Curable resin compositions, cured products, electronic components, optical components and composite components

Abstract

The curable resin composition of the present invention can form a heat-resistant curable suitable for use in printed wiring boards, semiconductor devices, light-emitting diodes (LEDs), or electronic components for automotive applications, etc. The curable resin composition contains: a silicon compound (A), comprising a sesquisiloxane group represented by one or both of the following formulas (1) or (2) and any one or more of the following formulas (3) to (5) as structural units, and having a weight average molecular weight of 3,000 to 1,000,000; and a compound (B) having any one or more of the elements Ce, La, Pr, Nd, Y, and Fe. (a represents the following structure; R1~R7 represent the specified bases.)

Description

[Technical Field]

[0001] This invention relates to a silicone polymer composition, a cured material, an electronic component, an optical component, and a composite component. [Previous Technology]

[0002] Silicone resins possess excellent electrical insulation, weather resistance, and heat resistance, making them suitable for use as sealants, adhesives, or protective materials in various electronic devices. In particular, due to the high bond energy of the siloxane bonds (Si-O-Si) that constitute the resin, it exhibits high heat resistance that is unattainable by general organic polymers.

[0003] In recent years, for printed wiring boards, semiconductor components, light-emitting diodes (LEDs) or electronic components for automotive applications, in order to ensure the reliability of components with higher density, higher output, and higher operating temperature, higher heat resistance is required than before, which previous silicone-based materials cannot meet.

[0004] As a method to improve heat resistance, there are techniques for adding various inorganic fillers (Patent Document 1, Patent Document 2). However, these techniques are not easily acceptable due to concerns about ensuring the dispersibility of the inorganic filler with the polymer system, or the decrease in transparency, toughness, or workability caused by the addition of fillers. In addition, depending on the type of filler, concerns about the reduction in electrical insulation have also been reported (Patent Document 3). Techniques for improving heat resistance by adding cerium salts have also been devised (Prior Document 4, Prior Document 5). However, these techniques also do not provide sufficient heat resistance to meet the aforementioned requirements.

[0005] On the other hand, silsesquioxanes are known as materials exhibiting high heat resistance. These materials not only exhibit excellent heat resistance but also high transparency and processability, and therefore have been actively researched and developed in recent years. In particular, polymers containing bilayer silsesquioxane structures with good properties such as solubility in organic solvents, control of refractive index, and photocurability have attracted considerable attention. Among these, silicate polymers containing bilayer silsesquioxanes have been reported to have high heat resistance (Patent Documents 6 and 7). However, even with the use of these silicate polymers exhibiting high heat resistance, further improvements in heat resistance are required. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2016 / 103654 [Patent Document 2] Japanese Patent Application Publication No. 2017-186497 [Patent Document 3] Japanese Patent Application Publication No. 2017-14399 [Patent Document 4] Japanese Patent Application Publication No. 2008-291148 [Patent Document 5] International Publication No. 2019 / 116892 [Patent Document 6] Japanese Patent Application Publication No. 2010-116464 [Patent Document 7] Japanese Patent Application Publication No. 2020-90572 [Summary of the Invention]

[0007] [The problem the invention aims to solve]

[0008] The present invention has been made in view of the aforementioned actual situation, and its object is to provide a curable resin composition capable of forming a heat-resistant curable material suitable for use in printed circuit boards, semiconductor elements, light-emitting diodes (LEDs), or automotive-grade electronic components, and electronic components, optical components, and composite components having said curable material. [Means for Solving the Problem]

[0009] The embodiments of the present invention made to solve the aforementioned problem include the following structure. [1] A curable resin composition comprising: a silicon compound (A) comprising any one or more of sesquisiloxanes represented by formula (1) or formula (2) and any one or more of siloxanes represented by formulas (3) to (5) and having a weight average molecular weight of 3,000 to 1,000,000; and a compound (B) having any one or more of the elements Ce, La, Pr, Nd, Y and Fe. [Chemical 1][Chemical 2] (R1 independently represents an aryl group with 6 to 20 carbon atoms, a cycloalkyl group with 5 or 6 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, or an alkyl group with 1 to 40 carbon atoms, wherein any hydrogen atom in the aryl group with 6 to 20 carbon atoms, the cycloalkyl group with 5 or 6 carbon atoms, or the arylalkyl group with 7 to 40 carbon atoms may be independently substituted with a fluorine atom or an alkyl group with 1 to 20 carbon atoms, wherein any hydrogen atom in the alkyl group with 7 to 40 carbon atoms may be substituted with a fluorine atom, and any -CH2- may be independently substituted with -O-, -CH=CH-, or an alkyl group with 5 to 20 carbon atoms, wherein any hydrogen atom in the alkyl group with 1 to 40 carbon atoms may be independently substituted with a fluorine atom, and any -CH2- may be independently substituted with -O- or an alkyl group with 5 to 20 carbon atoms; R2 independently represents an alkyl group with 1 to 8 carbon atoms or an aryl group with 6 to 20 carbon atoms; R3 represents a hydroxyl group;) R4 independently represents a hydroxyl group, hydrogen, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; R5 represents a hydroxyl group, an alkoxy group having 1 to 8 carbons, hydrogen, an alkenyl group having 2 to 40 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; a represents the following structure; [Chemistry 3]

[0010] R6 independently represents an alkyl group having 1 to 40 carbon atoms, wherein any -CH2- can be independently substituted by -O- or an alkyl group having 5 to 20 carbon atoms; R7 independently represents an aryl group with 6 to 20 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, or an alkyl group with 1 to 40 carbon atoms. In the aryl group with 6 to 20 carbon atoms, the cycloalkyl group with 5 to 6 carbon atoms, and the arylalkyl group with 7 to 40 carbon atoms, any hydrogen atom may be independently substituted with a fluorine atom or an alkyl group with 1 to 20 carbon atoms. In the alkyl group with 7 to 40 carbon atoms, any hydrogen atom may be substituted with a fluorine atom. Any -CH2- may be independently substituted with -O-, -CH=CH-, or an alkyl group with 5 to 20 carbon atoms. In the alkyl group with 1 to 40 carbon atoms, any hydrogen atom may be independently substituted with a fluorine atom. Any -CH2- may be independently substituted with -O- or an alkyl group with 5 to 20 carbon atoms. Furthermore, in this specification, * indicates a bond site. (The same applies below.)

[0011] [2] The curable resin composition as described in [1], wherein the silicone compound (A) comprises any one or more of the sesquioxanes represented by formula (1) or formula (2) and any one or more of the siloxanes represented by formula (6) or formula (7). [Chemical 4][Chemical 5] (R8 independently represents a hydroxyl group, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; R9 independently represents a hydroxyl group, an alkoxy group having 1 to 8 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons, and in formula (7), at least one R9 represents a hydroxyl group or an alkoxy group having 1 to 8 carbons.)

[0012] [3] The curable resin composition as described in any one of [1] to [2], wherein the silicon compound (A) is a compound represented by the following formula (8). [Chemical 6][Chemical 7] (R1 and R2 represent groups defined in the same way as R1 and R2 in the group represented by formula (1) as described in [1]; R8 and R9 represent groups defined in the same way as R8 and R9 in the group represented by formula (6) and formula (7) as described in [2], wherein in the group represented by formula (11), at least one R9 represents a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms; R10 represents a group represented by formula (9); R11 represents a group represented by formula (10) or formula (11); n is an average value satisfying 1 to 30; m is a positive average value satisfying 0 to 30; l is a value satisfying a weight average molecular weight of 3,000 to 1,000,000; p is 0 or 1)

[0013] [4] The curable resin composition as described in [2] or [3] further comprises a crosslinking agent (C) other than the silicon compound (A), the crosslinking agent (C) having two or more crosslinking groups that can chemically bond with the silicon compound (A).

[0014] [5] The curable resin composition as described in any one of [2] to [4], wherein the crosslinking group is any one of the following formulas (12) to (17) bonded to Si. [Chemical 8] (R12 represents an alkyl group having 1 to 8 carbon atoms.)

[0015] [6] The curable resin composition as described in any one of [2] to [5] further comprises a catalyst (D).

[0016] [7] The curable resin composition as described in any one of [2] to [6], wherein the catalyst (D) has one or more of Sn, Zr, Ti, Al, N and Pt.

[0017] [8] The curable resin composition as described in [1], wherein the silicone compound (A) comprises any one or more of the sesquioxanes represented by formula (1) or formula (2) and at least one of the siloxanes represented by formulas (18) to (20). [Chemical 9] [Chemical 10] (R13 independently represents hydrogen or an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; R14 independently represents hydrogen, a hydroxyl group, an alkoxy group having 1 to 8 carbons, an alkenyl group having 2 to 40 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; a represents the same group as a as described in [1])

[0018] [9] The curable resin composition as described in any one of [1] to [8], wherein the silicon compound (A) is a compound represented by the following formula (21). [Chemical 11][Chemical 12] (N is a value satisfying a weight average molecular weight of 3,000 to 1,000,000; R1 and R2 represent bases defined in the same way as R1 and R2 in the base represented by formula (1) as described in [1]; R15 represents the base represented by formula (22); R16 represents the base represented by formula (23) or formula (24); in the base represented by formula (24), R14 is the base defined in the same way as R14 in the base represented by formula (19); q is 0 or 1; X1 and X2 independently represent at least one of the repeating units selected from the following formulas (25) to (30); [Chemical 13] a represents the base defined in the same way as a as described in [1]; R13 represents the base defined in the same way as R13 in the base represented by formula (18) as described in [8]; x and z are average values ​​satisfying 0 to 30, and y is a positive average value satisfying 1 to 30.)

[0019]

[10] The curable resin composition as described in [8] or [9] further comprises a crosslinking agent (C) other than the silicon compound (A), the crosslinking agent (C) having two or more crosslinking groups that can chemically bond with the silicon compound (A).

[0020]

[11] The curable resin composition as described in any one of [8] to

[10] , wherein the crosslinking group is any one of the following formulas (12) to (17) or (31) bonded to Si. [Chemical 14] (R12 represents an alkyl group having 1 to 8 carbon atoms.)

[0021]

[12] The curable resin composition as described in any one of [8] to

[11] further comprises a catalyst (D).

[0022]

[13] The curable resin composition as described in any one of [8] to

[12] , wherein the catalyst (D) has one or more of Sn, Zr, Ti, Al, N and Pt.

[0023]

[14] A hardener, formed by hardening a hardening resin composition as described in any one of [1] to

[13] .

[0024]

[15] An electronic component having a hardened material as described in

[14] .

[0025]

[16] An optical component having a hardened material as described in

[14] .

[0026]

[17] A composite component comprising a first component and a resin-containing component in contact with the first component, and constituting part of an electrical component, wherein the resin-containing component comprises a hardened material as described in

[14] .

[0027]

[18] The composite component as described in

[17] , wherein the resin-containing component is a protective film covering at least a portion of the first component.

[0028]

[19] The composite component as described in

[18] , wherein the first component is a wiring substrate on a base material having wiring provided thereon, and the protective film has insulation and covers the wiring.

[0029]

[20] The composite component as described in

[17] further includes a second component in contact with the resin-containing component. [Effects of the Invention]

[0030] According to the present invention, a curable resin composition that provides a heat-resistant curable material suitable for use in electronic components and the like can be provided. In addition, a curable material obtained from the curable resin composition, and electronic components, optical components and composite components having the curable material can be provided.

Implementation Method

[0032] Hereinafter, a curable resin composition, a cured product, an electronic component, an optical component, and a composite component according to an embodiment of the present invention will be described in detail.

[0033] <Curing Resin Composition> The curing resin composition of the present invention contains a silicon compound (A); a compound (B) having any one or more elements selected from Ce, La, Pr, Nd, Y, and Fe. Additionally, the curing resin composition may also optionally contain a crosslinking agent (C) other than the silicon compound (A) having two or more crosslinking groups capable of chemically bonding with the silicon compound (A), a catalyst (D), other organic polysiloxanes besides the silicon compound (A) and the crosslinking agent (C), curing delay agents, adhesion promoters, fillers, ion traps, surfactants, flame retardants, ultraviolet absorbers and light stabilizers, antioxidants, solvents, and other components.

[0034] The curable resin composition of the present invention can be colorless or colored, and can be transparent or opaque. Furthermore, the curable resin composition of the present invention can also be prepared by mixing the components in a two-component or three-component form. Furthermore, components (A) to (D), and other components can be used individually or in combination of two or more. Hereinafter, the components constituting the curable resin composition of the present invention will be described in detail.

[0035] <Silicone Compound (A)> The curable resin composition of the present invention has a silicone compound (A) comprising a sesquisiloxane group represented by one or both of the following formulas (1) or (2), and any one or more structural units of siloxane groups represented by the following formulas (3) to (5), and having a weight average molecular weight of 3,000 to 1,000,000. [Chemical 15][Chemical 16]

[0036] In formulas (1) and (2), R1 independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms, respectively. In the aryl group having 6 to 20 carbon atoms, the cycloalkyl group having 5 or 6 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be independently substituted by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be substituted by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. The hydrogen atom may be substituted with a fluorine atom, and any -CH2- may be independently substituted with -O-, -CH=CH- or a cycloalkyl group having 5 to 20 carbon atoms. Among the alkyl groups having 1 to 40 carbon atoms, any hydrogen atom may be independently substituted with a fluorine atom, and any -CH2- may be independently substituted with -O- or a cycloalkyl group having 5 to 20 carbon atoms. For ease of manufacture, methyl, ethyl, isopropyl, isobutyl, phenyl, or cyclohexyl are preferred, and more preferably methyl, phenyl, or cyclohexyl.

[0037] R2 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, preferably methyl or phenyl.

[0038] In formula (1), R3 represents a hydroxyl group; in formulas (3) to (5), R4 independently represents a hydroxyl group, hydrogen, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; R5 represents a hydroxyl group, an alkoxy group having 1 to 8 carbons, hydrogen, an alkenyl group having 2 to 40 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; and a represents the following structure. [Chemical 17]

[0039] R6 independently represents an alkyl group having 1 to 40 carbon atoms, wherein any -CH2- can be independently substituted by -O- or an alkyl group having 5 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms.

[0040] R7 independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl group having 6 to 20 carbon atoms, the cycloalkyl group having 5 to 6 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be independently substituted by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be substituted by a fluorine atom or an alkyl group having 1 to 20 carbon atoms. It can be substituted with fluorine atoms. Any -CH2- can be independently substituted with -O-, -CH=CH-, or an alkyl group having 5 to 20 carbon atoms. Among the alkyl groups having 1 to 40 carbon atoms, any hydrogen atom can be independently substituted with fluorine atoms. Any -CH2- can be independently substituted with -O- or an alkyl group having 5 to 20 carbon atoms. For ease of manufacture, -CH2CH2CF3, phenyl, cyclohexyl, isobutyl, nonafluorohexyl, and pentafluorophenyl are preferred. Furthermore, as mentioned above, * in the formula indicates a bonding site.

[0041] In formulas (1) to (5), the hydroxyl, alkoxy, hydrogen, and alkenyl groups of R3 to R5 are crosslinking functional groups that bond with the Si in the silicon compound (A), and can bond with the silicon compound (A) itself or with other compounds such as the crosslinking agent (C) described later. The crosslinking functional groups can be all the same or different in a single silicon compound (A).

[0042] As a silicon compound (A), examples include: a compound comprising a sesquioxane having the crosslinking functional group and a siloxane represented by formula (3) to (5) without the crosslinking functional group; a compound comprising a sesquioxane without the crosslinking functional group and a siloxane represented by formula (3) to (5) with the crosslinking functional group; and a compound comprising a sesquioxane having the crosslinking functional group and a siloxane represented by formula (3) to (5) with the crosslinking functional group.

[0043] As a siloxane having the crosslinking functional group represented by formulas (3) to (5), examples include: a siloxane having the crosslinking functional group of formula (3) and formulas (4) and (5) without the crosslinking functional group; a siloxane having the crosslinking functional group of formulas (3) and (5) without the crosslinking functional group and formula (4) with the crosslinking functional group; a siloxane having the crosslinking functional group of formulas (4) and (5) without the crosslinking functional group and formula (3) with the crosslinking functional group; and a siloxane having the crosslinking functional group of formula (3) with the crosslinking functional group, formula (4) with the crosslinking functional group, and formula (5) with the crosslinking functional group.

[0044] The silicon compound (A) may further have sesquisiloxanes represented by formulas (1) and (2) and other structural units other than siloxanes represented by formulas (3) to (5). Preferably, the other structural units do not contain the crosslinking functional group. In addition, the content ratio of sesquisiloxanes represented by formulas (1) and (2) to other structural units other than siloxanes represented by formulas (3) to (5) is preferably 30 mol% or less, more preferably 20 mol% or less.

[0045] The molecular weight of the silicon compound (A) is preferably 3,000 to 700,000, more preferably 3,000 to 600,000, and even more preferably 3,000 to 500,000, so that the viscosity of the curable resin composition will not increase excessively.

[0046] <Silicon compounds (A) that do not contain hydrogen atoms bonded to Si other than the terminal Si as crosslinking functional groups> More specifically, examples include: silicon compounds containing structural units of one or both of the sesquioxanes represented by formula (1) or formula (2) and the siloxanes represented by formula (6) or formula (7) below, and having a weight average molecular weight of 3,000 to 1,000,000. [Chemical 18][Chemical 19]

[0047] In formula (6), R8 independently represents a hydroxyl group, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons. In formula (7), R9 independently represents a hydroxyl group, an alkoxy group having 1 to 8 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons. In formula (7), at least one R9 represents a hydroxyl group or an alkoxy group having 1 to 8 carbons.

[0048] More specifically, examples can be given of compounds represented by the following formula (8). [Chemical Engineering 20][Chemical Engineering 21]

[0049] In formula (8), R1 and R2 represent the same bases as R1 and R2 in formula (1), R8 is the same base as R8 in formula (6), and R10 represents the base represented by formula (9). In formula (9), R11 represents the base represented by formula (10) or formula (11), R9 in formula (11) represents the same base as R9 in formula (7), n is the average value satisfying 1 to 30, m is the positive average value satisfying 0 to 30, l is the value satisfying the weight average molecular weight of 3,000 to 1,000,000, and p is 0 or 1.

[0050] From the viewpoint of ease of obtaining raw materials, R8 is preferably methyl, phenyl or hydroxyl. In the case that R8 is hydroxyl, from the viewpoint of the toughness of the cured product, it is even more preferably 50 moles or less relative to the total mole number of all R8 in formula (8).

[0051] In formula (11), at least one R9 represents a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms, and is preferably a hydroxyl group in terms of reactivity.

[0052] The cured resin composition containing the silicone compound represented by formula (8) exhibits excellent balance between heat resistance and flexibility. The properties of the silicone compound (A) can be controlled by the ratio of the silsesquioxane group represented by formulas (1) and (2) to the silicone group represented by formulas (6) and (7). In formula (8), the ratio (α) of silicone group to silsesquioxane group is (n+ml) / (1+2p), (n+ml+1) / (1+2p), or (n+ml+2) / (1+2p) depending on the number of formulas (11) contained in R10 in formula (8). The smaller the ratio (α) of silicone group to silsesquioxane group, the stronger the tendency to be and the higher the tendency to be and the higher the tendency to be and the higher the tendency to be and the higher the flexibility. In terms of overall balance, α is preferably 1 to 20.

[0053] The molecular weight of the silicon compound represented by formula (8) is preferably 3,000 to 700,000, more preferably 3,000 to 600,000, and if it is 3,000 to 500,000, the viscosity of the curable resin composition will not increase excessively, which is even more preferred.

[0054] <Method for manufacturing a silicon compound that does not contain hydrogen or hydroxyl groups bonded to Si other than the terminal Si as crosslinking functional groups> In the silicon compound represented by formula (8), if R8 does not contain hydroxyl groups, it can be obtained by equilibrium polymerization of one or both of the compounds represented by formula (A-2) and formula (A-3) with the compound represented by formula (A-1) in the presence of a catalyst. Specific manufacturing methods can be cited, for example, as described in Japanese Patent Application Publication No. 2010-116464 and Japanese Patent Application Publication No. 2020-90572. [Chemical 22]

[0055] In formula (A-1), R1 and R2 are the same bases as R1 and R2 in formula (8).

[0056] In formula (A-2), k1 represents an integer from 0 to 30, RA1 independently represents a hydroxyl group, an alkoxy group with 1 to 8 carbon atoms, an alkyl group with 1 to 8 carbon atoms, or an aryl group with 6 to 20 carbon atoms. In formula (A-2), at least one RA1 represents a hydroxyl group or an alkoxy group with 1 to 8 carbon atoms. RA2 is an alkyl group with 1 to 8 carbon atoms or an aryl group with 6 to 20 carbon atoms.

[0057] From the viewpoint of ease of obtaining the compound, k1 in formula (A-2) is preferably 0 to 9, more preferably 0 to 5, and even more preferably 1 to 3.

[0058] In formula (A-3), h1 represents 3 to 6, and RA2 is the same group as RA2 in formula (A-2). From the viewpoint of ease of obtaining the compound, h1 in formula (A-3) is preferably 3 or 4.

[0059] Each compound represented by formula (A-1), formula (A-2), and formula (A-3) may be used in one form or in two or more forms. The ratio of the compound represented by formula (A-1) to the compounds represented by formulas (A-2) and (A-3) may be appropriately set according to the degree of polymerization of each structural unit in the silicon compound as the target material.

[0060] As the catalyst used in the method, an acid catalyst is preferred. Examples of acid catalysts include hydrochloric acid, sulfuric acid, fluorosulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, activated clay, sulfonic acid-based ion exchange resins, and cation exchange resins. Among these, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, activated clay, and cation exchange resins are preferred.

[0061] <Method for manufacturing a silicon compound containing hydroxyl groups bonded to Si other than terminal Si as crosslinking functional groups and free of hydrogen> In the silicon compound represented by formula (8), when R8 contains hydroxyl groups, it can be obtained, for example, by preparing a compound represented by formula (A-4) having hydrogen bonds to Si on its side chains, and converting the hydrogen to hydroxyl groups in the presence of a transition metal catalyst. [Chemical 23]

[0062] In formula (A-4) and formula (A-4'), RA2 is the same as RA2 in formula (A-2), R1, R2, n, l are the same as R1, R2, n, l in formula (8), and m1 and m2 are positive average values ​​of m1+m2 satisfying 0 to 30.

[0063] The method for producing the compound represented by formula (A-4) is not particularly limited. For example, it can be obtained by equilibrium polymerization of one or both of the compound represented by formula (A-7) and the compound represented by formula (A-3), or one or both of the compound represented by formula (A-5) and the compound represented by formula (A-6) with the compound represented by formula (A-1) in the presence of a catalyst. Specifically, the method described in Japanese Patent Application Publication No. 2010-116464 can be cited as an example.

[0064] In the aforementioned manufacturing method, solvents such as tetrahydrofuran, toluene, and ethyl acetate may also be used. It is preferable to carry out the reaction in the presence of an acid catalyst such as sulfuric acid. It is preferable to carry out the reaction in an inert gas environment such as nitrogen (N2). Furthermore, it is preferable to carry out the reaction while stirring. [Chemical 24]

[0065] In formulas (A-5) and (A-7), RA3 independently represents hydrogen, hydroxyl, alkoxy group with 1 to 8 carbons, alkyl group with 1 to 8 carbons, or aryl group with 6 to 20 carbons. In formulas (A-5) and (A-7), at least one RA3 represents a hydroxyl group or alkoxy group with 1 to 8 carbons. RA2 is the same group as RA2 in formula (A-2). k1, k2, and k3 independently represent integers from 0 to 30.

[0066] In formula (A-6), RA2 is the same base as RA2 in formula (A-2), and h2 represents an integer from 3 to 6.

[0067] Subsequently, by performing the step of converting all the hydrogens bonded to Si in the silicon compound containing the repeating unit represented by formula (A-4) into hydroxyl groups, a silicon compound containing the repeating unit represented by formula (A-4') containing hydroxyl groups bonded to Si can be obtained.

[0068] In the aforementioned step, for example, the hydrogen atoms bonded to Si in the silicon compound containing the repeating unit represented by formula (A-4) are converted to hydroxyl groups in the following manner: The silicon compound containing the repeating unit represented by formula (A-4) containing hydrogen atoms bonded to Si is dissolved in a solvent and added dropwise to a mixture of solvent, water, and transition metal catalyst while stirring. After hydrogen generation is complete, the reaction solution is aged. Subsequently, the transition metal catalyst is removed using a filter aid or the like, and an organic solvent such as ethyl acetate is added. The mixture is separated, and the organic layer is dried using sodium sulfate. Next, the sodium sulfate is removed, the solution is concentrated under reduced pressure, and then redeprecipitated using heptane or the like. The obtained precipitate is dried under vacuum to obtain the target product.

[0069] Examples of transition metal catalysts include palladium catalysts, platinum catalysts, rhodium catalysts, ruthenium catalysts, copper catalysts, and rhenium catalysts, with palladium catalysts being preferred. Examples of palladium catalysts include palladium hydroxide / carbon catalysts and palladium / carbon catalysts; from the viewpoint of reaction efficiency, palladium hydroxide / carbon catalysts are preferred. The amount of catalyst is not particularly limited, but from the viewpoint of reactivity and yield, it is preferably 1 mol% to 30 mol% relative to the matrix.

[0070] The reaction solvent used in this step is not particularly limited as long as it does not participate in the reaction. Examples include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate and ethyl acetate; and ether solvents such as tetrahydrofuran, diethyl ether, and cyclopentylmethyl ether. Preferably, it is a solvent that is mixed with water, and particularly preferably, it is tetrahydrofuran. The amount of solvent used is not particularly limited, but from the viewpoint of reactivity and workability, it is preferable to use it in a manner where the solid content concentration (solid content concentration = 100 × weight excluding solvent / total weight of reaction solution) is 1% by weight or more and 50% by weight or less.

[0071] There is no particular limitation on the amount of water to be added, but from the viewpoint of miscibility with the solvent, it is preferable to add 1% to 15% by weight relative to the solvent.

[0072] There is no particular limitation on the reaction time, but if the reaction time is too long, condensation of the hydroxyl groups bonded to Si may occur, or hydrogen and hydroxyl groups may exchange between the hydrogen and hydroxyl groups bonded to Si. Therefore, from the point of view of ensuring yield or preventing high molecular weight, it is preferable to be 15 minutes or more and 24 hours or less.

[0073] The reaction temperature is not particularly limited, but it is preferably above 1°C, more preferably above 5°C, and preferably below 50°C, more preferably below 40°C.

[0074] Specifically, for example, by using a palladium hydroxide / carbon catalyst in a mixed solvent of tetrahydrofuran and water, stirring a silicon compound containing repeating units represented by formula (A-4) with hydrogen bonds to Si in an inert gas environment, so that all the hydrogen bonds to Si are converted into hydroxyl groups, thereby obtaining a silicon compound containing repeating units represented by formula (A-4').

[0075] <Silicon compound (A) containing hydrogen atoms bonded to Si other than terminal Si as crosslinking functional groups> Examples of other silicon compounds (A) include silicon compounds containing at least one structural unit of sesquioxanes represented by one or both of the following formulas (1) or (2) and siloxanes represented by the following formulas (18) to (20), and having a weight average molecular weight of 3,000 to 1,000,000. [Chemical 25][Chemical 26]

[0076] In formulas (18) and (20), R13 independently represents hydrogen, an alkyl group having 1 to 8 carbons or an aryl group having 6 to 20 carbons, R14 independently represents hydrogen, a hydroxyl group, an alkoxy group having 1 to 8 carbons, an alkenyl group having 2 to 40 carbons, an alkyl group having 1 to 8 carbons or an aryl group having 6 to 20 carbons, and a represents the same group as a recorded in <Silicone Compound (A)>.

[0077] More specifically, compounds represented by the following formula (21) can be listed. [Chemical Engineering 27][Chemical Engineering 28]

[0078] In formula (21), N is a value that satisfies the weight average molecular weight of 3,000 to 1,000,000, R1 and R2 are the same as R1 and R2 in formula (1), R15 represents formula (22), R16 represents formula (23) or formula (24), in formula (24), R14 is the same as R14 in formula (19), q is 0 or 1, and X1 and X2 independently have at least one of the repeating units selected from those represented by formulas (25) to (30) below. [Chem. 29]

[0079] In formulas (25) to (30), a represents the same base as a recorded in <Silicone Compound (A)>, R13 represents the same base as formula (18), x and z are average values ​​satisfying 0 to 30, and y is a positive average value satisfying 1 to 30.

[0080] A curable resin composition containing the silicone compound represented by formula (21) can obtain a strong cured product. The properties of the silicone compound (A) can be controlled by the ratio of the sesquisiloxane group represented by formula (1) and formula (2) to the silicone alkyl group represented by formula (18) to formula (20). Regarding the expression of the ratio (β) of silicone alkyl group to sesquisiloxane group in formula (21), if x, y, and z in X1 and X2 in formula (21) are set as x1', y1', z1' and x1, y1, z1 respectively, then according to the number of formula (24) contained in R15 in formula (21), it becomes {(x1'+y1'+z1')+N(x1+y1+z1)} / (N+2q), { (x1'+y1'+z1')+N(x1+y1+z1)+1} / (N+2q), or {(x1'+y1'+z1')+N(x1+y1+z1)+2} / (N+2q), the smaller the ratio (β) of siloxane to sesquisiloxane, the more flexible and heat-resistant it tends to be, and the larger the ratio, the more robust it tends to be. In terms of overall balance, β is preferably 1 to 20.

[0081] The molecular weight of the silicon compound represented by formula (21) is preferably 3,000 to 700,000, more preferably 3,000 to 600,000, and if it is 3,000 to 500,000, the viscosity of the curable resin composition will not increase excessively, which is even more preferred.

[0082] <Method for manufacturing a silicon compound (A) containing hydrogen atoms bonded to Si other than terminal Si as crosslinking functional groups that do not contain a> There are many known methods for manufacturing the silicon compound (A) that does not contain a in the formula (21), i.e., z1=z1'=0. For example, it can be obtained by equilibrium polymerization of one or both of the following formulas (A-3) and (A-9), one or both of the following formulas (A-6) and (A-8) with the following formula (A-1) in the presence of a catalyst. Specifically, the method described in Japanese Patent Application Publication No. 2010-116464 can be cited as an example. [Chemical 30]

[0083] The formulas (A-1), (A-3), and (A-6) are the same as the compounds described in the <Method for Manufacturing a Silicon Compound Containing a Hydroxyl Group Bonded to Si Other Than the Terminal Si as a Crosslinking Functional Group and Not Containing Hydrogen>. In the formulas (A-8) and (A-9), RA2 is the same as RA2 in the formula (A-3). RA4 independently represents hydrogen, hydroxyl, alkoxy group with 1 to 8 carbons, alkenyl group with 2 to 40 carbons, alkyl group with 1 to 8 carbons, and aryl group with 6 to 20 carbons. In the formulas (A-8) and (A-9), at least one RA4 has a hydroxyl group or an alkoxy group with 1 to 8 carbons. k1, k2, and k3 are integers from 0 to 30.

[0084] <Method for manufacturing a silicon compound containing a in a silicon compound (A) containing hydrogen that is bonded to Si other than the terminal Si as a crosslinking functional group> When a is contained, i.e., when at least one of z1 or z1' is greater than 0, it can be manufactured by subjecting a compound (polyhedral oligomeric silsesquioxane (POSS)) corresponding to the structure of a to an addition reaction, desorption reaction or substitution reaction of the hydrogen bonded to Si in the silicon compound (A) containing hydrogen that is bonded to Si other than the terminal Si as a crosslinking functional group.

[0085] For example, it can be manufactured by introducing a compound corresponding to side chain a (POSS) into a silicon compound represented by formula (A-10) via an addition reaction, as shown in the following reaction formula. [Chemical 31]

[0086] In formula (A-10), x1, z1, x1', and z1' represent the positive average values ​​from 0 to 30, and y1 and y1' represent the positive average values ​​from 1 to 30.

[0087] The compound (POSS) corresponds to side chain a. In this example, the double bond of (POSS) undergoes an addition reaction with a portion of the hydrogen bonded to Si in formula (A-10). In this example, the structure of R6' of compound (POSS) is a structure obtained by subtracting two carbons from R6 (the two carbons become -CH=CH2 and participate in the addition reaction).

[0088] As compounds (POSS) corresponding to side chain a, examples include (POSS-1) to (POSS-8). [Chemical 32][Chemical 33][Chemical 34][Chemical 35][Chemical 36][Chemical 37][Chemical 38][Chemical 39]

[0089] In the examples described, reactive groups with R6' as part of the structure in the compound (POSS) are listed as -CH=CH2 and -CH2CH=CH2. However, when it is desired to introduce an alkyl group with 4 to 12 carbon atoms, the following groups are used: -CH2CH2CH=CH2, -CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2.

[0090] The silicon compounds of the present invention can be produced by reacting these compounds (POSS) with, for example, the formula (A-10) described above. A preferred example of the addition reaction is the hydrogenation of silicon using a Karstedt catalyst.

[0091] Furthermore, when introducing a side chain where R6 is -CH2-, the following compounds can be selected as starting materials as (POSS). [Chemical 40]

[0092] Alternatively, when a side chain of R6 is -O-, it can be manufactured, for example, by introducing a compound represented by compound (POSS-OH) into the silicon compound represented by formula (A-10) via a dehydrogenation reaction, as shown in the following reaction formula. [Chemical 41]

[0093] The compound (POSS-OH) corresponds to side chain a. In the example, the terminal silanol undergoes a dehydrogenation reaction in the presence of hydrogens bonded to Si in the silicon compound represented by formula (A-10) and a boron compound catalyst.

[0094] Alternatively, the silicon compound of the present invention can be manufactured by a desorption reaction or substitution reaction between a silicon compound (A-11) with a hydroxyl group as a part of its side chain and a compound (POSS-H). [Chemical 42]

[0095] In formula (A-11), x1, z1, x1', and z1' represent the positive average values ​​from 0 to 30, and y1 and y1' represent the positive average values ​​from 1 to 30.

[0096] The compound (POSS-H) corresponds to side chain a, and in this example, the terminal hydrogenated silane undergoes a dehydrogenation reaction in the presence of the hydroxyl group of the silicon compound represented by formula (A-11) bonded to Si and a boron compound catalyst. [Chemical 43]

[0097] The compound (POSS-OH) corresponds to side chain a, and in this example, the terminal silanol undergoes dehydration condensation with the Si-bonded hydroxyl group of the silicon compound (A-11) under acidic conditions. [Chemical 44]

[0098] The compound (POSS-Cl) corresponds to side chain a, and in this example, the terminal chlorosilane undergoes a dehydrochlorination reaction with the hydroxyl group of the silicon compound (A-11) bonded to Si. The reaction can be easily promoted by adding compounds with an amino group, such as triethylamine (TEA), or organic compounds exhibiting basicity.

[0099] Regarding the method for manufacturing the silicon compound represented by formula (A-11), it can be manufactured, for example, by reacting the silicon compound represented by formula (A-10) in the presence of a transition metal catalyst. [Chemical 45]

[0100] Next, a method for manufacturing the compound (POSS) will be described. For example, the compound represented by the following formula (POSS-2ph) can be manufactured by reacting the compound (POSS-0) with allyltrichlorosilane. [Chemical 46]

[0101] The compound (POSS-OH) can be produced by hydrolyzing the compound (POSS-Cl). [Chemistry 47]

[0102] The compound (POSS-Cl) can be prepared by reacting compound (POSS-O) with tetrachlorosilane. [Chem. 48]

[0103] Regarding compound (POSS-H), it can be prepared by reacting compound (POSS-O) with trichlorosilane. [Chem. 49]

[0104] Many examples of methods for manufacturing compound (POSS-0) are known, such as by hydrolysis and condensation polymerization of trifluoropropyltrimethoxysilane in the presence of an alkali metal hydroxide. [Chemical 50]

[0105] Regarding these manufacturing methods, for example, they are described in paragraph 0032 of Japanese Patent Application Publication No. 2005-15738.

[0106] <Compound (B) containing any one or more elements selected from Ce, La, Pr, Nd, Y, and Fe> The curable resin composition of the present invention contains compound (B), which contains any one or more elements selected from Ce, La, Pr, Nd, Y, and Fe. Heat resistance is improved by containing compound (B) containing any one or more elements selected from Ce, La, Pr, Nd, Y, and Fe.

[0107] The valence of Ce, La, Pr, Nd, Y and Fe can be divalent to tetravalent.

[0108] The compound (B) may contain one or more of the elements Ce, La, Pr, Nd, Y and Fe.

[0109] A compound (B) containing any one or more of the elements Ce, La, Pr, Nd, Y and Fe may be a hydrate or not.

[0110] Compounds (B) containing any one or more of the elements Ce, La, Pr, Nd, Y, and Fe, for example, include: cerium oxide (IV), cerium bromide (III), cerium acetone (III), cerium methoxyethanol (IV), cerium isopropoxide (IV), tris(isopropylcyclopentadienyl)cerium, tris(cyclopentadienyl)cerium, cerium silicate, diammonium nitrate (IV), cerium hydroxide (IV), cerium acetate (III), cerium tungstate (III), cerium oxalate (III), cerium perchlorate (III), cerium bromide (III), tetra(2,2,6,6-tetramethyl- Cerium compounds including cerium(IV)3,5-heptadecanoate, tris(1,2,3,4-tetramethyl-2,4-cyclopentadienyl)cerium(III), cerium(III)2,4-pentanedione, cerium(III)trifluoroacetyl acetone, cerium(III)fluoride, cerium(III)sulfide, cerium(III)phosphate, cerium(III)stearate, cerium(III)2-ethylhexanoate, cerium(III)trifluoromethanesulfonate, cerium(III)chloride, cerium(IV)fluoride, cerium(IV)sulfate, cerium(III)iodide, cerium(III)nitrate, cerium(III)carbonate, and cerium(IV)trifluoromethanesulfonate.

[0111] Yttrium oxide (III), yttrium isopropoxide (III), yttrium hexafluoroacetoacetone (III), tris(cyclopentadienyl)yttrium, tris(butylcyclopentadienyl)yttrium, tris(methylcyclopentadienyl)yttrium, tris(n-propylcyclopentadienyl)yttrium, tris[N,N-bis(trimethylsilyl)acetamide]yttrium (III), yttrium perchlorate (III), tris(2,2,6,6-tetramethyl-3,5-heptadecanoic acid)yttrium (III), yttrium acetoacetone (III) Yttrium chloride (III), yttrium oxalate (III), yttrium acetate (III), yttrium fluoride (III), yttrium iodide (III), yttrium 2-ethylhexanoate (III), yttrium nitrate (III), yttrium sulfide (III), yttrium bromide (III), yttrium trifluoromethanesulfonate (III), yttrium neodecanoate (III), yttrium phosphate (III), yttrium carbonate (III), yttrium sulfate (III), yttrium naphthenate (III), and other yttrium compounds;

[0112] Lanium oxide (III), Lanthanum isopropoxide (III), Tris(hexamethyldiasilazane)lanthanum, Lanthanum ethanol (III), Tris(cyclopentadienyl)lanthanum, Tris[N,N-bis(trimethylsilyl)acetylamine]lanthanum, Tris(isopropylcyclopentadienyl)lanthanum, Lanthanum carbonate, Tris(6,6,7,7,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione acid)lanthanum (III), Lanthanum perchlorate (III), Tris(2,2,6,6-tetramethyl-3,5-heptadecanedione acid)lanthanum (III), Tris[N,N-bis(tris[...]]lanthanum(...] Lanthanum (III) compounds containing lanthanum, including lanthanum (III) methylsilyl)acetylamine, lanthanum (III) acetoacetone, lanthanum chloride, lanthanum (III) sulfate, lanthanum (III) 2-ethylhexanoate, lanthanum (III) fluoride, lanthanum chloride, lanthanum (III) iodide, lanthanum boride, lanthanum sulfide, lanthanum (III) bromide, lanthanum (III) nitride, lanthanum (III) trifluoromethanesulfonate, lanthanum (III) nitrate, lanthanum (III) carbonate, lanthanum (III) acetate, tris(N,N'-diisopropylmethylamidine)lanthanum (III), and lanthanum (III) phosphate.

[0113] Titanium oxide (III), Titanium oxide (IV), Titanium hexafluoroacetoacetone (III), Titanium hexafluoro-2,4-pentanedione acid (III), Titanium acetoacetone (III), Tris(2,2,6,6-tetramethyl-3,5-heptadecanoic acid) Titanium (III), Tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione acid) Titanium (III) Tris(isopropylcyclopentadienyl)silane (III), isopropoxysilane (III), silane chloride (III), silane fluoride (III), silane acetate (III), silane sulfate (III), silane bromide (III), silane iodide (III), silane phosphate (III), silane carbonate (III), silane trifluoromethanesulfonate (III), silane nitrate (III), silane perchlorate (III), and other silane compounds;

[0114] Nd:Oxydium(III), Nd:Isopropoxide(III), Nd:Trifluoroacetoacetone(III), Tris(2,2,6,6-Tetramethyl-3,5-heptadecanoic acid)Nd: Tris(tetramethylcyclopentadienyl)Nd: Trifluoroacetoacetone, Tris(isopropylcyclopentadienyl)Nd: Neodymium(III) Trifluoromethanesulfonate, Nd:Fluoride, Tris(cyclopentadienyl)Nd: Neodymium(III) Perchlorate(III), Nd:Fluoride(III), Nd:2,4-pentanedione(III), Tris[N,N-bis(trimethylsilyl)acetoamine]Nd: Tris(2) Neodymium compounds including neodymium(III) (2,6,6-tetramethyl-3,5-heptadecanoic acid), neodymium(III) (tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanediocanoic acid), neodymium(III) hexafluoroacetoacetone, neodymium(III) 2-ethylhexanoate, neodymium(III) chloride, neodymium(III) titanate, neodymium(III) bromide, neodymium(III) iodide, neodymium(III) nitride, neodymium(III) acetate, neodymium(III) nitrate, neodymium carbonate, neodymium(III) sulfate, and neodymium(III) oxalate.

[0115] Iron oxide (II), iron oxide (III), ferric acetone (III), ferric ethoxide (III), ferric isopropoxide (III), ferric 2,4-pentanedione (III), ferric trifluoroacetone (III), tri(2,2,6,6-tetramethyl-3,5-pentanedione)ferric (III), tri(hexafluoroacetylpyruvate)ferric (III), ferric sulfate (III), ferric hexacyanate (II)ferric (III), ferric acrylate (III), ferric (III)-sodium ethylenediaminetetraacetate, ferric (III)ammonium citrate, triammonium trioxane (III), tri(2-ethylhexyl)ammonium triammonium triphosphate (III), Ferric compounds such as iron(III) hexanoate, iron(III) phosphate, iron(III) fluoride, iron(III) chloride, iron(III) hydroxide, iron(III) bromide, iron(III) trifluoromethanesulfonate, iron(III) tetraphenylporphyrin, ammonium iron(III) hexacyanoferrate, iron(III) nitrate, potassium iron(III) hexacyanoferrate, sodium ferric pentacyanide, iron(III) citrate, iron(III) diphosphate, iron(III) perchlorate, potassium ferric trioxalate, iron(III) 1,3,5-benzenetricarboxylate, and iron(III) phosphate.

[0116] In addition to the compounds listed above, compounds (B) containing one or more elements of Ce, La, Pr, Nd, Y, and Fe that have incorporated a siloxane skeleton can also be used. For example, in the case of compounds containing cerium, reaction products of cerium carboxylates and siloxane compounds containing carboxylates can be listed, as described in Japanese Patent Application Publication No. 2020-132789.

[0117] Among these, the preferred are cerium acetone (III), cerium nitrate (III), cerium 2-ethylhexanoate (III), tris(cyclopentadienyl)cerium, yttrium (III) (acetone), yttrium nitrate (III), yttrium 2-ethylhexanoate (III), tris(cyclopentadienyl)yttrium, lanthanum acetone (III), lanthanum 2-ethylhexanoate (III), tris(cyclopentadienyl)lanthanum, ferric nitrate (III), neodymium nitrate (III), neodymium 2-ethylhexanoate (III), tris(cyclopentadienyl)neodymium, ferric acetone (III), ferric 2,4-pentanedione (III), ferric tri(2,2,6,6-tetramethyl-3,5-heptanedione) (III), ferric acrylate (III), ferric tri(2-ethylhexanoate) (III), and ferric nitrate (III).

[0118] As a compound (B) having any one or more of the elements Ce, La, Pr, Nd, Y and Fe, commercially available products such as "Octope R" (manufactured by Hope Pharmaceutical Co., Ltd.) can be used.

[0119] The content of the compound (B) having any one or more of the elements Ce, La, Pr, Nd, Y and Fe is not particularly limited. In terms of the balance between heat resistance and solubility, it is preferred to be 5 ppm or more and less than 5,000 ppm of the total weight of the silicone compound (A) and crosslinking agent (C) in the curable resin composition of the present invention, more preferably 7 ppm or more and less than 3,000 ppm, and even more preferably 10 ppm or more and less than 2,000 ppm.

[0120] <Crosslinking agent (C)> The curable resin composition of the present invention may also contain a crosslinking agent (C) other than the silicone compound (A) having two or more crosslinking groups that can be chemically bonded to the silicone compound (A).

[0121] There are no particular restrictions on the crosslinking agent (C) as long as it has two or more crosslinking groups and can undergo a crosslinking reaction with the silicon compound (A).

[0122] As a crosslinking group, examples include those bonded to Si, such as the following formulas (12) to (17), formula (31), etc. [Chemical 51]

[0123] In the formula (12), R12 represents an alkyl group having 1 to 8 carbon atoms.

[0124] The crosslinking agent (C) can be linear, branched or cyclic.

[0125] The crosslinking agent (C) can specifically be listed as a compound having one or more structural units of the following formulas (C-1) to (C-4). [Chem. 52]

[0126] In formulas (C-1) to (C-3), RC1 can independently be any of the groups represented by formulas (12) to (17) and (31), or alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, phenyl, tolyl, xylyl, naphthyl, benzyl, phenylethyl, phenylpropyl, etc., or obtained by substituting part or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, bromine, chlorine, cyano, etc., for example, any of chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, and at least two RC1s represent the groups represented by formulas (12) to (17) and (31).

[0127] These compounds can be obtained, for example, by using at least one compound of the following formulas (C-5) and (C-6), and by known methods such as ring-opening polymerization, hydrolysis-condensation, or the methods described in International Publication No. 2014 / 098189. [Chemical 53]

[0128] In formula (C-5), RC2 can independently be any of the groups represented by formulas (12) to (17) and formula (31), or alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, phenyl, tolyl, xylyl, naphthyl, benzyl, phenylethyl, phenylpropyl, etc., or obtained by substituting part or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, bromine, chlorine, cyano, etc., such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, etc.

[0129] The RC3 in formula (C-6) can independently be any of the groups represented by formulas (12) to (17) and formula (31), or alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, phenyl, tolyl, xylyl, naphthyl, benzyl, phenylethyl, phenylpropyl, etc., or obtained by substituting part or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, bromine, chlorine, cyano, etc., such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, etc., and at least one RC3 represents any of the groups in formula (12) or formula (16).

[0130] In equations (C-5) and (C-6), c1 is an integer from 3 to 6, and c2 is an integer from 0 to 9.

[0131] Examples of crosslinking agents (C), more specifically, include: 1,3-dimethoxytetramethylsiloxane, 1,5-dimethoxyhexamethyltrisiloxane, polydimethylsiloxane with dimethylmethoxysilaneoxy-blocked ends, polymethylphenylsiloxane with dimethylmethoxysilaneoxy-blocked ends, polyphenylsiloxane with dimethylmethoxysilaneoxy-blocked ends, and polymethylmethoxysilane with dimethylmethoxysilaneoxy-blocked ends. Oxide-blocked dimethylsiloxane-dimethoxysiloxane copolymer, dimethylmethoxysilane-blocked methylphenylsiloxane-dimethoxysiloxane copolymer with both ends of the molecular chain, dimethylmethoxysilane-blocked diphenylsiloxane-dimethoxysiloxane copolymer with both ends of the molecular chain, methyldimethoxysilane-blocked polydimethylsiloxane with both ends of the molecular chain, methyldimethoxysilane-blocked polymethylphenylsiloxane with both ends of the molecular chain, and so on. Methyldimethoxysilyloxy-blocked polydiphenylsiloxane, methyldimethoxysilyloxy-blocked dimethylsiloxane-dimethoxysiloxane copolymer, methyldimethoxysilyloxy-blocked methylphenylsiloxane-dimethoxysiloxane copolymer, methyldimethoxysilyloxy-blocked diphenylsiloxane-dimethoxysiloxane copolymer, trimethoxysilyloxy-blocked polydimethylsiloxane Polymethylphenylsiloxane blocked by trimethoxysilyl groups at both ends of the molecular chain; polydiphenylsiloxane blocked by trimethoxysilyl groups at both ends of the molecular chain; dimethylsiloxane-dimethoxysiloxane copolymer blocked by trimethoxysilyl groups at both ends of the molecular chain; methylphenylsiloxane-dimethoxysiloxane copolymer blocked by trimethoxysilyl groups at both ends of the molecular chain; diphenylsiloxane-dimethoxysiloxane copolymer blocked by trimethoxysilyl groups at both ends of the molecular chain;

[0132] 1,3-Diethoxytetramethyldiasiloxane, 1,5-Diethoxyhexamethyltrisiloxane, polydimethylsiloxane with dimethylethoxysilane-blocked ends, polymethylphenylsiloxane with dimethylethoxysilane-blocked ends, polyphenylsiloxane with dimethylethoxysilane-blocked ends, dimethylethoxysilane-diethoxysiloxane-diethoxysiloxane, dimethylethoxysiloxane-diethoxysiloxane-diethoxysiloxane Oxyalkane copolymers, dimethylethoxysilane-blocked methylphenylsiloxane-diethoxysiloxane copolymers with both ends of the molecular chain, dimethylethoxysilane-blocked diphenylsiloxane-diethoxysiloxane copolymers with both ends of the molecular chain, methyldiethoxysilane-blocked polydimethylsiloxane, methyldiethoxysilane-blocked polymethylphenylsiloxane, methyldiethoxysilane-blocked poly(methylphenylsiloxane) Blocked polydiphenylsiloxane, dimethylsiloxane-diethoxysilane copolymer blocked by methyldiethoxysilane at both ends of the molecular chain, methylphenylsiloxane-diethoxysilane copolymer blocked by methyldiethoxysilane at both ends of the molecular chain, diphenylsiloxane-diethoxysilane copolymer blocked by methyldiethoxysilane at both ends of the molecular chain, triethoxysilane-blocked polydimethylsiloxane, and polydimethylsiloxane blocked by triethoxysilane at both ends of the molecular chain. Terminally triethoxysilane-blocked polymethylphenylsiloxane, molecular chain terminally triethoxysilane-blocked polydiphenylsiloxane, molecular chain terminally triethoxysilane-blocked dimethylsiloxane-diethoxysiloxane copolymer, molecular chain terminally triethoxysilane-blocked methylphenylsiloxane-diethoxysiloxane copolymer, molecular chain terminally triethoxysilane-blocked diphenylsiloxane-diethoxysiloxane copolymer;

[0133] 1,3-Dihydroxytetramethylsiloxane, 1,5-Dihydroxyhexamethyltrisiloxane, 1,5-Dihydroxyhexaphenyltrisiloxane, polydimethylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, polymethylphenylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, polyphenylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, polyphenylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain Dimethylsiloxane-dihydroxysiloxane copolymer, dimethylhydroxysiloxy-blocked methylphenylsiloxane-dihydroxysiloxane copolymer with dimethylhydroxysiloxy groups at both ends of the molecular chain, dimethylhydroxysiloxy-blocked diphenylsiloxane-dihydroxysiloxane copolymer with dimethylhydroxysiloxy groups at both ends of the molecular chain, polydimethylsiloxane with methyldihydroxysiloxy groups at both ends of the molecular chain, polymethylphenyl ... Methyldihydroxysiloxane-blocked polydiphenylsiloxane, methyldihydroxysiloxane-blocked dimethylsiloxane-dihydroxysiloxane copolymer with both ends of the molecular chain, methyldihydroxysiloxane-blocked methylphenylsiloxane-dihydroxysiloxane copolymer with both ends of the molecular chain, methyldihydroxysiloxane-blocked diphenylsiloxane-dihydroxysiloxane copolymer with both ends of the molecular chain, trihydroxysiloxane-blocked polydimethylsiloxane, Polymethylphenylsiloxane blocked by trihydroxysiloxy groups at both ends of the molecular chain, polydiphenylsiloxane blocked by trihydroxysiloxy groups at both ends of the molecular chain, dimethylsiloxane-dihydroxysiloxane copolymer blocked by trihydroxysiloxy groups at both ends of the molecular chain, methylphenylsiloxane-dihydroxysiloxane copolymer blocked by trihydroxysiloxy groups at both ends of the molecular chain, and diphenylsiloxane-dihydroxysiloxane copolymer blocked by trihydroxysiloxy groups at both ends of the molecular chain;

[0134] 1,3-Divinyltetramethyldisiloxane, 1,5-Divinylhexamethyltrisiloxane, polydimethylsiloxane blocked by dimethylvinylsiloxy groups at both ends of the molecular chain, polymethylphenylsiloxane blocked by dimethylvinylsiloxy groups at both ends of the molecular chain, polyphenylsiloxane blocked by dimethylvinylsiloxy groups at both ends of the molecular chain, dimethylvinylsiloxy blocked by dimethylsiloxane-divinylsiloxane Oxyalkane copolymers, dimethylvinylsilane-blocked methylphenylsiloxane-divinylsiloxane copolymers with both ends of the molecular chain, dimethylvinylsilane-blocked diphenylsiloxane-divinylsiloxane copolymers with both ends of the molecular chain, methyl divinylsilane-blocked polydimethylsiloxane, methyl divinylsilane-blocked polymethylphenylsiloxane, methyl divinylsilane-blocked polydiphenylsiloxane, methyl divinylsilane-blocked dimethylsiloxane-divinylsiloxane copolymers with both ends of the molecular chain, methyl divinylsilane-blocked dimethylsiloxane-divinylsiloxane copolymers with both ends of the molecular chain, trivinylsilane-blocked polydimethylsiloxane, and so on. Terminally trivinylsiloxy-blocked polymethylphenylsiloxane, molecular chain with two ends of trivinylsiloxy-blocked polydiphenylsiloxane, molecular chain with two ends of trivinylsiloxy-blocked dimethylsiloxane-divinylsiloxane copolymer, molecular chain with two ends of trivinylsiloxy-blocked methylphenylsiloxane-divinylsiloxane copolymer, molecular chain with two ends of trivinylsiloxy-blocked diphenylsiloxane-divinylsiloxane copolymer;

[0135] 1,1,3,3-Tetramethyldisiloxane, 1,1,3,3,5,5-Hexamethyltrisiloxane, polydimethylsiloxane blocked by dimethylhydrosiloxy groups at both ends of the molecular chain, polymethylphenylsiloxane blocked by dimethylhydrosiloxy groups at both ends of the molecular chain, polyphenylsiloxane blocked by dimethylhydrosiloxy groups at both ends of the molecular chain, dimethylsiloxane blocked by dimethylsiloxane groups at both ends of the molecular chain alkylene-dihydrosiloxane copolymer, dimethylhydrosiloxane-dihydrosiloxane copolymer with dimethylhydrosiloxane-oxy group blocked at both ends of the molecular chain, diphenylsiloxane-dihydrosiloxane copolymer with dimethylhydrosiloxane-oxy group blocked at both ends of the molecular chain, polydimethylsiloxane with methyldihydrosiloxane-oxy group blocked at both ends of the molecular chain, polymethylphenylsiloxane with methyldihydrosiloxane-oxy group blocked at both ends of the molecular chain, poly(methyldihydrosiloxane) ... Hydrosiloxane-blocked polydiphenylsiloxane, methyldihydrosiloxane-dimethylsiloxane-dihydrosiloxane copolymer with methyldihydrosiloxane-dimethylsiloxane-dihydrosiloxane at both ends of the molecular chain, methyldihydrosiloxane-methylphenylsiloxane-dihydrosiloxane copolymer with methyldihydrosiloxane-dimethylsiloxane at both ends of the molecular chain, methyldihydrosiloxane-dimethylsiloxane-dihydrosiloxane copolymer with methyldihydrosiloxane-dimethylsiloxane at both ends of the molecular chain, trihydrosiloxane-blocked polydimethylsiloxane, etc. Polymethylphenylsiloxane blocked by trihydrosiloxy groups at both ends of the molecular chain, polydiphenylsiloxane blocked by trihydrosiloxy groups at both ends of the molecular chain, dimethylsiloxane-dihydrosiloxane copolymer blocked by trihydrosiloxy groups at both ends of the molecular chain, methylphenylsiloxane-dihydrosiloxane copolymer blocked by trihydrosiloxy groups at both ends of the molecular chain, and diphenylsiloxane-dihydrosiloxane copolymer blocked by trihydrosiloxy groups at both ends of the molecular chain;

[0136] 1,3-Diethoxytetramethyldiasiloxane, 1,5-Diethoxyhexamethyltrisiloxane, polydimethylsiloxane with dimethylethoxysilaneoxy-blocked at both ends of the molecular chain, polymethylphenylsiloxane with dimethylethoxysilaneoxy-blocked at both ends of the molecular chain, polyphenylsiloxane with dimethylethoxysilaneoxy-blocked at both ends of the molecular chain, and dimethylethoxysilane-diethoxy-blocked at both ends of the molecular chain. Silicon oxane copolymers, dimethylacetoxysilane-blocked methylphenylsiloxane-diacetoxysilane copolymers with both ends of the molecular chain, dimethylacetoxysilane-blocked diphenylsiloxane-diacetoxysilane copolymers with both ends of the molecular chain, methyldiacetoxysilane-blocked polydimethylsiloxane, methyldiacetoxysilane-blocked polymethylphenylsiloxane, methyldiacetoxysilane Oxide-blocked polydiphenylsiloxane, methyldiacetoxysilane-blocked dimethylsiloxane-diacetoxysiloxane copolymer, methyldiacetoxysilane-blocked methylphenylsiloxane-diacetoxysiloxane copolymer, methyldiacetoxysilane-blocked diphenylsiloxane-diacetoxysiloxane copolymer, triacetoxysilane-blocked polydimethylsiloxane, [The last part, "molecular chain ends," appears to be a typographical error and is left untranslated.] Triacetyloxysilane-blocked polymethylphenylsiloxane, triacetyloxysilane-blocked polydiphenylsiloxane, triacetyloxysilane-blocked dimethylsiloxane-diacetyloxysiloxane copolymer, triacetyloxysilane-blocked methylphenylsiloxane-diacetyloxysiloxane copolymer, and triacetyloxysilane-blocked diphenylsiloxane-diacetyloxysiloxane copolymer.

[0137] 1,3-Diethylmethyl ketoxime tetramethyl disiloxane, 1,5-Diethylmethyl ketoxime hexamethyl trisiloxane, dimethyl ethyl ketoxime silalkoxy-blocked polydimethyl siloxane at both ends of the molecular chain, dimethyl ethyl ketoxime silalkoxy-blocked polymethyl phenyl siloxane at both ends of the molecular chain, dimethyl ethyl ketoxime silalkoxy-blocked polydiphenyl siloxane at both ends of the molecular chain, dimethyl ethyl ketoxime silalkoxy-blocked dimethyl siloxane-diethyl ketoxime silicon at both ends of the molecular chain Oxyalkane copolymers, dimethyl ethyl ketone oxime silaneoxy-blocked methylphenyl siloxane-diethyl ketone oxime siloxane copolymers, dimethyl ethyl ketone oxime silaneoxy-blocked diphenyl siloxane-diethyl ketone oxime siloxane copolymers, dimethyl diethyl ketone oxime silaneoxy-blocked polydimethyl siloxanes, dimethyl diethyl ketone oxime silaneoxy-blocked polymethylphenyl siloxanes, dimethyl diethyl ketone oxime silaneoxy-blocked polydimethyl ... Blocked polydiphenylsiloxane, dimethyl diethyl ketone oxime-diethyl ketone oxime-siloxane copolymer with methyl diethyl ketone oxime-siloxane at both ends of the molecular chain, methyl phenyl ketone oxime-diethyl ketone oxime-siloxane copolymer with methyl diethyl ketone oxime-diethyl ketone oxime at both ends of the molecular chain, triethyl ketone oxime-siloxane-blocked polydimethyl ketone oxime, and triethyl ketone oxime-siloxane at both ends of the molecular chain. Ethylmethyl ketone oxime silalkoxy-blocked polymethyl phenyl silicate, polydiphenyl silicate with triethylmethyl ketone oxime silalkoxy-blocked polydiphenyl silicate, dimethyl silicate-diethylmethyl ketone oxime silalkoxy-blocked dimethyl silicate-diethylmethyl ketone oxime silalkoxy-blocked copolymer, methyl phenyl silicate-diethylmethyl ketone oxime silalkoxy-blocked methyl silicate-diethylmethyl ketone oxime silalkoxy-blocked diphenyl silicate-diethylmethyl ketone oxime silalkoxy-blocked diphenyl silicate-diethylmethyl ketone oxime silalkoxy-blocked copolymer;

[0138] A copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OCH3)SiO2 / 2 units and (CH3)SiO3 / 2 units; a copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; a copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units; Copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; copolymers comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OC2H5)SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units;

[0139] A copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units, a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OH)SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units; Copolymers comprising (CH3)2(CH=CH2)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; copolymers comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(CH=CH2)SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(CH=CH2)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(CH=CH2)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units;

[0140] A copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units, a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)HSiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units, or a copolymer in which part or all of the methyl groups in these exemplary compounds are replaced by other alkyl groups such as ethyl or propyl or aryl groups such as phenyl;

[0141] Methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, glycidyltrimethoxysilane, mercaptotrimethoxysilane, mercaptotriethoxysilane, aminopropyltriethoxysilane, tetramethoxysilane, partially condensed tetramethoxysilane, tetraethoxysilane, partially condensed tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, isobutyltrimethoxysilane, ethyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, ethyltriethoxysilane, dibutoxydiacetyloxysilane Silane, phenyl-tripropoxysilane, methyltris(methylethylketoximo)silane, vinyl-tri-methylethylketoximosilane, methyltris(methylethylketoximino)silane, methyltris(isopropoxy)silane, vinyltris(isopropoxy)silane, polyethyl silicate, n-propyl orthosilicate, ethyl orthosilicate, dimethyltetraethoxydisiloxane, oxime silane, acetoxysilane, acetoxysilane, enoxysilane, etc.

[0142] Compounds having one or more structural units of formulas (C-1) to (C-4) also include the compounds shown below: 1,6-bis(trimethoxysilyl)hexane, bis(trialkoxysilylalkyl)amine, bis(dialkoxysilylalkyl)amine, bis(trialkoxysilylalkyl)N-alkylamine, bis(dialkoxysilylalkyl)N-alkylamine, bis(trialkoxysilylalkyl)urea, bis(dialkoxysilylalkyl)urea, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, bis(4-trimethoxysilylbutyl)amine, bis(4-triethoxysilylbutyl)amine, bis(3-trimethoxysilylpropyl)N-methylamine, bis(3-triethoxysilylpropyl)N-methylamine. Bis(4-trimethoxysilylbutyl)N-methylamine, Bis(4-triethoxysilylbutyl)N-methylamine, Bis(3-trimethoxysilylpropyl)urea, Bis(3-triethoxysilylpropyl)urea, Bis(4-trimethoxysilylbutyl)urea, Bis(4-triethoxysilylbutyl)urea, Bis(3-dimethoxymethylsilylpropyl)amine, Bis(3-diethoxymethylsilylpropyl)amine, Bis(4-dimethoxymethylsilylbutyl)amine, Bis(4-diethoxymethylsilylbutyl)amine, Bis(3-dimethoxymethylsilylpropyl)N-methylamine, Bis(3-diethoxymethylsilylpropyl) N-Methylamine, bis(4-dimethoxymethylsilylbutyl)N-methylamine, bis(4-diethoxymethylsilylbutyl)N-methylamine, bis(3-dimethoxymethylsilylpropyl)urea, bis(3-diethoxymethylsilylpropyl)urea, bis(4-dimethoxymethylsilylbutyl)urea, bis(4-diethoxymethylsilylbutyl)urea, bis(3-dimethoxyethylsilylpropyl)amine, bis(3-diethoxyethylsilylpropyl)amine, bis(4-dimethoxyethylsilylbutyl)amine, bis(4-diethoxyethylsilylbutyl)amine, bis(3-dimethoxyethylsilylpropyl)N-methylamine Bis(3-diethoxyethylsilylpropyl)N-methylamine, bis(4-dimethoxyethylsilylbutyl)N-methylamine, bis(4-diethoxyethylsilylbutyl)N-methylamine, bis(3-dimethoxyethylsilylpropyl)urea, bis(3-diethoxyethylsilylpropyl)urea, bis(4-dimethoxyethylsilylbutyl)urea, and / or bis(4-diethoxyethylsilylbutyl)urea; bis(triethoxysilylpropyl)amine, bis(trimethoxysilylpropyl)amine, bis(trimethoxysilylpropyl)urea, bis(triethoxysilylpropyl)urea, bis(diethoxymethylsilylpropyl)N-methylamine;Dialkoxysilane-terminated polydialkylsiloxanes or trialkoxysilane-terminated polydialkylsiloxanes, dialkoxysilane-terminated polyarylalkylsiloxanes or trialkoxysilane-terminated polyarylalkylsiloxanes, dialkoxysilane-terminated polypropylene oxide or trialkoxysilane-terminated polypropylene oxide, polyurethane, polyacrylate; polyisobutylene; diacetoxy-terminated polydialkyl or triacetoxy-terminated polydialkyl; polyarylalkylsiloxanes; dioxime-silane-terminated polydialkyl or trioxime-silane-terminated polydialkyl; polyarylalkylsiloxanes; and diacetoneoxy-terminated polydialkyl or polyarylalkyl or triacetoneoxy-terminated polydialkyl or polyarylalkyl compounds whose main chain contains an organic group.

[0143] Commercially available products as crosslinking agents (C) include: Silaplane FM11 series, Silaplane FM22 series, Silaplane FM88 series, Silaplane FM99 series, and Silaplane FM08 series (all trade names) manufactured by JNC Corporation; SR series (trade names) manufactured by Konishi Chemical Industry Co., Ltd.; MKC silicate MS57 (trade name), MKC silicate MS51 (trade name) (tetramethoxysilane average pentamer), MKC silicate MS56, and MS56S (all trade names) manufactured by Mitsubishi Chemical Co., Ltd.; and methyl silicate (methyl... 51 (tetramethoxysilane average tetramer), 53 (tetramethoxysilane average heptamer), 40 (tetraethoxysilane average pentamer), 48 (tetraethoxysilane average decamer), etc.

[0144] For example, when the silicon compound (A) is a silicon compound containing one or both of the structural units of a sesquisiloxane group represented by formula (1) or formula (2) and a siloxane group represented by formula (6) or formula (7), and has a weight average molecular weight of 3,000 to 1,000,000, the crosslinking group is preferably any one of formulas (12) to (17) bonded to Si. [Chemical 54][Chemical 55]

[0145] Formulas (1), (2), (6), and (7) are the same as those described in the <Silicone Compound (A)>.

[0146] Specifically, as an example of a preferred crosslinking agent, it is preferably a structure having one or more of the formulas (C-1) to (C-4), and at least two of the RC1s in the same formula are any one of the formulas (12) to (17).

[0147] More specifically, examples of preferred crosslinking agents include: 1,3-dimethoxytetramethyldisiloxane, 1,5-dimethoxyhexamethyltrisiloxane, dimethylmethoxysilyloxy-blocked polydimethylsiloxane, dimethylmethoxysilyloxy-blocked polymethylphenylsiloxane, dimethylmethoxysilyloxy-blocked polyphenylsiloxane, dimethylmethoxysilyloxy-blocked polyphenylsiloxane, dimethylmethoxysilyloxy-blocked dimethylsiloxane-dimethoxysiloxane copolymer, and dimethylmethoxysilyloxy-blocked methylphenylsiloxane-dimethoxysiloxane copolymer. Dimethylmethoxysilane-blocked diphenylsiloxane-dimethoxysiloxane copolymer, trimethoxysilane-blocked polydimethylsiloxane, trimethoxysilane-blocked polymethylphenylsiloxane, trimethoxysilane-blocked polydiphenylsiloxane, trimethoxysilane-blocked dimethylsiloxane-dimethoxysiloxane copolymer, trimethoxysilane-blocked methylphenylsiloxane-dimethoxysiloxane copolymer, trimethoxysilane-blocked diphenylsiloxane-dimethoxysiloxane copolymer;

[0148] 1,3-Diethoxytetramethyldiasiloxane, 1,5-Diethoxyhexamethyltrisiloxane, polydimethylsiloxane with dimethylethoxysilaneoxy-blocked ends, polymethylphenylsiloxane with dimethylethoxysilaneoxy-blocked ends, polyphenylsiloxane with dimethylethoxysilaneoxy-blocked ends, dimethylethoxysilane-diethoxysiloxane copolymer with dimethylethoxysilaneoxy-blocked ends, methylphenylsiloxane-diethoxysiloxane copolymer with dimethylethoxysilaneoxy-blocked ends, diphenylsiloxane-diethoxysiloxane copolymer with dimethylethoxysilaneoxy-blocked ends Silicon oxane copolymers, diphenylsiloxane-diethoxysilane copolymers blocked by methyldiethoxysilanes at both ends of the molecular chain, polydimethylsiloxane blocked by triethoxysilanes at both ends of the molecular chain, polymethylphenylsiloxane blocked by triethoxysilanes at both ends of the molecular chain, polydiphenylsiloxane blocked by triethoxysilanes at both ends of the molecular chain, dimethylsiloxane-diethoxysilane copolymers blocked by triethoxysilanes at both ends of the molecular chain, methylphenylsiloxane-diethoxysilane copolymers blocked by triethoxysilanes at both ends of the molecular chain, and diphenylsiloxane-diethoxysilane copolymers blocked by triethoxysilanes at both ends of the molecular chain;

[0149] 1,3-Dihydroxytetramethylsiloxane, 1,5-Dihydroxyhexamethyltrisiloxane, 1,5-Dihydroxyhexaphenyltrisiloxane, polydimethylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, polymethylphenylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, polyphenylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, dimethylsiloxane-dihydroxysiloxane copolymer blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, methylphenylsiloxane-dihydroxysiloxane copolymer blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, molecular Dimethyl hydroxysiloxane-blocked diphenylsiloxane-dihydroxysiloxane copolymer, trihydroxysiloxane-blocked polydimethylsiloxane, trihydroxysiloxane-blocked polymethylphenylsiloxane, trihydroxysiloxane-blocked polydiphenylsiloxane, trihydroxysiloxane-blocked dimethylsiloxane-dihydroxysiloxane copolymer, trihydroxysiloxane-blocked methylphenylsiloxane-dihydroxysiloxane copolymer, trihydroxysiloxane-blocked diphenylsiloxane-dihydroxysiloxane copolymer;

[0150] 1,1,3,3-Tetramethyldisiloxane, 1,1,3,3,5,5-Hexamethyltrisiloxane, polydimethylsiloxane with dimethylhydrosiloxy-blocked ends, polymethylphenylsiloxane with dimethylhydrosiloxy-blocked ends, polyphenylsiloxane with dimethylhydrosiloxy-blocked ends, dimethylsiloxane-dihydrosiloxane copolymer with dimethylhydrosiloxy-blocked ends, methylphenylsiloxane-dihydrosiloxane copolymer with dimethylhydrosiloxy-blocked ends, and more. Dimethylsiloxane-blocked diphenylsiloxane-dihydrosiloxane copolymer, polydimethylsiloxane with trihydrosiloxane-blocked molecular chain at both ends, polymethylphenylsiloxane with trihydrosiloxane-blocked molecular chain at both ends, polydiphenylsiloxane with trihydrosiloxane-blocked molecular chain at both ends, dimethylsiloxane-dihydrosiloxane-dihydrosiloxane copolymer with trihydrosiloxane-blocked molecular chain at both ends, methylphenylsiloxane-dihydrosiloxane copolymer with trihydrosiloxane-blocked molecular chain at both ends, diphenylsiloxane-dihydrosiloxane copolymer with trihydrosiloxane-blocked molecular chain at both ends;

[0151] Methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, partially condensed tetramethoxysilane, tetraethoxysilane, partially condensed tetraethoxysilane;

[0152] A copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OCH3)SiO2 / 2 units and (CH3)SiO3 / 2 units; a copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; a copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units; Copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; copolymers comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OC2H5)SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units;

[0153] A copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units, a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3) (OH)SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units;

[0154] A copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units, a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)HSiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units, etc.

[0155] The crosslinking agent (C) may be one or more.

[0156] As for the content of crosslinking agent (C), the ratio of (number of crosslinking groups in crosslinking agent (C)) to (number of crosslinking functional groups in silicon compound (A)) is preferably 0.1 to 40, more preferably 0.3 to 35, and particularly preferably 0.5 to 30.

[0157] Additionally, for example, when the silicon compound (A) is a silicon compound containing one or more of the sesquioxanes represented by formula (1) or formula (2) and at least one of the siloxanes represented by formulas (18) to (20) and having a weight average molecular weight of 3,000 to 1,000,000, the crosslinking group is preferably any one of formulas (12) to (17) or (31) bonded to Si. [Chemical Engineering 56][Chemical Engineering 57]

[0158] Formulas (1), (2), (18) to (20), and a are the same as those described in the <Silicone Compound (A)>.

[0159] Specifically, as an example of a preferred crosslinking agent, it is preferred to have a structure having one or more of the formulas (C-1) to (C-4), and at least two of the RC1s in the same formula are any one of the formulas (12) to (17) or (31).

[0160] More specifically, examples of preferred crosslinking agents include: 1,3-dimethoxytetramethyldisiloxane, 1,5-dimethoxyhexamethyltrisiloxane, polydimethylsiloxane with dimethylmethoxysilaneoxy-blocked ends, polymethylphenylsiloxane with dimethylmethoxysilaneoxy-blocked ends, polyphenylsiloxane with dimethylmethoxysilaneoxy-blocked ends, and polymethylmethoxysilane with dimethylmethoxysilaneoxy-blocked ends. Oxide-blocked dimethylsiloxane-dimethoxysiloxane copolymer, dimethylmethoxysilane-blocked methylphenylsiloxane-dimethoxysiloxane copolymer with both ends of the molecular chain, dimethylmethoxysilane-blocked diphenylsiloxane-dimethoxysiloxane copolymer with both ends of the molecular chain, methyldimethoxysilane-blocked polydimethylsiloxane with both ends of the molecular chain, methyldimethoxysilane-blocked polymethylphenylsiloxane with both ends of the molecular chain, and so on. Methyldimethoxysilyloxy-blocked polydiphenylsiloxane, methyldimethoxysilyloxy-blocked dimethylsiloxane-dimethoxysiloxane copolymer, methyldimethoxysilyloxy-blocked methylphenylsiloxane-dimethoxysiloxane copolymer, methyldimethoxysilyloxy-blocked diphenylsiloxane-dimethoxysiloxane copolymer, trimethoxysilyloxy-blocked polydimethylsiloxane Polymethylphenylsiloxane blocked by trimethoxysilyl groups at both ends of the molecular chain; polydiphenylsiloxane blocked by trimethoxysilyl groups at both ends of the molecular chain; dimethylsiloxane-dimethoxysiloxane copolymer blocked by trimethoxysilyl groups at both ends of the molecular chain; methylphenylsiloxane-dimethoxysiloxane copolymer blocked by trimethoxysilyl groups at both ends of the molecular chain; diphenylsiloxane-dimethoxysiloxane copolymer blocked by trimethoxysilyl groups at both ends of the molecular chain;

[0161] 1,3-Diethoxytetramethyldiasiloxane, 1,5-Diethoxyhexamethyltrisiloxane, polydimethylsiloxane with dimethylethoxysilane-blocked ends, polymethylphenylsiloxane with dimethylethoxysilane-blocked ends, polyphenylsiloxane with dimethylethoxysilane-blocked ends, dimethylethoxysilane-diethoxysiloxane-diethoxysiloxane, dimethylethoxysilane-diethoxysiloxane-diethoxysiloxane Oxyalkane copolymers, dimethylethoxysilane-blocked methylphenylsiloxane-diethoxysiloxane copolymers with both ends of the molecular chain, dimethylethoxysilane-blocked diphenylsiloxane-diethoxysiloxane copolymers with both ends of the molecular chain, methyldiethoxysilane-blocked polydimethylsiloxane, methyldiethoxysilane-blocked polymethylphenylsiloxane, methyldiethoxysilane-blocked poly(methylphenylsiloxane) Blocked polydiphenylsiloxane, dimethylsiloxane-diethoxysilane copolymer blocked by methyldiethoxysilane at both ends of the molecular chain, methylphenylsiloxane-diethoxysilane copolymer blocked by methyldiethoxysilane at both ends of the molecular chain, diphenylsiloxane-diethoxysilane copolymer blocked by methyldiethoxysilane at both ends of the molecular chain, triethoxysilane-blocked polydimethylsiloxane, and polydimethylsiloxane blocked by triethoxysilane at both ends of the molecular chain. Terminally triethoxysilane-blocked polymethylphenylsiloxane, molecular chain terminally triethoxysilane-blocked polydiphenylsiloxane, molecular chain terminally triethoxysilane-blocked dimethylsiloxane-diethoxysiloxane copolymer, molecular chain terminally triethoxysilane-blocked methylphenylsiloxane-diethoxysiloxane copolymer, molecular chain terminally triethoxysilane-blocked diphenylsiloxane-diethoxysiloxane copolymer;

[0162] 1,3-Dihydroxytetramethylsiloxane, 1,5-Dihydroxyhexamethyltrisiloxane, 1,5-Dihydroxyhexaphenyltrisiloxane, polydimethylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, polymethylphenylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, polyphenylsiloxane blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, dimethylsiloxane-dihydroxysiloxane copolymer blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, methylphenylsiloxane-dihydroxysiloxane copolymer blocked by dimethylhydroxysiloxy groups at both ends of the molecular chain, molecular Dimethyl hydroxysiloxane-blocked diphenylsiloxane-dihydroxysiloxane copolymer, trihydroxysiloxane-blocked polydimethylsiloxane, trihydroxysiloxane-blocked polymethylphenylsiloxane, trihydroxysiloxane-blocked polydiphenylsiloxane, trihydroxysiloxane-blocked dimethylsiloxane-dihydroxysiloxane copolymer, trihydroxysiloxane-blocked methylphenylsiloxane-dihydroxysiloxane copolymer, trihydroxysiloxane-blocked diphenylsiloxane-dihydroxysiloxane copolymer;

[0163] 1,3-Divinyltetramethyldisiloxane, 1,5-Divinylhexamethyltrisiloxane, polydimethylsiloxane with dimethylvinylsiloxy-blocked molecular chains at both ends, polymethylphenylsiloxane with dimethylvinylsiloxy-blocked molecular chains at both ends, polyphenylsiloxane with dimethylvinylsiloxy-blocked molecular chains at both ends, dimethylvinylsiloxy-blocked dimethylsiloxane-divinylsiloxane copolymer, methylphenylsiloxane-divinylsiloxane copolymer with dimethylvinylsiloxy-blocked molecular chains at both ends, dimethylvinylethylene Diphenylsiloxane-divinylsiloxane copolymer with trivinylsiloxy blocking at both ends of the molecular chain, polydimethylsiloxane with trivinylsiloxy blocking at both ends of the molecular chain, polymethylphenylsiloxane with trivinylsiloxy blocking at both ends of the molecular chain, polydiphenylsiloxane with trivinylsiloxy blocking at both ends of the molecular chain, dimethylsiloxane-divinylsiloxane copolymer with trivinylsiloxy blocking at both ends of the molecular chain, methylphenylsiloxane-divinylsiloxane copolymer with trivinylsiloxy blocking at both ends of the molecular chain, and diphenylsiloxane-divinylsiloxane copolymer with trivinylsiloxy blocking at both ends of the molecular chain;

[0164] 1,1,3,3-Tetramethyldisiloxane, 1,1,3,3,5,5-Hexamethyltrisiloxane, polydimethylsiloxane with dimethylhydrosiloxy-blocked ends, polymethylphenylsiloxane with dimethylhydrosiloxy-blocked ends, polyphenylsiloxane with dimethylhydrosiloxy-blocked ends, dimethylsiloxane-dihydrosiloxane copolymer with dimethylhydrosiloxy-blocked ends, methylphenylsiloxane-dihydrosiloxane copolymer with dimethylhydrosiloxy-blocked ends, and more. Dimethylsiloxane-blocked diphenylsiloxane-dihydrosiloxane copolymer, polydimethylsiloxane with trihydrosiloxane-blocked molecular chain at both ends, polymethylphenylsiloxane with trihydrosiloxane-blocked molecular chain at both ends, polydiphenylsiloxane with trihydrosiloxane-blocked molecular chain at both ends, dimethylsiloxane-dihydrosiloxane-dihydrosiloxane copolymer with trihydrosiloxane-blocked molecular chain at both ends, methylphenylsiloxane-dihydrosiloxane copolymer with trihydrosiloxane-blocked molecular chain at both ends, diphenylsiloxane-dihydrosiloxane copolymer with trihydrosiloxane-blocked molecular chain at both ends;

[0165] A copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OCH3)SiO2 / 2 units and (CH3)SiO3 / 2 units; a copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; a copolymer comprising (CH3)2(OCH3)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units; Copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; copolymers comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OC2H5)SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(OC2H5)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units;

[0166] A copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units, a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(OH)SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2(OH)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units; Copolymers comprising (CH3)2(CH=CH2)SiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units; copolymers comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)(CH=CH2)SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(CH=CH2)SiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units; copolymers comprising (CH3)2(CH=CH2)SiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units;

[0167] A copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units and SiO4 / 2 units, a copolymer comprising (CH3)3SiO1 / 2 units, (CH3)2SiO2 / 2 units, (CH3)HSiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units and (CH3)SiO3 / 2 units, a copolymer comprising (CH3)2HSiO1 / 2 units, (CH3)2SiO2 / 2 units, (C6H5)2SiO2 / 2 units and (CH3)SiO3 / 2 units, or a copolymer in which part or all of the methyl groups in these exemplary compounds are replaced by other alkyl groups such as ethyl or propyl or aryl groups such as phenyl; Methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, partially condensed tetramethoxysilane, tetraethoxysilane, partially condensed tetraethoxysilane, etc.

[0168] The crosslinking agent (C) may be one or more.

[0169] As for the content of crosslinking agent (C), the ratio of (number of crosslinking functional groups in the crosslinking agent) to (number of crosslinking functional groups in the silicon compound (A)) is preferably 0 to 40, more preferably 0 to 35, and particularly preferably 0 to 30.

[0170] <Catalyst (D)> The curable resin composition of the present invention may also contain a catalyst (D). For example, when the silicone compound (A) reacts chemically with each other, the catalyst (D) may promote chemical reactions between crosslinking functional groups in the silicone compound (A) or promote chemical reactions between the silicone compound (A) and the crosslinking agent (C).

[0171] The catalyst (D) of the present invention is not particularly limited as long as it acts on the chemical reaction.

[0172] As an example, catalysts having any one or more of Sn, Zr, Ti, Al, N and Pt can be listed.

[0173] As catalysts containing Sn, examples include: dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin maleate, dioctyltin maleate, tin 2-ethylhexanoate, etc.

[0174] As catalysts containing Zr, examples include: n-propyl zirconate, n-butyl zirconate, tetraacetyl acetone zirconium, monoacetyl acetone zirconium, etc.

[0175] Examples of catalysts containing Ti include: tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, titanium acetoacetone, titanium tetraacetoacetone, titanium acetoethyl acetate, titanium dodecylbenzenesulfonate compounds, titanium phosphate complexes, titanium octylene glycolate, titanium ammonium lactate, titanium lactate, titanium triethanolamine, etc.

[0176] As catalysts containing Al, examples include: aluminum dibutoxide, aluminum triacetone, aluminum diacetone, aluminum monoacetone, aluminum triacetone, etc.

[0177] As catalysts containing N, examples include: silazanes such as trimethylsilylamine, bis(trimethylsilyl)amine, tri(trimethylsilyl)amine, methyldiphenylsilylamine, bis(methyldiphenylsilyl)amine, and tri(methyldiphenylsilyl)amine; cyclic silazanes such as hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, decamethylcyclopentasilazane, trimethyltriphenylcyclotrisilazane, tetramethyltetraphenylcyclotetrasilazane, pentamethylpentaphenylcyclopentasilazane, hexaphenylcyclotrisilazane, octaphenylcyclotetrasilazane, and decaphenylcyclopentasilazane; inorganic polysilazanes such as perhydropolysilazane and organic polysilazanes such as methylpolysilazane; Organic guanidines such as aminoguanidine, 1,1,3,3-tetramethylguanidine, n-dodecylguanidine, hydroxymethylguanidine, dihydroxymethylguanidine, 1-phenylguanidine, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, triphenylguanidine, and 1-benzyl-2,3-dimethylcyanoguanidine; Alkyl imidazoles such as 2-ethyl-4-methylimidazolium, 1-methylimidazolium, 1,2-dimethylimidazolium, 2-methylimidazolium, 2-ethylimidazolium, 2-undecylimidazolium, 2-heptadecanylimidazolium, and 2-isopropylimidazolium; aminomethylalkyl-substituted imidazoles such as 1-(2-aminomethylethyl)imidazolium; cyanoalkyl-substituted imidazoles such as 1-cyanoethyl-2-methylimidazolium; aromatic substituted imidazoles such as 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, and 1-benzyl-2-methylimidazolium; alkenyl-substituted imidazoles such as 1-vinyl-2-methylimidazolium; allyl-substituted imidazoles such as 1-allyl-2-ethyl-4-methylimidazolium; and imidazoles such as polyimidazolium.

[0178] Further examples include: dicyandiamide, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5, 2-ethylhexanoate of the DBU, formate of the DBU, phthalate of the DBU, p-toluenesulfonate of the DBU, phenolic varnish resin salt of the DBU, and trimellitate of the DBU;

[0179] In addition, ketimines, the reaction products of polyamines and carbonyl compounds, can also be listed. Examples of polyamines include: ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p,p'-diphenyldiamine, etc.; polyamines such as 1,2,3-triaminopropane, triaminobenzene, tris(2-aminoethyl)amine, tetra(aminomethyl)methane, etc.; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine, etc.; poly(ethylenetriamine), poly(ethylenetriamine), etc. Oxyalkyl polyamines and carbonyl compounds include: aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone; aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, and diisobutyl ketone; and β-dicarbonyl compounds such as acetone, methyl acetate, ethyl acetate, dimethyl malonate, diethyl malonate, methyl ethyl malonate, and dibenzoylmethane.

[0180] Examples of Pt-containing catalysts include platinum group compounds such as platinum micropowder, platinum black, silicon dioxide-supported platinum micropowder, activated carbon-supported platinum, chloroplatinic acid, alcoholic solutions of chloroplatinic acid, platinum olefin complexes, and platinum alkenyl silicate complexes. Examples of alkenyl silicates include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenyl silicates obtained by substituting a portion of the methyl group of these alkenyl silicates with ethyl, phenyl, or the like, and alkenyl silicates obtained by substituting the vinyl group of these alkenyl silicates with allyl, hexene, or the like.

[0181] Among these, preferred are dibutyltin dilaurate, n-propyl zirconate, n-butyl zirconate, tetraacetyl acetone zirconium, monoacetyl acetone zirconium, acetyl acetone titanium, tetraacetyl acetone titanium, acetyl acetate titanium, triacetyl acetone aluminum, diacetyl acetate monoacetyl acetone aluminum, triacetyl acetate aluminum, 1,3-divinyl-1,1,3,3-tetramethylsiloxane complex of platinum, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane complex of platinum, or alkenyl siloxanes obtained by substituting a portion of the methyl group of the alkenyl siloxanes with ethyl, phenyl, etc., or alkenyl siloxanes obtained by substituting the vinyl group of the alkenyl siloxanes with allyl, hexene, etc.

[0182] The catalyst (D) may be one type or two or more types.

[0183] The content of the catalyst (D) is preferably 0.00001 to 20 parts by weight, more preferably 0.00003 to 15 parts by weight, and particularly preferably 0.00005 to 10 parts by weight, relative to 100 parts by weight of the total weight of the silicon compound (A) and the crosslinking agent (C).

[0184] <Other Components> The curable resin composition of the present invention may also contain other components besides components (A) to (D) described above. Examples of other components include other organopolysiloxanes besides silicone compound (A) and crosslinking agent (C), curing delay agents, adhesion promoters, fillers, ion traps, surfactants, flame retardants, ultraviolet absorbers, light stabilizers, antioxidants, and solvents.

[0185] <Other organic polysiloxanes besides silicone compound (A) and crosslinking agent (C)> The curable resin composition of the present invention may also contain other organic polysiloxanes besides silicone compound (A) and crosslinking agent (C).

[0186] Other organopolysiloxanes are compounds having at least one structure of formula (E-1) to (E-4) below, and do not contain groups that crosslink with silicon compound (A). [Chemical 58]

[0187] In formulas (E-1) to (E-4), RE can independently include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, etc.; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; aralkyl groups such as benzyl, phenylethyl, phenylpropyl, etc.; or those obtained by substituting part or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, bromine, chlorine, cyano, etc., such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, etc.

[0188] The structures of other organic polysiloxanes can be linear, partially branched, cyclic, etc. Commercially available products include: KF-96L, KF-96A, KF-96, KF-96H, KF-50, KF-54, KF-965, KF-968, KF-410, and KF-412 (all trade names) manufactured by Shin-Etsu Chemical Industry Co., Ltd.; TSF451-0.65, TSF451-5A, TSF451-10, and TSF451-100 (all trade names) manufactured by Momentive Pharmaceuticals Co., Ltd.; and Wacker Asahikasei Silicone Co., Ltd.'s (registered trademark) Silicone Fluid AK0.65~10 and Silicone Fluid Fluid (registered trademark). FLUID AK20~5,000, WACKER (registered trademark) SILICONE FLUID AS100, WACKER (registered trademark) L053, WACKER (registered trademark) L060, WACKER (registered trademark) MQ803 (all are trade names), etc.

[0189] The content of other organopolysiloxanes is 0.1 to 30 parts by weight, more preferably 0.5 to 25 parts by weight, and even more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements selected from Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention.

[0190] <Curing Delay Agent> From the viewpoint of preservation stability, the curable resin composition of the present invention may also contain a curing delay agent.

[0191] As a curing delay agent, for example, known materials used in addition-curing compositions utilizing hydrosilicon catalysts can be used. Specifically, examples include: compounds containing two or more alkenyl groups, compounds containing aliphatic unsaturated bonds, organophosphorus compounds, tin-based compounds, and organic peroxides. These can be used alone or in combination of two or more.

[0192] Examples of compounds containing two or more alkenyl groups include: 1,3-divinyl-1,1,3,3-tetramethylsiloxane, 1,3-diallyl-1,1,3,3-tetramethylsiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenylsiloxane, 1,3-divinyl-1,1,3,3-tetraphenylsiloxane, and other disiloxanes, trisiloxanes, and cyclic siloxanes containing vinyl groups at both ends, such as 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane. Furthermore, the compounds containing two or more alkenyl groups may also function as crosslinking agents (C).

[0193] For example, compounds containing aliphatic unsaturated bonds include propargyl alcohols such as 3-methyl-1-dodecyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol, ene-yne ​​compounds, and maleic anhydride and dimethyl maleate, etc.

[0194] Examples of organophosphorus compounds include, for example, triorganophosphorus compounds, diorganophosphorus compounds, organophosphorus compounds, and triorganophosphites. Examples of tin group compounds include, for example, stannous halide dihydrate and stannous carboxylate. Additionally, examples of organic peroxides include, for example, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tributyl perbenzoate.

[0195] Among these, 1,3-divinyldisiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane or 1-ethynyl-1-cyclohexanol are preferred.

[0196] The content of the curing delay agent is 250 to 200,000 times the content (by weight) of the catalyst (D), preferably 500 to 100,000 times, and even more preferably 5,000 to 50,000 times.

[0197] <Adhesion Additive> From the viewpoint of adhesion, the curable resin composition of the present invention may also contain an adhesion additive.

[0198] As an adhesion promoter, an organosilicon compound having a hydroxyl group, a hydrogen atom bonded to Si, an alkoxy group bonded to Si, and an epoxy group is preferred; more preferably, it has at least one alkoxy group bonded to Si. Such a compound can undergo a crosslinking reaction with other components in the curable resin composition of the present invention, and can undergo a bonding reaction with components of a substrate or the like to which the curable resin composition of the present invention is laminated, thereby improving the adhesion of the obtained cured product. Furthermore, in terms of heat resistance, the adhesion promoter is more preferably one having a sesquioxane structure. As such a preferred adhesion promoter, compounds represented by formula (Z) can be listed. Moreover, the adhesion promoter having a hydroxyl group, a hydrogen atom bonded to Si, and an alkoxy group bonded to Si can also function as a crosslinking agent (C). [Chemical 59]

[0199] In formula (Z), RG1 is independently an alkyl, cyclopentyl, or cyclohexyl group having 1 to 4 carbon atoms. Z is independently a group represented by formula (Z1), formula (Z2), formula (Z31), formula (Z32), formula (Z33), or formula (Z41). When the average number of groups represented by formula (Z1) in each molecule of the compound represented by formula (Z) is set as z1, the average number of groups represented by formula (Z2) is set as z2, the average number of groups represented by formula (Z31), formula (Z32), or formula (Z33) is set as z3, and the average number of groups represented by formula (Z41) is set as z4, the following conditions are met: z1+2z2+z3+z4=4w, 0.5w≦z1≦3w, 0.25w≦z2≦w, 0.1w≦z3≦2w, and 0≦z4≦w. w is the average value that satisfies the range of 1 to 100.

[0200] As RG1, it is preferably alkyl, more preferably methyl. z1, z2, z3, and z4 are preferably w≦z1≦2w, 0.3w≦z2≦w, 0.3w≦z3≦w, and 0.3w≦z4≦w, respectively. The lower limit of w can be 3 or 5. Furthermore, the upper limit of w can be 30 or 15. [Chemical 60]

[0201] In Equations (Z1), (Z2), (Z31), (Z32), (Z33) and (Z41), * as described above indicates the bonding location.

[0202] In formula (Z2), RG2 is independently an alkyl, cyclopentyl, cyclohexyl, or phenyl group having 1 to 4 carbon atoms. g is an average value satisfying 1 to 20. As RG2, alkyl is preferred, and methyl is more preferred.

[0203] In formula (Z41), RG3 is independently methyl, ethyl, butyl or isopropyl. Methyl is preferred as RG3.

[0204] The amount of adhesive additive added is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 9 parts by weight, and even more preferably 0.5 to 8 parts by weight, relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements selected from Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention.

[0205] <Filler> From the viewpoints of heat resistance, optical properties, thixotropy, etc., the curable resin composition of the present invention may also contain a filler.

[0206] There are no particular limitations on the filler used; known materials can be used. Furthermore, the filler can be amorphous or crystalline. The combination of fillers is also not limited.

[0207] As a filler, various phosphors or metal oxides may be preferably used, for example.

[0208] As a phosphor, there are various phosphors, such as those emitting green light, blue light, yellow light, and red light. Specific phosphors used in the curable resin composition of the present invention include known phosphors such as organic phosphors, inorganic phosphors, fluorescent pigments, and fluorescent dyes. Examples of organic phosphors include allyl sulfonamide-melamine-formaldehyde co-condensation dyes or perylene-based phosphors; perylene-based phosphors are preferred for long-term use. Inorganic phosphors are particularly preferred for use in the present invention. The following describes inorganic phosphors used in the present invention.

[0209] Among phosphors that emit green light, there are [SrAl2O4:Eu], [Y2SiO5:Ce,Tb], [MgAl11O19:Ce,Tb], [Sr7Al12O25:Eu], [(at least one of Mg, Ca, Sr, Ba)Ga2S4:Eu].

[0210] For example, the phosphors that emit blue light include [Sr5(PO4)3Cl:Eu], [(SrCaBa)5(PO4)3Cl:Eu], [(BaCa)5(PO4)3Cl:Eu], [(at least one of Mg, Ca, Sr, Ba)2B5O9Cl:Eu, Mn], and [(at least one of Mg, Ca, Sr, Ba)(PO4)6Cl2:Eu, Mn].

[0211] As a phosphor emitting green to yellow light, there are yttrium-aluminum oxide phosphors activated with at least cerium, yttrium-thorium-aluminum oxide phosphors activated with at least cerium, yttrium-aluminum-garnet oxide phosphors activated with at least cerium, and yttrium-gallium-aluminum oxide phosphors activated with at least cerium (so-called yttrium aluminum garnet (YAG) series phosphors). Specifically, [Ln3M5O12:R (Ln is at least one selected from Y, Gd, and La, M includes at least one of Al and Ca, and R is a lanthanide.)] and [(Y1-xGax)3(Al1-yGay)5O12:R (R is at least one selected from Ce, Tb, Pr, Sm, Eu, Dy, and Ho, 0 < Rx < 0.5, 0 < y < 0.5.)] can be used.

[0212] For example, [Y2O2S:Eu], [La2O2S:Eu], [Y2O3:Eu], and [Gd2O2S:Eu] are phosphors that emit red light.

[0213] In addition, as phosphors that emit light corresponding to the currently mainstream blue LEDs, examples include YAG-based phosphors such as [Y3(Al,Ga)5O12:Ce, (Y,Gd)3Al5O12:Ce, Lu3Al5O12:Ce, Y3Al5O12:Ce], TAG-based phosphors such as [Tb3Al5O12:Ce], [(Ba,Sr)2SiO4:Eu]-based phosphors or [Ca3Sc2Si3O12:Ce]-based phosphors, and [(Sr,Ba,Mg)2SiO4:Eu]-based phosphors. Phosphors such as silicate-based phosphors, nitride-based phosphors such as [(Ca,Sr)2Si5N8:Eu], [(Ca,Sr)AlSiN3:Eu], and [CaSiAlN3:Eu], and oxide-based phosphors such as [Cax(Si,Al)12(O,N)16:Eu], can be further listed as phosphors such as [(Ba,Sr,Ca)Si2O2N2:Eu], [Ca8MgSi4O16Cl2:Eu], and [SrAl2O4:Eu, Sr4Al14O25:Eu].

[0214] Among these, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferred in terms of luminous efficiency or brightness. In addition, known phosphors may also be used depending on the application or the target emission color.

[0215] The amount of phosphor added is preferably 1 to 90 parts by weight, and more preferably 2 to 50 parts by weight, relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements of Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention.

[0216] Next, the case where the filler is a metal oxide will be explained. As a metal oxide, silicon dioxide, aluminum oxide, yttrium oxide, zinc oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, etc. are preferred.

[0217] Relative to 100 parts by weight of the total weight of silicon compound (A) + compound (B) having any one or more elements selected from Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention, the content of metal oxide in the curable resin composition of the present invention is preferably 1 part by weight to 70 parts by weight, more preferably 1 part by weight to 65 parts by weight, and even more preferably 1 part by weight to 60 parts by weight.

[0218] When titanium dioxide or aluminum oxide is used in the curable resin composition of the present invention, it can also be used as a reflector material, which is preferable. Polyphthalamide resin is widely used as a reflector material. However, it has been pointed out that polyphthalamide resin is prone to deterioration, particularly discoloration, due to prolonged use. The curable resin composition of the present invention solves this problem.

[0219] In the case of silica, silica obtained by finely granulating naturally occurring silica (natural silica) can be used, or industrially synthesized silica (synthetic silica) can be used. In the case of natural silica, since it is crystalline, it has a crystal axis. Therefore, although optical characteristics derived from crystallization can be expected, since its specific gravity is slightly higher than that of synthetic silica, it may affect the dispersion in curable resin compositions. In addition, when it is obtained by pulverizing natural materials, it may result in particles of amorphous shape or a material with a wide particle size distribution.

[0220] There are wet-synthetic silicon dioxide and dry-synthetic silicon dioxide, and there is no particular limitation on their use in this invention. However, in the synthesis of silicon dioxide, regardless of the method, there is always a possibility of water of crystallization. In cases where the water of crystallization may have some impact on the curable resin composition or cured product of this invention, or electronic components, it is preferable to also take into account the amount of water of crystallization when selecting the product.

[0221] Synthetic silica is not crystalline but amorphous, therefore lacking a crystal axis, and thus optical characteristics derived from crystals cannot be particularly expected. However, in addition to controlling particle distribution, features such as the ability to drastically reduce particle size can be effectively utilized. In particular, fumigated silica has nanoscale particle sizes and excellent thixotropic properties.

[0222] In addition, silicon dioxide is usually a material with a large surface area and is hydrophilic due to the effect of silanols present on the surface (hydrophilic silicon dioxide), and it can also be chemically modified to form hydrophobic silicon dioxide.

[0223] <Ion scavenger> From the viewpoint of insulation reliability, the curable resin composition of the present invention may also contain an ion scavenger.

[0224] There are no particular limitations on the ion trapping agent; examples include anion trapping agents, cation trapping agents, and dual-ion trapping agents. For example, examples include DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd., or the IXE300 series, IXEPLAS-A series, and IXEPLAS-B series manufactured by Toa Synthetic Co., Ltd. The average particle size of the ion trapping agent is preferably 0.1 μm to 3.0 μm, and the maximum particle size is preferably 10 μm or less.

[0225] The content of the ion scavenger is preferably 0.1 to 10 parts by weight, and more preferably 0.3 to 9 parts by weight, relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements of Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention.

[0226] <Surfactant> For the purpose of controlling the coatability to the substrate, the curable resin composition of the present invention may also contain a surfactant.

[0227] Specific examples of surfactants include: Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (these are trade names, manufactured by Kyoei Chemical Industry Co., Ltd.); Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164 Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-344, BYK-346 (These are trade names, BYK-Chemie Japan) (Japan) (manufactured); KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (the above are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.); Surflon SC-101, Surflon KH-40 (the above are trade names, manufactured by SEIMI Chemical Co., Ltd.); Ftergent 222F, Ftergent 251, FTX-218 (the above are trade names, manufactured by NEOS Co., Ltd.); TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2500, TEGO Rad 2600, TEGO Rad... Rad) 2700 (the above are product names, manufactured by Evonik Industries, Inc., Japan); EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (the above are product names, manufactured by Mitsubishi Materials, Inc.);Megafac F-171, Megafac F-177, Megafac F-475, Megafac F-477, Megafac F-556, Megafac R-08, Megafac R-30 (these are trade names, manufactured by DIC (stock)); fluoroalkylbenzene sulfonates, fluoroalkyl carboxylates, fluoroalkyl polyoxyethylene ethers, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonates, diglycerol tetra(fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl amino sulfonates, polyoxyethylene nonylphenyl ether, polyoxyethylene Allyl octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, dehydrated sorbitol laurate, dehydrated sorbitol palmitate, dehydrated sorbitol stearate, dehydrated sorbitol oleate, dehydrated sorbitol fatty acid ester, polyoxyethylene dehydrated sorbitol laurate, polyoxyethylene dehydrated sorbitol palmitate, polyoxyethylene dehydrated sorbitol stearate, polyoxyethylene dehydrated sorbitol oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, polyether-modified polydimethylsiloxane.

[0228] One or more surfactants may be used.

[0229] If the content of the surfactant is 0 to 3 parts by weight relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements of Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention, it tends to have excellent coating properties on the substrate.

[0230] <Flame Retardant> From the viewpoint of flame retardancy, the resin composition of the present invention may also contain a flame retardant. Since the curable resin composition of the present invention contains a flame retardant, the obtained cured film exhibits higher flame retardancy, which is therefore preferable. As a flame retardant, there are no particular limitations as long as it is a compound capable of imparting flame retardancy; however, from the viewpoint of low toxicity, low pollution, and safety, organophosphorus flame retardants are preferred.

[0231] As organophosphorus flame retardants, examples include: triphenyl phosphate, tricresyl phosphate, tri-dimethyl phosphate, toluene phosphate, 2-ethylhexyl diphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0232] One or more flame retardants may be used.

[0233] The content of the flame retardant is preferably 0 to 50 parts by weight relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements of Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention.

[0234] <Ultraviolet absorber and light stabilizer> In order to prevent the obtained hardened film from deteriorating due to backlight or other light, the curable resin composition of the present invention may also contain ultraviolet absorber and light stabilizer (hindered amine light stabilizer (HALS)).

[0235] Examples of ultraviolet absorbers include: benzotriazole compounds such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole; triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol; benzophenone compounds such as 2-hydroxy-4-n-octyloxybenzophenone; and oxaliplatin compounds such as 2-ethoxy-2'-ethyloxoacetic acid bisphenylamine.

[0236] As light stabilizers (HALS), examples include: TINUVIN (registered trademark) 5100, TINUVIN 292 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN 152 (compound name: 2,4-bis[N-butyl-N-(1- Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine), TINUVIN 144 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate), TINUVIN 123 (compound name: sebacic acid, bis(2,2,6,6) The reaction product of tetramethyl-1-(octyloxy)-4-piperidinyl) ester (in the presence of 1,1-dimethylethyl hydroperoxide and octane)), TINUVIN 111FDL (approximately 50%, TINUVIN 622, compound name: (in the presence of succinic acid polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl)ethanol); approximately 50%, CHIMASSORB 119, compound name: N -N'-N''-N'''-Tetra(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine) (all manufactured by BASF), Adekastab LA series (manufactured by Adeka), specifically LA-52, LA-57, LA-62, and LA-67.

[0237] One or more ultraviolet absorbers and light stabilizers may be used.

[0238] Relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements of Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention, the content of each of the ultraviolet absorber and light stabilizer is preferably 0 parts by weight to 20 parts by weight.

[0239] <Antioxidant> In order to prevent oxidation of the obtained hardened film, etc., the curable resin composition of the present invention may also contain an antioxidant.

[0240] As antioxidants, examples include: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis-[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Hindered phenolic compounds such as phenyl propionate and diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; amine compounds such as n-butylamine, triethylamine, and diethylaminomethyl methacrylate; sulfur compounds such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearate-3,3'-thiodipropionate; and triphenyl phosphite, diphenylisodecyl phosphite, and phenyl diisodecyl phosphite. Tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclonepentetretetrayl bis(octadecyl) phosphite, cyclonepentetretetrayl bi(2,4-di-tert-butylphenyl) phosphite, cyclonepentetretetrayl bi(2,4-di-tert-butyl-4-methylphenyl) phosphite, bis[2-tert-butyl-6-methyl-4-{2-(octadecyl)- Phosphorus compounds, including alkoxycarbonyl)ethyl}phenyl]hydrophosphite, oxaphosphaphenanthrene oxides (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decoxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.).

[0241] One or more antioxidants may be used.

[0242] The content of antioxidant is preferably 0 to 10 parts by weight relative to 100 parts by weight of the total weight of silicon compound (A) + compound (B) having any one or more elements of Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention.

[0243] <Solvent> The curable resin composition of the present invention may also contain a solvent.

[0244] Examples of solvents that can be used in this invention include: methanol, ethanol, propanol, isopropanol, butanol, tributyl alcohol, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, benzonitrile, ethyl acetate, isobutyl acetate, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 2-hydroxyisobutyrate, 2 2-Oxypropionic acid methyl ester, 2-Oxypropionic acid ethyl ester, 2-Oxypropionic acid propyl ester, 2-Methoxypropionic acid methyl ester, 2-Methoxypropionic acid ethyl ester, 2-Methoxypropionic acid propyl ester, 2-Ethoxypropionic acid methyl ester, 2-Ethoxypropionic acid ethyl ester, 2-Oxy-2-methylpropionic acid ethyl ester, 2-Methoxy-2-methylpropionic acid methyl ester, 2-Ethoxy-2-methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetone, ethyl acetone, diethyl ether, diethylene glycol, propylene glycol, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene ... Fiber ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, cyclohexanol, 1,4-butanediol, triethylene glycol, tripropylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate Ester, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, hexane, heptane, cyclohexane, toluene, xylene, anisole, benzaldehyde, 1,3-dimethoxybenzene, acetophenone, 4'-methoxyacetophenone, 4'-ethoxyacetophenone, phenyl acetate, 3-methoxyphenol, 1,2-methylenedioxybenzene, 2-phenoxyethanol, diethylene glycol monophenyl ether, 1,2,4-trimethoxybenzene, 2'-hydroxyacetophenone, 1,4-diethoxybenzene, 1,3,5-Trimethoxybenzene, tert-butyl benzoate, benzyl alcohol, 1,4-dimethoxybenzene, 1,2,3-trimethoxybenzene, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,5-dimethyl anisole, phenyl methyl sulfide (thioanisole), 4-ethyl anisole, tert-butylbenzene, 4-tert-butyltoluene, 2-phenyl anisole, tert-anisole, 3,4-dimethoxytoluene, γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolinone, dimethyl sulfoxide, etc.

[0245] Among these, from the viewpoint of solubility in curable resin components, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, butyl acetate, methyl 3-methoxypropionate, acetone, propylene glycol monomethyl ether acetate, toluene, anisole, benzaldehyde, benzonitrile, tetrahydrofuran, diethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, 1,3-dimethoxybenzene, acetophenone, 4'-methoxyacetophenone, 4'-ethoxyacetophenone, phenyl acetate, 3-methoxyphenol, 1,2-methylenedioxy... Benzene, 2-phenoxyethanol, 1,2,4-trimethoxybenzene, 2'-hydroxyacetophenone, 1,4-diethoxybenzene, 1,3,5-trimethoxybenzene, benzyl alcohol, 1,4-dimethoxybenzene, 1,2,3-trimethoxybenzene, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,5-dimethylanisole, phenyl methyl sulfide (thioanisole), 4-ethylanisole, tributylbenzene, 4-tributyltoluene, 2-phenylanisole, 3,4-dimethoxytoluene, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, and dimethyl sulfide.

[0246] One or more solvents may be used.

[0247] The solvent content is preferably 0 to 900 parts by weight relative to 100 parts by weight of the total weight of the silicone compound (A) + compound (B) having any one or more elements selected from Ce, La, Pr, Nd, Y and Fe + crosslinking agent (C) + catalyst (D) in the curable resin composition of the present invention. It is even more preferably 0 to 400 parts by weight.

[0248] <Preparation Method> The preparation method of the curable resin composition of the present invention is not particularly limited, and it can be prepared by means of methods such as mixing the components using a known mixer.

[0249] For example, the following methods can be used: using a stirrer, homogenizer, homomixer, universal mixer, planetary mixer, kneader, three-roll mill or bead mill, at room temperature or with heating, the silicon compound (A), the compound (B) having any one or more elements of Ce, La, Pr, Nd, Y and Fe, and crosslinking agent (C), catalyst (D), other organopolysiloxanes, curing delay agents, adhesion promoters, fillers, ion traps, surfactants, flame retardants, ultraviolet absorbers and light stabilizers, antioxidants and solvents, etc., in specified amounts.

[0250] In addition, the curable resin composition of the present invention can also be prepared by mixing the components in a two-component or three-component form. Each of the components (A) to (D) and other components can be used alone or in combination of two or more.

[0251] <Applications> The curable resin composition of the present invention is suitable for use as printed wiring boards, semiconductor elements, light-emitting diodes (LEDs), or electronic components for automotive applications, etc. Specifically, examples include: buffer coatings, reinforcing films, interlayer insulating films, planarization films, insulating films, protective films, sealants, underfill materials, grain bonding materials, sealing materials, optical lenses, adhesives, etc., contained in electronic components. Furthermore, when the curable resin composition of the present invention contains a phosphor as a filler, it can be used as a material for forming wavelength conversion layers in light-emitting devices such as optical semiconductor devices; and when it contains a white pigment as a filler, it can preferably be used as a material for forming light reflectors in light-emitting devices such as optical semiconductor devices.

[0252] <Curved Material> The cured material of the present invention is obtained by curing the curable resin composition of the present invention, specifically by heating the curable resin composition, for example, by forming it on the surface of a substrate.

[0253] The hardened material of the present invention can suppress the decomposition, discoloration, cracking and other phenomena caused by heating, and has excellent heat resistance.

[0254] Therefore, the hardened material of the present invention is applicable to buffer coatings, reinforcing films, interlayer insulating films, planarization films, insulating films, protective films, sealants, underfill materials, grain fixation materials, sealing materials, optical lenses, adhesives, wavelength conversion agents, light reflectors, etc. contained in electronic components. Examples of electronic components include printed circuit boards, semiconductor elements, light-emitting diodes (LEDs), etc.

[0255] <Curing Method> The cured product of the present invention can be obtained, for example, by applying the curable resin composition of the present invention to the surface of a substrate by means of a desired printing method, dispenser, spin coating, etc., drying as needed to form a coating film (coating film forming process); and subjecting the obtained coating film to a heating process to thereby harden the coating film.

[0256] <Coating Formation Process> In the coating formation process, the curable resin composition of the present invention is coated onto the surface of a substrate to form a coating film. Examples of substrates include: semiconductor substrates such as aluminum substrates, glass substrates, and Si substrates (silicon wafers), copper substrates, copper alloy substrates, polyimide substrates, ceramic substrates, printed circuit boards, stainless steel substrates, and fiber-reinforced substrates such as carbon fiber reinforced plastic (CFRP) or glass fiber reinforced plastic (GFRP).

[0257] In the case of a curable resin composition containing a solvent, a drying process can be performed for the purpose of removing the solvent before curing. Depending on the composition of the curable resin composition, the drying temperature is typically 50°C to 250°C; the drying time is 5 minutes to 120 minutes. By this drying process, a coating film that can maintain its shape can be formed on the substrate.

[0258] <Heating Process> After the coating is formed, it is usually heated at 70°C to 350°C. The heating process usually lasts for 10 minutes to 200 minutes.

[0259] Furthermore, the term "cured material" is not limited to any material that has undergone a cross-linking reaction in at least a portion of the components in the curable resin composition of the present invention, resulting in reduced fluidity. That is, the cured material may also include cured materials that are elastic or viscous, or cured materials that soften or melt upon heating.

[0260] The cured material may be a B-stage cured material. A B-stage cured material refers to a cured material in a semi-cured state. Specifically, a B-stage cured material is preferably a cured material that is solid at 25°C and has a softening point in the range of 50°C to 200°C. A B-stage cured material can be obtained by heating the curing resin composition at a temperature range of, for example, 100°C to 350°C for 1 hour to 5 hours.

[0261] The shape of the hardened material is not particularly limited; for example, it can be in the form of powder, granules, plates, or flakes. Alternatively, it can be molded into a specified shape.

[0262] <Molded Body> One embodiment of the molded body of the present invention is a molded body obtained from the curable resin composition or cured product of the present invention. Examples of such molded bodies include: buffer coatings, reinsertion insulating films, interlayer insulating films, planarization films, insulating films, protective films, sealants, underfill materials, grain fixing materials, sealing materials, optical lenses, adhesives, wavelength conversion agents, light reflectors, etc.

[0263] The molded body may be a molded body formed by using a mold or the like to harden the curable resin composition of the present invention into a predetermined shape, or a molded body formed by processing the hardened material into a predetermined shape. In addition, it also includes molded bodies formed by further heating and hardening the hardened material in a semi-hardened state, etc.

[0264] <Electronic Components> An electronic component according to one embodiment of the present invention is an electronic component comprising a cured material of the present invention. The cured material is preferably manufactured based on the curing method of a curable resin composition according to the present invention. Examples of such electronic components include printed circuit boards, semiconductor elements, and light-emitting diodes (LEDs).

[0265] The electronic component of the present invention contains the hardened material of the present invention, which has excellent heat resistance, and thus becomes an electronic component with excellent reliability.

[0266] Hereinafter, the uses of the cured product of the present invention will be described again. The cured product of the present invention has excellent heat resistance, excellent insulation, excellent adhesion, excellent transparency, and is also flexible. Therefore, it can be used for a variety of applications.

[0267] The hardened material of the present invention is suitable as a material constituting all or part of an optical component due to its excellent transparency. In this specification, "optical component" is used as a general term for components having optical functions. Optical components are broadly classified into individual optical elements that have the function of individually changing the properties of light, and electro-optical elements that participate in the interaction with electrons to achieve a specified function.

[0268] Individual optical elements have the function of changing the transmission or reflection characteristics of incident light. Specific examples of this function include polarization adjustment, light intensity adjustment, hue adjustment, and optical path adjustment. Specific examples of individual optical elements include polarizing components, coloring components, dimming components, wavelength conversion components, light-blocking components, light-reducing components, reflecting components, lenses, and mirrors. Electro-optical elements have the function of changing the characteristics of incident light based on electrical signals, or of converting optical signals into electrical signals based on photoelectric conversion, or of emitting light based on electrical signals. Specific examples of elements with the former function include electrochromic elements or liquid crystal elements. Specific examples of elements with the latter function include image sensors, LEDs, or organic light-emitting diodes (OLEDs).

[0269] The cured material of the present invention is transparent and has adhesive properties, and therefore, like previous optically clear adhesives, it can be preferably used as a protective member or bonding member disposed in or near an optical path. Previous optically clear adhesive films (optical clear adhesives (OCA)) essentially contain adhesive materials and therefore do not easily possess high heat resistance. However, the cured material of the present invention also has excellent heat resistance, and therefore can be preferably used for applications with high light transmittance, such as large projectors for projection mapping. In the case where the cured material of the present invention is a B-Stage cured material, it is possible to use the cured material of the present invention or a resin-containing component containing the cured material of the present invention as a substitute for previous OCA materials.

[0270] As another example of the use of the cured material of the present invention, a composite component comprising a resin-containing component containing the cured material and another component (a first component) disposed in contact with the resin-containing component can be cited as part of an electrical component. As described above, the cured material of the present invention has excellent various properties, therefore the resin-containing component may be composed solely of the cured material of the present invention, but other materials may also be included to obtain the desired properties. Examples of such materials include hard or soft resin materials, inorganic fillers, and other non-resin materials.

[0271] Specific examples of electrical components include integrated circuit devices, power components, switching components, sensor components, actuator components such as microelectromechanical systems (MEMS), the aforementioned electro-optical components, energy storage components such as capacitors, inductors such as chokes or transformers, resistors, etc. Examples of uses for such electrical components include devices for movement in at least one area selected from the group consisting of above ground, underground, air, space, sea, and ocean. Specific examples of such devices include vehicles, ships, aircraft, etc., which may be manned or unmanned (drone) devices. Other examples of uses for electrical components include electrical devices selected from the group consisting of household appliances, information devices, imaging and audio devices, gaming devices, and hybrid devices of these.

[0272] One example of the use of the resin-containing component in the composite component is a protective film covering at least a portion of the first component. Specific examples of the first component include: semiconductor substrates such as Si, GaN, and SiC; metallic substrates such as copper-based materials, aluminum-based materials, and steel such as stainless steel; ceramic substrates such as alumina; glass substrates; and resin-based substrates. The resin-containing component containing the cured material of the present invention exhibits excellent adhesion to such substrates and is therefore preferably used as a protective film.

[0273] In particular, the cured material of the present invention, because it contains siloxyalkyl or siloxane bonds (Si-O-Si), exhibits superior heat resistance compared to resin-based materials that do not possess such bonds, and therefore has particularly excellent adhesion to glass substrates, semiconductor substrates, and metal substrates. Furthermore, because the cured material of the present invention contains a specified proportion of siloxane bonds (Si-O-Si), it generates less global warming gas per unit weight compared to resin-based cured materials that do not contain such bonds (epoxy resins are a specific example).

[0274] The first component may also be a wiring substrate on which wiring is provided. In this case, the protective film containing the resin-containing material containing the cured material of the present invention preferably has insulating properties, and thus becomes an insulating film covering the wiring. The cured material of the present invention also has excellent insulating properties, so even when the resin-containing material contains the cured material of the present invention, it can function appropriately as a protective film.

[0275] In this case, wiring can also be further provided on the protective film to form a multilayer wiring structure. At this time, the resin-containing material containing the hardened material of the present invention is positioned in the component having a multilayer wiring structure as a planarization film, a rewiring insulation film, or an interlayer insulation film.

[0276] The first component may also be formed by forming an integrated circuit on the base material. In this case, the protective film containing the resin-containing material is preferably insulating, and the protective film is positioned as a buffer coating covering the integrated circuit.

[0277] Other specific examples of the use of the resin-containing component in the composite component include sealing materials that effectively utilize their sealing properties. In this case, specific examples of the first component are integrated circuit devices, power components, switching components, and sensing components. Since the resin-containing component has excellent heat resistance, it is particularly suitable for high-temperature environment applications as a replacement material for sealing materials that previously included epoxy resin, etc.

[0278] The composite component may also include a second component that is different from the first component and is in contact with the resin-containing component. In this case, the resin-containing component has a joining function that allows the first component and the second component to be joined. Specific examples of the first component are also equivalent to specific examples of the second component.

[0279] As a specific example of the application of a resin-containing component with regard to the bonding function, a filling member disposed in the gap between the first component and the second component can be cited. The cured material of the present invention has high adhesion to the first and second components, so the resin-containing component containing the cured material of the present invention can adequately ensure the gap between the first and second components even when subjected to external force. As a specific example of the filling member, a bottom filler can be cited. Sometimes silicon dioxide particles are contained in the bottom filler as a filler, but the cured material of the present invention has excellent adhesion to silicon dioxide particles because it has siloxane bonds (Si-O-Si). Therefore, a bottom filler containing silicon dioxide particles is a particularly suitable example for use as a resin-containing component.

[0280] As another specific example of a resin-containing component with regard to the bonding function, a sealing material provided in a manner that covers the gap between the first component and the second component can be cited. The hardened material of the present invention not only has high adhesion to the first component and the second component, but also has flexibility, so that the resin-containing component containing the hardened material of the present invention can maintain a state of contact with the first component and a state of contact with the second component even when subjected to external force.

[0281] In applications where resin-containing components function as bonding agents, the first component may be a mounting substrate, and the second component may be an electrical component including electrodes. Electrical components sometimes generate heat or vibrate due to energization, but the hardened material of the present invention exhibits excellent heat resistance, excellent adhesion, and high flexibility, thus enabling it to appropriately maintain the electrical component on the mounting substrate. One example of such an application is a grain-attach material.

[0282] Furthermore, in recent years, there has been an increasing demand for high-output or high-density installation of electrical components, leading to a pursuit of high heat resistance in installation technologies. Resin-containing components containing the hardened material of the present invention can meet these requirements. As one such installation technology for meeting high heat resistance, power overlay (POL) technology can be cited as an example. As a joining component for the aforementioned applications, resin-containing components containing the hardened material of the present invention can preferably be used.

[0283] In one example of POL technology, an adhesive layer is formed on a substrate containing a heat-resistant resin such as polyimide, and the electrode side of the electrical component is brought into contact with the adhesive layer to fix the electrical component to the substrate. Then, a through-hole is formed on the substrate from the side opposite to the side where the electrical component is mounted (the back side) (by a removal process), exposing the electrode side. The through-hole is then filled with a conductive material such as copper, and a wiring pattern is formed on the back side using a plating technique. After covering the back side with the wiring pattern with an insulating film, a portion of the insulating film is removed to form an external electrode connected to the wiring pattern. Furthermore, the surface of the electrical component is sealed with a resin-based material, and a heat dissipation component is provided as needed.

[0284] Resin-containing components containing the cured product of the present invention exhibit excellent adhesion and high heat resistance, and are therefore preferably used as adhesive layers formed on the surface of a substrate. Additionally, they can also be used as resin-based materials covering electrical components that generate heat when energized. In this case, it may be preferable to use resin-containing components in which a material with high thermal conductivity, such as alumina, is dispersed, effectively utilizing the excellent heat resistance and excellent adhesion of the cured product of the present invention. [Example]

[0285] The present invention will be described in more detail based on the embodiments. Furthermore, the present invention is not limited to the following embodiments. Hereinafter, an analytical method for the synthesized organosilicon compounds is shown.

[0286] <Number Average Molecular Weight and Weight Average Molecular Weight> High-performance liquid chromatography (HPLC) systems (AS-4050, PU-4180, CO-4060, RI-4030) manufactured by Nippon Spectrophotometry Co., Ltd. were used for the determination. The sample was dissolved in tetrahydrofuran to prepare a 0.5% by weight solution, and 100 μL of this solution was introduced into the sample chamber. The determination was performed under the following conditions, and polystyrene conversion was performed to determine the number average molecular weight and weight average molecular weight. Column: Shodex KF805L [Manufactured by Showa Denko Co., Ltd.] Column: Shodex KF804L [Manufactured by Showa Denko Co., Ltd.] (Two columns connected in series) Column temperature: 40°C Detector: RI Dissolution solution: Tetrahydrofuran dissolution solution Flow rate: 1.0 mL per minute

[0287] <Nuclear Magnetic Resonance (NMR) > Measurements were performed using a JNM-ECZ500R manufactured by Nippon Electron Ltd. For 1H-NMR measurements, the sample was dissolved in a deuterated solvent such as heavy acetone (manufactured by Wako Pure Chemical Industries, Ltd.), and the measurement was performed at room temperature, 500 MHz, and a cumulative count of 16. The ratio (α) or (β) of the siloxane to sesquioxane introduced into the synthesized silicon compound was determined based on the 1H-NMR integral ratio. For Si-NMR measurements, the sample was dissolved in tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and tetramethylsilane (99.9+%, NMR grade) (manufactured by Fisher Scientific) was added, and the measurement was performed at room temperature, 500 MHz, and a cumulative count of 800. The ratio (β) of siloxane to sesquioxane introduced into the synthesized silicon compound was determined based on the Si-NMR integral ratio.

[0288] [Synthesis Example 1] <Synthesis of a sesquioxane derivative (DD-4OH)> The sesquioxane derivative (DD-4OH) represented by the following formula was synthesized using the method disclosed in Japanese Patent No. 5704168. [Chemical 61]

[0289] [Synthesis Example 2] <Synthesis of a sesquioxane derivative (DD(Me)-OH)> A sesquioxane derivative (DD(Me)-OH) represented by the following formula was synthesized using the method disclosed in Japanese Patent No. 4379120. Furthermore, the sesquioxane derivative (DD-4OH) synthesized in Synthesis Example 1 was used as a starting material. [Chemical 62]

[0290] [Synthesis Example 3] <Synthesis of Silicon Compound (AI)> Under nitrogen atmosphere, 150 g of sesquioxane derivative (DD(Me)-OH), 33.8 g of octamethylcyclotetrasiloxane (D4), 11.8 g of sulfuric acid, 156 g of toluene, and 39.1 g of 4-methyltetrahydropyran were placed in a reactor, heated to 100°C, and stirred for 5 hours. Water was added to the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, an aqueous sodium bicarbonate solution, and saturated brine, and then dried with anhydrous sodium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by reprecipitation (2-propanol:ethyl acetate = 50:7, weight ratio) to obtain compound (AI) (161 g). Analysis by 1H-NMR and gel permeation chromatography (GPC) confirmed that the obtained white solid was an organosilicone compound represented by formula (8) described in [Means for Solving the Problem], and was a silicon compound (AI) in which R1 is phenyl, R8 is methyl and R10 is hydrogen, the ratio (α) of siloxane to sesquisiloxane is 3.0, the number average molecular weight is 23,000 and the weight average molecular weight is 46,000.

[0291] [Synthesis Example 4] <Synthesis of Silicon Compound (A-II)> Under nitrogen atmosphere, 150 g of sesquioxane derivative (DD(Me)-OH), 54.4 g of octamethylcyclotetrasiloxane (D4), 15.2 g of sulfuric acid, 176 g of toluene, and 43.9 g of 4-methyltetrahydropyran were placed in a reactor, heated to 100°C, and stirred for 5 hours. Water was added to the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, an aqueous sodium bicarbonate solution, and saturated brine, and then dried with anhydrous sodium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by reprecipitation (2-propanol:ethyl acetate = 50:7, weight ratio) to obtain compound (A-II) (152 g). By 1H-NMR and GPC analysis, the obtained white solid was confirmed to be an organosilicone compound represented by formula (8) described in [Means for Solving the Problem], and it is a silicon compound (A-II) as follows: R1 is phenyl, R8 is methyl and R10 is hydrogen in formula (8), the ratio (α) of siloxane to sesquisiloxane is 4.1, the number average molecular weight is 21,000 and the weight average molecular weight is 36,000.

[0292] [Synthesis Example 5] <Synthesis of Silicon Compound (A-III)> Under nitrogen atmosphere, 150 g of sesquioxane derivative (DD(Me)-OH), 56.3 g of octamethylcyclotetrasiloxane (D4), 6.20 g of sulfuric acid, 170 g of toluene, and 42.5 g of 4-methyltetrahydropyran were placed in a reactor, heated to 100°C, and stirred for 5 hours. Water was added to the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, an aqueous sodium bicarbonate solution, and saturated brine, and then dried with anhydrous sodium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by reprecipitation (2-propanol:ethyl acetate = 50:7, weight ratio) to obtain compound (A-III) (157 g). By 1H-NMR and GPC analysis, it was confirmed that the obtained white solid was a silicon compound represented by formula (8) described in [Means for Solving the Problem], and was a silicon compound (A-III) as follows: R1 is phenyl, R8 is methyl and R10 is hydrogen in formula (8), the ratio (α) of siloxyalkyl to sesquisiloxyalkyl is 4.2, the number average molecular weight is 29,000 and the weight average molecular weight is 55,000.

[0293] [Synthesis Example 6] <Synthesis of Silicon Compound (A-IV)> Under nitrogen atmosphere, 150 g of sesquioxane derivative (DD(Me)-OH), 68.7 g of octamethylcyclotetrasiloxane (D4), 7.02 g of sulfuric acid, 181 g of toluene, and 45.1 g of 4-methyltetrahydropyran were added to a reactor, heated to 100°C, and stirred for 6 hours. Water was added to the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, an aqueous sodium bicarbonate solution, and saturated brine, and then dried with anhydrous sodium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by reprecipitation (2-propanol:ethyl acetate = 29:2, by weight) to obtain compound (A-IV) (156 g). By 1H-NMR and GPC analysis, it was confirmed that the obtained white solid was a silicon compound represented by formula (8) described in [Means for Solving the Problem], and was a silicon compound (A-IV) as follows: R1 is phenyl, R8 is methyl and R10 is hydrogen in formula (8), the ratio (α) of siloxyalkyl to sesquisiloxyalkyl is 4.9, the number average molecular weight is 29,000 and the weight average molecular weight is 52,000.

[0294] [Synthesis Example 7] <Synthesis of Silicon Compound (AV)> Silicon compound (AV) was obtained using the method described in International Publication No. 2022 / 030353. By 1H-NMR, 29Si-NMR and GPC analysis, it was confirmed that the obtained white solid was the silicon compound represented by formula (21) described in [Means for Solving the Problem], and was the following silicon compound (AV), namely, R1 in formula (21) is phenyl, R2 is methyl and R15 is represented by formula (24), in formula (24) R14 is methyl, the ratio (β) of siloxyalkyl to sesquioxyalkyl is 4.4, the number average molecular weight is 33,000 and the weight average molecular weight is 68,000. Furthermore, the average values ​​of x and y in X1 and X2 in formula (21) are 2.8 and 1.6 respectively and z is 0.

[0295] [Synthetic Example 8] <Synthesis of a sesquioxane derivative (POSS-2)> The sesquioxane derivative (POSS-2) represented by the following formula was synthesized using the method described in International Publication No. 2022 / 030353. [Chemical 63]

[0296] [Synthesis Example 9] <Synthesis of Silicon Compound (A-VI)> Silicon compound (A-VI) was obtained using the method described in International Publication No. 2022 / 030353. By 1H-NMR and GPC analysis, it was confirmed that the obtained white solid was the silicon compound represented by formula (21) described in [Means for Solving the Problem], and was the following silicon compound (A-VI), namely, R1 in formula (21) is phenyl, R2 is methyl and R15 is represented by formula (24), in formula (24) R14 is methyl, the ratio (β) of siloxyalkyl to sesquisiloxyalkyl is 4.4, the number average molecular weight is 35,000 and the weight average molecular weight is 100,000. And the average values ​​of x, y and z in X1 and X2 in formula (21) are 2.8, 1.12 and 0.48, respectively.

[0297] The following shows the components used in the preparation of the curable resin composition. <Silicone Compound (A)> Silicon Compounds (AI) to (A-IV): Silicon Compounds (AI) to (A-IV) synthesized in Synthetic Examples 3 to 6 <Compounds (B) containing any one or more of Ce, La, Pr, Nd, Y, and Fe> Ce(acac)3·nH2O: Cerium acetone(III)·n-hydrate (manufactured by Sigma-Aldich) Ce(acac)3: Cerium acetone(III) (manufactured by Strem Chemicals) Ce(NO3)3·6H2O: Cerium nitrate(III) hexahydrate (manufactured by Fujifilm and Hikari Pure Chemicals) Fe(acac)3: Iron acetone(III) (manufactured by Strem Chemicals) <Crosslinking Agent (C)> MS51: Partial condensate of tetramethoxysilane (MKC silicate MS51 manufactured by Mitsubishi Chemical Co., Ltd.) ES40: Partial condensate of tetraethoxysilane (Ethyl silicate 40 manufactured by Colcoat Co., Ltd.) TMPS: Trimethoxyphenylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) DVTS: 1,5-Divinylhexamethyltrisiloxane (manufactured by Fujifilm and Hikari Pure Chemical Co., Ltd.) <Catalyst (D)> ZC150: Zirconium tetraacetone (manufactured by Matsumoto Fine Chemical Co., Ltd.) Pt-VTSC-3.0X: Platinum 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane complex (manufactured by Umicore Japna Co., Ltd.) <Soluble Medium> Anisole (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.)

[0298] [Examples 1 to 10 and Comparative Examples 1 to 5] <Preparation of curable resin composition 1 to curable resin composition 9, curable resin composition R1 to curable resin composition R4> Each component was uniformly mixed and dissolved in the weights shown in Tables 1 to 4 to prepare curable resin composition 1 to curable resin composition 9 and curable resin composition R1 to curable resin composition R4.

[0299] <Preparation of Cured Material> The obtained curable resin components were coated onto a 10 cm glass substrate using a coating applicator. The substrate was then placed in an oven and heated at 200°C for 1 hour, followed by heating at 300°C for 2 hours to obtain a cured material with a thickness of 100 μm. The thickness of the cured material was measured using a digital indicator (Mitutoyo ID-H0530).

[0300] <Evaluation of Heat Resistance (TG-DTA)> The hardened material obtained by cutting was used to evaluate the heat resistance using a thermogravimetric-differential thermal analyzer (TG-DTA) (Rigaku Thermo plus EVOII TG8120) under nitrogen atmosphere and a heating rate of 10°C / min. The temperatures at which the weight decreased by 1% (Td1) and 3% (Td3) were used as indicators of heat resistance, with the initial weight set at 100%.

[0301] <Evaluation of Heat Resistance (Solid-State NMR)> The hardened films obtained in Example 2 and Comparative Example 2 were cut using a cutting machine and heated under nitrogen atmosphere at 400°C for 3 hours (heating rate of 20°C / min) using the TG-DTA described above. The structural changes caused by heating were evaluated using solid-state NMR (VARIAN NMR SYSTEM manufactured by Varian) for samples before and after heating. As an evaluation index, the integral value of the absorption (-80 ppm) from (C6H5)SiO3 was unified among the samples, and the reduction rate of the D-body was estimated using the integral value of the absorption (-23 ppm) from Me2SiO2 (D-body) using the following formula. The measurement was conducted under the following conditions: cumulative number of scans: 6,000, recycle time: 10 seconds. The evaluation results are recorded in Table 4 for Example 10 and Comparative Example 5. D-body reduction rate = (Integral value of D-body absorption after heating - Integral value of D-body absorption before heating) / (Integral value of D-body absorption before heating)

[0302] The results are shown in Tables 1 to 4. Furthermore, the quantities of each component in Tables 1 to 4 are in g units.

[0303] [Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Curable resin composition 1 2 3 4 5 Silicon compound (A) artificial intelligence 10 A-II 10 10 A-III 10 A-IV 10 Compound (B) Ce(acac)3·nH2O 0.001 0.001 0.002 0.001 0.001 Ce(acac)3 Ce(NO3)3·6H2O Crosslinking agent (C) MS51 0.63 0.69 0.69 0.5 0.5 ES40 TMPS Catalyst (D) ZC150 0.01 0.01 0.01 0.01 0.01 solvent aniline 6.8 8.26 8.26 8.1 8.3 Heat resistance TG-DTA (Nitrogen environment) Td1[℃] 461 468 473 479 472 Td3[℃] 491 495 498 496 490

[0304] [Table 2] Table 2 Example 6 Example 7 Example 8 Example 9 Curable resin composition 6 7 8 9 Silicon compound (A) artificial intelligence A-II 10 10 10 10 A-III A-IV Compound (B) Ce(acac)3·nH2O 0.001 0.001 Ce(acac)3 0.001 Ce(NO3)3·6H2O 0.001 Crosslinking agent (C) MS51 0.69 0.69 ES40 0.89 TMPS 0.24 Catalyst (D) ZC150 0.01 0.01 0.01 0.01 solvent aniline 8.26 8.26 8.26 8.26 Heat resistance TG-DTA (Nitrogen environment) Td1[℃] 473 464 468 457 Td3[℃] 495 493 496 487

[0305] [Table 3] Table 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Curable resin composition R1 R2 R3 R4 Silicon compound (A) artificial intelligence 10 A-II 10 A-III 10 A-IV 10 Compound (B) Ce(acac)3·nH2O Ce(acac)3 Ce(NO3)3·6H2O Crosslinking agent (C) MS51 0.63 0.69 0.5 0.5 ES40 TMPS Catalyst (D) ZC150 0.01 0.01 0.01 0.01 solvent aniline 6.8 8.3 8.1 8.3 Heat resistance TG-DTA (Nitrogen environment) Td1[℃] 443 449 459 454 Td3[℃] 476 479 484 478

[0306] As shown in Tables 1 to 3, the heat resistance of the hardened material obtained in the examples is excellent compared with that of the comparative examples.

[0307] The hardened products obtained in the examples shown in Tables 1 to 3 contain silicon compound (A) and compound (B), and the heat resistance is improved by nearly 10°C to 20°C compared with the comparative example which contains only silicon compound (A).

[0308] In addition, according to Examples 1, 2, 4, 5 and Comparative Examples 1 to 4, improvements in heat resistance can be found in silicon compounds (A) with different ratios of sesquisiloxane to siloxane or different weight average molecular weights.

[0309] According to Examples 2, 6 to 9, even if the compound (B) and crosslinking agent (C) are different, the same improvement in heat resistance can be found.

[0310] Furthermore, as in Example 3, by increasing the amount of compound (B) added, a further improvement in heat resistance can also be observed.

[0311] [Table 4] Table 4 Example 10 Comparative Example 5 Curable resin composition 2 R2 Silicon compound (A) A-II 10 10 Compound (B) Ce(acac)3·nH2O 0.001 Crosslinking agent (C) MS51 0.69 0.69 Catalyst (D) ZC150 0.01 0.01 solvent aniline 8.26 8.3 Heat resistance Solid NMR D-body reduction rate [%] -8 -26

[0312] As shown in Table 4, the hardened product containing silicon compound (A) and compound (B) (Example 10) has a smaller reduction rate of D body compared to the hardened product without compound (B) (Comparative Example 5), and the structural changes caused by heating are suppressed.

[0313] [Example 11 and Comparative Example 6] <Evaluation of Heat Resistance (TG-DTA)> The hardened films obtained in Example 2 and Comparative Example 2 were cut using a cutting machine, and their heat resistance was evaluated using TG-DTA (manufactured by Rigaku Corporation) under air conditions and a heating rate of 10°C / min. The temperatures at which the weight before heating decreased by 1% (Td1) and 3% (Td3) were used as indicators of heat resistance. The evaluation results are recorded in Table 5 for Example 11 and Comparative Example 6.

[0314] The results are shown in Table 5. Furthermore, the quantities of each component in Table 5 are in g units.

[0315] [Table 5] Table 5 Example 11 Comparative Example 6 Curable resin composition 2 R2 Silicon compound (A) A-II 10 10 Compound (B) Ce(acac)3·nH2O 0.001 Crosslinking agent (C) MS51 0.69 0.69 Catalyst (D) ZC150 0.01 0.01 solvent aniline 8.26 8.3 Heat resistance TG-DTA (Air environment) Td1[℃] 455 410 Td3[℃] 472 457

[0316] As shown in Table 5, it also has good heat resistance in air environment.

[0317] [Example 12] <Evaluation of Heat Resistance (TG-DTA)> The hardening composition 10 described in Table 6 was prepared using the same method as in Examples 1 to 9, thereby producing a hardened product. Heat resistance (TG-DTA) was then evaluated using the same method as in Comparative Example 6. The temperature at which the weight before heating decreased by 1% (Td1) and the temperature at which the weight decreased by 3% (Td3) were used as indicators of heat resistance. The evaluation results are described in Table 6 as Example 12, along with Comparative Examples 6 and 11, which were used as comparison objects.

[0318] The results are shown in Table 6. The amounts of each component in Table 6 are in g units.

[0319] [Table 6] Table 6 Example 11 Example 12 Comparative Example 6 Curable resin composition 2 10 R2 Silicon compound (A) A-II 10 10 10 Compound (B) Ce(acac)3·nH2O 0.001 Fe(acac)3 0.001 Crosslinking agent (C) MS51 0.69 0.69 0.69 Catalyst (D) ZC150 0.01 0.01 0.01 solvent aniline 8.26 8.26 8.3 Heat resistance TG-DTA (Air environment) Td1[℃] 455 450 410 Td3[℃] 472 477 457

[0320] As can be seen from Table 6, Example 12 exhibits the same degree of heat resistance as Example 11. This result suggests that even if compound (B) is a compound other than a cerium compound, the cured product of the curable resin composition also has good heat resistance.

[0321] [Examples 13-15 and Comparative Examples 7-8] <Evaluation of Heat Resistance (TG-DTA)> Curable components 11-13 and R8-R9 as described in Table 7 were prepared using the same method as in Examples 1-9. The heating was changed to 100°C for 1 hour and 250°C for 3 hours. Otherwise, the cured products were prepared using the same method as in Examples 1-9. The heat resistance (TG-DTA) was then evaluated using the same method as in Example 12. The temperature at which the weight before heating was reduced by 1% (Td1) and the temperature at which the weight was reduced by 3% (Td3) were used as indicators of heat resistance. The evaluation results are recorded in Table 7 as Examples 13-15 and Comparative Examples 7-8.

[0322] The results are shown in Table 7. The amounts of each component in Table 7 are in g units.

[0323] [Table 7] Table 7 Example 13 Example 14 Example 15 Comparative Example 7 Comparative Example 8 Curable resin composition 11 12 13 R8 R9 Silicon compound (A) AV 10 10 10 A-VI 10 10 Compound (B) Ce(acac)3 0.001 0.001 0.001 Crosslinking agent (C) DVTS 0.75 Catalyst (D) Pt-VTSC-3.0X 0.00001 0.00001 0.00001 solvent PGMEA 10 10 9.44 10 9.33 Heat resistance TG-DTA (Air environment) Td1[℃] 428 425 404 411 389 Td3[℃] 448 444 425 433 410

[0324] As can be seen from Table 7, in AV and A-VI, which have a different skeleton from AI to A-IV as silicon compound (A), by including compound (B), a curable resin composition with good heat resistance can be obtained.

[0325] [Examples 16-21] <Evaluation of Adhesion> Except for changing the coating substrate to the substrates described below, the curable resin compositions (1, 2, 4, 5, 11, 13) of Examples 1, 2, 4, 5, 13, and 15 were coated and heated using the same method as the method for preparing the cured materials to produce substrates with a 10 μm thick curable film. Each substrate was subjected to a 10-minute conditioning treatment using an ASM2001N UV / O3 cleaning and conditioning apparatus manufactured by Asumi Giken before coating. The adhesion of the prepared substrates with the curable film was evaluated using a cross-cutting method (1 mm interval, 10×10 pieces) based on the following evaluation criteria. The tape used was No. 31B manufactured by Nitto Denko Corporation. The evaluation results for Examples 16-21 are recorded in Table 8. <Substrate> Glass: Eagle-XG (trade name, manufactured by Musashino Fine Glass Co., Ltd.) Si: High-purity silicon wafers for research (4×P type), manufactured by ASONE Co., Ltd. Cu: C1020P-1 / 2H (trade name, manufactured by Standard-Testpiece Co., Ltd.) Al: A1050P-H24 (trade name, manufactured by Standard-Testpiece Co., Ltd.) SUS: SUS304-2B (trade name, manufactured by Standard-Testpiece Co., Ltd.) Fe: SPCC-SD (trade name, manufactured by Standard-Testpiece Co., Ltd.) <Evaluation Criteria> ◎: Peeling area less than 3% ○: Peeling area more than 3% but less than 5% △: Peeling area more than 5% but less than 50% ×: Peeling area more than 51%

[0326] The results are shown in Table 8. The amounts of each component in Table 8 are in g units.

[0327] [Table 8] Table 8 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Curable resin composition 1 2 4 5 11 13 Silicon compound (A) AI 10 A-II 10 A-III 10 A-IV 10 AV 10 A-VI 10 Compound (B) Ce(acac)3·nH2O 0.001 0.001 0.001 0.001 Ce(acac)3 0.001 0.001 Crosslinking agent (C) MS51 0.63 0.69 0.5 0.5 Catalyst (D) ZC150 0.01 0.01 0.01 0.01 Pt-VTSC-3.0X 0.00001 solvent aniline 6.8 8.26 8.1 8.3 PGMEA 10 9.44 Tightness Glass ◎ ◎ ◎ ◎ ◎ ◎ Si ◎ ◎ ◎ ◎ ◎ ◎ Cu ○ ○ ○ ○ ◎ ○ Al ○ ○ ○ ○ ○ ○ SUS ◎ ◎ ◎ ◎ ◎ ○ Fe ◎ ◎ ◎ ◎ ◎ ○

[0328] As shown in Table 8, when any one of AI to A-VI is used as the silicon compound (A), the curing film containing the curable resin composition of compound (B) has good adhesion to various substrates.

[0329] [Examples 22-23] <Evaluation of Adhesion> The heating conditions for making the substrate with the hardened film were changed to heating at 70°C for 20 minutes, then at 100°C for 20 minutes, and then at 200°C for 2 hours. The substrate was changed to polyimide film (R) 200H (PI: polyimide (manufactured by ASONE (stock)). Otherwise, the adhesion was evaluated using the same method and the same evaluation criteria as in Examples 16-21.

[0330] The results are shown in Table 9. The amounts of each component in Table 9 are in g units.

[0331] [Table 9] Table 9 Example 22 Example 23 Curable resin composition 2 4 Silicon compound (A) A-II 10 A-III 10 Compound (B) Ce(acac)3·nH2O 0.001 0.001 Crosslinking agent (C) MS51 0.69 0.5 Catalyst (D) ZC150 0.01 0.01 solvent aniline 8.26 8.1 Tightness PI ◎ ◎

[0332] As shown in Table 9, the cured film of the curable resin composition containing compound (B) also has good adhesion to the polyimide substrate.

[0333] [Examples 24-29] <Evaluation of Total Light Transmittance> Using curable resin composition 1, curable resin composition 2, curable resin composition 4, curable resin composition 5, curable resin composition 11, and curable resin composition 13, the coating substrate was changed to Eagle-XG (manufactured by Musashino Fine Glass Co., Ltd.) after demolding treatment. Otherwise, coating was performed using the same method as in Examples 1, 2, 4, 5, 13, and 15, and the substrate was heated. After heating, the film was peeled off from the substrate to produce a 100 μm thick curable film. The total light transmittance was measured using the prepared curable film by the following method. The evaluation results are recorded in Table 10 as Examples 24-29.

[0334] <Total Light Transmittance> As an indicator of the transparency of the hardened film, the total light transmittance was measured using a haze meter (NDH-5000SP, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

[0335] The results are shown in Table 10. The amounts of each component in Table 10 are in g units.

[0336] [Table 10] Table 10 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Curable resin composition 1 2 4 5 11 13 Silicon compound (A) artificial intelligence 10 A-II 10 A-III 10 A-IV 10 AV 10 A-VI 10 Compound (B) Ce(acac)3·nH2O 0.001 0.001 0.001 0.001 Ce(acac)3 0.001 0.001 Crosslinking agent (C) MS51 0.63 0.69 0.5 0.5 Catalyst (D) ZC150 0.01 0.01 0.01 0.01 Pt-VTSC-3.0X 0.00001 solvent aniline 6.8 8.26 8.1 8.3 PGMEA 10 9.44 Total light transmittance % 92.3 91.6 91.7 91.5 92.8 92.5 As shown in Table 10, the hardened films of each embodiment all possess high transparency.

[0337] [Examples 30-35] <Evaluation of Volume Resistivity> Except for changing the substrate to the chromium substrate described below (manufactured by Mitsuru Optical Research Institute Co., Ltd.), the substrate was coated and heated using the same method as in Examples 16-21. A substrate with a 15 μm thick hardened film was fabricated using hardened resin composition 1, hardened resin composition 2, hardened resin composition 4, hardened resin composition 5, hardened resin composition 11, and hardened resin composition 13. A femto / picoamperemeter B2981A (manufactured by Keysight Technologies) and a high-voltage power supply HER-3P10 (manufactured by Matsusada Precision Co., Ltd.) were connected to the substrate with the hardened film, and the volume resistivity was measured when 250 V was applied.

[0338] The results are shown in Table 11. The amounts of each component in Table 11 are in g units.

[0339] [Table 11] Table 11 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Curable resin composition 1 2 4 5 11 13 Silicon compound (A) artificial intelligence 10 A-II 10 A-III 10 A-IV 10 AV 10 A-VI 10 Compound (B) Ce(acac)3·nH2O 0.001 0.001 0.001 0.001 Ce(acac)3 0.001 0.001 Crosslinking agent (C) MS51 0.63 0.69 0.5 0.5 Catalyst (D) ZC150 0.01 0.01 0.01 0.01 Pt-VTSC-3.0X 0.00001 solvent aniline 6.8 8.26 8.1 8.3 PGMEA 10 9.44 Volume resistivity (250 V) Ω·cm 10 16 10 16 10 16 10 16 10 16 10 16

[0340] As shown in Table 11, the cured films formed from the curable resin compositions of each embodiment all possess high insulation properties. [Industrial Applicability]

[0341] The curable resin composition of the present invention can provide a curable resin composition capable of forming a heat-resistant curable material suitable for use in applications such as printed wiring boards, semiconductor elements, light-emitting diodes (LEDs) or electronic parts for automotive applications, and an electronic part having said curable material. [Simplified Explanation of the Diagram]

[0031] None

Claims

1. A curable resin composition comprising: a silicon compound (A) containing one or more of the silsesquioxanes represented by formula (1) or formula (2), two of the silsesquioxanes represented by formula (1) or formula (4), and one or more of the siloxanes represented by formula (3) or formula (5), and having a weight average molecular weight of 3,000 to 1,000,000; and a compound (B) having one or more of the elements Ce, La, Pr, Nd, and Fe. R1 independently represents an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. In the aryl group having 6 to 20 carbon atoms, the cycloalkyl group having 5 or 6 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms, any hydrogen atom may be independently substituted with a fluorine atom or an alkyl group having 1 to 20 carbon atoms. In the alkyl group having 7 to 40 carbon atoms, any hydrogen atom may be substituted with a fluorine atom. Any -CH2- may be independently substituted with -O-, -CH=CH-, or an alkyl group having 5 to 20 carbon atoms. In the alkyl group having 1 to 40 carbon atoms, any hydrogen atom may be independently substituted with a fluorine atom. Any -CH2- may be independently substituted with -O- or an alkyl group having 5 to 20 carbon atoms. R2 independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms. R3 represents a hydroxyl group. R4 independently represents a hydroxyl group, hydrogen, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; R5 represents a hydroxyl group, an alkoxy group having 1 to 8 carbons, hydrogen, an alkenyl group having 2 to 40 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; a represents the following structure; R6 independently represents an alkyl group having 1 to 40 carbons, wherein any -CH2- group may be independently substituted with -O- or an alkyl cycloalkyl group having 5 to 20 carbons; R7 independently represents an aryl group with 6 to 20 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, an arylalkyl group with 7 to 40 carbon atoms, or an alkyl group with 1 to 40 carbon atoms. In the aryl group with 6 to 20 carbon atoms, the cycloalkyl group with 5 to 6 carbon atoms, and the arylalkyl group with 7 to 40 carbon atoms, any hydrogen atom may be independently substituted by a fluorine atom or an alkyl group with 1 to 20 carbon atoms. In the alkyl group with 7 to 40 carbon atoms, any hydrogen atom may be substituted by a fluorine atom. Any -CH2- may be independently substituted by -O-, -CH=CH-, or an alkyl group with 5 to 20 carbon atoms. In the alkyl group with 1 to 40 carbon atoms, any hydrogen atom may be independently substituted by a fluorine atom. Any -CH2- may be independently substituted by -O- or an alkyl group with 5 to 20 carbon atoms. Furthermore, * in the formula indicates a bonding site.

2. The curable resin composition as claimed in claim 1, wherein the silicone compound (A) comprises one or more of the sesquisiloxanes represented by formula (1) or formula (2), two of the sesquisiloxanes represented by formula (1) or the silicones represented by formula (7), and one or more of the silicones represented by formula (6), wherein R8 independently represents a hydroxyl group, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; and R9 independently represents a hydroxyl group, an alkoxy group having 1 to 8 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons, wherein at least one of the groups represented by formula (7) represents a hydroxyl group or an alkoxy group having 1 to 8 carbons.

3. The curable resin composition as claimed in claim 1, wherein the silicone compound (A) is a compound represented by the following formula (8), where R1 and R2 represent groups defined in the same way as R1 and R2 in the group represented by formula (1) as claimed in claim 1; R8 and R9 represent groups defined in the same way as R8 and R9 in the group represented by formula (6) and formula (7) as claimed in claim 2, and in the group represented by formula (11), at least one R9 represents a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms; R10 represents a group represented by formula (9); R11 represents a group represented by formula (10) or formula (11); n is an average value satisfying 1 to 30; m is a positive average value satisfying 0 to 30; l is a value satisfying a weight average molecular weight of 3,000 to 1,000,000; and p is 0 or 1.

4. The curable resin composition as claimed in claim 2, further comprising a crosslinking agent (C) other than the silicon compound (A), the crosslinking agent (C) having two or more crosslinking groups capable of chemically bonding with the silicon compound (A).

5. The curable resin composition as claimed in claim 4, wherein the crosslinking group is any one of the following formulas (12) to (17) bonded to Si, where R12 represents an alkyl group having 1 to 8 carbon atoms.

6. The curable resin composition as claimed in claim 2 further comprises a catalyst (D).

7. The curable resin composition as claimed in claim 6, wherein, The catalyst (D) has one or more of Sn, Zr, Ti, Al, N and Pt.

8. The curable resin composition as claimed in claim 1, wherein, The silicon compound (A) comprises any one or more of the silsesquioxanes represented by formula (1) or formula (2), two of one or both of the silsesquioxanes represented by formula (1) or formula (19), and at least one of the siloxanes represented by formula (18) or formula (20); R13 independently represents hydrogen or an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; R14 independently represents hydrogen, a hydroxyl group, an alkoxy group having 1 to 8 carbons, an alkenyl group having 2 to 40 carbons, an alkyl group having 1 to 8 carbons, or an aryl group having 6 to 20 carbons; and a represents the same group as a as claimed in claim 1.

9. The curable resin composition as claimed in claim 1, wherein, The silicon compound (A) is a compound represented by the following formula (21), where N is a value satisfying a weight average molecular weight of 3,000 to 1,000,000; R1 and R2 represent the same bases as R1 and R2 in the base represented by formula (1) as claimed in claim 1; R15 represents the base represented by formula (22); R16 represents the base represented by formula (23) or formula (24); in the base represented by formula (24), R14 is the same base as R14 in the base represented by formula (19) as claimed in claim 8; q is 0 or 1; X1 and X2 independently represent at least one repeating unit selected from the following formulas (25) to (30); a represents the same base as a as claimed in claim 1; R13 represents the same base as R13 in the base represented by formula (18) as claimed in claim 8. x and z are average values ​​satisfying 0 to 30, and y is a positive average value satisfying 1 to 30.

10. The curable resin composition as claimed in claim 8, further comprising a crosslinking agent (C) other than the silicone compound (A), the crosslinking agent (C) having two or more crosslinking groups capable of chemically bonding with the silicone compound (A).

11. The curable resin composition as claimed in claim 10, wherein the crosslinking group is any one of the following formulas (12) to (17) or (31) bonded to Si, where R12 represents an alkyl group having 1 to 8 carbon atoms.

12. The curable resin composition as described in claim 8 further comprises a catalyst (D).

13. The curable resin composition as claimed in claim 12, wherein, The catalyst (D) has one or more of Sn, Zr, Ti, Al, N and Pt.

14. A curing compound formed for curing a curable resin composition as described in any one of claims 1 to 13.

15. An electronic component having a hardened material as described in claim 14.

16. An optical component having a hardened material as described in claim 14.

17. A composite component comprising a first component and a resin-containing component in contact with the first component, and forming part of an electrical component, wherein the resin-containing component comprises a hardened material as described in claim 14.

18. The composite component as claimed in claim 17, wherein, The resin-containing component is a protective film covering at least a portion of the first component.

19. The composite component as claimed in claim 18, wherein, The first component is a wiring substrate with wiring provided on the base material, and the protective film is insulating and covers the wiring.

20. The composite component as claimed in claim 17, further comprising a second component in contact with the resin-containing component.

Images