UV curable silicone composition, encapsulant or sheet film using the same

Abstract

To provide an ultraviolet curable silicone composition excellent in curability caused by ultraviolet irradiation.SOLUTION: An ultraviolet curable silicone composition includes a photoinitiator miscible to silicone selected from a combination of (A) an organopolysiloxane composition selected from an organopolysiloxane composition (A-1) including molecule chain both terminal alkenyl group seal linear organopolysiloxane and / or branched organopolysiloxane including at least two alkenyl groups at a molecule chain terminal and organopolysiloxane having a thiol group content of 1 mass% or more per molecule and including at least two thiol groups in the side chain of a molecule chain and two specific kinds of organopolysiloxane compositions except the organopolysiloxane composition and (B) α-hydroxy aceto phenone (B-1) or a compound specified therewith. The ratio (SH / Vi ratio) of the thiol group to the alkenyl group included in the organopolysiloxane composition is 0.6 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an ultraviolet curable silicone composition and an LED-related member obtained by curing the ultraviolet curable silicone composition by irradiating ultraviolet rays, particularly a sealing material or a sheet film.

Background Art

[0002] Curable silicone compositions are used in a wide range of industrial fields because they cure to form cured products having excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. The cured products of such curable silicone compositions are less likely to discolor compared to other organic materials, and also have small changes in physical properties, so they are also suitable as optical materials.

[0003] However, conventional thermosetting curable silicone compositions have a problem that a large warp or dimensional error occurs in the cured product due to heating. In particular, when attempting to seal a flexible substrate on which a semiconductor chip is mounted using a conventional thermosetting curable silicone composition, or when attempting to use it as a transfer stamp sheet film in the mask transfer process during chip mounting, a large warp or dimensional error occurs in the cured product due to heating, and problems such as inability to accurately seal and mount the semiconductor chip may occur. In addition, thermosetting curable silicone compositions need to be heated at a high temperature for a long time to cure, resulting in low process efficiency and possible damage to electronic components.

[0004] Therefore, it has been proposed to use an ultraviolet curable silicone composition as a curable silicone composition for electronic components such as semiconductor devices. For example, Patent Documents 1 to 8 disclose various ultraviolet curable silicone compositions.

Prior Art Documents

Patent Documents

[0005] Patent Document 1 Japanese Patent Publication No. 2017-502102 Patent Document 2 WO2018 / 112254 Patent Document 3 Japanese Patent Publication No. 2017-508853 Patent Document 4 Korean Patent No. 101224780 Patent Document 5 Japanese Unexamined Patent Application Publication No. 2013-253179 Patent Document 6 Japanese Unexamined Patent Application Publication No. 2016-60782 Patent Document 7 Japanese Unexamined Patent Application Publication No. 2002-371261 Patent Document 8 Japanese Unexamined Patent Application Publication No. 2012-144704 Summary of the Invention Problems to be Solved by the Invention

[0006] However, in the conventional ultraviolet-curable curable silicone composition, there is still a problem that the curability described above is insufficient and the dimensional stability is poor.

[0007] An object of the present invention is to provide an ultraviolet-curable silicone composition having excellent curability by ultraviolet irradiation.

[0008] Another object of the present invention is to provide a sheet film or a sealing material having excellent dimensional stability and little warpage, which is obtained by curing an ultraviolet-curable silicone composition. Means for Solving the Problems

[0009] In order to solve the above problems, as a result of intensive studies, the present inventor surprisingly found that a specific thiol functional Sex O lgano Poly siloxane or a specific thiol compound is included Mu O lgano PolyIt has been found that a combination of a siloxane composition and a specific photoinitiator can provide an ultraviolet curable silicone composition having excellent curability by ultraviolet irradiation, and thus the present invention has been achieved.

[0010] Accordingly, the present invention relates to (A) An organopolysiloxane composition selected from the following: (A-1) A linear organopolysiloxane having alkenyl groups blocked at both ends of the molecular chain and / or a branched organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, and an organopolysiloxane having a thiol group content of 1% by mass or more per molecule and containing a thiol group in the side chain of the molecular chain At least two An organopolysiloxane composition containing an organopolysiloxane having a thiol group content of 1% by mass or more per molecule and containing a thiol group in the side chain of the molecular chain (A-2) A linear organopolysiloxane having thiol groups blocked at both ends of the molecular chain and having a thiol group content of 1% by mass or more per molecule, and an organopolysiloxane having an alkenyl group in the side chain of the molecular chain and / or a resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, or At least two (A-3) An organopolysiloxane composition containing an alkenyl group- and aryl group-containing organopolysiloxane and a polyfunctional thiol compound, provided that when the polyfunctional thiol compound contains only a bifunctional thiol compound, the organopolysiloxane composition further contains a resinous organopolysiloxane containing an alkenyl group and, and (B) A photoinitiator miscible with silicone and selected from the following: (B-1) α-Hydroxyacetophenone (B-2) A combination of α-hydroxyacetophenone and α-aminoalkylphenone, or (B-3) A combination of α-hydroxyacetophenone and monoacylphosphine oxide The present invention relates to an ultraviolet curable silicone composition in which the ratio (SH / Vi ratio) of the thiol group (-SH group) to the alkenyl group contained in the organopolysiloxane composition is 0.6 or more.

[0011] It is preferable that the organopolysiloxane containing at least two thiol groups (-SH groups) in the molecular chain side chain of the component (A-1) has a linear or branched structure.

[0012] It is preferable that the organopolysiloxane containing at least two alkenyl groups in the molecular chain side chain of the component (A-2) has a linear structure.

[0013] It is preferable that the polyfunctional thiol compound of the component (A-3) is a compound containing a 2- to 6-functional thiol group.

[0014] It is preferable that the thiol group (-SH group) and the alkenyl group in the organopolysiloxane composition of the component (A) are contained such that the thiol group is 0.6 to 5 moles per mole of the alkenyl group.

[0015] It is preferable that the photoinitiator of (B-1) further contains a compound having an acetophenone structure other than α-hydroxyacetophenone.

[0016] It is preferable that the content of the component (B) is 0.001% by mass or more and 5% by mass or less based on the total mass of the ultraviolet curable silicone composition.

[0017] The present invention also relates to a sealing material and a sheet film comprising a cured product of the ultraviolet curable silicone composition according to the present invention.

Advantages of the Invention

[0018] According to the ultraviolet curable silicone composition of the present invention, excellent curability by ultraviolet irradiation is exhibited. Therefore, a cured product having excellent dimensional stability and little warpage can be formed. Further, according to the sealing material and the sheet film of the present invention, since they have excellent dimensional stability and little warpage, a highly reliable electronic device can be provided.

Embodiments for Carrying Out the Invention

[0019] [Ultraviolet curable silicone composition] The curable silicone composition according to the present invention is (A) An organopolysiloxane composition selected from the following: (A-1) An organopolysiloxane composition containing a linear organopolysiloxane blocked with alkenyl groups at both ends of the molecular chain and / or a branched organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, and an organopolysiloxane containing a thiol group in the molecular chain side chain with a thiol group content of 1% by mass or more per molecule, (A-2) A linear organopolysiloxane blocked with thiol groups at both ends of the molecular chain with a thiol group content of 1% by mass or more per molecule, and an organopolysiloxane containing an alkenyl group in the molecular chain side chain and / or a resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, or, (A-3) An organopolysiloxane composition containing an alkenyl group and aryl group-containing organopolysiloxane and a polyfunctional thiol compound, provided that when the polyfunctional thiol compound contains only a bifunctional thiol compound, it further contains a resinous organopolysiloxane containing an alkenyl group And, (B) A photoinitiator miscible with silicone containing a compound selected from the following: (B-1) α-Hydroxyacetophenone, (B-2) A combination of α-hydroxyacetophenone and α-aminoalkylphenone, or (B-3) A combination of α-hydroxyacetophenone and monoacylphosphine oxide It contains, and the ratio of the thiol group (-SH group) to the alkenyl group (SH / Vi ratio) contained in the organopolysiloxane composition is 0.6 or more.

[0020] Hereinafter, each component of the ultraviolet curable silicone composition of the present invention will be described in detail.

[0021] (A) Organopolysiloxane composition Component (A) is an organopolysiloxane composition, which is the main component of the ultraviolet curable silicone composition of the present invention. In the present invention, component (A) is selected from the following (A-1) to (A-3): (A-1) An organopolysiloxane composition comprising a straight-chain organopolysiloxane blocked with alkenyl groups at both ends of the molecular chain and / or a branched organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, and an organopolysiloxane containing at least two thiol groups in the side chains of the molecular chain, wherein the content of the thiol groups is 1% by mass or more per molecule. (A-2) An organopolysiloxane composition comprising a straight-chain organopolysiloxane blocked with thiol groups at both ends of the molecular chain, wherein the content of the thiol groups is 1% by mass or more per molecule, and an organopolysiloxane containing at least two alkenyl groups in the side chains of the molecular chain and / or a resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, or (A-3) An organopolysiloxane composition comprising an organopolysiloxane containing alkenyl groups and aryl groups, and a polyfunctional thiol compound, provided that when the polyfunctional thiol compound contains only a bifunctional thiol compound, it further comprises a resinous organopolysiloxane containing alkenyl groups. Hereinafter, each component will be described in detail.

[0022] (A-1) Component is an organopolysiloxane composition comprising a straight-chain organopolysiloxane blocked with alkenyl groups at both ends of the molecular chain and / or a branched organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, and an organopolysiloxane containing at least two thiol groups in the side chains of the molecular chain.

[0023] The straight-chain organopolysiloxane blocked with alkenyl groups at both ends of the molecular chain in component (A-1) has the structural formula (I): R 1 R 2 2SiO(R 2 2SiO) n SiR 1 R2 2, and in formula (I), R 1 is an alkenyl group, R 2 are each independently a monovalent hydrocarbon group, and n is 10 mPa as viscosity. s Here, the linear organopolysiloxane capped at both molecular chain terminals with alkenyl groups may be used alone or in combination of two or more kinds.

[0024] The branched organopolysiloxane containing at least two alkenyl groups at the molecular chain terminals in the component (A-1) is represented by the average unit formula (II): (R 2 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R 2 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e In the above formula (II), R 2 is the same as above, except that in one molecule, (R 2 3SiO 1 / 2 ) R in the unit 2 At least two of the R 2 is an alkenyl group, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e are preferably expressed as numbers satisfying 0≦a≦1.0, 0≦b≦0.5, 0≦c≦0.5, 0≦d≦1.0, and 0≦e<0.4, and a+b+c+d=1.0. Also, c+d may be greater than 0. The branched organopolysiloxane containing at least two alkenyl groups at the molecular chain terminal may be used alone or in combination of two or more. In other words, the branched organopolysiloxane containing at least two alkenyl groups at the molecular chain terminal in the component (A-1) contains an alkenyl group in the M unit. The D, T, and / or Q units may contain an alkenyl group, but preferably do not contain an alkenyl group.

[0025] In addition, in this specification, the viscosity of the organopolysiloxane component can be measured at 25°C using a rotational viscometer conforming to JIS K7117-1.

[0026] In the above formulas (I) and (II), R 1 and R 2 contain an alkenyl group. Examples of such alkenyl groups include alkenyl groups having 2 to 12 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, and dodecenyl group. Alkenyl groups having 2 to 6 carbon atoms are preferred, and a vinyl group is particularly preferred.

[0027] In the above formulas (I) and (II), examples of the monovalent hydrocarbon group other than the alkenyl group of R 2 include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group; aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, xylyl group, and naphthyl group; aralkyl groups having 7 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine atom, chlorine atom, and bromine atom. Preferably, it is an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. Further, in one embodiment, R 2 is a monovalent hydrocarbon group other than a phenyl group. Further, in another embodiment, R 2 is a monovalent hydrocarbon group other than an aryl group.

[0028] (A-1) The amount of alkenyl groups contained in the linear organopolysiloxane with alkenyl groups blocked at both ends of the molecular chain or the branched organopolysiloxane containing at least two alkenyl groups at the molecular chain ends in the component is not particularly limited, provided that preferably 0.01 to 50 mol%, 0.03 to 40 mol%, or 0.05 to 32 mol% of the total of the functional groups R are alkenyl groups. The content of alkenyl groups can be determined, for example, by analysis using a Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), etc.

[0029] Examples of the structure of the organopolysiloxane containing at least two thiol groups in the side chain of the molecular chain in the component (A-1) include linear, linearly branched with partial branching, branched chain, cyclic, and three-dimensional network structures. The organopolysiloxane containing at least two thiol groups in the side chain of the molecular chain in the component (A-1) may be only one type or a combination of two or more types. Preferably, the component (A-1) contains an organopolysiloxane having at least two thiol groups in the side chain of a linear molecular chain structure.

[0030] The organopolysiloxane containing at least two thiol groups in the side chain of the molecular chain is preferably an organopolysiloxane composed of only M and D and T units among the siloxane units (M units) represented by the general formula of organopolysiloxane: R3SiO 1 / 2 the siloxane units (D units) represented by the general formula: R2SiO 2 / 2 the siloxane units (T units) represented by the general formula: RSiO 3 / 2 and the siloxane units (Q units) represented by the formula: SiO 4 / 2

[0031] (A-1) The organopolysiloxane containing at least two thiol groups in the side chain of the molecular chain in the component has an average unit formula (III): (R 2 3SiO 1 / 2 ) a (R 3 2SiO 2 / 2 ) b (R 3 SiO3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e is preferably represented thereby. In the above formula (III), R 2 is the same as described above, R 3 is a monovalent hydrocarbon group other than an alkenyl group or a thiol group, provided that in one molecule, at least two R 3 are thiol groups, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e are such that 0≦a≦1.0, 0≦b≦1.0, 0≦c<0.9, 0≦d<0.5, 0≦e<0.4, and a + b + c + d = 1.0.

[0032] In the above formula (III), R 3 is a monovalent hydrocarbon group other than an alkenyl group or a thiol group. Examples of this monovalent hydrocarbon group other than an alkenyl group are the same as the monovalent hydrocarbon group of the above R 2 . Examples of the thiol group include, for example, a structure of -(CH2) X -SH, where x is an integer from 1 to 30. As the alkyl group of X, an alkyl group having 1 to 3 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, and a propyl group are exemplified.

[0033] In the above formula (III), a is preferably in the range of 0≦a≦0.9, more preferably in the range of 0≦a≦0.7, and preferentially in the range of 0≦a≦0.5. In formula (III), b is preferably in the range of 0.1≦b≦1.0, more preferably in the range of 0.3≦b≦1.0, and particularly in the range of 0.5≦b≦1.0. In formula (III), c is preferably in the range of 0≦c≦0.5, more preferably in the range of 0≦c≦0.3, and particularly in the range of 0≦c≦01. In formula (III), d is preferably in the range of 0≦d≦0.4, more preferably in the range of 0≦d≦0.2, and particularly in the range of 0≦d≦0.1. In formula (III), e is preferably in the range of 0≦e≦0.3, more preferably in the range of 0≦e≦0.2, and particularly in the range of 0≦e≦0.1.

[0034] (A-1) The amount of thiol groups contained in the organopolysiloxane containing at least two thiol groups in the molecular chain side chains in component (A-1) is 1% by mass or more, preferably 1.2% by mass or more, for example 30% by mass or less, preferably 25% by mass or less. The content (% by mass) of thiol groups can be calculated, for example, as the mass % of thiol groups per molecular weight.

[0035] (A-1) The amount of the organopolysiloxane containing at least two thiol groups in the molecular chain side chains in component (A-1) is not particularly limited, but based on the total mass of component (A-1), it can be 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, and can also be 90% by mass or less, 85% by mass or less, 80% by mass or less.

[0036] (A-2) Component is an organopolysiloxane composition containing a linear organopolysiloxane blocked with thiol groups at both ends of the molecular chain having a thiol group content of 1% by mass or more per molecule, an organopolysiloxane containing at least two alkenyl groups in the molecular chain side chains and / or a resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain ends.

[0037] (A-2) The linear organopolysiloxane blocked with thiol groups at both ends of the molecular chain in component (A-2) has the structural formula (IV): R 4 R 5 2SiO(R 5 2SiO) p SiR 4 R 5 2 and is preferably represented by, where in formula (IV), R 4 is a thiol group, and R 5 are each independently monovalent hydrocarbon groups other than alkenyl groups, and p is a numerical value such that the viscosity is 10 mPa or more. The linear organopolysiloxane blocked with thiol groups at both ends of the molecular chain may be only one kind or a combination of two or more kinds may be used.

[0038] In the above formula (IV), R4 is a thiol group, for example, -(CH2) X -SH structure (x is an integer from 1 to 30), which is a thiol group represented by the formula.

[0039] (A-2) The amount of the thiol group contained in the thiol group-blocked linear organopolysiloxane at both ends of the molecular chain in the component is 1% by mass or more per molecule, preferably 1.2% by mass or more, for example, 30% by mass or less, preferably 25% by mass or less. The content (% by mass) of the thiol group can be calculated, for example, as the mass% of the thiol group per molecular weight.

[0040] (A-2) The component contains an organopolysiloxane having at least two alkenyl groups in the side chain of the molecular chain and / or a resinous organopolysiloxane having at least two alkenyl groups at the terminal of the molecular chain.

[0041] (A-2) Examples of the structure of the organopolysiloxane having at least two alkenyl groups in the side chain of the molecular chain in the component include linear, linearly branched, branched chain, cyclic, and three-dimensional network structures. The organopolysiloxane having at least two alkenyl groups in the side chain of the molecular chain in the (A-2) component may be only one type, or two or more types may be used in combination. Preferably, the (A-2) component contains a linear organopolysiloxane having at least two thiol groups in the side chain of the molecular chain.

[0042] (A-2) The organopolysiloxane having at least two alkenyl groups in the side chain of the molecular chain in the component has an average unit formula (V): (R 5 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R 2 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e and is preferably represented by. In the above formula (V), R5 is the same as described above, and R 2 is a monovalent hydrocarbon group, provided that in one molecule, at least two Rs 2 is an alkenyl group, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e satisfy 0 ≦ a ≦ 1.0, 0 ≦ b ≦ 1.0, 0 ≦ c < 0.9, 0 ≦ d < 0.5, 0 ≦ e < 0.4, and are numbers satisfying a + b + c + d = 1.0.

[0043] In the above formula (V), R 2 is a monovalent hydrocarbon group containing an alkenyl group. Examples of this alkenyl group include the same ones as the above R 1 and examples of the monovalent hydrocarbon group include the same ones as the monovalent hydrocarbon group of the above R 2 . Examples of the thiol group include, for example, a structure of -(CH2) X -SH, where x is an integer from 1 to 30. As the alkyl group of X, an alkyl group having 1 to 3 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, and a propyl group are exemplified.

[0044] In the above formula (V), a is preferably in the range of 0 ≦ a ≦ 0.9, more preferably in the range of 0 ≦ a ≦ 0.7, and preferentially in the range of 0 ≦ a ≦ 0.5. In formula (V), b is preferably in the range of 0.1 ≦ b ≦ 1.0, more preferably in the range of 0.3 ≦ b ≦ 1.0, and particularly in the range of 0.5 ≦ b ≦ 1.0. In formula (V), c is preferably in the range of 0 ≦ c ≦ 0.5, more preferably in the range of 0 ≦ c ≦ 0.3, and particularly in the range of 0 ≦ c ≦ 0.1. In formula (V), d is preferably in the range of 0 ≦ d ≦ 0.4, more preferably in the range of 0 ≦ d ≦ 0.2, and particularly in the range of 0 ≦ d ≦ 0.1. In formula (V), e is preferably in the range of 0 ≦ e ≦ 0.3, more preferably in the range of 0 ≦ e ≦ 0.2, and particularly in the range of 0 ≦ e ≦ 0.1.

[0045] (A-2) The organopolysiloxane containing at least two alkenyl groups in the molecular chain side chain is preferably linear. Therefore, the structural formula (VI): R 53SiO(R 2 2SiO) q SiR 5 3 is preferably represented thereby. Here, in formula (VI), R 2 is the same as described above, R 5 is the same as described above, provided that in one molecule, at least two R 2 are alkenyl groups, and q is in the range of 10 mPas or more in viscosity.

[0046] (Component (A-2) may include a resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain ends. As used herein, the resinous organopolysiloxane means an organopolysiloxane having a branched or network structure in the molecular structure. In one embodiment, the resinous organopolysiloxane that may be included in component (A-2) has at least one RSiO 3 / 2 -represented siloxane unit (T unit) and / or SiO 4 / 2 -represented siloxane unit (Q unit) in its molecular structure.

[0047] (The resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain ends in component (A-2) has an average unit formula (VI I ): (R 2 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R 2 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e and is preferably represented thereby. In formula (VI I ), R 2 is a monovalent hydrocarbon group, provided that in one molecule, among the R 2 in the (R 1 / 2 3SiO 2 ) unit, at least two of the R 2is an alkenyl group, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e satisfy 0 ≦ a ≦ 1.0, 0 ≦ b ≦ 1.0, 0 ≦ c < 0.9, 0 ≦ d ≦ 1.0, 0 ≦ e < 0.4, a + b + c + d = 1.0, and c + d > 0 。Good Alternatively, in the resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain terminals in the component (A-2), alkenyl groups are present only in the M units and not in the D, T, and / or Q units. R 2 Examples of the alkenyl group of R 1 are the same as those described above for R 2 and examples of the monovalent hydrocarbon group are the same as those described above for R

[0048] The amount of the alkenyl group contained in the organopolysiloxane containing at least two alkenyl groups in the side chains of the molecular chain and the resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain terminals in the component (A-2) is not particularly limited. For example, it is preferably 0.01 to 50 mol%, 0.05 to 40 mol%, or 0.09 to 32 mol% of the total of the functional groups R that are alkenyl groups. The content of the alkenyl group can be determined, for example, by analysis using a Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), or the like.

[0049] The amount of the organopolysiloxane containing at least two alkenyl groups in the side chains of the molecular chain and / or the resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain terminals in the component (A-2) is not particularly limited. Based on the total mass of the component (A-2), it can be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, and can also be 90% by mass or less, 85% by mass or less, or 80% by mass or less.

[0050] (Component (A-3)) is an organopolysiloxane composition containing an alkenyl group- and aryl group-containing organopolysiloxane and a polyfunctional thiol compound.

[0051] Examples of the structure of the alkenyl group- and aryl group-containing organopolysiloxane in component (A-3) include linear, linearly branched with some branches, branched-chain, cyclic, and three-dimensional network structures. The alkenyl group- and aryl group-containing organopolysiloxane in component (A-3) may be only one type, or two or more types may be used in combination. Preferably, component (A-3) contains a linear alkenyl group- and aryl group-containing organopolysiloxane.

[0052] The alkenyl group- and aryl group-containing organopolysiloxane in component (A-3) has an average unit formula (VII I ):(R 2 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R 2 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e and is preferably represented by. In the above formula (VII I ), R 2 is the same as described above, a monovalent hydrocarbon group containing an alkenyl group, provided that in one molecule, at least 2 R 2 are alkenyl groups, and at least 1 R 2 is an aryl group, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e are such that 0≦a≦1.0, 0≦b≦1.0, 0≦c<0.9, 0≦d≦1.0, 0≦e<0.4, and a + b + c + d = 1.0.

[0053] In the above formula (VII I ), R 2 is a monovalent hydrocarbon group containing an alkenyl group, and as this alkenyl group, the above R 1The same ones are exemplified, and as the monovalent hydrocarbon group, the above R 2 or R 5 The same ones are exemplified. The aryl group is preferably a phenyl group. As the alkyl group of X, an alkyl group having 1 to 3 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, and a propyl group are exemplified.

[0054] (In the component (A-3), the aryl group of the alkenyl group and aryl group-containing organopolysiloxane may be contained in either the molecular chain terminal or the molecular chain side chain, but is preferably contained in the molecular chain side chain, and more preferably contained only in the molecular chain side chain. Further, the alkenyl group of the alkenyl group and aryl group-containing organopolysiloxane in the component (A-3) may be contained in either the molecular chain terminal or the molecular chain side chain.)

[0055] (The alkenyl group and aryl group-containing organopolysiloxane in the component (A-3) is preferably linear, and therefore, the structural formula ( IX ): R 7 R 6 2SiO(R 8 2SiO) r SiR 6 2R 7 is preferably represented by. Here, in the formula ( IX ), R 6 ~R 8 are each independently a monovalent hydrocarbon group containing an alkenyl group, provided that among R 6 ~R 8 , at least 2 are alkenyl groups and at least 1 is an aryl group in one molecule, and r is in a range satisfying a viscosity of 10 mPas or more.)

[0056] In the above formula ( IX ), as the alkenyl group of R 6 ~R 8 , the same ones as the above R 1 are exemplified, and as the monovalent hydrocarbon group, the same ones as the above R 2 or R 5 are exemplified. In a preferred embodiment, R6 is an alkenyl group, and R 7 are each independently a monovalent hydrocarbon group other than an alkenyl group, and R 8 is a monovalent hydrocarbon group other than an alkenyl group, provided that in one molecule, at least one R 8 is an aryl group, preferably a phenyl group.

[0057] (A-3) The amount of the alkenyl group contained in the alkenyl group- and aryl group-containing organopolysiloxane in the component is not particularly limited. For example, 0.01 to 50 mol%, 0.05 to 40 mol%, or 0.1 to 30 mol% of the total of the functional groups R is preferably an alkenyl group. The contents of the alkenyl group and the aryl group can be determined by analysis using, for example, a Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), or the like.

[0058] (A-3) The polyfunctional thiol compound in the component is a compound containing two or more thiol groups per molecule. The polyfunctional thiol compound may contain a tertiary thiol group.

[0059] Examples of the polyfunctional thiol compound are not particularly limited, and include, for example, 2- to 6-functional primary and secondary thiol compounds. Preferably, the polyfunctional thiol compound contains a thiol compound having 3 or more functional groups.

[0060] Examples of the bifunctional secondary thiol compound include 1,4-bis(3-mercaptobutyryloxy)butane, bis(1-mercaptoethyl) phthalate, bis(2-mercaptopropyl) phthalate, bis(3-mercaptobutyl) phthalate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate) 、EThioglycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), ethylene glycol bis(4-mercaptovalerate), propylene glycol bis(4-mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate), propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate) and the like can be mentioned.

[0061] Examples of the trifunctional secondary thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), trimethylolpropane tris(4-mercaptovalerate), trimethylolpropane tris(3-mercaptovalerate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0062] Examples of the tetrafunctional secondary thiol compounds include dipentaerythritol Tetra kis(3-mercaptobutyrate), pentaerythritol tetrakis(2-mercaptopropionate), pentaerythritol tetrakis(3-mercapto-2-propionate), pentaerythritol tetrakis(2-mercaptoisobutyrate), pentaerythritol tetrakis(4-mercaptovalerate), pentaerythritol tetrakis(3-mercaptovalerate) and the like can be mentioned.

[0063] Examples of the 6-functional secondary thiol compound include dipentaerythritol hexakis(3-mercaptobutyrate), dipentaerythritol hexakis(2-mercaptopropionate), dipentaerythritol hexakis(2-mercaptoisobutyrate), dipentaerythritol hexakis(4-mercaptovalerate), dipentaerythritol hexakis(3-mercaptovalerate), and the like.

[0064] Examples of the 2-functional primary thiol compound include 2,2'-(ethylenedioxy)diethanethiol, ethylene glycol bis-mercaptoacetate, and the like.

[0065] Examples of the 3-functional primary thiol compound include trimethylolpropane tris(3-mercaptopropionate), and the like.

[0066] Examples of the 4-functional primary thiol compound include pentaery S lithol tetrakis(3-mercaptopropionate), and the like.

[0067] In a preferred embodiment, the polyfunctional thiol compound does not contain a hydroxyl group.

[0068] In the component (A-3), when only a 2-functional thiol compound is included as the polyfunctional thiol compound, from the viewpoint of curability, as the organopolysiloxane component, a resinous organopolysiloxane containing an alkenyl group is included. Examples of such a resinous organopolysiloxane containing an alkenyl group are the same as those described in the "Additional Component" column below as "resinous organopolysiloxane containing an alkenyl group".

[0069] The molecular weight of the polyfunctional thiol compound is not particularly limited, but for example, it is 100 or more, 120 or more, or 150 or more, and 10,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.

[0070] The amount of the polyfunctional thiol compound of the component (A-3) is not particularly limited, but based on the total mass of the component (A-3), it can be 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, and can also be 90% by mass or less, 70% by mass or less, or 50% by mass or less.

[0071] <Additional component> In addition to the above components, the organopolysiloxane composition of the component (A) may further contain a resinous organopolysiloxane containing an alkenyl group. For example, the organopolysiloxane composition of the component (A-1) and / or the component (A-3) may further contain a resinous organopolysiloxane containing an alkenyl group in addition to the above components.

[0072] In one embodiment of the present invention, the resinous organopolysiloxane that may be contained in the component (A) has an average unit formula (X ):(R 2 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R 2 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e and is preferably represented by the formula (X ) In the formula, R 2 is a monovalent hydrocarbon group, provided that in one molecule, at least 2 R 2 are alkenyl groups, X is a hydrogen atom or an alkyl group, a, b, c, d, and e are numbers such that 0≦a≦1.0, 0≦b≦1.0, 0≦c<0.9, 0≦d≦1.0, 0≦e<0.4, a + b + c + d = 1.0, and c + d>0. ) is. As the alkenyl group of R 2 , the same ones as the above R 1 are exemplified, and as the monovalent hydrocarbon group, the above R 2The same ones are exemplified. As the alkyl group of X, an alkyl group having 1 to 3 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, and a propyl group are exemplified.

[0073] Average unit formula (X ) In, a is preferably in the range of 0 ≦ a ≦ 0.9, more preferably in the range of 0 ≦ a ≦ 0.8, and particularly 0 ≦ a ≦ 0.7. In the average unit formula (X ) In, b is preferably in the range of 0 ≦ b ≦ 0.9, more preferably in the range of 0 ≦ b ≦ 0.7, and particularly in the range of 0 ≦ b ≦ 0.5. In the average unit formula (X ) In, c is preferably in the range of 0 ≦ c ≦ 0.9, more preferably in the range of 0 ≦ c ≦ 0.85, and particularly in the range of 0 ≦ c ≦ 0.8. In the average unit formula (X ) In, d is preferably in the range of 0 ≦ d ≦ 0.9, more preferably in the range of 0 ≦ d ≦ 0.8, and still more preferably in the range of 0 ≦ d ≦ 0.7. In the average unit formula (X ) In, e is preferably in the range of 0 ≦ e ≦ 0.3, more preferably in the range of 0 ≦ e ≦ 0.2, and particularly in the range of 0 ≦ e ≦ 0.1.

[0074] The content of the alkenyl group contained in the resinous organopolysiloxane that can be contained in the component (A) (mol% of the alkenyl group in the total silicon atom-bonded functional groups of the resinous organopolysiloxane) can be designed as desired, but is 0.5 mol% or more, preferably 1 mol% or more 、Sa and preferably may be 2 mol% or more, 40 mol% or less, preferably 35 mol% or less, more preferably 30 mol% or less, and preferentially may be 25 mol% or less. The content of the alkenyl group can be determined by analysis using, for example, a Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), or the like.

[0075] (A) The content of the resinous organopolysiloxane that can be contained in the component is not particularly limited, but it can be contained in an amount of 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, based on the total mass of the (A) organopolysiloxane composition. Further, the resinous organopolysiloxane that can be contained in the (A) component can be contained in an amount of 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, based on the total mass of the (A) organopolysiloxane composition.

[0076] (A) The molar ratio of the thiol group (-SH group) to the alkenyl group in the organopolysiloxane composition is not particularly limited, but preferably, the thiol group is 0.6 to 5 moles per mole of the alkenyl group, more preferably 0.7 to 3 moles. Here, the amount of the alkenyl group can be calculated based on the vinyl group (Vi group).

[0077] Further, the ratio (SH / Vi ratio) of the thiol group to the alkenyl group contained in the organopolysiloxane composition of the present invention is 0.6 or more. Here, the amount of the alkenyl group can be calculated based on the vinyl group (Vi group). Preferably, the ratio (SH / Vi ratio) of the thiol group to the alkenyl group contained in the organopolysiloxane composition of the present invention is 0.7 or more, and more preferably 0.8 or more.

[0078] (B) A photoinitiator miscible with silicone The ultraviolet curable silicone composition of the present invention contains, as the (B) component, a photoinitiator miscible with silicone. Here, "miscible" means the property that the photoinitiator and the (A) component organopolysiloxane composition are completely miscible. For example, in this specification, "miscible with silicone" means the property of dissolving 1 g / 100 mL or more in silicone oil.

[0079] (B) The photoinitiator miscible with silicone of the component is particularly as follows: (B-1) α-Hydroxyacetophenone (B-2) A combination of α-hydroxyacetophenone and α-aminoalkylphenone, or (B-3) Combination of α-hydroxyacetophenone and monoacylphosphine oxide It contains the following. Each component will be described in detail below.

[0080] (B-1) Examples of α-hydroxyacetophenone include 2-hydroxy-2-methyl-1-phenyl-1-propanone (manufactured by IGM Resins B.V., product name: Omnirad 1173), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (manufactured by IGM Resins B.V., product name: Omnirad 2959), oligo-[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)-phenyl]-propanone], 1,1'-(methylene-di-4,1-phenylene) bis[2-hydroxy-2-methyl-1-propanone] (manufactured by IGM Resins B.V., product name: Omnirad 127D), and 1-hydroxycyclohexyl-phenylketone (manufactured by IGM Resins B.V., product name: Omnirad 184).

[0081] (B-1) The photoinitiator may further contain a compound having an acetophenone structure other than α-hydroxyacetophenone in addition to α-hydroxyacetophenone. Compounds having such an acetophenone structure are not particularly limited, and examples include 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, and the like.

[0082] In a particularly preferred embodiment, the photoinitiator containing (B-1) α-hydroxyacetophenone consists only of α-hydroxyacetophenone and does not contain other photoinitiators, or the amount of other photoinitiators is 10% by mass or less, 5% by mass or less, or 3% by mass or less based on the total mass of component (B).

[0083] (B-2) In the combination of α-hydroxyacetophenone and α-aminoalkylphenone, examples of the α-aminoalkylphenone include 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-propan-1-one (manufactured by IGM Resins B.V., product name: Omnirad 907), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (manufactured by IGM Resins B.V., product name: Omnirad 379EG), 2-benzyl-2-dimethylamino-1-(3,4-dimethoxy-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (manufactured by IGM Resins B.V., product name: Omnirad 369), and 2-methyl-1-(4-methylsulfanyl-phenyl)-2-morpholin-4-yl-propan-1-one.

[0084] (B-2) In the combination of α-hydroxyacetophenone and α-aminoalkylphenone, the quantitative ratio of (B-2) α-hydroxyacetophenone to α-aminoalkylphenone is not particularly limited. For example, the mass ratio of α-hydroxyacetophenone to α-aminoalkylphenone is 0.1 to 100, preferably 0.5 to 50, and more preferably 1 to 20.

[0085] In a particularly preferred embodiment, the photoinitiator containing the combination of (B-2) α-hydroxyacetophenone and α-aminoalkylphenone consists only of α-hydroxyacetophenone and α-aminoalkylphenone, does not contain other photoinitiators, or the amount of other photoinitiators is 10% by mass or less, 5% by mass or less, or 1% by mass or less based on the total mass of component (B).

[0086] (B-3) In the combination of α-hydroxyacetophenone and monoacylphosphine oxide, examples of the monoacylphosphine oxide include( 2,4,6-trimethylbenzoyl)-diphenyl-phosphine oxide (manufactured by IGM Resins B.V., product name: Omnirad TPO-H) and ethyl phenyl-(2,4,6-trimethylbenzoyl)-phosphinate (manufactured by IGM Resins B.V., product name: Omnirad TPO-L) may be mentioned.

[0087] (B-3) In the combination of α-hydroxyacetophenone and monoacylphosphine oxide, (B- 3 ) The quantitative ratio of α-hydroxyacetophenone and monoacylphosphine oxide is not particularly limited. For example, the mass ratio of α-hydroxyacetophenone to monoacylphosphine oxide is 0.1 to 100, preferably 0.5 to 50, and more preferably 0.8 to 20.

[0088] In a particularly preferred embodiment, the photoinitiator containing the combination of (B-3) α-hydroxyacetophenone and monoacylphosphine oxide consists only of α-hydroxyacetophenone and monoacylphosphine oxide, does not contain other photoinitiators, or the amount of other photoinitiators is 10% by mass or less, 5% by mass or less, or 1% by mass or less based on the total mass of component (B).

[0089] In the present specification, "other photoinitiators" include, for example, photoinitiators other than the photoinitiators listed as the above components (B-1) to (B-3) such as bisacylphosphine oxide, trisacylphosphine oxide, phenylglyoxalate, thioxanthone, benzoin ether, oxime ester, etc., but are not limited thereto. The photoinitiator (B) of the present invention may not contain some of these other photoinitiators. Further, the photoinitiator (B) of the present invention may not contain photoinitiators other than α-hydroxyacetophenone, α-aminoalkylphenone, and monoacylphosphine oxide, or may be 10% by mass or less, 5% by mass or less, or 1% by mass or less based on the total mass of component (B).

[0090] (B) The content of the photoinitiator is not particularly limited, but preferably it is contained in an amount of 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more, preferentially 1% by mass or more, and particularly preferably 2% by mass or more, based on the total mass of the ultraviolet curable silicone composition. In a preferred embodiment, (B) the photoinitiator is contained in an amount of 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less, based on the total mass of the ultraviolet curable silicone composition.

[0091] The ultraviolet curable silicone composition of the present invention can be blended with optional components as long as the object of the present invention is not impaired. Examples of such optional components include amino group-containing siloxane compounds, glycidyl (epoxy) group-containing siloxane compounds, ionic liquids, acetylene compounds, organic phosphorus compounds, vinyl group-containing siloxane compounds, ultraviolet absorbers, sensitizers, light stabilizers, free radical scavengers, polymerization inhibitors, antioxidants, ultraviolet absorbers, defoamers, leveling agents, inorganic fillers, surfactants, coupling agents, tackifiers, release agents, metal soaps, heat resistance imparting agents, cold resistance imparting agents, thermal conductivity fillers, flame retardancy imparting agents, thixotropy imparting agents, phosphors, solvents, and the like.

[0092] Although not particularly limited, examples of the coincidence inhibitor (also referred to as a free radical scavenger) include alkoxytitanium and the following products: Genorad® 16, Genorad® 24 (both manufactured by Rahn AG); Sumilizer® GA-80, Sumilizer® GM, Sumilizer® GS (all manufactured by Sumitomo Chemical); Irgastab® UV10, Irgastab® UV22, Tinuvin® 460, Tinuvin® CGS20 (all manufactured by Ciba Specialty Chemicals); Floorstab® UV (UV-1, UV-2, UV-5, UV-8) (manufactured by Kromachem); and Additol® S (S100, S110, S120, S130) (manufactured by Cytec Surface Specialties).

[0093] The ultraviolet curable silicone composition of the present invention can be prepared by mixing each component. The mixing method of each component may be a conventionally known method and is not particularly limited, but usually, a uniform mixture is obtained by simple stirring. When a solid component such as an inorganic filler is included as an optional component, mixing using a mixing device is more preferable. There is no particular limitation on such a mixing device, and examples include single-screw or twin-screw continuous mixers, two-roll mills, Ross mixers, Hobart mixers, dental mixers, planetary mixers, kneader mixers, Henschel mixers, and the like.

[0094] [Use as a Sealing Material and Sheet Film] The present invention also relates to a sealing material or a sheet film obtained by curing the ultraviolet curable silicone composition of the present invention. The sheet film of the present invention is preferably used as a sealing material layer or an adhesive sheet film for mask transfer, and since it is obtained by curing the ultraviolet curable silicone composition of the present invention, it has excellent dimensional stability and little warpage. The electronic device in which the sheet film of the present invention is used is not particularly limited, but is preferably an opto-semiconductor device, and examples thereof include light emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid imaging, and light emitters and light receivers for photocouplers.

[0095] The sealing material or sheet film of the present invention can be obtained, for example, by applying the ultraviolet curable silicone composition of the present invention to a film-like, tape-like substrate, or sheet-like substrate, and then irradiating with ultraviolet rays to cure it, thereby forming a cured film on the surface of the substrate. The film thickness of the cured film is not particularly limited, but is preferably in the range of 1 μm to 10 mm, or in the range of 5 μm to 5 mm.

[0096] In this specification, the term "ultraviolet ray" is electromagnetic radiation having a wavelength of about 10 nm to about 400 nm, and in ultraviolet curing, the wavelength can be selected from the UVA and UVB wavelength bands located, for example, at 280 nm to 400 nm. Examples of the device for generating ultraviolet rays include high-pressure mercury lamps, medium-pressure mercury lamps, and ultraviolet LEDs. The irradiation amount of ultraviolet rays is not particularly limited, but at 365 nm, 1 to 1,000 mW / cm 2 is preferable, more preferably 5 to 500 mW / cm 2 and even more preferably 10 to 200 mW / cm 2 is.

Examples

[0097] The curable silicone composition of the present invention will be described in detail by the following examples and comparative examples.

[0098] In the following examples and comparative examples, the raw material components shown below were used. Hereinafter, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group. Component a-1-1: General formula ViMe2SiO(Me2SiO) 310 Linear organopolysiloxane with vinyl groups blocked at both ends of the molecular chain, represented by SiMe2Vi Component a-1-2: General formula ViMe2SiO(Me2SiO) 150 Linear organopolysiloxane with vinyl groups blocked at both ends of the molecular chain, represented by SiMe2Vi Component a-1-3: General formula ViMe2SiO(Me2SiO) 530 Linear organopolysiloxane with vinyl groups blocked at both ends of the molecular chain, represented by SiMe2Vi Component a-1-4: General formula ViMe2SiO(Me2SiO) 770 Linear organopolysiloxane with vinyl groups blocked at both ends of the molecular chain, represented by SiMe2Vi Component a-1-5: General formula ViMe2SiO(Me2SiO) n Linear organopolysiloxane with vinyl groups blocked at both ends of the molecular chain, having a viscosity of 60 mPas and a vinyl group content of 1.5 mol%, represented by SiMe2Vi Component a-2-1: Unit formula Me3SiO(MeViSiO) n (Me2SiO) m Linear organopolysiloxane with vinyl groups in the side chains of the molecular chain, represented by SiMe3; viscosity 35000 mPas, alkenyl group content 0.5 wt% Component a-2-2: Unit formula Me3SiO(MeViSiO) n (Me2SiO) m Linear organopolysiloxane with vinyl groups in the side chains of the molecular chain, represented by SiMe3; viscosity 8000 mPas, vinyl group content 0.3 wt% Component a-2-3: Unit formula ViMe2SiO(MeViSiO) n (Me2SiO) m Linear organopolysiloxane with vinyl groups in the terminal and side chains of the molecular chain, represented by SiMe2Vi; viscosity 370 cSt, vinyl group content 1.1 wt% Component a-2-4: 1,3,5,7-Tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane Component a-2-5: Branched alkenyl group-containing organosiloxane represented by (ViMe2SiO)3(PhSiO 3 / 2 ) Component a-3-1: Organopolysiloxane containing a thiol group in the side chain of the molecular chain, represented by the unit formula (Me2SiO) n (HSMeSiO) m ; Viscosity 100 mPas, thiol group content 3.6 wt% Component a-3-2: Organopolysiloxane containing a thiol group in the side chain of the molecular chain, represented by the unit formula (Me2SiO) n (HSMeSiO) m ; Viscosity 150 mPas, thiol group content 4.6 wt% Component a-3-3: Organopolysiloxane containing a thiol group in the side chain of the molecular chain, represented by the unit formula (Me2SiO) n (HSMeSiO) m ; Viscosity 150 mPas, thiol group content 1.5 wt% Component a-3-4: Organopolysiloxane containing a thiol group in the side chain of the molecular chain, represented by the unit formula (HSMeSiO) n ; Viscosity 100 mPas, thiol group content 23 wt% Component a’-3-5: Organopolysiloxane containing a thiol group in the side chain of the molecular chain, represented by the unit formula (Me2SiO) n (HSMeSiO) m ; Viscosity 150 mPas, thiol group content 0.8 wt% Component a-4-1: Linear organopolysiloxane blocked with thiol groups at both ends of the molecular chain, represented by the unit formula HSMe2SiO(Me2SiO) n SiMe2SH; Viscosity 90 mPas, thiol group content 1.4 wt% Component a-4-2: Linear organopolysiloxane blocked with thiol groups at both ends of the molecular chain, represented by the unit formula HSMe2SiO(Me2SiO) n SiMe2SH; Viscosity 55 mPas, thiol group content 2.0 wt% Component a-5-1: General formula ViMe2SiO(PhMeSiO) 20Linear organopolysiloxane containing phenyl groups blocked with vinyl groups at both ends of the molecular chain, represented by SiMe2Vi Component a-5-2: General formula ViMe2SiO(Me2SiO) 200 (Ph2SiO) 50 Linear organopolysiloxane containing phenyl groups blocked with vinyl groups at both ends of the molecular chain, represented by SiMe2Vi Component a-5-3: General formula ViMe2SiO(Me2SiO) 60 (Ph2SiO) 30 Linear organopolysiloxane containing phenyl groups blocked with vinyl groups at both ends of the molecular chain, represented by SiMe2Vi Component a-6-1: Unit formula (ViMe2SiO 1 / 2 )4(Me3SiO 1 / 2 ) 40 (SiO 4 / 2 ) 56 Resinous vinyl group-containing organopolysiloxane represented by Component a-6-2: Unit formula (ViMe2SiO 1 / 2 ) 11 (Me3SiO 1 / 2 ) 34 (SiO 4 / 2 ) 55 Resinous vinyl group-containing organopolysiloxane represented by Component a-6-3: Unit formula (ViMe2SiO 1 / 2 ) 15 (Me3SiO 1 / 2 ) 45 (SiO 4 / 2 ) 40 Resinous vinyl group-containing organopolysiloxane represented by Component a-6-4: Unit formula (ViMe2SiO 1 / 2 ) 10 (Me3SiO 1 / 2 ) 40 (SiO 4 / 2 ) 50 Resinous vinyl group-containing organopolysiloxane represented by Component a-6-5: Unit formula (ViMe2SiO 1 / 2 ) 25 (PhSiO 3 / 2 ) 75Resinous vinyl group- and phenyl group-containing organopolysiloxane represented by Component a-6-6: Unit formula (ViMe2SiO 1 / 2 ) 15 (Me2SiO 2 / 2 ) 35 (PhSiO 3 / 2 ) 50 Resinous vinyl group- and phenyl group-containing organopolysiloxane represented by Component a-6-7: Unit formula (ViMeSiO 2 / 2 ) 25 (Ph2SiO 2 / 2 ) 35 (PhSiO 3 / 2 ) 45 Resinous vinyl group- and phenyl group-containing organopolysiloxane represented by Component a-7-1: Tertiary thiol compound represented by the composition formula C 18 H 32 O6S3 trimethylolpropane tris(3-mercaptobutyrate) Component a-7-2: Primary thiol compound represented by the composition formula HSCH2CH2OCH2CH2OCH2CH2SH 2,2'-(ethylenedioxy)diethanethiol Component a-7-3: Primary thiol compound represented by the composition formula (HSCH2COOCH2)2 ethylene glycol bis(mercaptoacetate) Component a-7-4: Primary thiol compound represented by the composition formula (HSCH2CH2CO2CH2)3CC2H5 trimethylolpropane tris(3-mercaptopropionate) Component a-7-5: Primary thiol compound represented by the composition formula (HSCH2CH2COOCH2)4C pentaerythritol tetrakis(3-mercaptopropionate) Component a-7-6: Secondary thiol compound represented by the composition formula C 12 H 22 O4S2 1,4-bis(3-mercaptobutyryloxy)butane Component a-7-7: Composition formula C 18 H 27A trifunctional primary thiol compound represented by tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, N3O9S3 Component a-7-8: Composition formula C 21 H 33 A trifunctional secondary thiol compound represented by 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, C9H10O9N3S3 Component a-7-9: Composition formula C 21 H 36 A tetrafunctional secondary thiol compound represented by pentaerythritol tetrakis(3-mercaptobutyrate), C8H12O8S4 Component b-1: 2-Hydroxy-2-methyl-1-phenyl-1-propanone (manufactured by IGM Resins B.V., product name: Omnirad 1173) Component b-2: 1,1'-(Methylene-di-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone] (manufactured by IGM Resins B.V., product name: Omnirad 127D) Component b-3: 1-Hydroxycyclohexyl-phenyl ketone (manufactured by IGM Resins B.V., product name: Omnirad 184) Component b-4: 2-Methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-propan-1-one (manufactured by IGM Resins B.V., product name: Omnirad 907) Component b-5: 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (manufactured by IGM Resins B.V., product name: Omnirad 379EG) Component b-6: Ethyl phenyl-(2,4,6-trimethylbenzoyl)-phosphinate (manufactured by IGM Resins B.V., product name: Omnirad TPO-L) Component b-7: (2,4,6-Trimethylbenzoyl)-diphenyl-phosphine oxide (manufactured by IGM Resins B.V., product name: Omnirad TPO-H) Component b-8: 2-Benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (manufactured by IGM Resins B.V., product name: Omnirad 369) Component b'-1: Methylbenzoylformate (manufactured by IGM Resins B.V., product name: Omnirad MBF) Component b'-2: 2,4-Diethylthioxanthone-9-one (DETX) Component b'-3: Phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (manufactured by IGM Resins B.V., product name: Omnirad 819) Component b'-4: Ethyl 4-(dimethylamino)benzoate (manufactured by IGM Resins B.V., product name: Omnirad EDB) Component b'-5: 1,1'-(Oxydibis(4,1-phenylene))bis(2-hydroxy-2-methylpropan-1-one) (manufactured by LEHVOSS, product name: Esacure KIP160) Component b'-6: 1-[4-(4-Benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (manufactured by LEHVOSS, product name: Esacure E1001M) Component b'-7: Thioxanthone-based photoinitiator (manufactured by LEHVOSS, product name: Esacure One) Component b'-8: (4,4'-Bis(diethylamino)benzophenone (manufactured by IGM Resins B.V., product name: Omnirad EMK) Component b'-9: Polybutylene glycol bis(4-benzoylphenoxy)acetate (manufactured by IGM Resins B.V., product name: Omnipol BP) Component b'-10: 2,2-Dimethoxy-2-phenylacetophenone (manufactured by IGM Resins B.V., product name: Omnirad 651) Component c: Photosensitizer Anthracure® UVS-1331 (manufactured by Kawasaki Chemical Industry Co., Ltd.)

[0099] [Examples 1 to 53 and Comparative Examples 1 to 34] Each component was mixed in the compositions (mass %) shown in Tables 1 to 9 to prepare an ultraviolet curable silicone composition. In the tables, the "SH / Vi ratio" represents the molar ratio of the thiol group and vinyl group contained in the organopolysiloxane component.

[0100] [Evaluation] In each composition according to the examples or comparative examples, the curability was measured as follows, and the results are shown in Tables 1 to 9.

[0101] The composition obtained using a blade coater was applied at a thickness of 10 μm on a PET film. Using a metal halide lamp, ultraviolet light was irradiated as follows in (1) to (3) to cure the composition and obtain a film. (1) Wavelength 254 nm; 5.4 mJ / cm 2 (Irradiation for 1 minute) (2) Wavelength 365 nm; 12.3 J / cm 2 (Irradiation for 1 minute) (3) Wavelength 405 nm; 69.3 J / cm 2 (Irradiation for 1 minute)

[0102] The obtained film was cut into a size of 5 × 5 cm 2 and this sample was immersed in 50 mL of toluene, washed for 30 minutes, dried at 120 °C for 90 minutes, and the residual weight was measured (N = 4). The values of the obtained residual weight are shown in Tables 1 to 5 below. A composition having a residual weight of 50% or more can be judged to have excellent curability. In addition, those in which the (A) component and the (B) component did not mix were indicated as "did not mix", and those in which the composition did not cure were indicated as "did not cure".

[0103]

Table 1

[0104]

Table 2

[0105]

Table 3

[0106]

Table 4

[0107]

Table 5

[0108]

Table 6

[0109]

Table 7

[0110]

Table 8

[0111]

Table 9

[0112] As can be seen from the above results, the ultraviolet curable silicone compositions of Examples 1 to 53 of the present invention showed excellent curability upon ultraviolet irradiation. 。

Industrial Applicability

[0113] The ultraviolet curable silicone composition of the present invention is particularly useful for providing a sealing material for optical semiconductor devices such as electronic devices, particularly light emitters and light receivers for light emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state imaging, and photocouplers, and an adhesive sheet film for mass transfer.

Claims

1. (A) An organopolysiloxane composition selected from the following: (A-1) A molecular chain both-ends alkenyl group-blocked linear organopolysiloxane and / or a branched organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, wherein the organic group is selected from monovalent hydrocarbon groups other than aryl groups, and an organopolysiloxane containing at least two thiol groups in the molecular chain side chains, with the thiol group content being 1% by mass or more per molecule, (A-2) A molecular chain both-ends thiol group-blocked linear organopolysiloxane with the thiol group content being 1% by mass or more per molecule, and an organopolysiloxane containing at least two alkenyl groups in the molecular chain side chains and / or a resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain ends, (A-3) An organopolysiloxane composition containing an alkenyl group and aryl group-containing organopolysiloxane and a polyfunctional thiol compound that is not an organopolysiloxane, provided that when the polyfunctional thiol compound contains only bifunctional thiol compounds, it further contains a resinous organopolysiloxane containing alkenyl groups, and, (B) A silicone-compatible photoinitiator containing a compound selected from the following: (B-1) α-Hydroxyacetophenone (B-2) A combination of α-hydroxyacetophenone and α-aminoalkylphenone, or (B-3) A combination of α-hydroxyacetophenone and monoacylphosphine oxide and, The molar ratio (SH / Vi ratio) of the thiol groups (-SH groups) and alkenyl groups contained in the organopolysiloxane composition is 0.6 or more, (B) The photoinitiator contains a photoinitiator other than α-hydroxyacetophenone, α-aminoalkylphenone, and monoacylphosphine oxide in an amount of 0% by mass or more and 10% by mass or less based on the total mass of component (B). An ultraviolet curable silicone composition (However, when including the combination of (A-3) and (B-3), and when including (A-3), the organopolysiloxane composition (A) 100 parts by weight of an organopolysiloxane having an average of at least two alkenyl groups per molecule, a number average molecular weight of 1,000 to 50,000, and an average of 10 to 90 mol% of phenyl groups bonded to silicon per molecule, and (B) A curing agent, (1) A mixture containing (a) an organohydrogensiloxane having an average of at least two hydrogen atoms bonded to silicon per molecule in an amount sufficient to cure the composition, and (b) a catalytic amount of a hydrosilylation catalyst, and (2) A curing agent selected from a mixture containing (a) a mercapto-functional compound selected from (i) a mercapto-functional organosiloxane having an average of at least two mercaptoalkyl groups per molecule and (ii) a mercapto-functional organic compound having an average of at least two mercapto groups per molecule in an amount sufficient to cure the composition, and (b) a catalytic amount of a photoinitiator. (C) 1 to 200 parts by weight of a liquid crystal that is miscible in components (A) and (B), and the liquid crystal (i) Formula [Chemical formula 1] having at least one compound, and (ii) A mixture selected from (i) and 1 to 10% (w / w) of at least one terphenyl compound having the formula [Chemical formula 2] having. (wherein each R1 is independently selected from C1-C20 alkyl, C5-C8 cycloalkyl, -OR2, -O(=O)CR2, -C≡N, -NO2, -CH=CHCOOR2, -F, -Cl, -Br and -I, where R2 is C1-C20 alkyl, X is a divalent organic group selected from -CH=N-, -N=N-, -N=N(O)-, -CH=CH-, -C≡C-, -C(=O)O- and -CH=N-N=CH-, and n is 0 or 1); and (D) 1 to 20 parts by weight of a compatibilizer, (i) at least one silicone fluid having the formula R33SiO(R32SiO)wSiR33 and (ii) at least one biphenyl compound having the formula [Chemical Formula 3] and (iii) a compatibilizer selected from 1-phenylnaphthalene (wherein R1 is selected from C1-C20 alkyl, C5-C8 cycloalkyl, -OR2, -O(=O)CR2, -C≡N, -NO2, -CH=CHCOOR2, -F, -Cl, -Br and -I, where R2 is C1-C20 alkyl, each R3 is independently a C1-C6 hydrocarbyl not containing an unsaturated aliphatic group, where 40 to 90 mol% of R3 is phenyl, R4 is selected from R53Si(OSiR52)z(CH2)y- and R53Si(OSiR52)z(CH2)yO-, where R5 is a C1-C4 hydrocarbyl, y is an integer from 2 to 12, and z is an integer from 0 to 20, n is 0 or 1, and w has a value from 1 to 10), except when it is a silicone composition containing).

2. A sealing material or an adhesive sheet film for an optical semiconductor, comprising a cured product of the ultraviolet curable silicone composition according to Claim 1.

3. The ultraviolet curable silicone composition according to claim 1, which forms a cured product having transparency.

4. (A) An organopolysiloxane composition selected from the following: (A-1) A linear organopolysiloxane blocked at both ends of the molecular chain with alkenyl groups and / or a branched organopolysiloxane containing at least two alkenyl groups at the molecular chain terminals, and an organopolysiloxane containing at least two thiol groups in the side chains of the molecular chain, wherein the content of the thiol groups is 1% by mass or more per molecule, (A-2) A linear organopolysiloxane blocked at both ends of the molecular chain with thiol groups, wherein the content of the thiol groups is 1% by mass or more per molecule, and an organopolysiloxane containing at least two alkenyl groups in the side chains of the molecular chain and / or a resinous organopolysiloxane containing at least two alkenyl groups at the molecular chain terminals, or (A-3) An organopolysiloxane composition containing an alkenyl group- and aryl group-containing organopolysiloxane and a polyfunctional thiol compound, provided that when the polyfunctional thiol compound contains only a bifunctional thiol compound, it further contains a resinous organopolysiloxane containing an alkenyl group, (B) A photoinitiator miscible with silicone selected from the following compounds: (B-1) α-Hydroxyacetophenone (B-2) A combination of α-hydroxyacetophenone and α-aminoalkylphenone, or (B-3) A combination of α-hydroxyacetophenone and monoacylphosphine oxide, and (C) One or more components selected from the group consisting of a sensitizer, a free radical scavenger, and a polymerization inhibitor other than the photoinitiator (B) miscible with silicone consisting only of The molar ratio (SH / Vi ratio) of the thiol group (—SH group) to the alkenyl group contained in the organopolysiloxane composition is 0.6 or more, (B) The photoinitiator contains a photoinitiator other than α-hydroxyacetophenone, α-aminoalkylphenone, and monoacylphosphine oxide in an amount of 0% by mass or more and 10% by mass or less based on the total mass of the component (B). The ultraviolet curable silicone composition.

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