Photocurable silicone composition and its cured product

Abstract

The present invention provides a photoradical-curable silicone composition and its cured product that exhibit good adhesion to the components in contact with it during curing. [Solution] A photocurable silicone composition comprising the following components (A) to (C): (A) Organopolysiloxane having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl and methacryloyl groups per molecule: 100 parts by mass, (B) Photoradical polymerization initiator: 0.1 to 10 parts by mass, (C) Si-NR per molecule 1 Structure and Si-OR 2 Compounds having a structure [R 1 This is a monovalent hydrocarbon group having 1 to 12 carbon atoms or -R 3 -SiR 4 It is a group represented by 3, R 2 A photocurable silicone composition containing 0.1 to 10 parts by mass of , which is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms.

Description

【Technical Field】 【0001】 The present invention relates to a photocurable silicone composition and a cured product thereof. 【Background Art】 【0002】 Simplification and cost reduction in the manufacturing process overlap with the trend towards energy conservation considering the environment, and are being actively promoted in various fields. In particular, curable elastomers used in electronic components and structural components often involve a high-temperature heating process for curing, which requires a large amount of energy, time, and equipment, and thus improvement is demanded. Further, improvement of this heating process is also of great significance in terms of not only energy and cost but also manufacturing technology aspects such as not damaging other members. 【0003】 In recent years, in order to solve these problems, photocurable compositions have attracted attention. A photocurable composition contains a photoinitiator that is activated by irradiation with light, particularly ultraviolet light, and thereby a polymerization or crosslinking reaction proceeds, and it cures in a short time of usually several tens of seconds to ten and several minutes. Therefore, it is difficult to damage other members and large equipment is not required. Recently, ultraviolet irradiation devices using LEDs have also been developed, resulting in excellent manufacturing processes. 【0004】 Hitherto, for photocurable silicone compositions, methods using cationic photopolymerization (Patent Document 1), methods using radical polymerization (Patent Document 2), etc., have been proposed. In the former method, since the composition contains a compound that generates an acid upon light irradiation, when the above composition is used, for example, in an electric and electronic substrate, corrosion of the substrate is a concern. In the latter method, it has the characteristic that the reaction rate is fast due to its high reactivity and it cures in a short time, but on the other hand, it has a problem that it is difficult to adhere to members that are in contact during curing. 【Prior Art Documents】 【Patent Documents】 【0005】 【Patent Document 1】 Japanese Patent Publication No. 2024-025981 [Patent Document 2] Japanese Patent Publication No. 2023-071794 [Overview of the Initiative] [Problems that the invention aims to solve] 【0006】 The present invention has been made in view of the above circumstances, and aims to provide a photoradical-curable silicone composition and a cured product thereof that exhibit good adhesion to a component in contact with it during curing. [Means for solving the problem] 【0007】 In order to solve the above problems, the present invention provides: A photocurable silicone composition comprising the following components (A) to (C); (A) Organopolysiloxane having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl and methacryloyl groups in one molecule: 100 parts by mass, (B) Photoradical polymerization initiator: 0.1 to 10 parts by mass, (C) Si-NR in one molecule 1 Structure and Si-OR 2 Compounds having a structure [R 1 This is a monovalent hydrocarbon group having 1 to 12 carbon atoms or -R 3 -SiR 4 3 (wherein, R 3 R is a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms. 4 R is a group that is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a hydroxyl group. 2 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]: 0.1 to 10 parts by mass, The present invention provides a photocurable silicone composition characterized by containing [a specific substance]. 【0008】 Such a photocurable silicone composition is preferable because, by containing the above components (A) to (C), it can be cured in a short time by light irradiation, has good adhesion to the members it contacts during curing, and also has excellent storage stability. 【0009】 Moreover, in the photocurable silicone composition of the present invention, it is preferable that the component (C) is a compound represented by the following general formula (1). [Chemical Formula] (In the formula, R 1 and R 2 are as defined above, R 5 [[ID=1十七]]is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, q is an integer of 1 to 4, and r is 1 or 2.) 【0010】 [[ID=2十一]]If the component (C) is such a compound, it is preferable because it facilitates the compatibility of the adhesiveness and storage stability of the photocurable silicone composition of the present invention. 【0011】 Furthermore, in the photocurable silicone composition of the present invention, it is preferable that the component (A) is an organopolysiloxane represented by the following general formula (2). [[ID=二十八]][Chemical Formula] (In the formula, R 6 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 7 is independently a group having an acryloyl group or a methacryloyl group, s and t are integers of 1 to 3, and u is an integer of 10 to 5000.) 【0012】 With such a component (A), the photocurable silicone composition of the present invention can be made into a cured product having flexibility and being resistant to deformation. 【0013】 Furthermore, the photocurable silicone composition of the present invention may further contain (D) a bifunctional (meth)acrylate compound that does not contain a siloxane structure: 0.1 to 50 parts by mass. 【0014】 By adding such component (D), the hardness, tensile strength, and other properties of the cured product of the photocurable silicone composition of the present invention can be easily adjusted. 【0015】 Furthermore, the present invention can provide a cured product obtained by curing the photocurable silicone composition. 【0016】 The cured product of the photocurable silicone composition of the present invention exhibits excellent curability and good adhesion to various materials. [Effects of the Invention] 【0017】 As described above, the photocurable silicone composition and its cured product of the present invention can be cured in a short time by light irradiation, and also exhibits good adhesion to the components in contact with it during curing, as well as excellent storage stability, making them useful as adhesives for bonding various components. [Modes for carrying out the invention] 【0018】 As mentioned above, there was a need to develop a photoradical-curable silicone composition that exhibits good adhesion to the components in contact with it during curing. 【0019】 The inventors have conducted diligent studies to achieve the above objectives and have found that an organopolysiloxane having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl and methacryloyl groups in one molecule, a photoradical polymerization initiator, and Si-NR in one molecule 1 Structure and Si-OR 2 We discovered that a photocurable silicone composition containing a structured compound exhibits excellent curability, adhesion, and storage stability, thus completing the present invention. 【0020】 In other words, the present invention is A photocurable silicone composition comprising the following components (A) to (C); (A) Organopolysiloxane having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl and methacryloyl groups in one molecule: 100 parts by mass, (B) Photoradical polymerization initiator: 0.1 to 10 parts by mass, (C) Si-NR in one molecule 1 Structure and Si-OR 2 Compounds having a structure [R 1 This is a monovalent hydrocarbon group having 1 to 12 carbon atoms or -R 3 -SiR 4 3 (wherein, R 3 R is a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms. 4 R is a group that is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a hydroxyl group. 2 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]: 0.1 to 10 parts by mass, This is a photocurable silicone composition characterized by containing [a specific substance]. 【0021】 The present invention will be described in detail below, but the present invention is not limited to these descriptions. 【0022】 <Photocurable Silicone Composition> The photocurable silicone composition of the present invention contains the following components (A) to (C), and may optionally contain component (D) and other components. Each component will be described in detail below. 【0023】 <(A) component> Component (A) contained in the photocurable silicone composition of the present invention is an organopolysiloxane having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl and methacryloyl groups in one molecule, and is a component that cures by radical reaction. 【0024】 If there are two or more acryloyl groups or methacryloyl groups in a single molecule, or if there is one or more of both acryloyl and methacryloyl groups in a single molecule, and the total number of acryloyl and methacryloyl groups is one, the strength of the cured product will be insufficient. From the viewpoint of the flexibility of the cured product, it is preferable to have 2 to 20 groups per molecule, and more preferably 2 to 10 groups. 【0025】 The above component (A) is preferably an organopolysiloxane represented by the following general formula (2). [ka] (In the formula, R 6 These are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 7 (where is a group independently having either an acryloyl group or a methacryloyl group, s and t are integers from 1 to 3, and u is an integer from 10 to 5000.) 【0026】 In the above general formula (2), R 6 These are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably those having 1 to 8 carbon atoms and not having an aliphatic unsaturated bond. Specifically, these include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, or decyl groups, aryl groups such as phenyl, tolyl, xylyl, or naphthyl groups, aralkyl groups such as benzyl, phenylethyl, or phenylpropyl groups, or groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, or chlorine, or cyano groups, such as halogen-substituted alkyl groups such as chloromethyl, chloropropyl, bromoethyl, or trifluoropropyl groups, or cyanoethyl groups, but methyl or phenyl groups are preferred. 【0027】 In the above general formula (2), R 7These are groups that independently have an acryloyl group or a methacryloyl group, and specifically include acryloyloxy group, methacryloyloxy group, acryloyloxyalkyl group, methacryloyloxyalkyl group, acryloyloxyalkyloxy group, methacryloyloxyalkyloxy group, and the group represented by the following general formula (3). 【0028】 [ka] (In the formula, m is an integer from 0 to 20, n is 1 or 2, R 6 This is synonymous with the above, Z 1 Z is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, 2 (The atoms are oxygen atoms or divalent hydrocarbon groups with 1 to 10 substituted or unsubstituted carbon atoms, and the lines with wavy lines represent bonding bonds.) 【0029】 In the above general formula (3), m is an integer from 0 to 20, preferably from 0 to 5, and more preferably 0 or 1. Within this range, the methacrylic groups are fixed close together, resulting in good reactivity. 【0030】 In the above general formula (3), Z 1 Examples of divalent hydrocarbon groups represented by include alkylene groups such as methylene, ethylene, trimethylene, and propylene, and arylene groups such as phenylene. Among these, alkylene groups having 1 to 3 carbon atoms are preferred, and trimethylene groups are particularly preferred. 【0031】 In the above general formula (3), Z 2 Examples of divalent hydrocarbon groups represented by include alkylene groups such as methylene, ethylene, trimethylene, and propylene, and arylene groups such as phenylene. Among these, alkylene groups having 1 to 3 carbon atoms are preferred, and ethylene groups are particularly preferred. 【0032】 In the above general formula (2), R 7 The following groups are preferred. [ka] (In the equation, lines with a wavy line represent connections.) 【0033】 In the above general formula (2), s and t are integers from 1 to 3, and are preferably 2 or 3 from the viewpoint of further improving curability. 【0034】 In the above general formula (2), u is an integer between 10 and 5000, preferably between 10 and 1000. Within this range, a composition with good workability before curing and flexibility after curing is obtained. 【0035】 The viscosity of component (A) above at 25°C is preferably 10 to 1,000,000 mPa·s and it is liquid. The viscosity can be measured, for example, by a rotational viscometer. 【0036】 Specific examples of component (A) are shown below. The order of the diorganosiloxane units is arbitrary. [ka] 【0037】 Such organopolysiloxanes can be produced by known methods. For example, the polysiloxane represented by formula (4) above can be obtained as a hydrosilylation product of a trivinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer and 3-(1,1,3,3-tetramethyldisiloxanyl)propyl methacrylate (CAS No. 96474-12-3). 【0038】 The polysiloxanes represented by formulas (5) and (6) above can be obtained by reacting 2-hydroxyethyl acrylate with a hydrosilylated product of a dimethylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends or a dimethylsiloxane / diphenylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends and dichloromethylsilane. 【0039】 The polysiloxane represented by formula (7) above can be obtained as a hydrosilylation product of a dimethylsiloxane-diphenylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends and 3-(1,1,3,3-tetramethyldisiloxanyl)propyl methacrylate (CAS No. 96474-12-3). 【0040】 These (A) components may be used individually or in combination of two or more. 【0041】 <(B) component> Component (B) contained in the photocurable silicone composition of the present invention is a photoradical polymerization initiator that generates radicals upon exposure to light and cures the photocurable silicone composition of the present invention by a radical polymerization reaction. 【0042】 As component (B) above, any photoradical polymerization initiator known in the art for curing (meth)acrylate compounds such as benzoin and substituted benzoin, dialkoxyacetophenone such as diethoxyacetophenone, benzophenone and substituted benzophenone, acetophenone and substituted acetophenone, xanthone and substituted xanthone can be used. 【0043】 The amount of component (B) is 0.1 to 10 parts by mass, preferably 0.2 to 8 parts by mass, and more preferably 0.5 to 6 parts by mass, per 100 parts by mass of component (A). If the amount of component (B) is less than 0.1 parts by mass, the curability will be insufficient, and if it exceeds 10 parts by mass, the mechanical properties of the cured product may deteriorate. 【0044】 The above component (B) may be used alone or in combination of two or more types. 【0045】 <(C) component> The (C) component contained in the photocurable silicone composition of the present invention contains Si-NR in one molecule. 1 Structure and Si-OR 2It is a compound having a structure and is a component for imparting adhesion to the photocurable silicone composition of the present invention. [R 1 This is a monovalent hydrocarbon group having 1 to 12 carbon atoms or -R 3 -SiR 4 3 (wherein, R 3 R is a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms. 4 R is a group that is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a hydroxyl group. 2 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. 【0046】 The above R 1 This is a monovalent hydrocarbon group having 1 to 12 carbon atoms or -R 3 -SiR 4 3 (wherein, R 3 R is a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms. 4 This is a group that is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a hydroxyl group. 【0047】 The above R 1 and the above R 4 Preferably, monovalent hydrocarbon groups have 1 to 8 carbon atoms. Specifically, examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, or decyl groups; alkenyl groups such as vinyl, allyl, butenyl, hexenyl, or octenyl groups; aryl groups such as phenyl, tolyl, xylyl, or naphthyl groups; and aralkyl groups such as benzyl, phenylethyl, or phenylpropyl groups. Among these, methyl and phenyl groups are preferred. 【0048】 The above R 3The divalent hydrocarbon group is preferably one having 1 to 8 carbon atoms, and examples include alkylene groups such as methylene, ethylene, trimethylene, propylene, hexylene, and octylene, and arylene groups such as phenylene, with trimethylene being more preferred. 【0049】 The above R 4 The alkoxy group is preferably one having 1 to 4 carbon atoms, and examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, and t-butoxy groups, with methoxy and ethoxy groups being more preferred. 【0050】 The above -R 3 -SiR 4 Specific examples of the group represented by 3 include trimethylsilyl group, triethylsilyl group, dimethylvinylsilyl group, methylphenylvinylsilyl group, trimethoxysilyl group, triethoxysilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group, 3-trimethoxysilylpropyl group, and 3-triethoxysilylpropyl group, with trimethylsilyl group, trimethoxysilyl group, and 3-trimethoxysilylpropyl group being preferred. 【0051】 The above R 2 R is a monovalent hydrocarbon group consisting of a hydrogen atom or 1 to 12 carbon atoms. 1 and R 4 Examples of groups similar to those exemplified are given, with methyl and ethyl groups being preferred. 【0052】 From the viewpoint of storage stability and curability, it is preferable that component (C) described above does not have an NH structure. 【0053】 A preferred component (C) is a compound represented by the following general formula (1). By including a compound with such a structure as component (C), the photocurable silicone composition of the present invention can achieve both better adhesion and storage stability. [ka] (In the formula, R 1 and R 2 This is synonymous with the above, and R 5 (where is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, q is an integer from 1 to 4, and r is 1 or 2.) 【0054】 In the above general formula (1), R 5 Preferably, monovalent hydrocarbon groups have 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, or decyl groups; alkenyl groups such as vinyl, allyl, butenyl, hexenyl, or octenyl groups; aryl groups such as phenyl, tolyl, xylyl, or naphthyl groups; aralkyl groups such as benzyl, phenylethyl, or phenylpropyl groups, or groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, or chlorine, or cyano groups, such as halogen-substituted alkyl groups such as chloromethyl, chloropropyl, bromoethyl, or trifluoropropyl, or cyanoethyl groups. Among these, methyl and phenyl groups are preferred. 【0055】 In the above general formula (1), q is an integer from 1 to 4, and is preferably 1 or 2 from the viewpoint of adhesion. 【0056】 In the above general formula (1), r is 1 or 2, and r is preferably 2 from the viewpoint of adhesion. 【0057】 The amount of component (C) is 0.1 to 10 parts by mass, preferably 0.2 to 8 parts by mass, and more preferably 0.5 to 6 parts by mass, per 100 parts by mass of component (A). If the amount of component (C) is less than 0.1 parts by mass, the adhesion will be insufficient, and if it exceeds 10 parts by mass, the mechanical properties of the cured product may deteriorate. 【0058】 The above component (C) may be used alone or in combination of two or more types. 【0059】 <(D) component> The photocurable silicone composition of the present invention may contain, as component (D), 0.1 to 50 parts by mass of a bifunctional (meth)acrylate compound that does not contain a siloxane structure, per 100 parts by mass of component (A), for the purpose of adjusting the mechanical properties such as the hardness and tensile strength of the resulting cured product. From the viewpoint of the hardness and tensile strength of the cured product, the preferred amount to add is 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass. 【0060】 Specific examples of component (D) above include, but are not limited to, the following compounds. [ka] 【0061】 The above component (D) may be used alone or in combination of two or more types. 【0062】 <Other ingredients> Depending on the purpose, the photocurable silicone composition of the present invention may also contain other components besides component (C) above, such as adhesion improvers, radical reaction inhibitors, and reinforcing fillers. 【0063】 Other adhesion enhancers besides component (C) above can include organosilicon compounds such as silanes and siloxanes containing functional groups that impart adhesion, and non-silicone organic compounds. 【0064】 Examples of organosilicon compounds containing the functional group that imparts the above-mentioned adhesive properties include silane coupling agents, siloxanes having an alkoxysilyl group and an organic functional group, and compounds obtained by introducing an alkoxysilyl group into an organic compound having a reactive organic group. 【0065】 Examples of the non-silicone organic compounds mentioned above include allyl organic acid esters, epoxy ring-opening catalysts, organotitanium compounds, organozirconium compounds, and organoaluminum compounds. 【0066】 Examples of the radical reaction inhibitors mentioned above include phenolic antioxidants such as dibutylhydroxytoluene (BHT) and amine-based antioxidants such as diphenylamine derivatives. 【0067】 The above-mentioned reinforcing fillers may include inorganic fillers such as fine silica powder, crystalline silica, hollow fillers, and silsesquioxane, as well as fillers obtained by surface hydrophobizing these fillers with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds, silicone rubber powder, silicone resin powder, etc. 【0068】 Furthermore, monofunctional or trifunctional (meth)acrylate compounds may be added to the photocurable silicone composition of the present invention in order to adjust the viscosity and curability of the photocurable silicone composition before curing, and to improve the physical properties of the cured product. 【0069】 [Cured product] The photocurable silicone composition of the present invention can provide a cured product obtained by curing the photocurable silicone composition. 【0070】 The light source used for cleaving the photoradical polymerization initiator is not particularly limited, but an ultraviolet source is useful. Examples include UV-LED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and xenon lamps. A useful ultraviolet wavelength range is preferably 220 to 400 nm. 【0071】 For curing the photocurable silicone composition of the present invention, the irradiation intensity of the light source used is 30 to 2,000 mW / cm². 2 Preferably, the irradiation dose is 150 to 20,000 mJ / cm². 2 This is preferable. The irradiation temperature is preferably 10 to 60°C, and more preferably 20 to 40°C. 【0072】 The photocurable silicone composition of the present invention can be used as an adhesive. The material of the adherend to the adhesive containing the composition of the present invention is not limited, and examples include semiconductors, metals, organic resins, etc. [Examples] 【0073】 The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these. 【0074】 [Examples 1-6 and Comparative Examples 1-3] A photocurable silicone composition was prepared by mixing the components listed below in the amounts (parts by mass) shown in Table 1 below. Component (C-1) was prepared using the same method as described in Japanese Patent Publication No. 2011-162500, and component (C-2) was prepared using the same method as described in Japanese Patent Publication No. 2024-55241. 【0075】 (A) Ingredients: (A-1) An organopolysiloxane represented by the following formula (4) (viscosity at 25°C is 10 Pa·s, and the arrangement order of the diorganosiloxane units is undefined.) [ka] (A-2) Organopolysiloxane represented by the following formula (5) (viscosity 1.2 Pa·s at 25°C) [ka] (A-3) Organopolysiloxane represented by the following formula (6) (viscosity at 25°C is 3.4 Pa·s, and the arrangement order of diorganosiloxane units is undefined.) [ka] (A-4) Organopolysiloxane represented by the following formula (7) (viscosity at 25°C is 5.0 Pa·s, and the arrangement order of diorganosiloxane units is undefined.) [ka] 【0076】 (B) Ingredients: (B-1) Ethyl (2,4,6-trimethylbenzoyl)-phenyl phosphenate (Omnirad TPO-L, manufactured by IGM Resins BV) (B-2)2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)butan-1-one (Omnirad 379EG, manufactured by IGM Resins BV) 【0077】 (C) Ingredients: (C-1) Compound represented by the following structural formula (8) [ka] (C-2) Compound represented by the following structural formula (9) [ka] (C-3) (for comparison) 3-aminopropyltrimethoxysilane (C-4) (for comparison) N-2-(aminoethyl)-3-aminopromiltrimethoxysilane 【0078】 (D) Ingredients: Tricyclodecanedimethanol dimethacrylate (isomer mixture) 【0079】 [Table 1] 【0080】 The photocurable silicone compositions obtained in Examples 1-6 and Comparative Examples 1-3 were evaluated as follows, and the results are shown in Table 2. The compositions were cured using a lamp H(M)06-L-61 manufactured by iGraphics Co., Ltd., in air at room temperature, with an irradiation dose of 10,000 mJ / cm² of ultraviolet light at a wavelength of 365 nm. 2 Light irradiation was performed to achieve the following result. 【0081】 [Surface hardening] The composition was irradiated with light to produce a 10 mm thick cured product. Products with a solidified irradiated surface were considered good, while those that remained liquid in any part were considered poor. 【0082】 [Hardness] The composition was irradiated with light to produce a 6.0 mm thick cured material. The hardness immediately after curing at 25°C was measured using a durometer type A hardness tester. 【0083】 [Adhesiveness] The composition was dropped onto a copper plate, irradiated with light, and then left to stand for 24 hours at 25°C. Immediately afterward, the cured material was peeled off and tested. Materials that could not be peeled off and were destroyed were classified as bonded, while those that could be peeled off were classified as peeled. 【0084】 [Storage test] The composition was placed in a glass bottle, sealed, and stored at 23°C for two days. Afterward, surface hardening, hardness, and adhesion were confirmed using the method described above. 【0085】 [Table 2] 【0086】 As shown in Table 2 above, Examples 1 to 6 using the photocurable silicone composition of the present invention exhibited good surface curability, hardness, and adhesion, and their performance did not change even after storage at 23°C for two days. 【0087】 On the other hand, Comparative Example 1, which did not contain component (C) of the photocurable silicone composition of the present invention, showed no adhesive properties at all. Furthermore, Comparative Examples 2 and 3, in which an alkoxysilane compound having an amino group was added instead of component (C), showed deterioration in surface curability after storage at 23°C for 2 days, and the hardness of the cured product also decreased. 【0088】 This specification includes the following embodiments. [1]: A photocurable silicone composition comprising the following components (A) to (C); (A) Organopolysiloxane having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl and methacryloyl groups in one molecule: 100 parts by mass, (B) Photoradical polymerization initiator: 0.1 to 10 parts by mass, (C) Si-NR in one molecule 1 Structure and Si-OR 2 Compounds having a structure [R 1 This is a monovalent hydrocarbon group having 1 to 12 carbon atoms or -R 3 -SiR 4 3 (wherein, R 3 R is a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms. 4 R is a group that is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a hydroxyl group. 2 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. ]: 0.1 to 10 parts by mass, A photocurable silicone composition characterized by containing [a specific substance]. [2]: The photocurable silicone composition according to [1], characterized in that the (C) component is a compound represented by the following general formula (1). [ka] (In the formula, R 1 and R 2 This is synonymous with the above, and R 5 (where is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, q is an integer from 1 to 4, and r is 1 or 2.) [3]: The photocurable silicone composition according to [1] or [2], characterized in that the component (A) is an organopolysiloxane represented by the following general formula (2). [ka] (In the formula, R 6 These are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 7(where is a group independently having either an acryloyl group or a methacryloyl group, s and t are integers from 1 to 3, and u is an integer from 10 to 5000.) [4]: The photocurable silicone composition comprises (D) a bifunctional (meth)acrylate compound that does not contain a siloxane structure: 0.1 to 50 parts by mass, A photocurable silicone composition according to any one of [1] to [3], characterized in that it further contains the following. [5]: A cured product of a photocurable silicone composition as described in any one of items [1] to [4]. 【0089】 It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

[Claim 1] A photocurable silicone composition comprising the following components (A) to (C): (A) Organopolysiloxane having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl and methacryloyl groups in one molecule: 100 parts by mass, (B) Photoradical polymerization initiator: 0.1 to 10 parts by mass, (C) Si-NR in one molecule １ Structure and Si-OR ２ Compounds having a structure [R １ is a monovalent hydrocarbon group having 1 to 12 carbon atoms or -R ３ -SiR ４ ３ (wherein R ３ is a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms, and R ４ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a hydroxy group).), and R ２ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms.]: 0.1 to 10 parts by mass, A photocurable silicone composition characterized by containing [a specific substance]. [Claim 2] The photocurable silicone composition according to claim 1, characterized in that the (C) component is a compound represented by the following general formula (1). 【Chemistry 1】 (In the formula, R １ and R ２ This is synonymous with the above, and R ５ (where is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, q is an integer from 1 to 4, and r is 1 or 2.) [Claim 3] The photocurable silicone composition according to claim 1, characterized in that the component (A) is an organopolysiloxane represented by the following general formula (2). 【Chemistry 2】 (In the formula, R ６ R is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, ７ (where is a group independently having either an acryloyl group or a methacryloyl group, s and t are integers from 1 to 3, and u is an integer from 10 to 5000.) [Claim 4] The photocurable silicone composition comprises (D) a difunctional (meth)acrylate compound that does not contain a siloxane structure: 0.1 to 50 parts by mass, The photocurable silicone composition according to claim 1, further comprising the above. [Claim 5] A cured product of a photocurable silicone composition according to any one of claims 1 to 4.

Images