Curable silicone composition, sealing material, and optical semiconductor device

Abstract

The objective of this invention is to provide a curable silicone composition exhibiting excellent thixotropic properties and reduced shape change or shrinkage during curing. This objective is achieved by a curable silicone composition comprising: (A) an alkenyl-containing organopolysiloxane having at least two alkenyl groups per molecule; (B) an organohydrogen-containing organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule; and (C) an epoxy-containing resinous organopolysiloxane represented by the following average unit formula (I): (R 1 3SiO 1 / 2 ) f (R 2 2SiO 2 / 2 ) g (R 1 SiO 3 / 2 ) h (SiO 4 / 2 ) i (XO 1 / 2 ) j In equation (I), R 1 Each is an independent monovalent hydrocarbon group, either halogenated or unsubstituted, wherein at least two R groups are halogenated or unsubstituted. 1 It is an alkenyl group, R 2 Each is independently a halogenated or unsubstituted monovalent hydrocarbon group or an epoxy-containing organic group, wherein at least one R 2 It is an organic group containing an epoxy group, where X is a hydrogen atom or an alkyl group, 0 ≤ f < 1, 0 <g<1,0≤h<0.9,0≤i<0.5,0<j<0.5,f+g+h+i+j=1.0,h+i> 0, and j / (f+g+h+i+j)>0.05}; and (D) the catalyst for curing.

Description

[Technical Field]

[0001] This invention relates to a curable silicone composition, and more specifically, to a curable silicone composition suitable for use as a sealing material in optoelectronic semiconductors. Furthermore, this invention also relates to an optoelectronic semiconductor device sealed using a sealing material composed of a cured product of the said curable silicone composition. [Background Technology]

[0002] Curable silicone compositions cure to form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency, and are therefore used in a wide range of industries. In particular, compared with other organic materials, this cured product is less prone to discoloration and exhibits less degradation in physical properties, thus it is widely used as an optical material, especially as a silicone sealing material in light-emitting diodes (LEDs) and other light semiconductor devices.

[0003] Generally, the adhesion of curable silicone compositions, especially hydrogen silane-curable silicone compositions, to substrates such as metals or resins is sometimes insufficient. Therefore, curable silicone compositions with adhesive-improving agents have been known in the past.

[0004] For example, Patent Document 1 describes an adhesion promoter, which is represented by the following average formula: R 1 a SiO (4-a) / 2 (where R is in the formula) 1 The group is selected from the group consisting of substituted or unsubstituted alkyl groups having 1-10 carbon atoms, alkenyl groups having 2-20 carbon atoms, aryl groups having 6-20 carbon atoms, alkoxy groups having 1-10 carbon atoms, and epoxy-containing organic groups, wherein, in one molecule, the content of the alkenyl group is all R 1 At least 5 mol%, the content of said aryl group is the total R 1 At least 5 mol%, the content of the alkoxy group is the total R 1 At least 5 mol%, the content of the epoxy-containing organic groups is the total R 1 At least 5 mol% of the adhesive (where a is a number satisfying 1.0 ≤ a < 4.0), and a curable organopolysiloxane composition comprising the adhesive promoter is also described.

[0005] Furthermore, Patent Document 2 discloses a curable organopolysiloxane composition comprising at least the following components (A), (B), (C), and (D), wherein (A) is a composition of average formula R 1 a SiO (4-a) / 2 (In the formula, each R) 1 It is a monovalent hydrocarbon group that is either unsubstituted or halogenated, wherein, in a molecule, at least two R groups are present.1 It is alkenyl, all R 1 (A) is an organopolysiloxane represented by at least 30 mol% of aryl groups, where a is a number from 0.6 to 2.1; (B) is an organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, and having at least 15 mol% of aryl groups in all organic groups bonded to silicon atoms; (C) is an organopolysiloxane represented by the average unit formula (R... 2 SiO 3 / 2 ) b (R 2 2SiO 2 / 2 ) c (R 2 3SiO 1 / 2 ) d (SiO 4 / 2 ) e (XO 1 / 2 ) f {In the formula, each R 2 Independently alkyl, alkenyl, aryl, or epoxy-containing organic groups, wherein, in one molecule, all R 2 The branched organopolysiloxane represents a compound containing at least 5 mol% alkenyl, at least 15 mol% aryl, and at least 10 mol% epoxy-containing organic groups, where X is a hydrogen atom or alkyl, b is a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, f is 0 or a positive number, and c / b is a number from 0 to 10, d / b is a number from 0 to 5, e / (b+c+d+e) is a number from 0 to 0.3, and f / (b+c+d+e) is a number from 0 to 0.02. D) is a catalyst for the hydrosilylation reaction, and the content of component (B) is relative to the alkenyl groups contained in component (A) and component (C), the amount of hydrogen atoms bonded to silicon atoms in component (B) is 0.1-5 in molar ratio, the content of component (C) is 0.1-20 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (B), and the content of component (D) is the amount that promotes the curing of this composition.

[0006] In addition, Patent Document 3 describes an adhesion promoter that satisfies [Chemical Formula 1]R 1 a SiO (4-a) / 2 In the chemical formula 1, R 1 R represents alkyl groups with 1-20 carbon atoms, cycloalkyl groups with 3-20 carbon atoms, alkenyl groups with 2-20 carbon atoms, aryl groups with 6-20 carbon atoms, arylalkyl groups with 6-20 carbon atoms, alkoxy groups with 1-20 carbon atoms, or epoxy-containing organic groups. 'a' is a number satisfying the condition 1.0 ≤ a < 4.0. 1One or more of the aryl groups are substituted or unsubstituted by at least one substituent selected from the group consisting of alkyl groups having 1-10 carbon atoms, aryl groups having 6-10 carbon atoms, and halogen groups. Within a molecule, the content of aryl groups is determined by R. 1 The percentage of all substituents is 20 mol% or more, and the content of epoxy-containing organic groups is determined by R. 1 The percentage of all substituents represented is 15-30 mol%, and the alkoxy group content is determined by R. 1 The total number of substituents represented is less than 5 mol%, and the molar ratio of alkenyl to epoxy-containing organic groups is 0.3:1-1.2:1. In addition, a curable organopolysiloxane composition containing the adhesive promoter is also described.

[0007] However, in conventional curable silicone compositions containing adhesion promoters, the phosphor exhibits low dispersibility when formulated, resulting in insufficient light extraction efficiency of the light-emitting element. The following problems exist: due to insufficient thixotropy of the curable silicone composition, even when applied directly and appropriately to the photo-semiconductor on the support substrate using a dispensing machine and cured, the applied curable silicone composition still flows, sometimes failing to achieve the desired cured shape. Furthermore, conventional hot-melt silicone compositions containing adhesion promoters also suffer from shape shrinkage during curing, resulting in occasional warping of the flexible substrate or reduced patterning accuracy during the semiconductor device encapsulation process.

[0008] [Existing Technical Documents]

[0009] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2007-327019

[0011] [Patent Document 2] Japanese Patent Application Publication No. 2010-1335

[0012] [Patent Document 3] Japanese Patent Application Publication No. 2016-138268 [Summary of the Invention]

[0013] [The technical problem that the invention aims to solve]

[0014] The purpose of this invention is to provide a curable silicone composition that can achieve both excellent adhesive strength and light extraction efficiency.

[0015] Another object of the present invention is to provide a sealing material comprising the curable silicone composition of the present invention. Furthermore, yet another object of the present invention is to provide an optical semiconductor device sealed by the sealing material of the present invention.

[0016] [Technical means used to solve the problem]

[0017] To address the aforementioned problems, the inventors conducted extensive research and unexpectedly discovered that curable silicone compositions containing epoxy-based resinous organopolysiloxanes with specific structures can achieve a balance between excellent adhesive strength and light extraction efficiency. Furthermore, the inventors found that by improving the dispersibility of fillers or phosphors when formulating the mixture, excellent light extraction efficiency can be maintained, and even with the addition of small amounts of fillers or phosphors, excellent thixotropy can be achieved, while reducing shape changes or shrinkage during curing, thus completing this invention.

[0018] Therefore, the present invention relates to a curable silicone composition comprising:

[0019] (A) Alkenyl-containing organopolysiloxanes having at least two alkenyl groups per molecule;

[0020] (B) Organohydrogen polysiloxanes in which each molecule has at least two hydrogen atoms bonded to silicon atoms;

[0021] (C) An epoxy-containing resinous organopolysiloxane represented by the following average unit formula (I): (R 1 3SiO 1 / 2 ) f (R 2 2SiO 2 / 2 ) g (R 1 SiO 3 / 2 ) h (SiO 4 / 2 ) i (XO 1 / 2 ) j

[0022] In equation (I), R 1 Each is an independent monovalent hydrocarbon group, either halogenated or unsubstituted, wherein at least two R groups are halogenated or unsubstituted. 1 It is an alkenyl group, R 2 Each is independently a halogenated or unsubstituted monovalent hydrocarbon group or an epoxy-containing organic group, wherein at least one R 2 It is an organic group containing an epoxy group, where X is a hydrogen atom or an alkyl group, 0 ≤ f < 1, 0 <g<1,0≤h<0.9,0≤i<0.5,0<j<0.5,f+g+h+i+j=1.0,h+i> 0, and j / (f+g+h+i+j)>0.05}; and

[0023] (D) Curing catalyst.

[0024] In the above formula (I), R is preferred. 1 At least 30 mol% of it is aryl.

[0025] The (A) alkenyl organopolysiloxane preferably comprises a resinous organopolysiloxane, a linear organopolysiloxane, or both, in which the aryl group accounts for more than 20 mol% of all functional groups bonded to silicon atoms.

[0026] Preferably, the (B) organohydrogen polysiloxane comprises both linear organohydrogen polysiloxane and resinous organohydrogen polysiloxane.

[0027] The curable silicone composition of the present invention may also contain silicon dioxide as an inorganic filler.

[0028] The present invention also relates to a sealing material composed of the curable silicone composition of the present invention.

[0029] The present invention also relates to an optical semiconductor device comprising the sealing material of the present invention.

[0030] [Invention Effects]

[0031] The curable silicone composition according to the present invention provides a curable silicone composition that can achieve both excellent adhesive strength and light extraction efficiency. Furthermore, it provides a curable silicone composition that, when containing fillers or phosphors, can achieve excellent thixotropy and light extraction efficiency by improving the dispersibility of the fillers or phosphors, and reduces shape change or shrinkage during curing. [Attached Image Description]

[0032] Figure 1 This is a cross-sectional view of an LED, which is an example of the optical semiconductor device of the present invention.

Detailed Implementation Methods

[0033] [Curing silicone composition]

[0034] The curable silicone composition of the present invention comprises at least:

[0035] (A) Alkenyl-containing organopolysiloxanes having at least two alkenyl groups per molecule;

[0036] (B) Organohydrogen polysiloxanes in which each molecule has at least two hydrogen atoms bonded to silicon atoms;

[0037] (C) An epoxy-containing resinous organopolysiloxane represented by the following average unit formula (I): (R 1 3SiO 1 / 2 ) f (R 2 2SiO 2 / 2 ) g (R 1 SiO 3 / 2 ) h (SiO 4 / 2 )i (XO 1 / 2 ) j

[0038] In equation (I), R 1 Each is an independent monovalent hydrocarbon group, either halogenated or unsubstituted, wherein at least two R groups are halogenated or unsubstituted. 1 It is an alkenyl group, R 2 Each is independently a halogenated or unsubstituted monovalent hydrocarbon group or an epoxy-containing organic group, wherein at least one R 2 It is an organic group containing an epoxy group, where X is a hydrogen atom or an alkyl group, 0 ≤ f < 1, 0 <g<1,0≤h<0.9,0≤i<0.5,0<j<0.5,f+g+h+i+j=1.0,h+i> 0, and j / (f+g+h+i+j)>0.05}; and

[0039] (D) Curing catalyst.

[0040] The components of the curable silicone composition of the present invention will now be described in detail.

[0041] (A) Alkenyl-containing organopolysiloxanes with at least two alkenyl groups per molecule

[0042] Component (A) is the main component of this composition and is a curable organopolysiloxane having at least two alkenyl groups in one molecule. The curable silicone composition of the present invention may contain one (A) alkenyl-containing organopolysiloxane or two or more (A) alkenyl-containing organopolysiloxanes.

[0043] Examples of molecular structures for component (A) include linear, partially branched linear, branched, resinous, cyclic, and three-dimensional network structures. Component (A) may also be a single organopolysiloxane having these molecular structures, or a mixture of two or more organopolysiloxanes having these molecular structures. The curable silicone composition of the present invention preferably comprises both a linear alkenyl organopolysiloxane and a resinous alkenyl organopolysiloxane as component (A). In this specification, resinous refers to a molecular structure having a branched or three-dimensional network structure.

[0044] Examples of alkenyl groups included in component (A) include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, etc., with 2 to 12 carbons, preferably vinyl.

[0045] As a group bonded to silicon atoms, other than alkenyl groups, included in component (A) may be a halogenated or unsubstituted monovalent hydrocarbon group, such as alkyl groups with 1-12 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups with 6-20 carbon atoms, including phenyl, tolyl, xylyl, and naphthyl; aralkyl groups with 7-20 carbon atoms, including benzyl, phenethyl, and phenylpropyl; and groups in which some or all of the hydrogen atoms of these groups are substituted by halogen atoms such as fluorine, chlorine, or bromine atoms. Furthermore, without hindering the purpose of the present invention, a small amount of hydroxyl or alkoxy groups such as methoxy or ethoxy may be present on the silicon atoms in component (A). (A) The groups bonded to silicon atoms, other than alkenyl groups, are preferably selected from alkyl groups having 1-6 carbon atoms, especially methyl groups, aryl groups having 6-20 carbon atoms, especially phenyl groups.

[0046] In one embodiment of the present invention, component (A) may comprise a resinous alkenyl-containing organopolysiloxane as component (A-1). The resinous alkenyl-containing organopolysiloxane (A-1) is preferably composed of an average unit formula (II): (R 3 3SiO 1 / 2 ) a (R 3 2SiO 2 / 2 ) b (R 3 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e

[0047] (In formula (II), R) 3 They are the same or different halogenated or unsubstituted monovalent hydrocarbon groups, wherein, in a molecule, at least two R groups are present. 3 It is represented by an alkenyl group, 0≤a<1, 0≤b<1, 0≤c<0.9, 0≤d<0.5, 0≤e<0.4, a+b+c+d=1.0, and c+d>0).

[0048] As R in the above equation (II) 3The halogenated or unsubstituted monovalent hydrocarbon group can be exemplified by alkyl groups having 1-12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups having 6-20 carbon atoms, such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups having 7-20 carbon atoms, such as benzyl, phenethyl, and phenylpropyl; alkenyl groups having 2-12 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, or bromine atoms. Within the scope of this invention, R 3 It can also be a small amount of hydroxyl or alkoxy groups such as methoxy and ethoxy. R 3 Preferably, it is selected from alkyl groups having 1-6 carbon atoms, especially methyl, alkenyl groups having 2-6 carbon atoms, especially vinyl, or aryl groups having 6-20 carbon atoms, especially phenyl.

[0049] In formula (II) above, X is a hydrogen atom or an alkyl group. Preferably, X is an alkyl group having 1 to 3 carbon atoms, and examples include methyl, ethyl and propyl.

[0050] In formula (II) above, a is preferably in the range of 0.1 ≤ a ≤ 0.8, more preferably in the range of 0.15 ≤ a ≤ 0.6, and even more preferably in the range of 0.2 ≤ a ≤ 0.4. In formula (II) above, b is preferably in the range of 0 ≤ b ≤ 0.6, more preferably in the range of 0 ≤ b ≤ 0.5, and especially in the range of 0 ≤ b ≤ 0.4. In formula (II) above, c is preferably in the range of 0.2 ≤ c < 0.9, more preferably in the range of 0.3 ≤ c ≤ 0.85, and especially in the range of 0.4 ≤ c ≤ 0.8. In formula (II) above, d is preferably in the range of 0 ≤ d ≤ 0.4, more preferably in the range of 0 ≤ d ≤ 0.25, and especially in the range of 0 ≤ d ≤ 0.1. In formula (II) above, e is preferably in the range of 0 ≤ e ≤ 0.15, more preferably in the range of 0 ≤ e ≤ 0.1, and especially in the range of 0 ≤ e ≤ 0.05.

[0051] In a preferred embodiment of the present invention, in the above formula (II), c is greater than 0, that is, the resinous alkenyl-containing organopolysiloxane of component (A-1) comprises SiO 3 / 2 The term represents a siloxane unit (T unit). The resinous organopolysiloxane of component (A-1) may or may not contain SiO₂. 4 / 2 The siloxane unit (Q unit) is indicated, but preferably not included.

[0052] In a preferred embodiment of the present invention, the resinous alkenyl-containing organopolysiloxane of component (A-1) contains an alkenyl group at the molecule's end. The resinous organopolysiloxane of component (A-1) is preferably formed from SiO₂. 1 / 2 The siloxane unit (M unit) represents an alkenyl group, which is present on the side chain of the molecular chain (i.e., composed of SiO2). 2 / 2 The siloxane unit (D unit) and the siloxane unit represented by SiO2 3 / 2 The siloxane unit (T unit) may or may not contain an alkenyl group, but it is preferred that it does not contain one.

[0053] The content of alkenyl groups in the resinous alkenyl-containing organopolysiloxane of component (A-1) is not particularly limited. For example, it can be 5 mol% or more of the total amount of organic groups bonded to silicon atoms, preferably 10 mol% or more, more preferably 15 mol% or more, and can be 40 mol% or less of the total amount of organic groups bonded to silicon atoms, preferably 30 mol% or less, more preferably 20 mol% or less. In addition, the content of alkenyl groups can be determined by analytical methods such as Fourier Transform Infrared Spectrometer (FT-IR), Nuclear Magnetic Resonance (NMR), or the titration method described below.

[0054] A method for quantifying the amount of alkenyl groups in each component by titration is described. The alkenyl content in organopolysiloxane components can be quantified with high precision using the well-known Widmanstätten titration method. The principle is as follows. First, as shown in formula (1), the alkenyl groups in the organopolysiloxane raw material undergo an addition reaction with iodine monochloride. Next, through the reaction shown in formula (2), excess iodine monochloride reacts with potassium iodide to release iodine. Then, the released iodine is titrated with sodium thiosulfate solution.

[0055] Equation (1) CH2=CH-+2ICl→CH2I-CHCl-+ICl (excess)

[0056] Equation (2) ICl + KI → I2 + KCl

[0057] The amount of alkenyl groups in the component can be quantified by the difference between the amount of sodium thiosulfate required for titration and the titration amount of a separately prepared blank solution.

[0058] In a preferred embodiment of the present invention, the resinous alkenyl-containing organopolysiloxane of component (A-1) contains aryl groups in the organic groups bonded to silicon atoms. That is, in formula (II) above, at least one R 3The aryl group may be present. In a preferred embodiment of the invention, the resinous alkenyl-containing organopolysiloxane of component (A-1) contains an aryl group bonded to a silicon atom on the side chain of the molecular chain, i.e., the D unit or the T unit. The resinous alkenyl-containing organopolysiloxane of component (A-1) may or may not contain an aryl group at the molecular end, i.e., the M unit, but it is preferred that it does not contain an aryl group. In addition, aryl groups with 6 to 20 carbon atoms can be listed as aryl groups, especially phenyl, tolyl, xylyl, and naphthyl.

[0059] When the resinous organopolysiloxane of component (A-1) contains aryl groups, its content (the mol% of aryl groups in all functional groups bonded to silicon atoms in the resinous organopolysiloxane) can be designed as needed, typically 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, further preferably 20 mol% or more, preferably 30 mol% or more, especially preferably 40 mol% or more, and can be 80 mol% or less, preferably 70 mol% or less, more preferably 65 mol% or less, preferably 60 mol% or less, especially preferably 55 mol% or less. Furthermore, the aryl content can be determined by analysis, for example, using Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0060] The organopolysiloxane of component (A-1) is preferably solid or semi-solid at 25°C. The number average molecular weight of the organopolysiloxane of component (A-1) is not particularly limited, but is preferably in the range of 500-10,000.

[0061] When component (A) contains (A-1) resinous organopolysiloxane, its content is not particularly limited. Based on the total mass of all organopolysiloxane components contained in the curable silicone composition of the present invention, it is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and especially preferably 50% by mass or more. Furthermore, based on the total mass of all organopolysiloxane components, the content of component (A-1) is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and especially preferably 65% ​​by mass or less.

[0062] Component (A) may also include a linear alkenyl-containing organopolysiloxane as component (A-2). The linear alkenyl-containing organopolysiloxane in component (A-2) is preferably composed of...

[0063] Average structure (III): R 3 3SiO(R 3 2SiO 2 / 2 ) m SiR 3 3

[0064] (In formula (III), R) 3They are the same or different halogenated or unsubstituted monovalent hydrocarbon groups, wherein, in a molecule, at least two R groups are present. 3 (where m is 1-500) represents an alkenyl group.

[0065] In equation (III) above, R 3 The halogenated or unsubstituted monovalent hydrocarbon group can be the same group as that in formula (II) above.

[0066] In the above formula (III), m is preferably 2-300, more preferably 5-200, even more preferably 10-150, and especially preferably 15-100.

[0067] Examples of this (A-2) component include dimethylpolysiloxanes whose molecular chains are capped at both ends by dimethylvinylsiloxy groups, dimethylpolysiloxanes whose molecular chains are capped at both ends by diphenylvinylsiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymers whose molecular chains are capped at both ends by dimethylvinylsiloxy groups, dimethylsiloxane-diphenylsiloxane copolymers whose molecular chains are capped at both ends by dimethylvinylsiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymers whose molecular chains are capped at both ends by diphenylvinylsiloxy groups, and dimethylsiloxane-methylvinylsiloxane copolymers whose molecular chains are capped at both ends by dimethylvinylsiloxy groups. The copolymers of dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane with both ends capped by dimethylvinylsiloxy groups, the copolymers of dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane with both ends capped by dimethylvinylsiloxy groups, the copolymers of methylvinylpolysiloxane with both ends capped by trimethylsiloxy groups, the copolymers of methylvinylsiloxane-methylphenylsiloxane with both ends capped by trimethylsiloxy groups, the copolymers of methylvinylsiloxane-diphenylsiloxane with both ends capped by trimethylsiloxy groups, and the copolymers of dimethylsiloxane-methylvinylsiloxane with both ends capped by trimethylsiloxy groups.

[0068] In a preferred embodiment of the present invention, the linear organopolysiloxane containing alkenyl groups in component (A-2) can be a linear organopolysiloxane with alkenyl groups at both ends of the molecular chain, or with the ends of the molecular chain capped by alkenyl groups. The linear organopolysiloxane in component (A-2) may or may not contain alkenyl groups on the side chains (i.e., D units) of the molecular chain, but preferably does not contain alkenyl groups.

[0069] The content of alkenyl groups in the linear organopolysiloxane of component (A-2) (the molar percentage of alkenyl groups in all functional groups bonded to silicon atoms in the linear organopolysiloxane) can be designed as needed, typically 0.05 mol% or more, preferably 0.01 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, more preferably 10 mol% or less, and most preferably 7 mol% or less. Furthermore, the content of alkenyl groups can be determined by analysis, for example, Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), and the titration method described above.

[0070] In one embodiment of the present invention, the linear organopolysiloxane of component (A-2) contains aryl groups in the organic groups bonded to silicon atoms. That is, in formula (III) above, at least one R 3 It can be aryl. In a preferred embodiment of the invention, the linear alkenyl-containing organopolysiloxane of component (A-2) contains aryl groups bonded to silicon atoms on the side chains of the molecular chain. The linear organopolysiloxane of component (A-2) may or may not contain aryl groups at the ends of the molecular chain (i.e., M units), but preferably does not.

[0071] When the linear organopolysiloxane of component (A-2) contains aryl groups, its content (the mol% of aryl groups in all functional groups bonded to silicon atoms in the linear organopolysiloxane) can be designed as needed, typically 15 mol% or more, preferably 20 mol% or more, more preferably 25 mol% or more, further preferably 30 mol% or more, and can be 75 mol% or less, preferably 65 mol% or less, more preferably 60 mol% or less, preferably 55 mol% or less, and especially preferably 50 mol% or less. Furthermore, the aryl content can be determined by analysis, for example, using Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0072] When component (A) contains linear organopolysiloxane (A-2), its content is not particularly limited. Based on the total mass of all organopolysiloxane components contained in the curable silicone composition of the present invention, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and especially preferably 15% by mass or more. Furthermore, based on the total mass of all organopolysiloxane components, the content of component (A-2) is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and especially preferably 20% by mass or less.

[0073] Component (A) may also include a cyclic alkenyl-containing organopolysiloxane as component (A-3). The cyclic alkenyl-containing organopolysiloxane in component (A-3) is preferably composed of...

[0074] Average structural formula (IV): (R)3 2SiO) n

[0075] (In formula (IV), R) 3 The R groups are the same or different halogenated or unsubstituted monovalent hydrocarbon groups, wherein, in a molecule, at least two R groups are present. 3 (where n is an alkenyl group and n is a number representing a viscosity of less than 1000 mPa at 25°C).

[0076] In equation (IV) above, R 3 The halogenated or unsubstituted monovalent hydrocarbon group can be the same group as that in formula (II) above.

[0077] In the above formula (IV), n is a number for a viscosity of 1000 mPa or less at 25°C, for example, 4-15, preferably 4-10, and more preferably 4-8. Furthermore, in this specification, the viscosity of the organopolysiloxane component can be measured at 25°C using a rotational viscometer according to JIS K7117-1.

[0078] In one embodiment, the content of alkenyl groups in the cyclic alkenyl-containing organopolysiloxane of component (A-3) (the molar percentage of alkenyl groups in all functional groups bonded to silicon atoms in the cyclic organopolysiloxane) can be designed as needed, typically 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, preferably 45 mol% or more, and can be 80 mol% or less, preferably 70 mol% or less, more preferably 60 mol% or less, and preferably 55 mol% or less. Furthermore, the content of alkenyl groups can be determined by analysis, for example, using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), and the titration method described above.

[0079] When component (A) contains the cyclic organopolysiloxane of component (A-3), its content is not particularly limited. Based on the total mass of all organopolysiloxane components contained in the curable silicone composition of the present invention, it is 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and especially preferably 0.15% by mass or more. Furthermore, based on the total mass of all organopolysiloxane components, the content of component (A-3) is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and especially preferably 1% by mass or less.

[0080] The curable silicone composition of the present invention preferably comprises (A-1) a resinous organopolysiloxane and (A-2) a linear organopolysiloxane as component (A). The mass ratio of (A-1) resinous organopolysiloxane to (A-2) linear organopolysiloxane is not particularly limited, but the mass ratio of (A-2) linear organopolysiloxane to (A-1) resinous organopolysiloxane is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.25 or more, and preferably 3 or less, more preferably 1 or less, further preferably 0.7 or less, more preferably 0.5 or less, and particularly preferably 0.4 or less.

[0081] In a preferred embodiment, component (A) comprises an alkenyl organopolysiloxane containing a large number of aryl groups in the functional groups bonded to silicon atoms. Specifically, it comprises a (A-1) resinous organopolysiloxane, (A-2) linear organopolysiloxane, or both of the above, in which the amount of aryl groups in all functional groups bonded to silicon atoms is 20 mol% or more, preferably 25 mol% or more, and more preferably 30 mol% or more.

[0082] The total content of component (A) is not particularly limited, but based on the total mass of the curable silicone composition, it is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and especially preferably 70% by mass or more. In a preferred embodiment, based on the total mass of the curable silicone composition, the content of component (A) is 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less.

[0083] (B) Organohydrogen polysiloxanes with at least two hydrogen atoms bonded to silicon atoms per molecule.

[0084] Component (B) acts as a crosslinking agent in the curable silicone composition through a hydrogenation-silanization curing reaction, and is an organohydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule. The curable silicone composition of the present invention may contain one or more (B) organohydrogen polysiloxanes.

[0085] Examples of molecular structures for component (B) include linear, partially branched linear, branched, resinous, cyclic, and three-dimensional network structures. Component (B) may also be one organohydrogen polysiloxane having these molecular structures, or a mixture of two or more organohydrogen polysiloxanes having these molecular structures. The curable silicone composition of the present invention preferably comprises both a linear organohydrogen polysiloxane and a resinous organohydrogen polysiloxane as component (B).

[0086] As included in component (B), groups bonded to silicon atoms, excluding hydrogen atoms bonded to silicon atoms, can include halogenated or unsubstituted monovalent hydrocarbon groups other than alkenyl groups. Examples include alkyl groups with 1-12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups with 6-20 carbon atoms such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups with 7-20 carbon atoms such as benzyl, phenethyl, and phenylpropyl; and groups in which some or all of the hydrogen atoms of these groups are replaced by halogen atoms such as fluorine, chlorine, or bromine atoms. Furthermore, without hindering the purpose of this invention, a small amount of hydroxyl or alkoxy groups such as methoxy or ethoxy may be present on the silicon atoms in component (B). (B) The groups bonded to silicon atoms, excluding hydrogen atoms bonded to silicon atoms, are preferably selected from alkyl groups having 1-6 carbon atoms, especially methyl groups, and aryl groups having 6-20 carbon atoms, especially phenyl groups.

[0087] In one embodiment of the present invention, component (B) may comprise a resinous organohydrogen polysiloxane as component (B-1). The resinous organohydrogen polysiloxane (B-1) is preferably composed of...

[0088] Average unit form (V): (R) 4 3SiO 1 / 2 ) a (R 4 2SiO 2 / 2 ) b (R 4 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e

[0089] (In formula (V), R) 4 It is a hydrogen atom or a halogenated or unsubstituted monovalent hydrocarbon group other than an alkenyl group, wherein, in a molecule, at least two R groups are present. 4 Let be a hydrogen atom, 0≤a<1, 0≤b<1, 0≤c<0.9, 0≤d<0.5, 0≤e<0.4, a+b+c+d=1.0, and c+d>0).

[0090] R in the above equation (V) 4The halogenated or unsubstituted monovalent hydrocarbon group other than the alkenyl group can be exemplified by alkyl groups having 1-12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups having 6-20 carbon atoms, such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups having 7-20 carbon atoms, such as benzyl, phenethyl, and phenylpropyl; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, or bromine atoms. Within the scope of this invention, R 4 It can also be a small amount of hydroxyl or alkoxy groups such as methoxy and ethoxy. R 4 Preferably selected from hydrogen atoms, alkyl groups having 1-6 carbon atoms, especially methyl, or aryl groups having 6-20 carbon atoms, especially phenyl.

[0091] In the above formula (V), X is a hydrogen atom or an alkyl group. Preferably, the alkyl group of X is an alkyl group having 1 to 3 carbon atoms, specifically exemplified by methyl, ethyl, and propyl.

[0092] In the above formula (V), a is preferably in the range of 0.1 ≤ a ≤ 0.9, more preferably in the range of 0.3 ≤ a ≤ 0.8, and even more preferably in the range of 0.5 ≤ a ≤ 0.7. In the above formula (V), b is preferably in the range of 0 ≤ b ≤ 0.5, more preferably in the range of 0 ≤ b ≤ 0.3, and especially in the range of 0 ≤ b ≤ 0.1. In the above formula (V), c is preferably in the range of 0.1 ≤ c ≤ 0.7, more preferably in the range of 0.2 ≤ c ≤ 0.6, and especially in the range of 0.3 ≤ c ≤ 0.5. In the above formula (V), d is preferably in the range of 0 ≤ d ≤ 0.4, more preferably in the range of 0 ≤ d ≤ 0.25, and especially in the range of 0 ≤ d ≤ 0.1. In the above formula (V), e is preferably in the range of 0 ≤ e ≤ 0.15, more preferably in the range of 0 ≤ e ≤ 0.1, and especially in the range of 0 ≤ e ≤ 0.05.

[0093] In a preferred embodiment of the present invention, in the above formula (V), c is greater than 0, that is, the resinous organohydrogen polysiloxane of component (B-1) contains T units. The resinous organohydrogen polysiloxane of component (B-1) may or may not contain Q units, but preferably does not.

[0094] In a preferred embodiment of the invention, the resinous organohydrogen polysiloxane of component (B-1) contains hydrogen atoms bonded to silicon atoms at the molecular ends. The resinous organohydrogen polysiloxane of component (B-1) preferably has hydrogen atoms bonded to silicon atoms on the M units, and may or may not contain hydrogen atoms bonded to silicon atoms on the molecular chain side chains (i.e., D units and T units), but preferably does not.

[0095] In a preferred embodiment of the invention, the resinous organohydrogen polysiloxane of component (B-1) contains aryl groups in the organic groups bonded to silicon atoms. That is, in the above formula (V), at least one R 4 The aryl group may be present. In a preferred embodiment of the invention, the resinous organohydrogen polysiloxane of component (B-1) contains an aryl group bonded to a silicon atom on its molecular side chain, i.e., the D unit or the T unit, preferably the T unit. The resinous organohydrogen polysiloxane of component (B-1) may or may not contain an aryl group at its molecular terminal, i.e., the M unit, but it is preferred that it does not contain an aryl group. In addition, aryl groups with 6 to 20 carbon atoms can be listed as aryl groups, especially phenyl, tolyl, xylyl, and naphthyl.

[0096] When the resinous organohydrogen polysiloxane of component (B-1) contains aryl groups, its content (the mol% of aryl groups in all functional groups bonded to silicon atoms in the resinous organohydrogen polysiloxane) can be designed as needed, typically 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 13 mol% or more, especially preferably 16 mol% or more, and can be 50 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, more preferably 30 mol% or less, especially preferably 25 mol% or less. Furthermore, the aryl content can be determined by analysis, for example, using Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0097] The viscosity of the organopolysiloxane component (B-1) is not particularly limited, for example, it is in the range of 10 mPa to 1000 mPa at 25°C. In this specification, the viscosity of the organopolysiloxane component can be determined at 25°C by a rotational viscometer according to JIS K7117-1.

[0098] When component (B) contains (B-1) resinous organohydrogen polysiloxane, its content is not particularly limited. Based on the total mass of all organopolysiloxane components contained in the curable silicone composition of the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1.5% by mass or more, and especially preferably 2.5% by mass or more. Furthermore, based on the total mass of all organopolysiloxane components, the content of component (B-1) is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and especially preferably 5% by mass or less.

[0099] Component (B) may also include linear organohydrogen polysiloxanes as component (B-2). The linear organohydrogen polysiloxanes of component (B-2) are preferably composed of...

[0100] Average structure (VI): R 4 3SiO(R 42SiO 2 / 2 ) m SiR 4 3

[0101] (In formula (VI), R) 4 It is a hydrogen atom or a halogenated or unsubstituted monovalent hydrocarbon group other than an alkenyl group, wherein, in a molecule, at least two R groups are present. 4 (where m is a hydrogen atom, and m is 1-100).

[0102] In the above equation (VI), R 4 The same groups as those in formula (V) above can be used for halogenated or unsubstituted monovalent hydrocarbon groups other than alkenyl groups.

[0103] In the above formula (VI), m is preferably 1-50, more preferably 1-20, even more preferably 1-10, and especially preferably 1-5.

[0104] In a preferred embodiment of the present invention, the linear organohydrogen polysiloxane of component (B-2) contains hydrogen atoms bonded to silicon atoms at both ends of the molecular chain. The linear organohydrogen polysiloxane of component (B-2) has hydrogen atoms bonded to silicon atoms on the M unit, and may or may not contain hydrogen atoms bonded to silicon atoms on the D unit, but preferably does not contain them.

[0105] The linear organohydrogen polysiloxane of component (B-2) preferably contains aryl groups bonded to silicon atoms on the side chains of the molecular chain. The linear organopolysiloxane of component (B-2) may or may not contain aryl groups at the ends of the molecular chain, but it is preferred that it does not contain them.

[0106] In one embodiment of the present invention, when the linear organohydrogen polysiloxane of component (B-2) contains aryl groups, the content of aryl groups in all organic groups bonded to silicon atoms is not particularly limited. For example, it can be 10 mol% or more of the total amount of organic groups bonded to silicon atoms, preferably 15 mol% or more, more preferably 20 mol% or more, and can be 50 mol% or less of the total amount of organic groups bonded to silicon atoms, preferably 40 mol% or less, more preferably 30 mol% or less. Furthermore, the content of aryl groups can be determined by analysis, for example, using Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0107] When component (B) contains (B-2) linear organohydrogen polysiloxane, its content is not particularly limited. Based on the total mass of all organopolysiloxane components of the curable silicone composition of the present invention, it is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, based on the total mass of all organopolysiloxane components, it may be 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0108] (B) The total content of component (B) is not particularly limited. Based on the total mass of the curable silicone composition, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and especially preferably 12% by mass or more. In a preferred embodiment, based on the total mass of the curable silicone composition, the content of component (B) may be 40% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.

[0109] Furthermore, in one embodiment of the present invention, the ratio of alkenyl groups bonded to silicon atoms to hydrogen atoms in the organopolysiloxane component (B) is such that, relative to 1 mole of alkenyl groups bonded to silicon atoms in the curable silicone composition, the amount of hydrogen atoms bonded to silicon atoms is 0.3 moles or more, preferably 0.5 moles or more, more preferably 0.7 moles or more. For example, relative to 1 mole of alkenyl groups bonded to silicon atoms in the curable silicone composition, the amount of hydrogen atoms bonded to silicon atoms can be 5 moles or less, preferably 4 moles or less, more preferably 3 moles or less, further preferably 2 moles or less, and particularly preferably 1.6 mol% or less.

[0110] (C) Epoxy-containing resin-like organopolysiloxanes

[0111] The curable silicone composition of the present invention comprises an epoxy-containing resinous organopolysiloxane represented by the following average unit formula (I) as component (C).

[0112] Average unit form (I): (R) 1 3SiO 1 / 2 ) f (R 2 2SiO 2 / 2 ) g (R 1 SiO 3 / 2 ) h (SiO 4 / 2 ) i (XO 1 / 2 ) j

[0113] In equation (I), R 1Each is an independent monovalent hydrocarbon group, either halogenated or unsubstituted, wherein at least two R groups are halogenated or unsubstituted. 1 It is an alkenyl group, R 2 Each is independently a halogenated or unsubstituted monovalent hydrocarbon group or an epoxy-containing organic group, wherein at least one R 2 It is an organic group containing an epoxy group, where X is a hydrogen atom or an alkyl group, 0 ≤ f < 1, 0 <g<1,0≤h<0.9,0≤i<0.5,0<j<0.5,f+g+h+i+j=1.0,h+i> 0, and j / (f+g+h+i+j)>0.05}.

[0114] The curable silicone composition of the present invention may contain one (C) epoxy-containing resin-like organopolysiloxane, or two or more (C) epoxy-containing resin-like organopolysiloxanes.

[0115] In the above equation (I), as R 1 and R 2 The halogenated or unsubstituted monovalent hydrocarbon group can be exemplified by alkyl groups with 1-12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; aryl groups with 6-20 carbon atoms, such as phenyl, tolyl, xylyl, and naphthyl; alkenyl groups with 2-12 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl; and groups in which some or all of the hydrogen atoms of these groups are replaced by halogen atoms such as fluorine, chlorine, and bromine atoms. R 1 Preferably, it is selected from alkyl groups having 1-6 carbon atoms, especially methyl, alkenyl groups having 2-6 carbon atoms, especially vinyl groups, aryl groups having 6-20 carbon atoms, especially phenyl groups, and 3-epoxypropoxypropyl groups.

[0116] Furthermore, in the above equation (I), as R 2 The epoxy-containing organic group can be exemplified by epoxypropoxyalkyl groups such as 2-epoxypropoxyethyl, 3-epoxypropoxypropyl, and 4-epoxypropoxybutyl; epoxycycloalkylalkyl groups such as 2-(3,4-epoxycyclohexyl)-ethyl and 3-(3,4-epoxycyclohexyl)-propyl; and epoxyalkyl groups such as 3,4-epoxybutyl and 7,8-epoxyoctyl; preferably epoxypropoxyalkyl, and particularly preferably 3-epoxypropoxypropyl. 1 Preferably, it is selected from alkyl groups having 1-6 carbon atoms, especially methyl; alkenyl groups having 2-6 carbon atoms, especially vinyl; aryl groups having 6-20 carbon atoms, especially phenyl; and 3-epoxypropoxypropyl. 2 Preferably, it is selected from alkyl groups having 1-6 carbon atoms, especially methyl and 3-epoxypropoxypropyl.

[0117] In the above formula (I), X is a hydrogen atom or an alkyl group. Preferably, the alkyl group of X is an alkyl group having 1 to 3 carbon atoms, specifically methyl, ethyl and propyl.

[0118] In the above formula (I), based on f+g+h+i+j=1.0, f is preferably in the range of 0.03≤f≤0.7, more preferably in the range of 0.06≤f≤0.5, and even more preferably in the range of 0.09≤f≤0.3. In the above formula (I), g is preferably in the range of 0.05≤g≤0.6, more preferably in the range of 0.1≤g≤0.4, and especially in the range of 0.2≤g≤0.3. In the above formula (I), h is preferably in the range of 0.1≤h≤0.8, more preferably in the range of 0.25≤h≤0.7, and especially in the range of 0.4≤h≤0.6. In the above formula (I), i is preferably in the range of 0≤i≤0.4, more preferably in the range of 0≤i≤0.25, and especially in the range of 0≤i≤0.1. In the above formula (I), j is preferably in the range of 0.05≤j≤0.4, more preferably in the range of 0.1≤j≤0.3, and especially in the range of 0.15≤j≤0.25.

[0119] In equation (I) above, j / (f+g+h+i+j) is greater than 0.05. j / (f+g+h+i+j) is preferably greater than 0.08, more preferably greater than 0.11, and even more preferably greater than 0.14. Furthermore, j / (f+g+h+i+j) is generally less than 0.5, preferably less than 0.4, even more preferably less than 0.3, and particularly preferably less than 0.25.

[0120] In a preferred embodiment of the present invention, in the above formula (I), h is greater than 0, that is, the epoxy-containing resinous organopolysiloxane of component (C) comprises SiO 3 / 2 The term represents the siloxane unit (T unit). (C) The epoxy-containing resinous organopolysiloxane of component (C) may or may not contain SiO₂. 4 / 2 The siloxane unit (Q unit) is indicated, but preferably not included.

[0121] In a preferred embodiment of the present invention, the epoxy-containing resinous organopolysiloxane of component (C) contains an alkenyl group at the molecule's end. The epoxy-containing resinous organopolysiloxane of component (C) is preferably formed from SiO₂. 1 / 2 The siloxane unit (M unit) represents an alkenyl group, which is present on the molecular side chain (i.e., composed of SiO2). 2 / 2 The siloxane unit (D unit) and the siloxane unit represented by SiO2 3 / 2 The siloxane unit (T unit) may or may not contain an alkenyl group, but it is preferred that it does not contain one.

[0122] (C) The content of alkenyl groups in all organic groups bonded to silicon atoms in the epoxy-containing resinous organopolysiloxane is not particularly limited. For example, it can be 1 mol% or more of the total amount of organic groups bonded to silicon atoms, preferably 5 mol% or more, more preferably 8 mol% or more, and can be 30 mol% or less of the total amount of organic groups bonded to silicon atoms, preferably 20 mol% or less, more preferably 15 mol% or less. In addition, the content of alkenyl groups can be determined by analytical methods such as Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), or the titration method described above.

[0123] In a preferred embodiment of the present invention, the epoxy-containing resinous organopolysiloxane of component (C) contains aryl groups in the organic groups bonded to silicon atoms. That is, in the above formula (I), R 1 and R 2 At least one of them may be an aryl group. In a preferred embodiment of the invention, the epoxy-containing resinous organopolysiloxane of component (C) contains an aryl group bonded to a silicon atom on the side chain of the molecular chain, i.e., the D unit or the T unit, preferably on the T unit. The epoxy-containing resinous organopolysiloxane of component (C) may or may not contain an aryl group at the molecular end, i.e., the M unit, but it is preferred that it does not contain one. In addition, aryl groups with 6 to 20 carbon atoms can be listed as aryl groups, especially phenyl, tolyl, xylyl, and naphthyl.

[0124] When the epoxy-containing resin-like organopolysiloxane of component (C) contains aryl groups, its content (the mol% of aryl groups in all functional groups bonded to silicon atoms in the epoxy-containing resin-like organopolysiloxane) can be designed as needed, preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, especially preferably 30 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, especially preferably 40 mol% or less. Furthermore, the aryl content can be determined by analysis such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0125] (C) The amount of epoxy-containing organic groups among all organic groups bonded to silicon atoms in the epoxy-containing resinous organopolysiloxane is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, especially preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, especially preferably 25 mol% or less. Furthermore, the amount of epoxy-containing organic groups can be determined by analysis, for example, using Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0126] (C) The viscosity of the epoxy-containing resinous organopolysiloxane component is not particularly limited, for example, it is in the range of 50 mPa to 3000 mPa at 25°C. In this specification, the viscosity of the organopolysiloxane component can be determined at 25°C by a rotational viscometer according to JIS K7117-1.

[0127] The content of the epoxy-containing resinous organopolysiloxane in component (C) is not particularly limited. Based on the total mass of all organopolysiloxane components contained in the curable silicone composition of the present invention, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and especially preferably 2% by mass or more. Furthermore, based on the total mass of all organopolysiloxane components, the content of component (A-1) is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and especially preferably 3% by mass or less.

[0128] (D) Curing catalyst

[0129] The curing catalyst for component (D) is a curing catalyst for hydrosilylation reaction, and is also a catalyst used to promote the curing of the curable silicone composition of the present invention. Examples of such component (D) include platinum-based catalysts such as chloroplatinic acid, alcoholic solutions of chloroplatinic acid, platinum-olefin complexes, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes, and platinum-supported powders; palladium-based catalysts such as tetra(triphenylphosphine)palladium, and mixtures of palladium black and triphenylphosphine; and rhodium-based catalysts, with platinum-based catalysts being particularly preferred.

[0130] The amount of component (D) is the amount of catalyst. More specifically, when a platinum catalyst is used as component (D), the amount of platinum atoms relative to the total mass of the curable silicone composition of the present invention is preferably 0.01 ppm or more, more preferably 0.1 ppm or more, and even more preferably 1 ppm or more. Furthermore, the amount of platinum atoms relative to the total mass of the curable silicone composition of the present invention is preferably 20 ppm or less, more preferably 15 ppm or less, even more preferably 10 ppm or less, and particularly preferably 5 ppm or less.

[0131] Within the scope of the present invention, the curable silicone composition of the present invention can be formulated with any components. Examples of such arbitrary components include, for instance, acetylene compounds, organophosphorus compounds, vinyl siloxane compounds, ground quartz, silica, titanium dioxide, magnesium carbonate, zinc oxide, iron oxide, diatomaceous earth, and other inorganic fillers; inorganic fillers obtained by hydrophobically treating the surface of the inorganic filler with an organosilicon compound; hydrogen silanization reaction inhibitors; organopolysiloxanes that do not contain hydrogen atoms bonded to silicon atoms or alkenyl groups bonded to silicon atoms; tackifiers different from component (C); heat-resistant agents; cold-resistant agents; thermally conductive fillers; flame-retardant agents; thixotropic agents; phosphors; solvents, etc.

[0132] Among inorganic filler materials, silica can be categorized into various types, such as fumed silica, dry silica, wet silica, crystalline silica, and precipitated silica. Furthermore, silica can be surface-hydrophobicated using organosilicon compounds such as organoalkoxysilanes, organochlorosilanes, organosilazanes, and low-molecular-weight siloxanes, or silane coupling agents and titanate coupling agents.

[0133] Based on the total mass of the composition of the present invention, the inorganic filler material is preferably included in the curable silicone composition of the present invention in an amount of 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, and is preferably included in the curable silicone composition of the present invention in an amount of 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0134] Hydrosilylation reaction inhibitors are components used to inhibit the hydrosilylation reaction of curable silicone compositions. Examples of such curing reaction inhibitors include alkynols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; enynyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; alkenyl-containing low molecular weight siloxanes such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; and alkynyloxysilanes such as methyltris(1,1-dimethylpropynyloxy)silane and vinyltris(1,1-dimethylpropynyloxy)silane. The hydrosilylation reaction inhibitor is preferably selected from alkynols, and particularly preferably 1-ethynyl-1-cyclohexanol. The amount of reaction inhibitor added is typically 0.001-5% of the total mass of the composition.

[0135] Examples of phosphors include yellow, red, green, and blue phosphors, as well as mixtures of at least two of them, which are widely used in light-emitting diodes (LEDs) and comprised of oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, sulfide phosphors, and fluoride phosphors. Examples of oxide phosphors include YAG-type green-yellow phosphors containing cerium ions (yttrium, aluminum, garnet), TAG-type yellow phosphors containing cerium ions (terbium, aluminum, garnet), and silicate-type green-yellow phosphors containing cerium or europium ions. Examples of oxynitride phosphors include silane-type red-green phosphors containing europium ions (silicon, aluminum, oxygen, nitrogen). Examples of nitride phosphors include Cushing-type red phosphors containing europium ions (calcium, strontium, aluminum, silicon, nitrogen). Examples of sulfide phosphors include ZnS-type green phosphors containing copper or aluminum ions. Examples of oxide phosphors include Y₂O₂S-type red phosphors containing europium ions. Examples of fluoride phosphors include KSF phosphors (K₂SiF₆:Mn₂). 4+ )wait.

[0136] The curable silicone composition of the present invention can be cured to form a cured product with high hardness. The cured product obtained by curing the curable silicone composition of the present invention preferably has a D-type hardness of 20 or higher, or more preferably 30 or higher, at 25°C. Furthermore, this D-type hardness is determined using a D-type hardness tester according to JIS K6253-1997 "Test Method for Hardness of Vulcanized Rubber and Thermoplastic Rubber".

[0137] The curable silicone composition of the present invention can be cured to form a cured product with good transparency. Specifically, the transmittance of the cured product of the curable silicone composition of the present invention at wavelengths of 400 nm to 700 nm is preferably 80% or more, more preferably 83% or more, and particularly preferably 85% or more. Furthermore, the transmittance of the cured product of the curable silicone composition can be determined, for example, by measuring a cured product with an optical path length of 1 mm using a spectrophotometer.

[0138] The curable silicone composition of the present invention has a high refractive index. For example, the refractive index of the curable silicone composition of the present invention at 25°C is measured using an Abbe refractometer, and is preferably 1.4 or higher, more preferably 1.43 or higher, and even more preferably 1.45 or higher.

[0139] The curable silicone composition of the present invention can be cured to form a cured product with high tensile strength. For example, the curable silicone composition of the present invention is coated into a sheet to form a 1 mm thick sheet of cured product, which is then punched into a dumbbell shape No. 3 as specified in JIS K6251-1993 "Tension Test Method for Vulcanized Rubber". The tensile strength (MPa) is measured using an Autograph manufactured by Shimadzu Corporation at a tensile speed of 500 mm / min. In this case, the tensile strength is preferably 1.8 MPa or more, more preferably 2 MPa or more, and even more preferably 2.2 MPa or more.

[0140] The curable silicone composition of the present invention can be prepared by mixing the components. The mixing method can be any method known in the past and is not particularly limited; generally, a homogeneous mixture is formed by simple stirring. Furthermore, when solid components such as inorganic fillers are included as arbitrary components, it is more preferable to use a mixing device for mixing. The mixing device is not particularly limited and examples include single-shaft or twin-shaft continuous mixers, two-roll mills, Ross mixers, Hobart mixers, dental mixers, planetary mixers, kneading mixers, Henschel mixers, etc.

[0141] [Sealing materials, films]

[0142] This invention also relates to a sealing material for semiconductors using the curable silicone composition of this invention. The shape of the sealing material of this invention is not particularly limited, but a dome-shaped or sheet-like shape is preferred. The semiconductor sealed by the sealing material or film of this invention is not particularly limited, and examples include semiconductors such as SiC and GaN, especially power semiconductors or light-emitting diodes and other optical semiconductors.

[0143] The sealing material according to the present invention exhibits excellent thixotropy due to the use of the curable silicone composition of the present invention, and has minimal shape change or shrinkage during curing. Therefore, it is possible to manufacture semiconductor packages with excellent reliability.

[0144] [Optical Semiconductor Components]

[0145] The present invention also relates to an optical semiconductor element comprising the sealing material of the present invention. Examples of optical semiconductor elements include light-emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state cameras, light-emitting elements for optocouplers, and photosensitive elements, with light-emitting diodes (LEDs) being particularly preferred.

[0146] Since light-emitting diodes (LEDs) emit light from all sides of a semiconductor element, the components constituting an LED are preferably made of materials that absorb light, rather than materials with high light transmittance or high reflectivity. Therefore, the substrate on which the semiconductor element is mounted is also preferably made of materials with high light transmittance or high reflectivity. Examples of substrates for mounting the semiconductor element include conductive metals such as silver, gold, and copper; non-conductive metals such as aluminum and nickel; thermoplastic resins mixed with white pigments such as PPA and LCP; thermosetting resins containing white pigments such as epoxy resin, BT resin, polyimide resin, and silicone resin; and ceramics such as alumina and aluminum nitride.

[0147] A cross-sectional view of an example of a semiconductor device including the optical semiconductor element of the present invention, namely a monolithic surface-mount LED, is shown in the figure. Figure 1 .exist Figure 1 In the LED shown, the light-emitting element (LED chip) 1 is soldered onto the lead frame 2, and the light-emitting element (LED chip) 1 is connected to the lead frame 3 via a bonding wire 4. A frame 5 is provided around the light-emitting element (LED chip) 1, and the light-emitting element (LED chip) 1 inside the frame 5 is sealed by a cured product 6 of the curable silicone composition of the present invention.

[0148] As manufacturing Figure 1 The method for surface-mount LED shown can be exemplified as follows: a light-emitting element (LED chip) 1 is soldered onto a lead frame 2, and the light-emitting element (LED chip) 1 is wire-connected to the lead frame 3 via gold bonding wires 4. Then, the curable silicone composition of the present invention is filled into the inner side of the frame material 5 surrounding the light-emitting element (LED chip) 1, and then cured by heating at 50°C-200°C.

[0149] Because the optical semiconductor element of the present invention is sealed by the sealing material of the present invention, it has excellent reliability.

[0150] [Example]

[0151] The curable silicone compositions of the present invention will be described in detail through the following examples and comparative examples.

[0152] The curable silicone composition is prepared by mixing the components according to the composition (parts by mass) shown in the table. In the following text, Me represents methyl, Vi represents vinyl, Ph represents phenyl, and Ep represents 3-epoxypropoxypropyl. Furthermore, the structure of the organopolysiloxane component is simplified in the table, with functional groups other than Me on the M, D, or T units indicated in parentheses. Additionally, H / Vi represents the molar ratio of hydrogen atoms (H) bonded to silicon atoms to vinyl groups (Vi) in the organopolysiloxane component.

[0153] (Ingredient a: Alkenyl organopolysiloxane)

[0154] Component a-1: composed of the average unit cell (ViMe2SiO) 1 / 2 ) 25 (PhSiO 3 / 2 ) 75 Resin-like alkenyl-containing organopolysiloxanes

[0155] Component a-2: composed of the average unit cell (ViMeSiO) 2 / 2 ) 25 (Ph2SiO 2 / 2 ) 30 (PhSiO 3 / 2 ) 45 Resin-like alkenyl-containing organopolysiloxanes

[0156] Component a-3: composed of the average unit formula (Me3SiO) 1 / 2 ) 14 (ViMe2SiO 1 / 2 ) 11 (MeSiO 3 / 2 ) 53 (PhSiO 3 / 2 ) 22 Resin-like alkenyl-containing organopolysiloxanes

[0157] Component a-4: Composed of the average structural formula ViMe2SiO(Me2SiO) 20 SiMe2Vi represents a linear alkenyl-containing organopolysiloxane.

[0158] Component a-5: Composed of the average structural formula ViMe2SiO(Ph2SiO) 30 (Me2SiO) 60 SiMe2Vi represents a linear alkenyl-containing organopolysiloxane.

[0159] Component a-6: Cyclic alkenyl-containing organopolysiloxane represented by the average unit formula (ViMeSiO)4 (Component b: Organohydrogen polysiloxane)

[0160] Component b-1: composed of the average unit formula (HMe2SiO) 1 / 2 ) 60 (PhSiO 3 / 2 ) 40 Resin-like organohydrogen polysiloxane

[0161] Component b-2: A linear organohydrogen polysiloxane represented by the average structural formula HMe2SiO(Ph2SiO)SiMe2H.

[0162] (Component c: epoxy-based resin-like organopolysiloxane)

[0163] Component c-1: composed of the average unit cell (ViMe2SiO) 1 / 2 ) 13 (EpMeSiO 2 / 2 ) 24 (PhSiO 3 / 2 ) 46 (OMe) 17 The term refers to epoxy-containing resin-like organopolysiloxanes.

[0164] Component c'-2: composed of the average unit cell (ViMe2SiO) 1 / 2 ) 18 (EpMeSiO 2 / 2 ) 29 (PhSiO 3 / 2 ) 53 The term refers to epoxy-containing resin-like organopolysiloxanes.

[0165] Component c'-3: composed of the average unit formula (ViMeSiO) 2 / 2 ) 24 (PhMeSiO 2 / 2 ) 15 (EpSiO 3 / 2 ) 19 (OMe) 42 The term refers to epoxy-containing resin-like organopolysiloxanes.

[0166] Component d: A complex of platinum (4.0% by mass) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0167] Ingredient e: 1-Ethynyl-2-cyclohexanol

[0168] Component f: Fumed silica

[0169] [Example 1 and Comparative Examples 1-2]

[0170] The curable silicone composition was prepared by mixing the components according to the proportions (parts by weight) shown in Table 1. The following evaluation was then conducted, and the results are summarized in Table 1.

[0171] [Chip Shear Strength]

[0172] A curable silicone composition for chip bonding was applied to an aluminum substrate using a chip bonding machine (AD830PLUS manufactured by ASM), and a 300μm substrate was placed on it. 2 The LED chips were cured at 150°C for 2 hours. The chip shear strength was then measured using a chip shear strength tester (Nordson DAGE4000 bond tester).

[0173] [Light extraction efficiency]

[0174] A phosphor was added to the obtained curable silicone composition and mixed, then injected into... Figure 1 In the optical semiconductor device shown, it was cured by heating at 150°C for 2 hours. The light extraction efficiency of the obtained optical semiconductor device was determined by measuring the initial total radiative flux using an integrating sphere.

[0175] [Table 1]

[0176] Table 1

[0177]

[0178] Based on the test results of Example 1 and Comparative Examples 1-2 above, the curable silicone composition of the present invention exhibits the highest total luminous flux value and a chip shear strength exceeding 400. Therefore, the curable silicone composition of the present invention can form a cured product that combines excellent adhesive strength and light extraction efficiency.

[0179] [Examples 2-3 and Comparative Examples 3-4]

[0180] The curable silicone composition was prepared by mixing the components according to the proportions (parts by weight) shown in Table 2. The following evaluation was then conducted, and the results are summarized in Table 2.

[0181] [Tensile strength and elongation]

[0182] The silicone compositions of Examples 2-3 and Comparative Examples 3-4 were coated into sheets and heated at 120°C for 5-10 minutes to produce 180 μm thick sheet-like thermoplastic cured products. The melt modulus of these thermoplastic cured products at 100°C was measured using a viscoelastic analyzer (Anton Paar MCR302), and found to be 30-300 Pa. They were then punched into dumbbell shape No. 3 as specified in JIS K 6251-1993 "Tension Test Method for Vulcanized Rubber," and the tensile strength (MPa) and elongation at break (%) were measured using an automatic plotter manufactured by Shimadzu Corporation at a tensile speed of 500 mm / min. It can be said that thermoplastic cured products with a tensile strength of 2 MPa or higher and an elongation at break of 200% or higher have excellent workability as sealing material films or laminated films.

[0183] [Heat shrinkage rate]

[0184] The obtained hot-melt curable silicone composition was formed into a 300 μm coating on a release film using an automated coating apparatus (TESTER SANGYO Co., Ltd. / PI-1210). The coating was then cured in an oven at 120°C for 5-10 minutes to obtain a hot-melt cured product. The melt modulus of these hot-melt cured products at 100°C was measured using a viscoelastic analyzer (MCR302, manufactured by Anton Pareto), and was found to be 30-300 Pa. The dimensions of the obtained coating before and after heating were measured and defined as the shrinkage rate. The shrinkage rate is preferably less than 1%.

[0185] [Table 2]

[0186] Table 2

[0187]

[0188] [Example 4 and Comparative Example 5]

[0189] The curable silicone composition was prepared by mixing the components according to the proportions (parts by weight) shown in Table 3. The following evaluation was then conducted, and the results are summarized in Table 3.

[0190] [Refractive Index]

[0191] The refractive index of the cured silicone composition at 25°C was determined using an Abbe refractometer. A 589 nm light source was used during the measurement.

[0192] [Hardness of the cured product]

[0193] The obtained curable silicone composition was heated at 150°C for 2 hours to produce a 10 mm thick cured material. The hardness of the cured material was determined using a type D hardness tester as specified in JIS K 7215-1986 "Method for Hardness Testing of Plastics".

[0194] [Viscosity and Thixotropic Index]

[0195] Viscoelasticity was measured using a viscoelasticity measuring apparatus (MCR302, manufactured by Anton Paar). A cone plate with a diameter of 40 mm and a cone angle of 2° was used to rotate the curable silicone composition in the same direction at shear rates of 1 / s and 10 / s. The measurement temperature was uniformly set to 25°C. The thixotropic index was calculated as the viscosity ratio of (1 / s) / (10 / s).

[0196] [Light transmittance of cured material]

[0197] The obtained curable silicone composition was placed between two transparent glass plates and cured at 150°C for 1 hour to form a test specimen with an optical path length of 1 mm. The transmittance of this test specimen was measured at 25°C using an automated recording spectrophotometer capable of measuring at any wavelength within the visible light range (400 nm-700 nm). The transmittance value at a wavelength of 450 nm is also listed in Table 3.

[0198] [Shape stability]

[0199] The obtained curable silicone composition was applied to a glass substrate at a height of approximately 1 mm using dispensing molding. The silicone was then cured in a constant temperature bath at 150°C for 60 minutes. The ratio of the height to the diameter of the cured material before and after curing was measured, and the change rate (%) of this ratio was calculated. It can be said that the lower the change rate, the more stable the shape.

[0200] [Table 3]

[0201] Table 3

[0202]

[0203] As can be seen from the results in Tables 2 and 3 above, the curable silicone composition of the present invention containing fillers exhibits excellent thixotropy and light extraction efficiency, and the shape change or shrinkage during curing is reduced.

[0204] [Industry availability]

[0205] The curable silicone composition of the present invention can form a cured product that combines excellent adhesive strength and light extraction efficiency. Furthermore, when fillers or phosphors are included, the improved dispersibility of the fillers or phosphors results in a cured product that maintains excellent light extraction efficiency while achieving excellent thixotropy even with the addition of small amounts of fillers or phosphors, and reduces shape change or shrinkage during curing. Therefore, the curable silicone composition of the present invention is very useful, for example, as a dome-shaped or sheet-shaped sealing material in the manufacture of semiconductor packages.

[0206] [Attached image labels]

[0207] 1. Light-emitting element

[0208] 2. Lead frame

[0209] 3. Lead frame

[0210] 4. Joint line

[0211] 5. Frame Material

[0212] 6. Cured products of curable silicone compositions

Claims

1. A curable silicone composition comprising: (A) Alkenyl-containing organopolysiloxanes having at least two alkenyl groups per molecule; (B) Organohydrogen polysiloxanes, each molecule having at least two hydrogen atoms bonded to silicon atoms; (C) An epoxy-containing resinous organopolysiloxane represented by the following average unit formula (I): (R 1 3SiO 1 / 2 ) f (R 2 2SiO 2 / 2 ) g (R 1 SiO 3 / 2 ) h (SiO 4 / 2 ) i (XO 1 / 2 ) j In equation (I), R 1 Each is an independent monovalent hydrocarbon group, either halogenated or unsubstituted, wherein at least two R groups are halogenated or unsubstituted. 1 It is an alkenyl group, R 2 Each is independently a halogenated or unsubstituted monovalent hydrocarbon group or an epoxy-containing organic group, wherein at least one R 2 X is an epoxy-containing organic group, where X is a hydrogen atom or an alkyl group, 0 ≤ f < 1, 0 < g < 1, 0 ≤ h < 0.9, 0 ≤ i < 0.5, 0 < j < 0.5, f + g + h + i + j = 1.0, h + i > 0, and j / (f + g + h + i + j) > 0.

05. Resin-like refers to a molecular structure with branched or three-dimensional network structures; and (D) Curing catalyst.

2. The curable silicone composition according to claim 1, wherein, In the above formula (I), R 1 At least 30 mol% of it is aryl.

3. The curable silicone composition according to claim 1 or 2, wherein, The (A) alkenyl organopolysiloxane comprises a resinous organopolysiloxane, a linear organopolysiloxane, or both, in which the aryl group accounts for more than 20 mol% of all functional groups bonded to silicon atoms.

4. The curable silicone composition according to claim 1 or 2, wherein, The (B) organohydrogen polysiloxane includes both linear organohydrogen polysiloxanes and resinous organohydrogen polysiloxanes.

5. The curable silicone composition according to claim 1 or 2, wherein, It also contains silica as an inorganic filler material.

6. A sealing material comprising the curable silicone composition according to any one of claims 1 to 5.

7. An optical semiconductor device comprising the sealing material of claim 6.

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