ガラス性マスタおよびエポキシ樹脂に対する離型性に優れ、エポキシ樹脂の複製回数が良好であることがわかる。
一方、本発明の（Ｂ）成分を用いていない比較例１～３では、ガラスおよびエポキシ樹脂から剥離し難くなり、エポキシ樹脂の複製回数も少なく、型取りに適したものではないことがわかる。 As shown in Table 2, the cured product obtained from the molding silicone composition of the present invention prepared in Examples 1 to 3 has excellent mold releasability with respect to the glassy master and the epoxy resin, and is a replica of the epoxy resin. It can be seen that the number of times is good.
On the other hand, in Comparative Examples 1 to 3 in which the component (B) of the present invention is not used, it is difficult to peel off from the glass and the epoxy resin, the number of duplications of the epoxy resin is small, and it is found that the epoxy resin is not suitable for molding.
一方、本発明の（Ｂ）成分を用いていない比較例１～３では、ガラスおよびエポキシ樹脂から剥離し難くなり、エポキシ樹脂の複製回数も少なく、型取りに適したものではないことがわかる。 As shown in Table 2, the cured product obtained from the molding silicone composition of the present invention prepared in Examples 1 to 3 has excellent mold releasability with respect to the glassy master and the epoxy resin, and is a replica of the epoxy resin. It can be seen that the number of times is good.
On the other hand, in Comparative Examples 1 to 3 in which the component (B) of the present invention is not used, it is difficult to peel off from the glass and the epoxy resin, the number of duplications of the epoxy resin is small, and it is found that the epoxy resin is not suitable for molding.
１ ガラス製マスタ
２ 枠
３ 型取り用シリコーンゴム組成物
４ シリコーンゴム型
４Ａ 空隙部
５ エポキシ樹脂
６ エポキシ樹脂製複製品 1Glass master 2 Frame 3 Silicone rubber composition for molding 4 Silicone rubber mold 4A Void part 5 Epoxy resin 6 Epoxy resin replica
２ 枠
３ 型取り用シリコーンゴム組成物
４ シリコーンゴム型
４Ａ 空隙部
５ エポキシ樹脂
６ エポキシ樹脂製複製品 1
Claims (5)
- （Ａ）ケイ素原子と結合したアルケニル基を１分子中に少なくとも２個有するオルガノポリシロキサン：１００質量部、
（Ｂ）下記平均式（１）
（Ｒ1 3ＳｉＯ1/2）s［Ｒ1 1（Ｈ）ＳｉＯ2/2］t（Ｒ1 2ＳｉＯ2/2）u （１）
（式中、Ｒ1は、それぞれ独立して、付加反応性炭素－炭素不飽和結合を有しない非置換または置換の１価炭化水素基を表し、ｓは、０または２であり、ｔおよびｕは、２≦ｔ、５≦ｔ＋ｕ≦８００、かつ、０．１≦ｔ／（ｔ＋ｕ）≦０．４を満たす数を表す。）
で表される直鎖状または環状のオルガノハイドロジェンポリシロキサン：（Ａ）成分中のケイ素原子と結合したアルケニル基１個あたりの（Ｂ）成分中のケイ素原子と結合した水素原子の数が０．５～５．０個となる量、および
（Ｃ）ヒドロシリル化反応触媒
を含有することを特徴とする型取り用シリコーンゴム組成物。 (A) Organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule: 100 parts by mass,
(B) The following average formula (1)
(R 1 3 SiO 1/2 ) s [R 1 1 (H) SiO 2/2 ] t (R 1 2 SiO 2/2 ) u (1)
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, s is 0 or 2, and t and u. Represents a number that satisfies 2 ≦ t, 5 ≦ t + u ≦ 800, and 0.1 ≦ t / (t + u) ≦ 0.4.
Linear or cyclic organohydrogenpolysiloxane represented by: The number of hydrogen atoms bonded to the silicon atom in the component (B) per alkenyl group bonded to the silicon atom in the component (A) is 0. A silicone rubber composition for molding, which comprises an amount of .5 to 5.0 and (C) a hydrosilylation reaction catalyst. - （Ｄ）シリカを、（Ａ）成分１００質量部に対して５～１００質量部含有する請求項１記載の型取り用シリコーンゴム組成物。 The silicone rubber composition for molding according to claim 1, which contains (D) silica in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the component (A).
- 請求項１または２記載の型取り用シリコーンゴム組成物からなるガラス用型取り剤。 A molding agent for glass, which comprises the silicone rubber composition for molding according to claim 1 or 2.
- 請求項１または２記載の型取り用シリコーンゴム組成物を硬化させてなるシリコーンゴム型。 A silicone rubber mold obtained by curing the silicone rubber composition for molding according to claim 1 or 2.
- 請求項４記載のシリコーンゴム型を用いることを特徴とするエポキシ樹脂製複製品の製造方法。 A method for producing an epoxy resin replica, which comprises using the silicone rubber mold according to claim 4.
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|---|---|---|---|
| JP2019-084875 | 2019-04-26 | ||
| JP2019084875A JP7120145B2 (en) | 2019-04-26 | 2019-04-26 | Silicone rubber composition for molding and silicone rubber mold |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5859260A (en) * | 1981-10-02 | 1983-04-08 | Toray Silicone Co Ltd | Organopolysiloxane composition |
| JPS60252404A (en) * | 1984-05-28 | 1985-12-13 | Shin Etsu Chem Co Ltd | Cold-curing impression material composition |
| JPH05339505A (en) * | 1992-06-09 | 1993-12-21 | Shin Etsu Chem Co Ltd | Curable silicone composition and cured product thereof |
| JP2019218495A (en) * | 2018-06-21 | 2019-12-26 | 信越化学工業株式会社 | Ultraviolet-curable silicone rubber composition and cured product |
-
2019
- 2019-04-26 JP JP2019084875A patent/JP7120145B2/en active Active
-
2020
- 2020-03-23 WO PCT/JP2020/012573 patent/WO2020217805A1/en active Application Filing
- 2020-04-15 TW TW109112625A patent/TW202111007A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5859260A (en) * | 1981-10-02 | 1983-04-08 | Toray Silicone Co Ltd | Organopolysiloxane composition |
| JPS60252404A (en) * | 1984-05-28 | 1985-12-13 | Shin Etsu Chem Co Ltd | Cold-curing impression material composition |
| JPH05339505A (en) * | 1992-06-09 | 1993-12-21 | Shin Etsu Chem Co Ltd | Curable silicone composition and cured product thereof |
| JP2019218495A (en) * | 2018-06-21 | 2019-12-26 | 信越化学工業株式会社 | Ultraviolet-curable silicone rubber composition and cured product |
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| JP2020180235A (en) | 2020-11-05 |
| JP7120145B2 (en) | 2022-08-17 |
| TW202111007A (en) | 2021-03-16 |
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