Double-curing silicone composition

Abstract

A dual-cure silicone composition is provided. The composition includes (A) an epoxy-functional silicone, (B) at least one radically polymerizable compound having at least one acrylic or methacrylic group per molecule, (C) a photoacid generator and / or a thermal acid generator, and (D) a photoradical polymerization initiator and / or a thermal radical polymerization initiator. The composition generally has excellent curability that is not inhibited by air or amine compounds.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and all advantages of U.S. Provisional Patent Application No. 63 / 213,281, filed on 22 June 2021, the contents of which are incorporated herein by reference.

[0002] The present invention relates to a bicurable silicone composition. [Background technology]

[0003] Epoxy-functional silicones are used in curable silicone compositions that can be cured by irradiation with ultraviolet light ("UV"). For example, Patent Document 1 discloses a curable silicone composition comprising an epoxy-functional organopolysiloxane resin, an epoxy-functional organosiloxane oligomer, and a cationic photoinitiator. Patent Document 2 also discloses a curable silicone composition comprising an epoxy group-containing cationic polymerizable organopolysiloxane, a photoacid generator, and an acrylic-silicone graft copolymer.

[0004] However, such curable silicone compositions have the problem of not curing sufficiently with amine compounds or other types of strong bases that are typically used to neutralize photoresist materials commonly applied in various electrical / electronic applications. In other words, residual amine compounds or strong bases on the substrate cause serious curing inhibition for the curable silicone composition.

[0005] On the other hand, acrylic-based UV-curable compositions are well known. For example, Patent Document 3 discloses a photocurable resin composition containing a polyol acrylate compound, a compound containing an acrylic group or a methacrylic group and a carboxyl group, a siloxane compound containing a glycidyl group, and a photoradical generator.

[0006] However, such a photocurable resin composition has a problem that it is not sufficiently cured by oxygen in the atmosphere. As a result, the cured product exhibits a sticky surface with worse mechanical properties.

[0007] Therefore, there is still an opportunity to develop a curable silicone composition having excellent curability without being inhibited by air or amine compounds.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0009] An object of the present invention is to provide a dual-curable silicone composition having excellent curability without being inhibited by air and amine compounds.

Means for Solving the Problems

[0010] The dual-curable silicone composition of the present invention is (A) The following average unit formula (1): (R 1~6 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 [[ID=6,6]]) d (In the formula, each R 1 is a C 1~6 monovalent aliphatic hydrocarbon group, C6~10 The same or different organic groups selected from monovalent aromatic hydrocarbon groups and monovalent epoxy-substituted organic groups, provided that at least about 15 mol% of all R 1 is a monovalent aromatic hydrocarbon group; "a", "b", "c", and "d" are numbers satisfying the conditions of 0 ≦ a < 0.4, 0 < b < 0.5, 0 < c < 1, 0 ≦ d < 0.4, 0.1 ≦ b / c ≦ 0.6, and a + b + c + d = 1, and about 2 to about 30 mol% of all siloxane units have the monovalent epoxy-substituted organic group), an epoxy-functional silicone resin (A1) represented by 6~10 or a mixture of the above component (A1) and an epoxy-functional silicone (A2) represented by the following general formula (2): or, the above component (A1) and the following general formula (2): X 1 -R 2 2SiO(SiR 2 2O) m SiR 2 2-X 1 (In the formula, each R 2 is the same or different organic group selected from a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon group, and each X 1~6 is a monovalent epoxy-substituted organic group and the following general formula (3): 6~10 a monovalent aromatic hydrocarbon group, and each X 1 is a monovalent epoxy-substituted organic group and the following general formula (3): X 2 -R 3 2SiO(SiR 3 2O)​​​​​​​​​​​​​​​​​​​(B) At least one radical polymerizable compound having at least one acrylic group or methacrylic group per molecule, in an amount of about 15% to about 75% by mass of the total mass of components (A) to (D); (C) A photoacid generator and / or thermoacid generator in an amount of approximately 0.1% to approximately 5% by mass of the total mass of components (A) to (D); and (D) A photoradical polymerization initiator and / or thermal radical polymerization initiator in an amount of approximately 0.1% to approximately 5% by mass of the total mass of components (A) to (D), Includes.

[0011] In various embodiments, the content of component (A2) is up to 80% by mass of the mixture of components (A1) and (A2).

[0012] In various embodiments, the monovalent epoxy-substituted organic group in component (A) is a glycidoxyalkyl group, a 3,4-epoxycyclohexylalkyl group, and an epoxyalkyl group.

[0013] In various embodiments, component (B) comprises or is at least one of isobornyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate diacrylate, or 2-phenoxyethyl acrylate.

[0014] In various embodiments, component (C) comprises or is at least one of a sulfonium salt or an iodonium salt.

[0015] In various embodiments, the photoradical polymerization initiator for component (D) comprises or is at least one of the following: acetophenone initiators, benzyl initiators, benzophenone initiators, thioxanthone initiators, acylphosphine oxide initiators, or oxime initiators.

[0016] In various embodiments, the thermal radical polymerization initiator for component (D) is an organic peroxide having a half-life of 10 hours at temperatures above 80°C. [Effects of the Invention]

[0017] The dual-curable silicone composition of the present invention has excellent curability without being inhibited by air and amine compounds. [Modes for carrying out the invention]

[0018] The terms “comprising” or “comprise” as used herein are used in their broadest sense to mean and encompass the concepts of “including,” “include,” “consisting essentially of,” and “consisting of.” The use of “for example,” “eg,” “such as,” and “including” to list examples is not limited to the examples listed. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to,” and encompasses other similar or equivalent examples. The term “about” as used herein serves to reasonably encompass or explain slight variations in numerical values ​​as a result of instrumental analysis or handling of samples. Such minor fluctuations may be around ±0-25%, ±0-10%, ±0-5%, or ±0-2.5% of the value. Furthermore, the term “approximately” applies to both numbers when relating to a range of values. Moreover, the term “approximately” may apply to multiple numbers even if not explicitly stated. In general, as used herein, ">" means “greater than” or “greater than,” “≧” means “at least” or “greater than or equal to,” “<” means “below” or “less than,” and “≦” means “at most” or “less than or equal to.”

[0019] As used herein, the terms “epoxy functional” or “epoxy substitution” refer to a functional group in which an epoxy substituent oxygen atom is directly bonded to two adjacent carbon atoms in a carbon chain or ring system. Examples of epoxy-substituted functional groups include, but are not limited to, glycidoxyalkyl groups such as 2-glycidoxyethyl, 3-glycidoxypropyl, and 4-glycidoxybutyl; (3,4-epoxycycloalkyl)alkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl, 2-(2,3-epoxycyclopentyl)ethyl, and 3-(2,3-epoxycyclopentyl)propyl; and epoxyalkyl groups such as 2,3-epoxypropyl, 3,4-epoxybutyl, and 4,5-epoxypentyl.

[0020] In this specification, "(meth)acrylate" means either acrylate or methacrylate, or both.

[0021] <Double-curing silicone composition> Component (A) is an epoxy-functionalized silicone selected from the following: (A1) The following is the average unit formula (1): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d An epoxy-functional silicone resin represented by the above (A1) component and (A2) the following general formula (2): X 1 -R 2 2SiO(SiR 2 20) m SiR 2 2-X 1

[0022] A mixture with epoxy-functionalized silicone represented by . In the formula, each R 1 C 1~6 Monovalent aliphatic hydrocarbon group, C 6~10 The same or different organic groups are selected from monovalent aromatic hydrocarbon groups and monovalent epoxy-substituted organic groups.

[0023] C in component (A1) 1~6 Examples of monovalent aliphatic hydrocarbon groups include C 1~6 Alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, and hexyl group); C 2~6 Alkenyl groups (e.g., vinyl groups, allyl groups, and hexenyl groups); and C 1~6 Examples include alkyl halogenated groups (e.g., 3-chloropropyl group and 3,3,3-trifluoropropyl group). Among these, the methyl group is generally preferred.

[0024] C in component (A1) 6~10 Examples of monovalent aromatic hydrocarbon groups include phenyl, tolyl, xylyl, and naphthyl groups. Among these, the phenyl group is generally preferred.

[0025] Examples of monovalent epoxy-substituted organic groups in component (A1) include glycidoxyalkyl groups (e.g., 3-glycidoxypropyl group, 4-glycidoxybutyl group, and 5-glycidoxypentyl group); 3,4-epoxycycloalkylalkyl groups (e.g., 2-(3,4-epoxysilohexyl)ethyl, 3-(3,4-epoxysilohexyl)propyl, 2-(3,4-epoxy-3-methylsilohexyl)-2-methylethyl, 2-(2,3-epoxysilopentyl)ethyl, and 3-(2,3-epoxysilopentyl)propyl); and epoxyalkyl groups (e.g., 2,3-epoxypropyl group, 3,4-epoxybutyl group, and 4,5-epoxypentyl group). Among these, 3,4-epoxycycloalkylalkyl groups are generally preferred.

[0026] In component (A1), total R 1At least about 15 mol%, optionally at least about 20 mol%, or optionally at least about 25 mol% is C 6~10 is a monovalent aromatic hydrocarbon group. When the content of the monovalent aromatic hydrocarbon group is at least the above lower limit, the mechanical properties of the cured product can be improved.

[0027] In formula (1), "a", "b", "c", and "d" are mole fractions and mole numbers that satisfy the following conditions: 0 ≦ a < 0.4, 0 < b < 0.5, 0 < c < 1, 0 ≦ d < 0.4, 0.1 ≦ b / c ≦ 0.6, and a + b + c + d = 1. Optionally, a = 0, 0 < b < 0.5, 0 < c < 1, 0 ≦ d < 0.2, 0.1 < b / c ≦ 0.6, and b + c + d = 1, or optionally a = 0, 0 < b < 0.5, 0 < c < 1, d = 0, 0.1 < b / c ≦ 0.6, and b + c = 1. "a" is 0 ≦ a < 0.4, optionally 0 ≦ a < 0.2, or optionally a = 0, which is because if the (R 1 3SiO 1 / 2 ) siloxane units are too many, the molecular weight of the epoxy-containing organopolysiloxane resin (A1) decreases, and also when (SiO 4 / 2 ) siloxane units are introduced, the hardness of the cured product of the epoxy-functional silicone resin (A1) increases significantly, and the cured product may become brittle. For this reason, "d" is 0 ≦ d < 0.4, optionally 0 ≦ d < 0.2, or optionally d = 0. In addition, the molar ratio "b / c" of the (R 1 2SiO 2 / 2 ) unit and the (R 1 SiO 3 / 2 ) unit can be about 0.1 or more and about 0.6 or less. In some examples, in the production of the epoxy-functional silicone resin (A1), deviating from the above range may result in insoluble by-products, the product becoming prone to cracking due to a decrease in toughness, or the strength and elasticity of the product being low, making the product prone to scratching. In some examples, the range of the molar ratio "b / c" is greater than about 0.1 and about 0.6 or less. The epoxy-functional silicone resin (A1) is the (R 1 2SiO 2 / 2 ) siloxane unit and (R 1 SiO3 / 2 ) It contains siloxane units, and its molecular structure is, in most cases, a network structure or a three-dimensional structure because the molar ratio of "b / c" is greater than about 0.1 and less than or equal to about 0.6. Therefore, in the epoxy-functional silicone resin (A1), (R 1 2SiO 2 / 2 ) siloxane units and (R 1 SiO 3 / 2 ) siloxane units are present, but (R 1 3SiO 1 / 2 ) siloxane units and (SiO 4 / 2 ) siloxane units are optional structural units. That is, an epoxy-functional silicone resin containing the following average unit formula may exist. (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d

[0028] In component (A1), approximately 2 mol% to approximately 30 mol%, optionally approximately 10 mol% to approximately 30 mol%, or optionally approximately 15 mol% to approximately 30 mol% of the total siloxane units in the molecule have epoxy-substituted organic groups. If such siloxane units are present in amounts greater than or equal to the lower limit of the above range, the crosslinking density during curing may be improved. On the other hand, if this amount is less than or equal to the upper limit of the above range, the heat resistance of the cured product can be improved, which may be preferable. In epoxy-functional monovalent hydrocarbon groups, the epoxy groups can be bonded to silicon atoms via alkylene groups, thereby preventing the epoxy groups from directly bonding to silicon atoms. Epoxy-functional silicone resin (A1) can be produced by well-known conventional manufacturing methods.

[0029] There are no particular restrictions on the weight-average molecular weight of the epoxy-functionalized silicone resin (A1), but considering the toughness of the cured product and its solubility in organic solvents, in some embodiments the molecular weight is about 10 3 More than and approximately 10 6 The following applies: In one embodiment, the epoxy-functional silicone resin (A1) comprises a combination of two or more such epoxy-functional silicone resins having different content and types of epoxy-containing organic groups and monovalent hydrocarbon groups, or having different molecular weights.

[0030] Component (A2) is an optional component used to impart flexibility and impact strength to the cured product.

[0031] In formula (2), each R 2 C 1~6 Monovalent aliphatic hydrocarbon groups and C 6~10 The same or different organic groups are selected from monovalent aromatic hydrocarbon groups.

[0032] C in component (A2) 1~6 Examples of monovalent aliphatic hydrocarbon groups include C 1~6 Alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, and hexyl group); C 2~6 Alkenyl groups (e.g., vinyl groups, allyl groups, and hexenyl groups); and C1~6 Examples include alkyl halogenated groups (e.g., 3-chloropropyl group and 3,3,3-trifluoropropyl group). Among these, methyl groups are generally preferred.

[0033] C in component (A2) 6~10 Examples of monovalent aromatic hydrocarbon groups include phenyl, tolyl, xylyl, and naphthyl groups. Among these, the phenyl group is generally preferred.

[0034] In formula (2), each 1 These are the same or different groups selected from monovalent epoxy-substituted organic groups and epoxy-functionalized siloxy groups represented by the following general formula (3): X 2 -R 3 2SiO(SiR 3 20) x SiR 3 2-R 4 -.

[0035] X 1 Examples of monovalent epoxy-substituted organic groups include: glycidoxyalkyl groups (e.g., 3-glycidoxypropyl group, 4-glycidoxybutyl group, and 5-glycidoxypentyl group); 3,4-epoxycycloalkylalkyl groups (e.g., 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl, 2-(2,3-epoxycyclopentyl)ethyl, and 3-(2,3-epoxycyclopentyl)propyl); and epoxyalkyl groups (2,3-epoxypropyl group, 3,4-epoxybutyl group, and 4,5-epoxypentyl group). Among these, 3,4-epoxycycloalkylalkyl groups are generally preferred.

[0036] In formula (3), each R 3 are the same or different C 1~6 It is a monovalent aliphatic hydrocarbon group. 3 C 1~6 Examples of monovalent aliphatic hydrocarbon groups include C 1~6Alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, and hexyl group); C 2~6 Alkenyl groups (e.g., vinyl groups, allyl groups, and hexenyl groups); and C 1~6 Examples include alkyl halogenated groups (e.g., 3-chloropropyl group and 3,3,3-trifluoropropyl group). Among these, methyl groups are generally preferred.

[0037] In formula (3), R 4 is C 2~6 It is an alkylene group. 4 C 2~6 Examples of alkylene groups include ethylene, methylethylene, propylene, butylene, and hexylene. Among these, the ethylene group is generally preferred.

[0038] In the above equation (3), X 2 X is a monovalent epoxy-substituted organic group. 2 Examples of monovalent epoxy-substituted organic groups include: glycidoxyalkyl groups (e.g., 3-glycidoxypropyl group, 4-glycidoxybutyl group, and 5-glycidoxypentyl group); 3,4-epoxycycloalkylalkyl groups (e.g., 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl, 2-(2,3-epoxycyclopentyl)ethyl, and 3-(2,3-epoxycyclopentyl)propyl); and epoxyalkyl groups (2,3-epoxypropyl group, 3,4-epoxybutyl group, and 4,5-epoxypentyl group). Among these, 3,4-epoxycycloalkylalkyl groups are generally preferred.

[0039] In equation (3) above, "x" is a number that is approximately 0 to approximately 5, arbitrarily selected from approximately 0 to approximately 2, or arbitrarily selected from approximately 0.

[0040] In equation (2) above, "m" is a number between approximately 0 and 100, optionally between approximately 0 and 20, or optionally between approximately 0 and 10. When "m" is below the upper limit of the above range, the mechanical strength of the cured product can be improved.

[0041] The state of component (A2) at 25°C is not limited, but is generally liquid. The viscosity of component (A2) at 25°C is not limited, but is generally in the range of approximately 5 to approximately 100 mPa·s. In this specification, viscosity is the value measured at 23±2°C using a B-type viscometer according to ASTM D1084.

[0042] The content of component (A2) in the mixture of component (A1) and component (A2) is not limited, but generally it is a maximum of 80% by mass, optionally up to 70% by mass, optionally about 10% to about 70% by mass, or optionally about 15% to about 65% by mass of the mixture of component (A1) and component (A2). If the content of component (A2) is above the lower limit of the above range, the curing sensitivity of the cured product to amines can be improved. On the other hand, if the content is below the upper limit of the above range, inhibition and delay by oxygen may occur in the cured product, which may lead to a decrease in elastic modulus and tensile strength.

[0043] Component (B) is at least one radical polymerizable compound having at least one acrylic group or methacrylic group per molecule. Component (B) includes mono(meth)acrylates (e.g., isobornyl acrylate, 2-hydroxyethyl methacrylate, and 2-phenoxyethyl acrylate); dihydric alcohol (meth)acrylate compounds (e.g., ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, isoprene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, octa Diamine diol di(meth)acrylate, 1,2-cyclohexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate diacrylate, etc.; (meth)acrylate compounds of trihydric alcohols (e.g., glycerol di(meth)acrylate, glycerol tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris[(meth)acryloxyethyl]isocyanurate, etc.);(Meth)acrylate compounds of tetrahydric alcohols (e.g., erythritol tri(meth)acrylate, erythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc.); (Meth)acrylate compounds of pentahydric alcohols (e.g., Examples include triglycerol tetra(meth)acrylate, triglycerol penta(meth)acrylate, etc.; hexahydric alcohol (meth)acrylate compounds (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.); and (meth)acrylate silanes or siloxanes (e.g., 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, siloxanes having a (meth)acrylate group at one molecular terminus, etc.).

[0044] Component (B) is commercially available and includes, for example, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.); dipentaerythritol tetraacrylate (KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.); dipentaerythritol penta(meth)acrylate (KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.); dipentaerythritol hexa(meth)acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E, manufactured by Shin Nakamura Chemical Industry Co., Ltd.); and compounds having a structure in which a (meth)acryloyl group is linked via an ethylene glycol and / or propylene glycol residue (for example, SR454 and SR499, commercially available from Sartomer).

[0045] The content of component (B) is approximately 15% to 75% by mass of the total mass of components (A) to (D), optionally approximately 15% to 65% by mass, or optionally approximately 15% to 60% by mass. If the content is above the lower limit of the above range, the oxygen-induced inhibition of the composition may increase, and the mechanical strength may decrease. On the other hand, if the content is below the upper limit of the above range, the curing inhibition of the cured product by amine compounds may increase.

[0046] Component (C) is a photoacid generator and / or thermal acid generator that improves curing component (A). Any acid generator known to those skilled in the art can be used, such as sulfonium salts, iodonium salts, selenonium salts, phosphonium salts, diazonium salts, p-toluenesulfonates, trichloromethyl-substituted triazines, and trichloromethyl-substituted benzenes. Among these, sulfonium salts and iodonium salts are preferred because the composition exhibits excellent curability upon ultraviolet irradiation or thermal / ultraviolet irradiation. For example, sulfonium salts are UV-activated acid generators that absorb relatively long wavelength light (up to 365 nm), and iodonium salts are thermal / UV-activated acid generators that absorb short wavelength light (less than 350 nm).

[0047] An example of a sulfonium salt is the formula R c 3S + X - We can give an example of a salt represented by the formula. In the formula, R c These include methyl groups, ethyl groups, propyl groups, butyl groups, and other C groups. 1~6 Alkyl groups; phenyl group, naphthyl group, biphenyl group, tolyl group, propylphenyl group, decylphenyl group, dodecylphenyl group, and other C groups. 1~24 It may represent an aryl group or a substituted aryl group. Also, in the formula, X - SbF6 - AsF6 - PF6 - BF4 - , B(C6F5)4 - HSO4 - ClO4 - CF3SO3 -, and other non-nucleophilic nonbasic anions may be represented.

[0048] An example of an iodonium salt is, formula R c 2I + X - Examples of salts represented by formula R include, for example, selenonium salts, c 3Se + X - Examples of salts represented by formula R can be given, and an example of a phosphonium salt is, c 4P + X - Examples of salts represented by formula R include, and an example of a diazonium salt is, c N2 + X - We can list the salts represented by the formula, where R c and X - R c 3S + X - This is the same as described in this specification.

[0049] An example of a p-toluenesulfonate is the formula CH3C6H4SO3R c1 Examples of compounds represented by the formula include R c1 This refers to an organic group containing an electron-withdrawing group, such as a benzoylphenylmethyl group, a phthalimide group, or similar groups.

[0050] An example of a trichloromethyl-substituted triazine is [CC13]2C3N3R c2 Examples of compounds represented by the formula include R c2 This represents phenyl, substituted or unsubstituted phenylethyl, substituted or unsubstituted furanylethynyl, and other electron-withdrawing groups.

[0051] An example of a trichloromethyl-substituted benzene is CCl3C6H3R c R c3 Examples of compounds represented by the formula include R c R c 3S + X -This is the same as described herein, and R c3 This represents a halogen group, a halogen-substituted alkyl group, and other halogen-containing groups.

[0052] Examples of acid generators include triphenylsulfonium tetrafluoroborate, di(p-tert-butylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium hexafluoroantimonate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate salt, and p-chlorophenyldiazonium tetrafluoroborate.

[0053] The content of component (C) is approximately 0.1% to 5% by mass of the total mass of components (A) to (D), optionally approximately 0.5% to 5% by mass, optionally approximately 0.1% to 3% by mass, or optionally approximately 0.1% to 2% by mass. If the content of component (C) is above the lower limit of the above range, the curable silicone composition may yellow, or the curing speed may be too fast, resulting in a poor pot life. On the other hand, if the content is below the upper limit of the above range, the curing speed of the cured product may be slowed down, and it may not ultimately cure completely.

[0054] Component (D) is a photoradical polymerization initiator and / or thermal radical polymerization initiator for promoting the polymerization of component (B). Any radical polymerization initiator known to those skilled in the art can be used.

[0055] Examples of photoradical polymerization initiators for component (D) include acetophenone-based initiators (e.g., diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1 -Hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and benzoin isobutyl ether, as well as oligomers of 2-hydroxy-2-methyl-1-[4-vinyl-(1-methylvinyl)phenyl]propanone, etc.); benzyl initiators (e.g.) For example, diphenyldiketone and bis(4-methoxyphenyl)diketone); benzophenone initiators (for example, benzophenone, o-benzoylmethylbenzoate, Michlar's ketone, 4,4'-bisdiethylaminobenzophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide); thioxanthone initiators (for example, thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthio) Xanthones and 2,4-diethylthioxanthones, etc.; Acylphosphine oxide initiators (e.g., 2-methylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl2,4,6-trimethylbenzoylphenylphosphinenate, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc.);and oxime initiators (e.g., 1-{(4-phenylthio)phenyl}-1,2-butanedione-2-(O-benzoyl oxime), 1-{(4-phenylthio)phenyl}-1,2-octanedione-2-(O-benzoyl oxime), 1-{(4-phenylthio)phenyl}-1-octanone-1-(O-acetyl oxime), 1-{4-(2-hydroxyethoxyphenylthio)phenyl}-1,2-propanedione-2-(O-acetyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-cal Examples include [bazole-3-yl]ethanone-1-(O-acetyloxime) and (9-ethyl-6-nitro-9H-carbazole-3-yl){4-(2-methoxy)-1-methylethoxy}-2-methylphenyl}methanone (O-acetyloxime, etc.). Benzophenone-based initiators are preferred as photoradical polymerization initiators due to the good reactivity of component (B), and 2-hydroxy-2-methylpropiophenone is even more preferred. The photoradical polymerization initiator may be used alone or in combination of two or more.

[0056] Examples of thermal radical polymerization initiators for component (D) include azo compounds (e.g., azobenzene, azobenzene-p-sulfonic acid, azobisdimethylvaleronitrile, azobisisobutyronitrile, and combinations thereof); and organic peroxide compounds (e.g., benzoyl peroxide, dibenzoyl peroxide, 4-monochlorobenzoyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, tert-butylperoxybenzoate, 2,4-dichlorobenzoyl peroxide) Di-tert-butyl peroxide, di-tert-hexyl peroxide, tert-butylcumyl peroxide, 1,1-bis(t-butylperoxy)-335-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, di-(tert-butylperoxyisopropyl)benzene, 1,6-bis(tert-butylperoxycarboxy)hexane, di-(4-methylbenzoyl) peroxide, di-(2-methylbenzoyl) peroxide Examples include tert-butylperoxyisopropyl monocarbonate, di-(2-tert-butylperoxyisopropyl)benzene, or a combination of two or more of these. The thermal radical polymerization initiator used as component (D) in the present invention is preferably an organic peroxide having a half-life of 10 hours at temperatures of 80°C or higher, optionally 90°C or higher, and optionally 100°C or higher. This is because the composition exhibits good stability at room temperature when the temperature is above the lower limit. The upper limit of the temperature is not particularly limited, but it is preferably 130°C or lower, as the composition tends not to cure sufficiently at temperatures that are too high. Examples of such organic peroxides include dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyn-3, and di-(2-tert-butylperoxyisopropyl)benzene. Generally, dicumyl peroxide is most preferred due to its good miscibility with other components in the composition.

[0057] The content of component (D) is approximately 0.1% to 5% by mass of the total mass of components (A) to (D), optionally approximately 0.1% to 3% by mass, optionally approximately 0.1% to 2% by mass, or optionally approximately 0.5% to 2% by mass. If the content of component (D) is above the lower limit of the above range, the curable silicone composition will not be stable at room temperature and its pot life will be poor. On the other hand, if the content is below the upper limit of the above range, the radical components in the cured product may not be sufficiently cured, and more inhibition by oxygen may be observed.

[0058] This composition contains the above components (A) to (D), but in order to impart better adhesive and mechanical properties to the cured product of this composition, an adhesion promoter and / or a photosensitizer and / or an alcohol and / or an inorganic filler may be used.

[0059] Examples of adhesion promoters include epoxy-functionalized alkoxysilanes (e.g., 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof); unsaturated alkoxysilanes (e.g., vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxy Examples include propyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof); epoxy-functionalized siloxanes having silicon atom-bonded alkoxy groups (e.g., reaction products of hydroxy-terminated polyorganosiloxanes and epoxy-functionalized alkoxysilanes (e.g., any of the above), or physical blends of hydroxy-terminated polyorganosiloxanes and epoxy-functionalized alkoxysilanes). Adhesion promoters may include combinations of epoxy-functionalized alkoxysilanes and epoxy-functionalized siloxanes. For example, adhesion promoters are exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and a reaction product of hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

[0060] The amount of adhesion promoter is not limited, but is generally about 0.01 to 5% by mass of the total mass of components (A) to (D), or optionally about 0.1 to 2% by mass. If the amount is above the lower limit of the above range, the adhesive properties of the cured product may be improved. On the other hand, if the amount is below the upper limit of the above range, the mechanical properties of the cured product may be improved.

[0061] Examples of photosensitizers include isopropyl-9H-thioxanthene-9-one, anthrone, 1-hydroxycyclohexyl-phenyl ketone, 2,4-diethyl-9H-thioxanthene-9-one, 2-isopropylthioxanthene, 2-hydroxy-2-methylphenylpropane-1-one, 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT), and pentaerythritol tetrakis[3-(3,5-di-tert-br]. [3,5-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[{3,5-bis(1,1-di-tert-butyl-4-hydroxyphenyl)methyl}phosphonate, 3 Examples include 3',3'',5,5',5''-hexane-tert-butyl-4-a,a',a''-(mesitylene-2,4,6-tolyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], and hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0062] The amount of photosensitizer is not limited, but if used, it is generally within the range of approximately 0.001 to 1% by mass, optionally within the range of approximately 0.005 to 0.5% by mass, or optionally within the range of approximately 0.005 to 0.1% by mass, based on the total mass of components (A) to (D) and the photosensitizer. If the amount of photosensitizer is above the lower limit of the above range, the curability of the cured product may be improved. On the other hand, if it is below the upper limit of the above range, the optical clearance of the cured product may be improved.

[0063] Examples of alcohols include monohydric alcohols (e.g., ethyl alcohol, isopropyl alcohol, isobutyl alcohol, 1-decanol, 1-dodecanol, 1-octanol, oleyl alcohol, 1-hexadecanol, and stearyl alcohol, etc.) and polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, propylene glycol, 1,10-decanediol, glycerol, and pentaerythritol, etc.).

[0064] The alcohol content is not limited, but if used, it is generally about 0.01 to about 10% by mass of the total mass of components (A) to (D) and alcohol, or optionally about 0.1 to about 10% by mass.

[0065] Inorganic fillers enhance the mechanical strength of the hardened material. Examples of fillers include pulverized or untreated precipitated silica or fumed silica; precipitated or pulverized calcium carbonate, zinc carbonate; clay (e.g., pulverized kaolin); quartz powder; aluminum hydroxide; zirconium silicate; diatomaceous earth; wollastonite; pyrophyllite; and one or more metal oxides (e.g., fumed or precipitated titanium dioxide, cerium oxide, magnesium oxide powder, zinc oxide, iron oxide, etc.).

[0066] The content of the filler is not limited, but if used, it is generally within the range of approximately 1% to approximately 95% by mass, optionally within the range of approximately 5% to approximately 95% by mass, or optionally within the range of approximately 5% to approximately 90% by mass, of the total mass of components (A) to (D) and the filler.

[0067] This composition can be cured by irradiation with UV light (i.e., ultraviolet ("UV") light) and / or heating. For example, low-pressure, high-pressure, or ultra-high-pressure mercury lamps, metal halide lamps, (pulsed) xenon lamps, or electrodeless lamps are useful as UV lamps.

[0068] This composition forms a cured product when cured by irradiation with UV light. The cured product according to the present invention has a hardness in the range of at least 20 to 95, typically at least 30 to 80, and more typically at least 30 to 70, when measured using the Shore A hardness scale as defined in ASTM D2240. Furthermore, the cured product according to the present invention has a hardness of up to 60, and typically up to 50, when measured using the Shore D hardness scale as defined in ASTM D2240. The reason for this is as follows: if the hardness of the cured product is below the lower limit of the range described, the strength of the cured product may be insufficient, while if it exceeds the upper limit of the range described, the flexibility of the cured product tends to be insufficient.

[0069] Because the cured material is flexible and highly transparent, it is useful as an optical component or part that is transparent to light, such as visible light, infrared light, ultraviolet light, far ultraviolet light, X-rays, and lasers. The cured material is also useful as an optical component or part that must be flexible for use in bent or curved states, and is also useful as an optical component or part for devices that use high-energy, high-power light. In addition, by creating a composite material in which the cured product is formed with any various substrates on a single article or body, it is possible to create an article or part with a flexible cured layer, and shock absorption and stress relief functions can be expected from the cured layer. [Examples]

[0070] Here, the bicurable silicone composition of the present invention will be described in detail using examples and comparative examples. Note that in the formula, "Me", "Pr", "Ph", and "Ep" represent a methyl group, a propyl group, a phenyl group, and a 2-(3,4-epoxycyclohexyl)ethyl group, respectively. The structure of the epoxy-functionalized silicone resin used in the examples is as follows: 13 1C NMR and 29The molecular weight was determined by Si NMR measurement. The weight-average molecular weight of the epoxy-functionalized silicone resin was calculated using GPC based on comparison with a polystyrene standard. The viscosity of the epoxy-functionalized silicone and silicone resin was measured as follows.

[0071] <Viscosity> The viscosity at 23±2℃ was measured using a B-type viscometer (Brookfield HA or HB Type rotational viscometer, using spindle #52, 5 rpm) in accordance with ASTM D1084 "Standard Test Methods for Viscosity of Adhesive".

[0072] <Examples 1-10 and Comparative Examples 1-7> The following components were used to prepare the bi-curable silicone compositions (mass%) shown in Table 1.

[0073] The following epoxy-functionalized silicone resin was used as component (A1). (a1): Epoxy-functional silicone resin having a weight-average molecular weight of 2,000 to 6,000 and represented by the following average unit formula: (MePhSiO 2 / 2 ) 0.34 (PrSiO 3 / 2 ) 0.50 (EpSiO 3 / 2 ) 0.16

[0074] The following epoxy-functionalized silicone was used as component (A2). (a2): An epoxy-functional silicone having a viscosity of 40 mPa·s and a weight-average molecular weight of 382, ​​represented by the following formula: Ep-SiMe2OSiMe2-Ep

[0075] The following acrylic monomers were used as component (B). (b1): Isobornyl acrylate (b2): 2-hydroxyethyl methacrylate (b3): ​​3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate diacrylate (b4): 2-Phenoxyethyl acrylate

[0076] The following photo- and thermal acid-generating agents were used as component (C). (c1): 4-Isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) borate (TR-PAG-30408, manufactured by TRONYL) (c2): Triarylsulfonium borate (CPI-310B, manufactured by TRONYL).

[0077] The following photo / thermal radical initiator was used as component (D). (d1): 2-Hydroxy-2-methylpropiophenone (d2): Dicumyl peroxide

[0078] <Curability of the double-curing silicone composition> Approximately 0.1 to 3 g of each bi-curable silicone composition was filled into glass slides pre-coated with triethylamine or triisopropanolamine. After leveling the surface with a bar coater, it was subjected to a 5000 mW / cm² treatment. 2 The double-curable silicone composition was cured by passing it through a metal halide UV lamp with a D-type bulb of a certain light intensity, or by heating it in air (150°C for 1 hour). The curability of the double-curable silicone composition was evaluated. The results are shown in Table 1.

[0079] <Hardness of hardened material> The hardness of the cured material was measured using the Shore D hardness scale or the Shore A hardness scale as specified in ASTM D2240.

[0080] <Surface tackiness of cured products> The surface tackiness of the cured material was evaluated by touching it with a finger.

[0081] [Table 1]

[0082] [Table 2]

[0083] [Table 3] [Industrial applicability]

[0084] The dual-curable silicone composition of the present invention can be cured without being inhibited by air or amine compounds. Therefore, this composition is useful as a variety of adhesives, encapsulants, coatings, etc., for electrical / electronic applications. The present invention can provide the following aspects. [1] A double-curable silicone composition comprising: (A) The following average unit formula (1): (R 1 3 SiO 1 / 2 ) a (R 1 2 SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (where each R 1 is the same or different organic group selected from a C 1~6 monovalent aliphatic hydrocarbon group, a C 6~10 monovalent aromatic hydrocarbon group, and a monovalent epoxy-substituted organic group, provided that at least about 15 mol% of all R 1 is a C 6~10 monovalent aromatic hydrocarbon group; "a", "b", "c", and "d" are numbers satisfying the conditions of 0 ≦ a < 0.4, 0 < b < 0.5, 0 < c < 1, 0 ≦ d < 0.4, 0.1 ≦ b / c ≦ 0.6, and a + b + c + d = 1, and about 2 to about 30 mol% of all siloxane units have the monovalent epoxy-substituted organic group) represented by an epoxy-functional silicone resin (A1); or a mixture of the component (A1) and an epoxy-functional silicone (A2) represented by the following general formula (2): X 1 -R 2 2 SiO(SiR 2 2 O) m SiR 2 2 -X 1 (where each R 2 is the same or different organic group selected from a C 1~6 monovalent aliphatic hydrocarbon group and a C 6~10 monovalent aromatic hydrocarbon group, each X 1 is the same or different group selected from a monovalent epoxy-substituted organic group and an epoxy-functional siloxy group represented by the following general formula (3): X 2 -R 3 2 SiO(SiR 3 2 O) x SiR 3 2 -R 4 - (where each R 3 is the same or different C 1~6 monovalent aliphatic hydrocarbon group, R 4 is a C 2~6 alkylene group, X 2 is a monovalent epoxy-substituted organic group, "x" is a number from about 0 to about 5, and "m" is a number from about 0 to about 100)); (B) At least one radically polymerizable compound having at least one acrylic group or methacrylic group per molecule and present in an amount of about 15% to about 75% by mass of the total mass of components (A) to (D); (C) A photoacid generator and / or a thermal acid generator present in an amount of about 0.1% to about 5% by mass of the total mass of components (A) to (D); and (D) A photo radical polymerization initiator and / or a thermal radical polymerization initiator present in an amount of about 0.1% to about 5% by mass of the total mass of components (A) to (D), comprising a double-curable silicone composition. [2] The double-curable silicone composition according to [1] above, wherein the content of component (A2) is at most 80% by mass of the mixture of components (A1) and (A2). [3] The double-curable silicone composition according to [1] or [2] above, wherein the monovalent epoxy-substituted organic group in component (A) is a glycidoxyalkyl group, a 3,4-epoxycyclohexylalkyl group, or an epoxyalkyl group. [4] The double-curable silicone composition according to [1], [2], or [3] above, wherein component (B) is isobornyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate diacrylate, or 2-phenoxyethyl acrylate. [5] A double-curable silicone composition according to any one of the above items [1] or [2] to [4], wherein component (C) is a sulfonium salt or an iodonium salt. [6] The double-curable silicone composition according to any one of the above [1] or [2] to [5], wherein the photoradical polymerization initiator of component (D) is an acetophenone-based initiator, a benzyl-based initiator, a benzophenone-based initiator, a thioxanthone-based initiator, an acylphosphine oxide-based initiator, or an oxime-based initiator. [7] The double-curable silicone composition according to any one of the above [1] or [2] to [6], wherein the thermal radical polymerization initiator of component (D) is an organic peroxide having a half-life of 10 hours at a temperature of 80°C or higher.

Claims

1. A double-curing silicone composition, (A) The following average unit formula (1): (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ SiO ３／２ ) ｃ (SiO ４／２ ) ｄ (In the formula, each R １ C １～６ Monovalent aliphatic hydrocarbon group, C ６～１０ The same or different organic groups selected from monovalent aromatic hydrocarbon groups and monovalent epoxy-substituted organic groups, provided that all R １ At least 15 mol% of C ６～１０ An epoxy-functional silicone resin (A1) is represented by a monovalent aromatic hydrocarbon group; "a", "b", "c", and "d" are numbers satisfying the conditions 0 ≤ a < 0.4, 0 < b < 0.5, 0 < c < 1, 0 ≤ d < 0.4, 0.1 ≤ b / c ≤ 0.6, and a + b + c + d = 1, and 2 to 30 mol% of the total siloxane units have the monovalent epoxy-substituted organic group. Alternatively, the above-mentioned component (A1) and the following general formula (2): X １ -R ２ ２ SiO(SiR ２ ２ O) ｍ SiR ２ ２ -X １ (In the formula, each R ２ C １～６ Monovalent aliphatic hydrocarbon group and C ６～１０ The same or different organic groups selected from monovalent aromatic hydrocarbon groups, each X １ This includes monovalent epoxy-substituted organic groups and the following general formula (3): X ２ -R ３ ２ SiO(SiR ３ ２ O) ｘ SiR ３ ２ -R ４ - (In the formula, each R ３ are the same or different C １～６ It is a monovalent aliphatic hydrocarbon group, R ４ C ２～６ It is an alkylene group, X ２ An epoxy-functional silicone selected from a mixture with epoxy-functional silicone (A2) represented by a monovalent epoxy-substituted organic group, where "x" is a number from 0 to 5 and "m" is a number from 0 to 100, and which is the same or a different group from the epoxy-functional siloxy groups represented by (A2); (B) At least one radical polymerizable compound having at least one acrylic group or methacrylic group per molecule, in an amount of 15% to 75% by mass of the total mass of components (A) to (D); (C) A photoacid generator and / or thermoacid generator in an amount of 0.1% to 5% by mass of the total mass of components (A) to (D); and (D) A photoradical polymerization initiator and / or thermal radical polymerization initiator in an amount of 0.1% to 5% by mass of the total mass of components (A) to (D), A double-curing silicone composition containing the following:

2. The double-curable silicone composition according to claim 1, wherein the content of component (A2) is up to 80% by mass of the mixture of components (A1) and (A2).

3. The bicurable silicone composition according to claim 1 or claim 2, wherein the monovalent epoxy-substituted organic group in component (A) is a glycidoxyalkyl group, a 3,4-epoxycyclohexylalkyl group, or an epoxyalkyl group.

4. The double-curable silicone composition according to claim 1 or claim 2, wherein component (B) is isobornyl acrylate, 2-hydroxylethyl methacrylate, 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate diacrylate, or 2-phenoxyethyl acrylate.

5. The bicurable silicone composition according to claim 1 or claim 2, wherein component (C) is a sulfonium salt or an iodonium salt.

6. The bicurable silicone composition according to claim 1 or claim 2, wherein the photoradical polymerization initiator of component (D) is an acetophenone-based initiator, a benzyl-based initiator, a benzophenone-based initiator, a thioxanthone-based initiator, an acylphosphine oxide-based initiator, or an oxime-based initiator.

7. The double-curable silicone composition according to claim 1 or claim 2, wherein the thermal radical polymerization initiator of component (D) is an organic peroxide having a half-life of 10 hours at a temperature of 80°C or higher.

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