Dual cure 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 TO RELATED APPLICATIONS This application claims priority to and all benefits of U.S. Provisional Patent Application No. 63 / 213,281, filed June 22, 2021, the contents of which are incorporated herein by reference.

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

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

[0004] However, such curable silicone compositions have the problem that they are not sufficiently cured by amine compounds or other types of strong bases that are typically used to neutralize photoresist materials commonly applied in various electrical / electronic applications, i.e., residual amine compounds or strong bases on the substrate cause serious cure 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 photocurable resin compositions have the problem that they are not sufficiently cured by atmospheric oxygen, and as a result, the cured products exhibit a sticky surface with poorer mechanical properties.

[0007] Therefore, there remains an opportunity to develop a curable silicone composition that has excellent curing properties without being inhibited by air or amine compounds. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] US Patent Application Publication No. 2014 / 154626A1 [Patent Document 2] Patent Publication No. 2013-095874A [Patent Document 3] European Patent Application Publication No. 2772505A1 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a dual-cure silicone composition that has excellent curing properties without being inhibited by air and amine compounds. [Means for solving the problem]

[0010] The dual cure silicone composition of the present invention comprises: (A) 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 (In the formula, each R 1 is C 1~6 Monovalent aliphatic hydrocarbon radical, C6~10 The same or different organic groups selected from a monovalent aromatic hydrocarbon group and a monovalent epoxy-substituted organic group, 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), represented by an epoxy-functional silicone resin (A1). 6~10 Or, a mixture of the above component (A1) and the following general formula (2): Or, a mixture of 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 is a monovalent epoxy-substituted organic group and the following general formula (3): 1 is a monovalent epoxy-substituted organic group and the following general formula (3): X 2 -R 3 2SiO(SiR 3 2O) x SiR 3 2-R 4 - (In the formula, each R 3 is the same or different monovalent aliphatic hydrocarbon group, R 1~6 is an alkylene group, X 4 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), and is selected from the same or different groups represented by an epoxy-functional siloxy group), represented by an epoxy-functional silicone (A2)), represented by an epoxy-functional silicone selected from a mixture of (A2). 2~6 アルキレン基であり、X 2 は、一価エポキシ置換有機基であり、「x」は、約0~約5の数であり、「m」は約0~約100の数である)で表されるエポキシ官能性シロキシ基から選択される、同じか又は異なる基である)で表されるエポキシ官能性シリコーン(A2)との混合物から選択される、エポキシ官能性シリコーン; (B) at least one radically polymerizable compound having at least one acrylic or methacrylic group per molecule, in an amount of about 15% by weight to about 75% by weight of the total weight of components (A)-(D); (C) a photoacid generator and / or a thermal acid generator in an amount of about 0.1% to about 5% by weight of the total weight of components (A)-(D); and (D) a photoradical polymerization initiator and / or a thermal radical polymerization initiator in an amount of about 0.1% by mass to about 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 weight of the mixture of components (A1) and (A2).

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

[0013] In various embodiments, component (B) includes 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) includes or is at least one of a sulfonium salt or an iodonium salt.

[0015] In various embodiments, the photoradical polymerization initiator for component (D) includes or is at least one of an acetophenone-based initiator, a benzil-based initiator, a benzophenone-based initiator, a thioxanthone-based initiator, an acylphosphine oxide-based initiator, or an oxime-based initiator.

[0016] In various embodiments, the thermal radical polymerization initiator for component (D) is an organic peroxide that has a half-life of 10 hours at a temperature of 80° C. or greater. Effect of the Invention

[0017] The dual-cure silicone composition of the present invention has excellent curability without being inhibited by air or amine compounds. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The terms "comprising" or "comprise" are used herein in their broadest sense to mean and encompass the ideas of "including," "include," "consist(ing) essentially of," and "consist(ing) of." The use of "for example," "eg," "such as," and "including" to list examples does not limit the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples. As used herein, the term "about" serves to reasonably encompass or account for slight variations in numerical values ​​as determined by instrumental analysis or as a result of handling samples. Such minor variations may be as little as ±0-25%, ±0-10%, ±0-5%, or ±0-2.5% of the numerical value. Furthermore, the term "about" applies to both numerical values ​​when referring to a range of values. Furthermore, the term "about" may apply to multiple numerical values, even if not expressly stated otherwise. In general, as used herein, ">" means "greater than" or "more 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 term "epoxy functional" or "epoxy substituted" refers to a functional group in which the oxygen atom of the epoxy substituent is directly bonded to two adjacent carbon atoms of 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 groups; (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 groups; and epoxyalkyl groups such as 2,3-epoxypropyl, 3,4-epoxybutyl, and 4,5-epoxypentyl groups.

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

[0021] <Dual-cure silicone composition> Component (A) is an epoxy-functional silicone selected from the following: (A1) 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 or a mixture of the above component (A1) and (A2) an epoxy-functional silicone resin represented by the following general formula (2): X 1 -R 2 2SiO(SiR 2 2O) m SiR 2 2-X 1

[0022] In the formula, each R 1 is C 1~6 Monovalent aliphatic hydrocarbon radical, C 6~10 are the same or different organic groups 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 are C 1~6 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, and hexyl groups); C 2~6 Alkenyl groups (e.g., vinyl, allyl, and hexenyl groups); and C 1~6 Halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl are included. Among these, methyl groups are generally preferred.

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

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

[0026] In component (A1), all R 1At least about 15 mol%, optionally at least about 20 mol%, or optionally at least about 25 mol% is C 6~10 A monovalent aromatic hydrocarbon group. If 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, because if the (R 1 3SiO 1 / 2 ) siloxane unit is too much, the molecular weight of the epoxy-containing organopolysiloxane resin (A1) decreases, and when the (SiO 4 / 2 ) siloxane unit is 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 the formation of 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 ) siloxane units, and its molecular structure is in most cases a network structure or a three-dimensional structure, since the molar ratio of "b / c" is greater than about 0.1 and less than about 0.6. Thus, 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 ) The siloxane unit is an optional building block. That is, there may be an epoxy-functional silicone resin having the average unit formula: (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), about 2 mol% to about 30 mol%, optionally about 10 mol% to about 30 mol%, or optionally about 15 mol% to about 30 mol% of the siloxane units in the molecule have an epoxy-substituted organic group. If such siloxane units are present at or above the lower limit of the above range, the crosslink density during curing can be improved. On the other hand, if this amount is below the upper limit of the above range, the heat resistance of the cured product can be improved, which may be preferable. In the epoxy-functional monovalent hydrocarbon group, the epoxy group can be bonded to the silicon atom via an alkylene group, so that the epoxy group is not directly bonded to the silicon atom. The epoxy-functional silicone resin (A1) can be produced by known conventional manufacturing methods.

[0029] There is no particular limitation on the weight average molecular weight of the epoxy-functional silicone resin (A1). However, taking into consideration the toughness of the cured product and its solubility in organic solvents, in some embodiments, the molecular weight is about 10 3 More than or equal to about 10 6 In one embodiment, the epoxy-functional silicone resin (A1) comprises a combination of two or more such epoxy-functional silicone resins having different contents and types of epoxy-containing organic groups and monovalent hydrocarbon groups, or having different molecular weights.

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

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

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

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

[0035] X 1 Examples of monovalent epoxy-substituted organic groups include: glycidoxyalkyl groups (e.g., 3-glycidoxypropyl, 4-glycidoxybutyl, and 5-glycidoxypentyl groups, etc.); 3,4-epoxycycloalkyl 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, etc.); and epoxyalkyl groups (2,3-epoxypropyl, 3,4-epoxybutyl, and 4,5-epoxypentyl groups, etc.). Among them, 3,4-epoxycycloalkylalkyl groups are generally preferred.

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

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

[0038] In the above formula (3), X 2 is a monovalent epoxy-substituted organic group. 2 Examples of monovalent epoxy-substituted organic groups include: glycidoxyalkyl groups (e.g., 3-glycidoxypropyl, 4-glycidoxybutyl, and 5-glycidoxypentyl groups, etc.); 3,4-epoxycycloalkyl 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, etc.); and epoxyalkyl groups (2,3-epoxypropyl, 3,4-epoxybutyl, and 4,5-epoxypentyl groups, etc.). Among them, 3,4-epoxycycloalkylalkyl groups are generally preferred.

[0039] In the above formula (3), "x" is a number from about 0 to about 5, optionally from about 0 to about 2, or optionally about 0.

[0040] In the above formula (2), "m" is a number of about 0 to about 100, optionally about 0 to about 20, or optionally about 0 to about 10. When "m" is equal to or less than 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 a liquid. The viscosity of component (A2) at 25°C is not limited, but is generally within the range of about 5 to about 100 mPa s. In this specification, the viscosity is a value measured at 23±2°C using a B-type viscometer in accordance with ASTM D1084.

[0042] The content of component (A2) in the mixture of components (A1) and (A2) is not limited, but is generally up to 80% by weight, optionally up to 70% by weight, optionally about 10% to about 70% by weight, and optionally about 15% to about 65% by weight of the mixture of components (A1) and (A2). If the content of component (A2) is equal to or greater than 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 equal to or less than the upper limit of the above range, inhibition and delay due to oxygen in the cured product may occur, leading to a decrease in elastic modulus and tensile strength.

[0043] Component (B) is at least one radically polymerizable compound having at least one acrylic or methacrylic group per molecule. Examples of the component (B) include mono(meth)acrylates (e.g., isobornyl acrylate, 2-hydroxyethyl methacrylate, and 2-phenoxyethyl acrylate); (meth)acrylate compounds of dihydric alcohols (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, octadec ... cyclohexanediol 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., , triglycerol tetra(meth)acrylate, triglycerol penta(meth)acrylate, etc.); (meth)acrylate compounds of hexahydric alcohols (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 end, etc.);

[0044] Component (B) is commercially available, and examples thereof include 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 Co., Ltd.); and compounds having a structure in which a (meth)acryloyl group is bonded via an ethylene glycol and / or propylene glycol residue (e.g., SR454 and SR499 commercially available from Sartomer).

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

[0046] Component (C) is a photoacid generator and / or a thermal acid generator that improves the curing of 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, paratoluenesulfonates, trichloromethyl-substituted triazines, and trichloromethyl-substituted benzenes. Among these, sulfonium salts and iodonium salts are preferred because the composition exhibits excellent curability upon exposure to ultraviolet light or heat and ultraviolet light. 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] Examples of sulfonium salts include those of the formula R c 3S + X - In the formula, R c is a methyl group, an ethyl group, a propyl group, a butyl group, and other C 1~6 Alkyl groups: phenyl, naphthyl, biphenyl, tolyl, propylphenyl, decylphenyl, dodecylphenyl, and other C 1~24 In addition, in the formula, X may represent an aryl group or a substituted aryl group. - is SbF6 - , AsF6 - , PF6 - , BF4 - , B(C6F5)4 - , HSO4 - , ClO4 - , CF3SO3 -, and other non-nucleophilic non-basic anions.

[0048] Examples of iodonium salts include those of the formula R c 2I + X - Examples of selenonium salts include salts represented by the formula R c 3Se + X - Examples of phosphonium salts include salts represented by the formula R c 4P + X - Examples of diazonium salts include salts represented by the formula R c N2 + X - In addition, the salt represented by the formula c and X - is R c 3S + X - is the same as that described herein.

[0049] Examples of paratoluenesulfonates include those of the formula CH3C6H4SO3R c1 In addition, the compound represented by the formula c1 represents an organic group containing an electron withdrawing group such as a benzoylphenylmethyl group, a phthalimido group, and the like.

[0050] Examples of trichloromethyl-substituted triazines include [CC13]2C3N3R c2 In addition, the compound represented by the formula c2 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 In addition, the compound represented by the formula c is R c 3S + X -is the same as described herein for R c3 represents halogen groups, halogen-substituted alkyl groups, 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 about 0.1% by mass to about 5% by mass, optionally about 0.5% by mass to about 5% by mass, optionally about 0.1% by mass to about 3% by mass, or optionally about 0.1% by mass to about 2% by mass, based on the total mass of components (A) to (D). If the content of component (C) is equal to or greater than the lower limit of the above range, the curable silicone composition may turn yellow or the curing speed may be too fast, resulting in a shortened pot life. On the other hand, if the content is equal to or less than the upper limit of the above range, the curing speed of the cured product may be slowed down, and the product may not be completely cured in the end.

[0054] Component (D) is a photoradical polymerization initiator and / or a 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 the photoradical polymerization initiator of 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-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1 -hydroxycyclohexyl phenyl 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; benzyl initiators (e.g. For example, diphenyl diketone, and bis(4-methoxyphenyl) diketone; benzophenone-based initiators (for example, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide); thioxanthone-based initiators (for example, thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropyl ... xanthone, and 2,4-diethylthioxanthone, etc.); acylphosphine oxide initiators (e.g., 2-methylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphineate, 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-benzoyloxime), 1-{(4-phenylthio)phenyl}-1,2-octanedione-2-(O-benzoyloxime), 1-{(4-phenylthio)phenyl}-1-octanone-1-(O-acetyloxime), 1-{4-(2-hydroxyethoxyphenylthio)phenyl}-1,2-propanedione-2-(O-acetyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazolyl]-1,2-dione-2-(O-acetyloxime), Examples of the photoradical polymerization initiator include (9-ethyl-6-nitro-9H-carbazol-3-yl){4-(2-methoxy)-1-methylethoxy}-2-methylphenyl}methanone (O-acetyloxime, etc.). As the photoradical polymerization initiator, a benzophenone-based initiator is preferred, and 2-hydroxy-2-methylpropiophenone is more preferred, because the reactivity of component (B) is good. The photoradical polymerization initiator may be used alone or in combination of two or more kinds.;

[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-butyl peroxybenzoate, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate ... , 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 , tert-butylperoxyisopropyl monocarbonate, di-(2-tert-butylperoxyisopropyl)benzene, or a combination of two or more thereof. 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 a temperature of 80°C or higher, optionally 90°C or higher, and further optionally 100°C or higher. When the temperature is equal to or higher than the above lower limit, the composition exhibits good stability at room temperature. The upper limit of the temperature is not particularly limited, but is preferably 130°C or lower, since the composition tends not to be sufficiently cured if the temperature is 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)hexyne-3, di-(2-tert-butylperoxyisopropyl)benzene, and the like. In general, dicumyl peroxide is most preferred due to its good miscibility with other components in the composition.

[0057] The content of component (D) is about 0.1% by mass to about 5% by mass, optionally about 0.1% by mass to about 3% by mass, optionally about 0.1% by mass to about 2% by mass, or optionally about 0.5% by mass to about 2% by mass, based on the total mass of components (A) to (D). If the content of component (D) is equal to or greater than the lower limit of the above range, the curable silicone composition is not stable at room temperature and its pot life is reduced. On the other hand, if the content is equal to or less than the upper limit of the above range, the radical components in the cured product cannot be sufficiently cured, and inhibition by oxygen may occur more frequently.

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

[0059] Examples of adhesion promoters include epoxy-functional 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-methacryloyloxysilane, 3-methylphenyltrimethoxysilane, 3-methylphenyltriethoxy ... propyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof; epoxy-functional siloxanes having alkoxy groups bonded to silicon atoms, such as the reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane (such as any of those described above), or a physical blend of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane. The adhesion promoter may include a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the adhesion promoter is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane with a reaction product of hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane with hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

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

[0061] Examples of photosensitizers include isopropyl-9H-thioxanthen-9-one, anthrone, 1-hydroxycyclohexyl-phenyl ketone, 2,4-diethyl-9H-thioxanthen-9-one, 2-isopropylthioxanthen, 2-hydroxy-2-methyl-phenylpropan-1-one, 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT), pentaerythritol tetrakis[3-(3,5-di-tert-butyl)phenyl]-2,3-dihydro-2,4-trimethylphenyl]-2,5-triazabicyclo[3-(3,5-di-tert-butyl) ... octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[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 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, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], and hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0062] The content of the photosensitizer is not limited, but if used, it is generally within the range of about 0.001 to about 1 mass %, optionally within the range of about 0.005 to about 0.5 mass %, or optionally within the range of about 0.005 to about 0.1 mass % of the total mass of components (A) to (D) and the photosensitizer. If the content of the photosensitizer is equal to or higher than the lower limit of the above range, the curability of the cured product may be improved. On the other hand, if the content is equal to or lower than 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); and polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, propylene glycol, 1,10-decanediol, glycerol, and pentaerythritol).

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

[0065] Inorganic fillers increase the mechanical strength of the cured product. Examples of fillers include one or more of micronized or untreated precipitated silica, or fumed silica; precipitated or ground calcium carbonate, zinc carbonate; clays (such as micronized kaolin, etc.); ground quartz; aluminum hydroxide; zirconium silicate; diatomaceous earth; wollastonite; pyrophyllite; and metal oxides (such as fumed or precipitated titanium dioxide, cerium oxide, magnesium oxide powder, zinc oxide, iron oxide, etc.).

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

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

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

[0069] The cured product is flexible and highly transparent, and is therefore useful as an optical member or part that is transparent to light, such as visible light, infrared light, ultraviolet light, far ultraviolet light, X-rays, lasers, and the like. The cured product is also useful as an optical member or part that must be flexible, for example, for use in a bent or curved state, and is also useful as an optical member or part for a device involving high-energy, high-output light. In addition, by producing a composite material in which the cured product is formed into a single article or body together with any of a variety of substrates, an article or part having a flexible cured product layer can be produced, and impact and stress relaxation functions can also be expected from the cured product layer. EXAMPLES

[0070] Here, the dual curing silicone composition of the present invention will be described in detail with examples and comparative examples. Please note that in the formula, "Me", "Pr", "Ph" and "Ep" respectively represent methyl, propyl, phenyl and 2-(3,4-epoxycyclohexyl)ethyl groups. The structure of the epoxy-functional silicone resin used in the examples is: 13 C NMR and 29The molecular weights of the epoxy-functional silicone resins were determined by Si NMR measurements. The weight average molecular weights of the epoxy-functional silicone resins were calculated using GPC based on comparison with polystyrene standards. The viscosities of the epoxy-functional silicones and silicone resins were measured as follows.

[0071] <Viscosity> The viscosity at 23±2° C. was measured according to ASTM D1084 “Standard Test Methods for Viscosity of Adhesive” by using a Brookfield HA or HB Type rotational viscometer (using spindle #52, 5 rpm).

[0072] <Examples 1 to 10 and Comparative Examples 1 to 7> The following components were used to prepare the dual-cure silicone compositions shown in Table 1 (by weight):

[0073] The following epoxy-functional silicone resin was used as component (A1): (a1): An 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-functional silicones were used as component (A2): (a2): An epoxy-functional silicone having a viscosity of 40 mPa·s, a weight average molecular weight of 382, ​​and 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] As component (C), the following photo- or thermal acid generator was used. (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 light / thermal radical initiators were used as component (D): (d1): 2-hydroxy-2-methylpropiophenone (d2): Dicumyl peroxide

[0078] <Curability of dual-cure silicone composition> Approximately 0.1 to 3 g of each dual-cure silicone composition was loaded onto a slide glass previously coated with triethylamine or triisopropanolamine. After flattening the surface level with a bar coater, the slide glass was coated with 5000 mW / cm 2 The dual cure silicone composition is cured by passing it through a metal halide UV lamp with a D-type bulb with a light intensity of 1000 nm or by heating in air (150° C. for 1 hour). The curability of the dual cure silicone composition was evaluated. The results are shown in Table 1.

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

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

[0081] [Table 1]

[0082] [Table 2]

[0083] [Table 3] [Industrial Applicability]

[0084] The dual-cure silicone composition of the present invention can be cured without inhibition by air and amine compounds, and is therefore useful as a variety of adhesives, encapsulants, coatings, and the like for electrical / electronic applications.

Claims

1. A dual-curing 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 (In the formula, each R １ is the same or different organic group selected from C １～６ monovalent aliphatic hydrocarbon group, C ６～１０ monovalent aromatic hydrocarbon group, and monovalent epoxy-substituted organic group. However, at least about 15 mol% of all R １ is C ６～１０ monovalent aromatic hydrocarbon group; "a", "b", "c", and "d" satisfy 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 Or, the component (A1) and the following general formula (2): X １ -R ２ ２ SiO(SiR ２ ２ ) ｍ SiR ２ ２ -X １ (In the formula, each R ２ is the same or different organic group selected from C １～６ monovalent aliphatic hydrocarbon group and C ６～１０ 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 ２ O) ｘ SiR ３ ２ -R ４ - (In the formula, each R ３ is the same or different C １～６ monovalent aliphatic hydrocarbon group, and 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), and is selected from the same or different groups selected from epoxy-functional siloxy groups represented by), an epoxy-functional silicone selected from a mixture with an epoxy-functional silicone (A2); (B) At least one radically polymerizable compound having at least one acrylic group or methacrylic group per molecule and in an amount of about 15% by mass to about 75% by mass of the total mass of components (A) to (D); (C) A photoacid generator and / or a thermal acid generator in an amount of about 0.1% by mass 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 in an amount of about 0.1% by mass to about 5% by mass of the total mass of components (A) to (D), A dual-curable silicone composition containing.

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

3. The dual-curable 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-hydroxyethyl methacrylate, 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate diacrylate, or 2-phenoxyethyl acrylate.

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

6. The double-curable silicone composition according to claim 1 or claim 2, wherein the photo radical 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.