UV-curable silicone composition and cured product thereof

Abstract

To provide a UV-curable silicone composition that yields a cured product having releasability.SOLUTION: A silicone composition comprises: (A) a polysiloxane having (a) a unit represented by the following formula (1): (R1 represents a monovalent hydrocarbon group, R2 represents an oxygen atom or the like, R3 represents an acryloyloxyalkyl group or the like, p represents 0≤p≤10, and a represents 1≤a≤3), and (b) a unit of R1Rf1SiO2 / 2 (R1 is the same as above; Rf1 represents a C1-8 fluorinated alkyl group), wherein 5% or more of the monovalent organic groups on Si are the fluorinated alkyl group Rf1; (B) a polysiloxane resin in which 5% or more of the monovalent organic groups on Si are CF3 groups; and (C) a photopolymerization initiator.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an ultraviolet-curable silicone composition and a cured product thereof. [Background technology]

[0002] For materials with fine patterns formed on their surfaces, such as lens materials for 3D sensors, imprint molding using a mold is generally used. There are two types of imprint molding: one is to mold the desired material directly from a metal mold, and the other is to create a replica mold from the metal mold and then replicate the lens material from the replica mold. The latter method is much more advantageous in terms of production efficiency. In this case, in order to improve yields, it is common to apply a release treatment to the surfaces of the metal mold and the replica mold material to prevent the lens material and the replica mold from sticking together, but there is a need to simplify the process of applying the release agent.

[0003] One such material known to be suitable for this purpose is a fluorine-containing acrylic resin (Patent Document 1). However, the technology using this material requires washing with a solvent and heating after molding the replica mold material, and there was a need to simplify the process. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6881567 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and has as its object to provide an ultraviolet-curable silicone composition that gives a cured product that has mold releasability, and a cured product thereof. [Means for solving the problem]

[0006] As a result of intensive research conducted by the present inventors in order to achieve the above-mentioned object, they have discovered that by using a specific organopolysiloxane having a (meth)acryloyloxy-containing group and a fluorinated alkyl group bonded to a silicon atom, and an organopolysiloxane resin having a (meth)acryloyloxy-containing group and a fluorinated alkyl group bonded to a silicon atom, it is possible to obtain an ultraviolet-curable silicone composition that cures rapidly upon exposure to ultraviolet light and gives a cured product that has releasability, and have completed the present invention.

[0007] That is, the present invention provides 1. (A)(a) The following general formula (1) [ka] (In the formula, R 1 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; R 2 represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms, R 3 each independently represents an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group, p represents a number satisfying 0≦p≦10, and a represents a number satisfying 1≦a≦3. The units are denoted by, and (b)R 1 Rf 1 SiO 2 / 2 (R 1 has the same meaning as above, and Rf 1 represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom.) and 5% or more of the total number of monovalent organic groups bonded to silicon atoms are fluorine-substituted alkyl groups having 1 to 8 carbon atoms: 100 parts by mass (B)(c) the following general formula (2) or the following general formula (2') [ka] (In the formula, R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; R7 represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms, R 8 each independently represents an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group, q represents a number satisfying 0≦q≦10, and c represents a number satisfying 1≦c≦3; (d)Rf 2 SiO 3 / 2 (Rf 2 represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom; and 5% or more of the total number of monovalent organic groups bonded to silicon atoms are trifluoropropyl groups: 1 to 1,000 parts by mass of an organopolysiloxane resin, (C) Photopolymerization initiator: 0.01 to 20 parts by mass, An ultraviolet-curable silicone composition comprising: 2. (D) an ultraviolet-curable silicone composition containing 1 to 1,000 parts by mass of a monofunctional (meth)acrylate compound not containing a siloxane structure, per 100 parts by mass of the component (A); 3. A cured product of the ultraviolet-curable silicone composition according to 1 or 2. 4. The hardened product of 3 has a Type D hardness of 30 or more as specified in JIS K6253-3:2012 to provide. Effect of the Invention

[0008] The ultraviolet-curable silicone composition of the present invention cures well when irradiated with ultraviolet light, and the cured product has excellent releasability, making it suitable as a replica molding material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be described in detail below. The ultraviolet-curable silicone composition according to the present invention comprises: (A) (a) a unit represented by the following general formula (1), and (b) R 1 Rf 1 SiO2 / 2 (R 1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; Rf 1 represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom.) Organopolysiloxane having a unit represented by the formula: 100 parts by mass (B) (c) a unit represented by the following general formula (2), and (d) Rf 2 SiO 3 / 2 (Rf 2 represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom; and 5% or more of the total number of monovalent organic groups bonded to silicon atoms are trifluoropropyl groups: 1 to 1,000 parts by mass of an organopolysiloxane resin, (C) Photopolymerization initiator: 0.01 to 20 parts by mass.

[0010] (A) Organopolysiloxane The component (A) used in the present invention is a crosslinking component of the composition, and is composed of the following (a) a siloxane unit represented by the following general formula (1) and (b) R 1 Rf 1 SiO 2 / 2 and the main chain is essentially composed of repeating diorganosiloxane units.

[0011] [ka]

[0012] In formula (1), R 1 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, excluding an aliphatic unsaturated group; R 2 represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms; R 3each independently represents an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group.

[0013] In formula (1), R 1 The monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, and n-decyl; alkenyl groups such as vinyl, allyl (2-propenyl), 1-propenyl, isopropenyl, and butenyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl. In addition, some or all of the hydrogen atoms bonded to the carbon atoms of these monovalent hydrocarbon groups may be substituted with other substituents, specific examples of which include halogen-substituted hydrocarbon groups such as chloromethyl, bromoethyl, trifluoropropyl, and cyanoethyl groups, and cyano-substituted hydrocarbon groups. Among these, R 1 As the alkyl group, an alkyl group having 1 to 5 carbon atoms and a phenyl group are preferable, and a methyl group, an ethyl group and a phenyl group are more preferable.

[0014] Also, R 2 The alkylene group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, isobutylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decylene groups. Among these, R 2 is preferably an oxygen atom, a methylene, an ethylene or a trimethylene group, and more preferably an oxygen atom or an ethylene group.

[0015] In addition, R 3The number of carbon atoms of the alkyl (alkylene) group in the acryloyloxyalkyl group, methacryloyloxyalkyl group, acryloyloxyalkyloxy group, or methacryloyloxyalkyloxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5. Specific examples of these alkyl groups include R 1 Among the groups exemplified above, those having 1 to 10 carbon atoms are included. R 3 Specific examples of the above include those represented by the following formulas, but are not limited thereto.

[0016] [ka]

[0017] In the above formula, b is a number that satisfies 1≦b≦4, and preferably satisfies 1≦b≦3. R 5 is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, and among these, methylene, ethylene and trimethylene groups are preferred, with an ethylene group being more preferred.

[0018] In formula (1), p is a number that satisfies 0≦p≦10, preferably 0≦p≦5, and more preferably 0 or 1. a is a number satisfying 1≦a≦3, and is preferably 1 or 2.

[0019] The position of the siloxane unit represented by (a) above in the organopolysiloxane molecule of component (A) may be at one or both ends of the molecular chain, and the molecular chain may further contain the unit represented by (a) above on a side chain; however, from the perspective of the mechanical properties of the resulting cured product, it is preferred that the unit represented by (a) above be present only at both ends.

[0020] (b)R 1 Rf 1 SiO 2 / 2 In the siloxane unit represented by the formula: 1has the same meaning as above, and among them, an alkyl group having 1 to 5 carbon atoms and a phenyl group are preferable, and a methyl group, an ethyl group and a phenyl group are more preferable.

[0021] Rf 1 represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom. Examples of the fluorine-substituted alkyl group include trifluoromethyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,5-heptafluoropentyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl, and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl groups, with 3,3,3-trifluoropropyl being preferred.

[0022] In the component (A), siloxane units other than the above (a) and (b), such as R 1 2 SiO 2 / 2 Units and R 1 3 SiO 1 / 2 Units (wherein R 1 has the same meaning as above.) etc.

[0023] Of the total number of monovalent organic groups bonded to silicon atoms in component (A), at least 5%, preferably 5 to 50%, and more preferably 10 to 50% are fluorine-substituted alkyl groups having 1 to 8 carbon atoms. If the amount of fluorine-substituted alkyl groups having 1 to 8 carbon atoms is less than 5%, the resulting cured product may have insufficient releasability.

[0024] The viscosity of the organopolysiloxane of component (A) at 25° C. is preferably 10 to 200,000 mPa·s, and more preferably 10 to 100,000 mPa·s, in order to improve the workability of the composition and the mechanical properties of the cured product. In the present invention, the viscosity can be measured by a rotational viscometer (for example, BL type, BH type, BS type, cone-plate type, rheometer, etc.) (hereinafter the same).

[0025] Specific examples of the organopolysiloxane of component (A) include those represented by the following formulas, but are not limited to these.

[0026] [ka] (In the formula, R 1 and Rf 1 has the same meaning as above, and n is a number that makes the viscosity of the organopolysiloxane the above value, and is preferably a number from 1 to 800, and more preferably from 10 to 500.

[0027] Such organopolysiloxanes can be produced by known methods. For example, the polysiloxane represented by the above formula (3) can be obtained by reacting 2-hydroxyethyl acrylate with the hydrosilylation reaction product of a dimethylsiloxane-trifluoropropylmethylsiloxane copolymer endblocked with dimethylvinylsiloxy groups and chlorodimethylsilane. The organopolysiloxanes represented by the above formulas (4) and (5) are obtained as the hydrosilylation reaction product of a dimethylsiloxane-trifluoropropylmethylsiloxane copolymer capped at both ends with dimethylvinylsiloxy groups and 3-(1,1,3,3-tetramethyldisiloxanyl)propyl methacrylate (CAS No. 96474-12-3). The organopolysiloxane represented by the above formula (6) can be obtained by reacting 2-hydroxyethyl acrylate with the hydrosilylation product of a dimethylsiloxane-diphenylsiloxane copolymer capped at both ends with dimethylvinylsiloxy groups and dichloromethylsilane.

[0028] (B) Organopolysiloxane resin The component (B) is one of the crosslinking components of the composition, and is composed of (c) a unit represented by the following formula (2) or the following general formula (2'), and (d) Rf 2 SiO 3 / 2 It is an organopolysiloxane resin having units.

[0029] [ka]

[0030] R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, excluding aliphatic unsaturated groups; R 7 represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms; R 8 each independently represents an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group.

[0031] R 6 The monovalent hydrocarbon group having 1 to 20 carbon atoms is the above-mentioned R 1 Examples of the alkyl group include those exemplified in the above, and an alkyl group having 1 to 5 carbon atoms and a phenyl group are preferred, with a methyl group, an ethyl group and a phenyl group being more preferred.

[0032] R 7 The alkylene group having 1 to 20 carbon atoms is the above-mentioned R 2 Examples of the same as those exemplified in R 7 is preferably an oxygen atom, a methylene, an ethylene or a trimethylene group, and more preferably an oxygen atom or an ethylene group.

[0033] R 8 The number of carbon atoms of the alkyl (alkylene) group in the acryloyloxyalkyl group, methacryloyloxyalkyl group, acryloyloxyalkyloxy group, or methacryloyloxyalkyloxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5. Specific examples of these alkyl groups include R 1 Among the groups exemplified above, those having 1 to 10 carbon atoms are included. R 3 As a specific example of R3 Examples of the exemplified materials include, but are not limited to, those listed above.

[0034] In formula (2), q is a number that satisfies 0≦q≦10, preferably 0≦q≦5, and more preferably 0 or 1. c is a number satisfying 1≦c≦3, and is preferably 1 or 2.

[0035] (d)Rf 2 SiO 3 / 2 In units, Rf 2 represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom, and the above Rf 1 Examples of the fluoroalkyl group include those exemplified in the above, and a 3,3,3-trifluoropropyl group is preferred.

[0036] In the component (B), siloxane units other than the above (c) and (d), such as R 1 3 SiO 1 / 2 Units, R 1 2 SiO 2 / 2 Units, R 1 Rf 2 SiO 2 / 2 Units and R 1 SiO 3 / 2 Units (wherein R 1 and Rf 2 has the same meaning as above.) etc.

[0037] The content of the (c) units is preferably 5 to 30 mol %, more preferably 10 to 25 mol %, based on the total siloxane units in the organopolysiloxane resin of component (B), in order to provide a cured product with good mechanical properties.

[0038] Of the total number of monovalent organic groups bonded to silicon atoms in component (B), at least 5%, preferably 5 to 90%, and more preferably 30 to 90% are fluorine-substituted alkyl groups having 1 to 8 carbon atoms. If the proportion of fluorine-substituted alkyl groups having 1 to 8 carbon atoms is less than 5%, the resulting cured product may have insufficient releasability.

[0039] The number average molecular weight of the (B) component is preferably 500 to 30,000, more preferably 1,000 to 20,000. Within such a range, the workability of the composition is improved. The number average molecular weight is a value calculated using standard polystyrene in gel permeation chromatography (GPC).

[0040] The blend amount of component (B) is 1 to 1,000 parts by mass, and more preferably 200 to 800 parts by mass, per 100 parts by mass of component (A). Within this range, the workability of the composition and the mechanical properties of the cured product are excellent. The component (B) may use one type alone, or two or more types in combination.

[0041] The organopolysiloxane resin of component (B) can be produced by known methods. For example, it can be produced by co-hydrolysis and condensation of a hydrolyzable silane mixture containing a fluorine-substituted alkyltrialkoxysilane and a (meth)acrylic group-containing dimethoxysilane. Examples of the fluorine-substituted alkyltrialkoxysilane include 3,3,3-trifluoropropyltrimethoxysilane, and examples of the (meth)acrylic group-containing dimethoxysilane include 3-(methacryloyloxy)propylmethyldimethoxysilane and the hydrosilylation reaction product of dimethoxymethylvinylsilane and 3-(1,1,3,3-tetramethyldisiloxanyl)propyl methacrylate.

[0042] (C) Photopolymerization initiator Specific examples of photoinitiators that can be used in the present invention include 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Omnirad 1173), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (Omnirad 127), phenylglyoxylic acid methyl ester (Omnirad MBF), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Omnirad 907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Omnirad 369), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one (Omnirad 379EG), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO), etc. (all manufactured by IGM Resins BV). These may be used alone or in combination of two or more.

[0043] As the component (C), from the viewpoint of being less susceptible to oxygen inhibition during UV curing and improving surface curing properties, an α-aminoacetophenone type photopolymerization initiator is preferred, and 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Omnirad 1173), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Omnirad 369), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one (Omnirad 379EG) (all manufactured by IGM Resins BV) are more preferred.

[0044] The amount of the photopolymerization initiator added is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of (A) from the viewpoint of curability.

[0045] The composition of the present invention may further contain (D) a monofunctional (meth)acrylate compound not containing a siloxane structure for the purpose of adjusting the mechanical properties and viscosity. Specific examples thereof include isoamyl acrylate, lauryl acrylate, stearyl acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, 2-ethylhexyl-diglycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, dimethylol-tricyclodecane diacrylate, and the like, and these may be used alone or in combination of two or more. Among these, isobornyl acrylate and dimethylol-tricyclodecane diacrylate are particularly preferable.

[0046] When the component (D) is used, the amount added is preferably within a range from 1 to 1,000 parts by mass per 100 parts by mass of the component (A).

[0047] In addition, the composition of the present invention may contain additives such as finely powdered silica, coloring materials (pigments or dyes), silane coupling agents, adhesion aids, polymerization inhibitors, antioxidants, ultraviolet absorbers, and light stabilizers, within the scope of not impairing the effects of the present invention. Furthermore, the composition of the present invention can also be used by appropriately mixing it with other resin compositions.

[0048] When improvements in the handleability, coatability onto substrates, etc. are required, the ultraviolet-curable silicone pressure-sensitive adhesive composition of the present invention can be diluted with an organic solvent prior to use as long as the properties of the present invention are not impaired.

[0049] The ultraviolet-curable silicone composition of the present invention can be obtained by mixing the above components (A) to (C), and optionally the component (D) and other components, in any order, followed by stirring, etc. There are no particular limitations on the equipment used for stirring, etc., and examples of the equipment include a crusher, a three-roll mill, a ball mill, a planetary mixer, etc. Furthermore, these equipment may be combined as appropriate.

[0050] From the viewpoint of moldability and workability during application, the viscosity of the UV-curable silicone pressure-sensitive adhesive composition of the present invention, when measured with a rotational viscometer at 23° C., is preferably 5,000 Pa·s or less, more preferably 3,000 Pa·s or less, and even more preferably 1,500 Pa·s or less. If it exceeds 5,000 Pa·s, the workability may be significantly impaired.

[0051] The ultraviolet-curable silicone composition of the present invention cures rapidly when irradiated with ultraviolet light. In this case, examples of the light source of the ultraviolet light to be irradiated include a UV LED lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a xenon lamp. The amount of ultraviolet light (accumulated light amount) is preferably 1 to 20,000 mJ / cm for a sheet formed from the composition of the present invention to a thickness of about 2.0 mm. 2 and more preferably 10 to 16,000 mJ / cm 2 That is, the illuminance is 100mW / cm 2 When ultraviolet light is used, the ultraviolet light may be irradiated for about 0.01 to 160 seconds.

[0052] The cured product of the adhesive ultraviolet-curable silicone composition of the present invention preferably has a type D hardness specified in JIS K6253-3:2012 of 30 or more, and more preferably 40 or more. EXAMPLES

[0053] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples. The compounds of the respective components used in the examples are as follows: Me represents a methyl group, Rf represents a 3,3,3-trifluoropropyl group, and Vi represents a vinyl group.

[0054] Component (A) [ka]

[0055] (B) Component (B-1) Unit represented by the following formula (7) / RfSiO 3 / 2 A 50% by mass solution of organopolysiloxane resin (number average molecular weight 1,200) with a unit molar ratio of 3 / 7 in 1,3-bis(trifluoromethyl)benzene (B-2) Unit represented by the following formula (8) / RfSiO 3 / 2 A 50% by mass solution of organopolysiloxane resin (number average molecular weight 1,115) with a unit molar ratio of 3 / 7 in 1,3-bis(trifluoromethyl)benzene (B-3) Unit represented by the following formula (8) / RfSiO 3 / 2A 50% by mass solution of organopolysiloxane resin (number average molecular weight 1,055) with a unit molar ratio of 1 / 9 in 1,3-bis(trifluoromethyl)benzene [ka]

[0056] (C) Component (C-1) 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (IGM Resins BV, Omnirad 1173) (D) Component (D-1) Isobornyl acrylate (Kyoeisha Chemical Co., Ltd., Light Acrylate IB-XA)

[0057] (E) Component [ka]

[0058] [Examples 1 to 8 and Comparative Example 1] The above components (A), (B), and (E) were mixed in the composition shown in Table 1, and 1,3-bis(trifluoromethyl)benzene was distilled off at 100°C under reduced pressure. After that, components (C) and (D) were mixed to prepare each of the silicone compositions shown in Table 1. The obtained compositions and cured products were evaluated for the following properties, and the results are shown in Table 1.

[0059] 〔viscosity〕 The viscosity of the composition was measured at 23° C. using a rotational viscometer. 〔hardness〕 The prepared UV-curable silicone composition was irradiated with UV light having a wavelength of 365 nm at a dose of 16,000 mJ / cm under a nitrogen atmosphere at room temperature (25°C) using an Eye UV electronic control device (model UBX0601-01) manufactured by Eye Graphics Co., Ltd. 2 The sheet was irradiated with ultraviolet light so as to cure. The thickness of the sheet was 2.0 mm. The hardness of the resulting cured product was measured in accordance with JIS K6253-3:2012. [Mold releasability] A dam was made between two glass plates using Teflon tape to a thickness of 230 μm, and the prepared UV-curable silicone composition was placed inside the dam. Using an Eye UV electronic control device (model UBX0601-01) manufactured by Eye Graphics Co., Ltd., the composition was irradiated with UV light having a wavelength of 365 nm at a dose of 16,000 mJ / cm under a nitrogen atmosphere at room temperature (25°C). 2 The composition was cured by irradiating with ultraviolet light so as to obtain a test piece. When the two glass plates of the obtained test piece were peeled off by hand, if the glass plates could be easily removed, it was evaluated as ◯, and if the adhesion was too strong and the glass plates could not be removed, it was evaluated as ×.

[0060] [Table 1]

[0061] As shown in Table 1, it is understood that the ultraviolet-curable silicone compositions prepared in Examples 1 to 5 have appropriate viscosities, and that the cured products have sufficient hardness and exhibit high demolding properties, making them extremely useful as replica mold materials. On the other hand, in Comparative Example 1, which does not contain the component (B), although there is releasability, the hardness of the material is not sufficient. Moreover, in Comparative Example 2 in which the component (A) was changed to the component (E), it was found that although the hardness was sufficient, the releasability was insufficient.

Claims

1. (A) (a) a compound represented by the following general formula (1): 【Chemistry 1】 (In the formula, R 1 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; R 2 represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms; R 3 are each independently an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group, p is a number satisfying 0≦p≦10, and a is a number satisfying 1≦a≦3. The units are denoted by, and (b) R 1 Rf 1 SiO ２／２ (R 1 has the same meaning as above, and Rf 1 represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom, and 5% or more of the total number of monovalent organic groups bonded to silicon atoms are fluorine-substituted alkyl groups having 1 to 8 carbon atoms: 100 parts by mass (B) (c) The following general formula (2) or the following general formula (2'): 【Chemistry 2】 (In the formula, R ６ each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; R ７ represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms; R ８ each independently represents an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group, q represents a number satisfying 0≦q≦10, and c represents a number satisfying 1≦c≦3; (d) Rf ２ SiO ３／２ (Rf ２ represents a fluorine-substituted alkyl group having 1 to 8 carbon atoms bonded to a silicon atom, and 5% or more of the total number of monovalent organic groups bonded to silicon atoms are trifluoropropyl groups: 1 to 1,000 parts by mass of an organopolysiloxane resin; (C) Photopolymerization initiator: 0.01 to 20 parts by mass, 1. An ultraviolet-curable silicone composition comprising:

2. 2. The ultraviolet-curable silicone composition according to claim 1, further comprising: (D) 1 to 1,000 parts by mass of a monofunctional (meth)acrylate compound not containing a siloxane structure, per 100 parts by mass of the component (A).

3. A cured product of the ultraviolet-curable silicone composition according to claim 1 or 2.

4. The cured product according to claim 3, having a type D hardness of 30 or more as defined in JIS K6253-3:2012.

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