Co-modified silicone

Abstract

Provided is, inter alia, a novel co-modified silicone.　This co-modified silicone includes a phenolic hydroxy group-containing structure and a polyether structure in a molecule.

Description

Co-modified silicone

[0001] The present invention relates to a co-modified silicone, an organic resin additive and a curable resin composition containing the co-modified silicone, a cured product obtained by curing the co-modified silicone, a semiconductor device containing the cured product, and a method for producing a semiconductor device.

[0002] In recent years, electronic devices such as mobile phones, smartphones, ultra-thin LCD displays, plasma TVs, and lightweight laptop computers have become increasingly miniaturized. This has led to increased integration and packaging density of electronic components, such as semiconductor devices, used in these electronic devices. Resin materials used in these electronic components are required to have low thermal expansion coefficients and elastic moduli to prevent warping after molding and delamination between components during the solder reflow process due to thermal stress during manufacturing and use. Furthermore, heat resistance is required to prevent manufacturing problems and ensure the reliability of electronic components. For example, Patent Document 1 (JP-A-2003-102666) discusses increasing the filler content in epoxy resins to reduce thermal stress. While increasing the filler content can reduce the coefficient of thermal expansion of the epoxy resin, this approach may not sufficiently suppress warpage when the support surface area is large, as in wafer-level packages and panel-level packages. Furthermore, the increased elastic modulus of epoxy resins reduces their strength, potentially resulting in damage to Si chips and substrates during heat cycle tests during manufacturing and use, such as the solder reflow process. Patent Documents 2 and 3 disclose another method for reducing thermal stress, in which epoxy-modified silicone is added to epoxy resin to reduce the elastic modulus of the epoxy resin. While this method is effective in reducing thermal stress, it does not sufficiently reduce the thermal expansion coefficient (linear expansion coefficient). In particular, it does not sufficiently reduce the thermal expansion coefficient at temperatures higher than the glass transition temperature. Furthermore, modified silicones having a polyether structure-containing group are sometimes used to improve compatibility with epoxy resins, but they suffer from a lack of heat resistance. Since epoxy resins can be exposed to temperatures as high as 175°C during molding and solder reflow processes, it is preferable that the silicone added also has heat resistance. It is generally known that heat resistance can be improved by replacing methyl groups on siloxane with phenyl groups, but the silicone additive itself has the problem of becoming highly viscous.

[0003] JP 2013-010940 A JP 2020-023643 A International Publication No. 2021 / 149727

[0004] Under these circumstances, the present invention provides novel co-modified silicones and the like.

[0005] The present invention provides the following co-modified silicones and the like. [1] A co-modified silicone containing a phenolic hydroxyl group-containing structure and a polyether structure in the molecule. [2] The co-modified silicone according to [1], which has a viscosity at 25°C in the range of 50 to 100,000 mPa·s. [3] A co-modified silicone represented by the average composition formula (1): R １ ａ R ２ ｂ R ３ ｃ R ４ ｄ SiO （４－ａ－ｂ－ｃ－ｄ）／２ In the average composition formula (1), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; R ２ each independently represents a group having a phenolic hydroxyl group represented by the following general formula (2), R ３ each independently represents a group containing a polyether structure represented by the following general formula (3), and R ４ each independently represent a monovalent hydrocarbon group or a silicon-containing organic group having 1 to 18 carbon atoms, and a, b, c, and d satisfy b>0, c>0, a≧0, d≧0, and a+b+c+d=4. The co-modified silicone according to [1] or [2]. (In the general formula (2), R ２’ represents a divalent hydrocarbon group having 1 to 18 carbon atoms bonded to a silicon atom, R ２” each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that R ２” At least one of the groups is a hydroxyl group. (In the general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms, a represents a number from 5 to 100, and Z represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group having 1 to 12 carbon atoms.) [4] Average composition formula (2): (R １ ２R'SiO １／２ ) ａ (R ２ R'SiO ２／２ ) ｂ (R ３ R'SiO ２／２ ) ｂ’ (R ４ R'SiO ２／２ ) ｂ” (R'SiO ３／２ ) ｃ (SiO ４／２ ) ｄ In the average composition formula (2), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; R ２ each independently represents a group having a phenolic hydroxyl group represented by the following general formula (2), R ３ each independently represents a group containing a polyether structure represented by the following general formula (3), and R ４ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a silicon-containing organic group, and each R' independently represents R １ , R ２ , R ３ or R ４ a, b, b', b", c, and d satisfy b > 0, b' > 0, a ≥ 0, b" ≥ 0, c ≥ 0, d ≥ 0, and 20 ≤ a + b + b' + b" + c + d ≤ 1000. (In the general formula (2), R ２’ represents a divalent hydrocarbon group having 1 to 18 carbon atoms bonded to a silicon atom, R ２” each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that R ２” At least one of the groups is a hydroxyl group. (In general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms, a represents a number from 5 to 100, and Z represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group having 1 to 12 carbon atoms.) [5] A co-modified silicone according to any one of [1] to [4], which has a structure represented by the following general formula (1): (In the general formula (1), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; R ２ R each independently represents a group having a phenolic hydroxyl group represented by the following general formula (2): ３ each independently represents a group containing a polyether structure represented by the following general formula (3), ４ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a silicon-containing organic group; １ , R ２ , R ３ or R ４ m represents a number from 0 to 100, provided that when m=0, at least one of X is R ２ n represents a number from 0 to 100, provided that when n=0, at least one of X is R ３ When m=n=0, each of the two Xs in the molecule is R ２ and R ３ and l represents a number from 0 to 1000. (In the general formula (2), R ２’ represents a divalent hydrocarbon group having 1 to 18 carbon atoms bonded to a silicon atom, R ２” each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that R ２” At least one of the groups is a hydroxyl group. (In general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms, a represents a number from 5 to 100, and Z represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group having 1 to 12 carbon atoms.) [6] An organic resin additive comprising the co-modified silicone according to any one of [1] to [5]. [7] The organic resin additive according to [6], wherein the organic resin comprises an epoxy resin. [8] A curable resin composition comprising the co-modified silicone according to any one of [1] to [5]. [9] The curable resin composition according to [8], wherein the curable resin comprises an epoxy resin.

[10] A cured product obtained by curing the curable resin composition according to [8] or [9].

[11] A semiconductor device comprising the cured product according to

[10] .

[12] A method for manufacturing a semiconductor device, comprising curing the curable resin composition according to [8] or [9].

[0006] According to one aspect of the present invention, there is provided a co-modified silicone that can provide an organic resin additive or curable resin composition that has excellent fluidity (flowability) during molding and can impart excellent heat resistance to the cured product. According to one aspect of the present invention, there is provided a co-modified silicone that can provide an organic resin additive or curable resin composition that can reduce the elastic modulus of the cured product. According to one aspect of the present invention, there is provided a co-modified silicone that can provide an organic resin additive or curable resin composition that can reduce the linear expansion coefficient of the cured product.

[0007] The upper and lower limit values ​​of the numerical ranges described herein can be arbitrarily combined. For example, when a numerical range is described as "preferably 30 to 100, more preferably 40 to 80," the ranges "30 to 80" and "40 to 100" are also included in the numerical ranges described herein. Furthermore, when a numerical range is described as "preferably 30 or more, more preferably 40 or more, and preferably 100 or less, more preferably 80 or less," the ranges "30 to 80" and "40 to 100" are also included in the numerical ranges described herein. In addition, when a numerical range described herein as "60 to 100," for example, means a range of "60 or more and 100 or less."

[0008] 1. Co-modified Silicone One aspect of the present invention provides a co-modified silicone (hereinafter also referred to as "the compound of the present invention"). The compound of the present invention contains a phenolic hydroxyl group-containing structure and a polyether structure in the molecule. A co-modified silicone containing both of these structures in the molecule can impart excellent heat resistance, a favorable low modulus of elasticity, and / or a favorable low coefficient of thermal expansion to a cured product obtained by curing a curable resin composition. The phenolic hydroxyl group-containing structure and the polyether structure will be described later.

[0009] The molecular structure of the compound of the present invention may be any of linear, partially branched linear, branched, cyclic, network, and dendritic. One embodiment of the compound of the present invention is a linear co-modified silicone. Another embodiment of the compound of the present invention is a branched co-modified silicone.

[0010] The compound of one embodiment of the present invention may be liquid (oil-like) or rubber-like at room temperature, but is preferably liquid. The viscosity of the compound of one embodiment of the present invention at 25°C is, for example, 50 to 100,000 mPa·s, preferably 100 to 10,000 mPa·s, more preferably 1,000 to 8,000 mPa·s, and particularly preferably 2,000 to 6,000 mPa·s. Adjusting the viscosity to within the above range can improve compatibility with resins and ease of handling during processing. In this specification, viscosity refers to a value measured at 25°C using an E-type viscometer.

[0011] The compound of one embodiment of the present invention is represented by the following average composition formula (1): １ ａ R ２ ｂ R ３ ｃ R ４ ｄ SiO （４－ａ－ｂ－ｃ－ｄ）／２ In the above average composition formula (1), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; R ２ each independently represents a group having a phenolic hydroxyl group represented by the following general formula (2), R ３ each independently represents a group containing a polyether structure represented by the following general formula (3), and R ４ each independently represents a monovalent hydrocarbon group or a silicon-containing organic group having 1 to 18 carbon atoms, and a, b, c, and d satisfy b>0, c>0, a≧0, d≧0, and a+b+c+d=4.

[0012] In the above average composition formula (1), a is preferably 0≦a<4.00, more preferably 1.50≦a≦3.98, and even more preferably 3.00≦a≦3.95. b is preferably 0<b≦0.90, more preferably 0.01≦b≦0.60, and even more preferably 0.02≦b≦0.30. c is preferably 0<c≦0.90, more preferably 0.01≦c≦0.60, and even more preferably 0.02≦c≦0.30. d is preferably 0≦d≦1.50, more preferably 0≦d≦1.00, and even more preferably 0≦d≦0.50. As mentioned above, a, b, c, and d are within the above numerical ranges and satisfy a+b+c+d=4.

[0013] In the above average composition formula (1), R １ The monovalent hydrocarbon group having 1 to 18 carbon atoms that can be selected as R may be linear, branched, cyclic, saturated, or unsaturated, and includes alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups. １may be the same or different. Specific examples of the alkyl group include methyl, ethyl, propyl groups such as n-propyl and isopropyl, butyl groups such as n-butyl, isobutyl, s-butyl, and t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, and octadecyl groups. These groups also include structural isomers. Specific examples of the cycloalkyl group include a monocyclic or polycyclic group, such as a cyclopentyl group or a cyclohexyl group. Specific examples of the alkenyl group include a vinyl group, an allyl group, a 3-butenyl group, and a 5-hexenyl group. Specific examples of the aryl group include a monocyclic or polycyclic group, such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The aralkyl group is an alkyl group substituted with an aryl group, and specific examples include a benzyl group, a phenethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. The halogenated alkyl group may be a group in which some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group have been substituted with halogen atoms such as chlorine atoms, fluorine atoms, or bromine atoms, and specific examples include a chloromethyl group, a bromoethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a chlorophenyl group, and a bromophenyl group. Among these, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms, and even more preferably a methyl group or a phenyl group.

[0014] In the above average composition formula (1), R ２ represents a group having a phenolic hydroxyl group represented by the following general formula (2).

[0015] In the above general formula (2), R ２’ represents a divalent hydrocarbon group having 1 to 18 carbon atoms bonded to a silicon atom, which may be linear, branched, cyclic, saturated, or unsaturated, and includes alkylene groups, cycloalkylene groups, arylene groups, aralkylene groups, and alkenylene groups. ２”each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that R ２” At least one of R is a hydroxyl group. ２” may be the same or different.

[0016] R ２’ Specific examples of alkylene groups having 1 to 18 carbon atoms that can be selected as aryl include various propylene groups such as methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, and 2,2-propylene, as well as butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene. These groups also include structural isomers. The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of cycloalkylene groups include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Specific examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, a naphthylene group, etc. Specific examples of the aralkylene group include a benzylene group, a phenylethylene group, a 3-phenylpropylene group, a 4-phenylbutylene group, etc. Specific examples of the alkenylene group include a vinylene group, a 1-methylvinylene group, a propenylene group, a butenylene group, a pentenylene group, etc.

[0017] R ２”The monovalent hydrocarbon group having 1 to 6 carbon atoms that can be selected as may be, for example, an alkyl group or an alkenyl group. The alkyl group may be linear, branched, or cyclic, and specific examples include propyl groups such as methyl, ethyl, n-propyl, and isopropyl, butyl groups such as n-butyl, isobutyl, s-butyl, and t-butyl, pentyl, and hexyl. These groups also include structural isomers. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl, and even more preferably methyl, ethyl, n-butyl, or t-butyl. Specific examples of the alkenyl group include vinyl and allyl groups.

[0018] R ２” Specific examples of alkoxy groups having 1 to 6 carbon atoms that can be selected as include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc. These groups also include structural isomers. The alkoxy group is preferably a methoxy group or an ethoxy group.

[0019] In one embodiment of the present invention, R in the above general formula (2) ２” A preferred combination of is a hydrogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms (for example, a methoxy group). A specific example of a compound having this combination is eugenol. That is, one aspect of the present invention may be a co-modified silicone in which eugenol has been introduced into the side chain via a divalent hydrocarbon group having 1 to 18 carbon atoms (for example, an alkylene group) bonded to a silicon atom.

[0020] In another embodiment of the present invention, R in the above general formula (2) ２” A preferred combination of is a hydrogen atom and a hydroxyl group. Specific compounds having this combination include catechol and phenol. That is, one embodiment of the present invention may be a co-modified silicone in which catechol or phenol has been introduced into the side chain via a divalent hydrocarbon group (e.g., an alkylene group) having 1 to 18 carbon atoms bonded to a silicon atom.

[0021] The co-modified silicone of one embodiment of the present invention may be a co-modified silicone having one or more selected from the group consisting of eugenol, catechol, and phenol in its side chain, via a divalent hydrocarbon group having 1 to 18 carbon atoms (for example, an alkylene group) bonded to a silicon atom.

[0022] In the above average composition formula (1), R ３ R represents a group containing a polyether structure represented by the following general formula (3): ３ may be the same or different. In the above general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms, a represents a number from 5 to 100, and Z represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group having 1 to 12 carbon atoms.

[0023] X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, which may be linear, branched, cyclic, saturated, or unsaturated, and includes alkylene groups, cycloalkylene groups, arylene groups, aralkylene groups, and alkenylene groups. Specific examples of the alkylene group include methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 2,2-propylene, and other propylene groups, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene groups. These groups also include structural isomers. The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Specific examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group. Specific examples of the aralkylene group include a benzylene group, a phenylethylene group, a 3-phenylpropylene group, and a 4-phenylbutylene group. Specific examples of the alkenylene group include a vinylene group, a 1-methylvinylene group, a propenylene group, a butenylene group, and a pentenylene group.

[0024] Specific examples of alkylene groups having 1 to 6 carbon atoms that can be selected as Y include various propylene groups such as methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, and 2,2-propylene, as well as butylene, pentylene, and hexylene. These groups also include structural isomers. The alkylene group is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, even more preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably one or more groups selected from an ethylene group and a propylene group. When multiple Ys are present, the multiple Ys may be ethylene groups alone, propylene groups alone, or a combination of ethylene and propylene groups (i.e., -Y-O- may be formed by ethylene oxide (EO) groups and propylene oxide (PO) groups bonded randomly or in blocks). Furthermore, -YO- comprises an ethylene oxide (EO) group and a propylene oxide (PO) group, and preferably contains at least one ethylene group or propylene group.

[0025] The value of a is preferably an integer of 5 to 80, more preferably an integer of 10 to 70, and even more preferably an integer of 15 to 60. When -Y-O- in one embodiment is composed of an ethylene oxide (EO) group and a propylene oxide (PO) group, the number of EO groups (a1) in a is preferably 0 to 70, may be 1 to 70, more preferably 5 to 50, and even more preferably 10 to 30. The number of PO groups (a2) in a is preferably 0 to 70, may be 1 to 70, more preferably 5 to 50, and even more preferably 10 to 40.

[0026] Specific examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms that can be selected as Z include alkyl groups, aryl groups, aralkyl groups, phenethyl groups, and halogenated alkyl groups. These groups are the same as those in the above average composition formula (1), R １ may be the same as the examples of the monovalent hydrocarbon groups having 1 to 12 carbon atoms that can be selected as

[0027] Specific examples of the acyl group having 1 to 12 carbon atoms that can be selected as Z include a formyl group (methanoyl group), an acetyl group (ethanoyl group), a propionyl group (propanoyl group), and a benzoyl group.

[0028] In one embodiment of the present invention, the group containing the polyether structure represented by the general formula (3) may have a hydrophilic structure such as glycerol as part of its structure. By introducing the glycerol group, the polyether can be branched, allowing the hydrophilic group to be locally arranged within the molecule. Furthermore, by leaving the hydroxyl group of the glycerol, the hydrophilicity can be further enhanced.

[0029] In the above average composition formula (1), R ４ The monovalent hydrocarbon group having 1 to 18 carbon atoms that can be selected as R may be linear, branched, cyclic, saturated, or unsaturated, and includes alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups. These groups are the same as those in the above average composition formula (1), R １ may be the same as the examples of the monovalent hydrocarbon groups having 1 to 18 carbon atoms that can be selected as

[0030] In the above average composition formula (1), R ４ The silicon-containing organic group that can be selected as R may be a silicon-containing organic group selected from a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure. For example, R ４ is represented by the following general formula (4) when i=1: (In the formula, R １ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, and R Ｃ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Z is a divalent organic group. ｉ where c is the number of generations, which is the number of repetitions of the silylalkyl group, and is an integer of 1 to c, and the number of generations c is an integer of 1 to 10; L ｉ＋１ is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i=c. ｉis a number ranging from 0 to 3; a silylalkyl group having a siloxane dendron structure represented by the following general formula (4'): (In the formula, R １１ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and R １１ at least one of which is the monovalent hydrocarbon group; t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500; and a chain organosiloxane group represented by the following general formula (4"): (In the formula, R １１ and r is as defined above.

[0031] R ４ may be the same or different. For example, a silylalkyl group having a carbosiloxidedendron structure and a group having a siloxane macromonomer structure may be contained in the same molecule, a silylalkyl group may be a combination of silicon-containing organic groups with different degrees of branching (generations), and a group having a siloxane macromonomer structure may be a combination of silicon-containing organic groups with different degrees of polymerization.

[0032] R ４ may be a silylalkyl group having a carbosiloxane dendrimer structure, and is defined as the silylalkyl group represented by the above general formula (4) when i = 1. The silylalkyl group having a carbosiloxane dendrimer structure has a structure in which carbosiloxane units spread out in a dendrimer-like manner, and is therefore a functional group that exhibits higher water repellency than linear or simply branched polysiloxane units.

[0033] In general formula (4), R Ｃ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and industrially, it is preferably a methyl group or a phenyl group.

[0034] In the general formula (4), i is L １where c is the number of generations, which is the number of repetitions of the silylalkyl group, and is an integer of 1 to c, and the number of generations c is an integer of 1 to 10; L ｉ＋１ is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i=c. In particular, it is preferably a methyl group when i=c.

[0035] Industrially, the number of generations c is preferably an integer of 1 to 3, and more preferably 1 or 2. ｉ The group represented by the formula: １ , R ｃ and Z is the same group as defined above.

[0036] When the number of layers c=1, L ｉ is represented by the following general formula (4-1).

[0037] When the number of layers c=2, L ｉ is represented by the following general formula (4-2).

[0038] In the above general formula (4), a ｉ are each independently a number ranging from 0 to 3, and in the structure represented by formula (4-1) to (4-2) when the number of generations is 1 to 2, a １ and a ２ are each independently a number ranging from 0 to 3. ｉ is particularly preferably a number in the range of 0 to 1, ｉ It is particularly preferred that is 0.

[0039] In the above general formula (4), each Z is independently a divalent organic group, and specific examples include divalent organic groups formed by addition reaction of a silicon-bonded hydrogen atom with a functional group having an unsaturated hydrocarbon group at its terminal, such as an alkenyl group, an acryloxy group, or a methacryloxy group. However, Z is not limited to these functional groups and can be appropriately selected depending on the method for introducing the silylalkyl group having a carbosiloxane dendrimer structure. In the present invention, Z is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and most preferably an ethylene group.

[0040] R ４ The group represented by may be a siloxane macromonomer structure-containing group bonded to a silicon atom constituting the main chain via an oxygen atom or an alkylene group, and is a hydrophobic functional group that exhibits a certain degree of water repellency or lipophilicity. ４ The group represented by may be the functional group represented by the above general formula (4') and general formula (4"). In these formulas, R １１ is industrially particularly preferably a methyl group, a phenyl group or a hydroxyl group, and R １１ A configuration in which a part of R is a methyl group and a part is a long-chain alkyl group having 8 to 30 carbon atoms is also suitable. １１ at least one of the groups is a monovalent hydrocarbon group such as a methyl group, t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500. From the viewpoint of compatibility with various oils, r is preferably a number in the range of 1 to 100, and particularly preferably a number in the range of 2 to 30.

[0041] The compound of one embodiment of the present invention is represented by the following average composition formula (2): (R １ ２ R'SiO １／２ ) ａ (R ２ R'SiO ２／２ ) ｂ (R ３ R'SiO ２／２ ) ｂ’ (R ４ R'SiO ２／２ ) ｂ” (R'SiO ３／２ ) ｃ (SiO４／２ ) ｄ In the above average composition formula (2), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; R ２ each independently represents a group having a phenolic hydroxyl group represented by the general formula (2), R ３ each independently represents a group containing a polyether structure represented by the general formula (3), R ４ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a silicon-containing organic group, and each R' independently represents R １ , R ２ , R ３ or R ４ a, b, b', b", c and d are such that b>0, b'>0, a≧0, b″≧0, c≧0, d≧0, and 20≦a+b+b'+b″+c+d≦1000.

[0042] In the above average composition formula (2), a is preferably 2≦a≦15, more preferably 2≦a≦10, and even more preferably 2≦a≦8. b is preferably 0<b≦100, more preferably 1≦b≦50, and even more preferably 1≦b≦20. b' is preferably 0<b'≦100, more preferably 1≦b'≦50, and even more preferably 1≦b'≦20. b" is preferably 0≦b"≦1000, more preferably 5≦b"≦500, and even more preferably 10≦b"≦300. c is preferably 0≦c≦15, more preferably 0≦c≦10, and even more preferably 0≦c≦5. Furthermore, as c becomes larger, the co-modified silicone will gel or solidify even at room temperature, so c is preferably within a range in which the compound of the present invention remains liquid (as defined by the Fire Service Act). d is preferably 0≦d≦15, more preferably 0≦d≦10, and even more preferably 0≦d≦5. Furthermore, as d becomes large, the co-modified silicone will gel or solidify even at room temperature, so c is preferably within a range in which the compound of the present invention remains liquid (as defined by the Fire Service Act). a + b + b' + b" + c + d is preferably 20 ≦ d ≦ 1000, more preferably 30 ≦ d ≦ 600, and even more preferably 40 ≦ d ≦ 350. As mentioned above, a, b, b', b", c, and d satisfy the above-mentioned numerical ranges.

[0043] In the above average composition formula (2), R １ The monovalent hydrocarbon group having 1 to 18 carbon atoms that can be selected as R １ may be the same as R １ may be the same or different.

[0044] In the above average composition formula (2), R ２ The group having a phenolic hydroxyl group that can be selected as R ２ may be the same as R ２ may be the same or different.

[0045] In the above average composition formula (2), R ３ The group containing a polyether structure that can be selected as R ３may be the same as R ３ may be the same or different.

[0046] In the above average composition formula (2), R ４ The monovalent hydrocarbon group having 1 to 18 carbon atoms or the silicon-containing organic group that can be selected as R ４ may be the same as R ４ may be the same or different.

[0047] In the average composition formula (2), each R' is independently R １ , R ２ , R ３ or R ４ and R １ , R ２ , R ３ or R ４ are as described above.

[0048] The compound according to one embodiment of the present invention may be a co-modified silicone having a structure represented by the following general formula (1).

[0049] In the above general formula (1), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms; R ２ each independently represents a group having a phenolic hydroxyl group represented by the general formula (2), ３ each independently represents a group containing a polyether structure represented by the above general formula (3), ４ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a silicon-containing organic group; １ , R ２ , R ３ or R ４ m represents a number from 0 to 100, provided that when m=0, at least one of X is R ２ n represents a number from 0 to 100, provided that when n=0, at least one of X is R ３ When m=n=0, each of the two Xs in the molecule is R２ and R ３ and l represents a number from 0 to 1000.

[0050] In the above general formula (1), R １ The monovalent hydrocarbon group having 1 to 18 carbon atoms that can be selected as R １ may be the same as R １ may be the same or different.

[0051] In the above general formula (1), R ２ The group having a phenolic hydroxyl group that can be selected as R ２ may be the same as R ２ may be the same or different.

[0052] In the above general formula (1), R ３ The group containing a polyether structure that can be selected as R ３ may be the same as R ３ may be the same or different.

[0053] In the above general formula (1), R ４ The monovalent hydrocarbon group having 1 to 18 carbon atoms or the silicon-containing organic group that can be selected as R ４ may be the same as R ４ may be the same or different.

[0054] In the general formula (1), each X is independently R １ , R ２ , R ３ or R ４ and R １ , R ２ , R ３ or R ４ are as described above.

[0055] In the above general formula (1), m is preferably 1 to 100, more preferably 1 to 50, and even more preferably 1 to 20. n is preferably 1 to 100, more preferably 1 to 50, and even more preferably 1 to 20. When m=n=0, two Xs in the molecule are each R ２ and R ３ and the R ２ and R ３ are as described above. l is preferably 0 to 1000, more preferably 5 to 500, and even more preferably 10 to 300. m+n+l is preferably 20 to 1000, more preferably 30 to 600, and even more preferably 40 to 350.

[0056] Here, in this specification, the organic group possessed by the co-modified silicone (i.e., R １ , R ２ , R ３ and R ４ ) structure, etc., １３ The structure and degree of polymerization of the siloxane units (i.e., M units, D units, T units, and Q units) contained in the co-modified silicone can be analyzed using C-NMR. ２９ Analysis can be performed using Si-NMR. By using these in combination, it is possible to identify the phenolic hydroxyl group-containing structure and polyether structure of the compound of the present invention, as well as the specific chemical structure of the siloxane main chain. Gas chromatography, liquid chromatography, or the like may also be used as necessary. Furthermore, for the purpose of managing or improving the performance and quality of the finally obtained co-modified silicone as a resin additive, or the like, the amounts of components other than the co-modified silicone, such as unreacted raw materials such as unreacted polyether raw materials, may be quantified.

[0057] 1.1 Method for Producing Co-Modified Silicone One aspect of the present invention provides a method for producing a co-modified silicone (hereinafter also referred to as the "production method of the present invention"). The production method of the present invention is not particularly limited as long as it is a method that can introduce the phenolic hydroxyl group-containing structure and polyether structure possessed by the compound of the present invention. For example, there is a method of subjecting an organopolysiloxane having a hydrogen atom bonded to a silicon atom (Si—H) to an addition reaction (e.g., a hydrosilylation reaction) with a phenolic hydroxyl group-containing precursor compound having a carbon-carbon double bond, and a polyether structure-containing precursor compound having a carbon-carbon double bond. Phenolic hydroxyl group-containing precursor compounds include compounds having a structure represented by general formula (2) described above in "1. Co-Modified Silicone," and specific examples include 2-allylphenol, eugenol, and the like. Polyether structure-containing precursor compounds include compounds having a structure represented by general formula (3) described above in "1. Co-Modified Silicone," and specific examples include polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer, and the like.

[0058] In one embodiment of the present invention, in addition to the phenolic hydroxyl group-containing precursor compound having a carbon-carbon double bond and the polyether structure-containing precursor compound having a carbon-carbon double bond, R in the average composition formula (1), the average composition formula (2), and the general formula (1) described in "1. Co-modified silicone" above may be further added. ４ A precursor compound having a group (a monovalent hydrocarbon group or a silicon-containing organic group having 1 to 18 carbon atoms) is subjected to an addition reaction with the organopolysiloxane to form a compound according to one embodiment of the present invention. ４ A group represented by the following formula may be introduced.

[0059] The order in which the above-described precursor compounds are added to the organopolysiloxane is not particularly limited. For example, the precursor compounds may be added simultaneously or separately.

[0060] The reaction temperature between the organopolysiloxane and each precursor compound is not particularly limited as long as the desired reaction proceeds. In one embodiment, the addition reaction may be carried out under heating. When the addition reaction is carried out under heating, the reaction temperature is preferably in the range of 30°C to 150°C.

[0061] The above addition reaction can be carried out at any pressure, and there is no particular limitation on the pressure, but if the target temperature cannot be reached when heated at normal pressure due to the relationship with the boiling points of the raw materials used, or if the time required to complete the reaction at normal pressure is significantly long, the reaction may be carried out under pressure. In order to shorten or omit the subsequent stripping for removing the solvent and unreacted raw materials, the reaction can also be carried out under reduced pressure, to the extent that the solvent and raw materials used are not removed from the system.

[0062] The addition reaction is preferably carried out under an inert gas atmosphere, for example, an inert gas atmosphere selected from nitrogen, argon, etc. It is also preferable to minimize the amount of water contained in the starting material organopolysiloxane having silicon-bonded hydrogen atoms and the precursor compound.

[0063] The above addition reaction may be carried out without solvent, or, if necessary, using an organic solvent selected from toluene, xylene, benzene, hexane, heptane, methylcyclohexane, ethylene chloride, chloroform, trichloroethylene, cyclohexane, ethyl acetate, methyl ethyl ketone, and isopropyl alcohol as a reaction solvent.

[0064] When an organopolysiloxane having silicon-bonded hydrogen atoms is subjected to a hydrosilylation reaction with a precursor compound, the catalyst used may be, for example, a catalyst based on a transition metal of Group VIII of the long periodic table, such as a platinum catalyst, a palladium catalyst, or a rhodium catalyst, with a platinum catalyst being preferred. Examples of such platinum catalysts include carbon powder carrying platinum metal, platinum black, platinic chloride, chloroplatinic acid, the reaction product of chloroplatinic acid with a monohydric alcohol, an alcohol solution of chloroplatinic acid, a platinum olefin complex, a platinum alkenylsiloxane complex, a platinum carbonyl complex, and platinum bisacetoacetate. The amount of catalyst used is not particularly limited as long as the desired reaction proceeds.

[0065] After the addition reaction, it is preferable to carry out a step of removing low-boiling compounds such as the solvent, low-boiling substances derived from the raw materials, and unreacted raw materials, etc. This can prevent problems such as voids that may occur during epoxy resin molding due to remaining low-boiling substances and contact failures in electronic devices.

[0066] Filtration can be performed before or after the low-boiling-point removal step. In addition to being able to remove precipitated solids, filtration using a filter or adsorbent with an adsorption effect can also remove ionic impurities such as halogens and metals. Furthermore, before or after filtration, in order to reduce or remove unreacted raw materials such as unreacted polyether raw materials, high purity can be achieved by washing with a poor solvent for the synthesized co-modified silicone, such as methanol. Furthermore, the co-modified silicone of the present invention may be treated in its production stage using an organic wax (e.g., PEG #20000 (polyethylene oxide with a molecular weight of 20,000, melting point of approximately 65°C)) as an adsorbent, similar to that described in WO 2014 / 104257, to remove or reduce impurities and achieve high purity.

[0067] 2. Additive for Organic Resins As one aspect, the present invention provides an additive for organic resins (hereinafter also referred to as "additive of the present invention") containing the co-modified silicone described above in "1. Co-modified silicone." The matters described above in "1. Co-modified silicone" apply to the co-modified silicone contained in the additive of the present invention. The co-modified silicone of the present invention has excellent heat resistance and curability, improves the adhesion and interaction between the curable resin and the filler (preferably an inorganic filler), and has flexibility derived from the silicone skeleton. Therefore, when added to a curable resin composition, it has the advantage of reducing the coefficient of linear expansion (CTE) of the final cured product without impairing the curing reactivity, and giving a cured product that is flexible and has excellent adhesion.

[0068] The content of the co-modified silicone contained in the additive of one embodiment of the present invention is not particularly limited, and may be 30 to 100% by mass, 40 to 100% by mass, or 50 to 100% by mass relative to the total amount (100% by mass) of the additive. In some embodiments, the additive of the present invention may consist essentially of the compound of one embodiment of the present invention. As used herein, "consisting essentially of the compound of one embodiment of the present invention" means that other components, such as impurities, which are inevitably contained in the production process of the co-modified silicone and are difficult to separate from each other or do not require separation, may also be included. In this embodiment, the additive of the present invention may contain, for example, 30% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.0% by mass or less, or 0.5% by mass or less of other components relative to the total amount (100% by mass) of the additive. For example, unreacted polyether raw material remaining in the system after production of the co-modified silicone may be contained as is in the additive of the present invention without being separated.

[0069] In the additive of one embodiment of the present invention, the organic resin may be a thermosetting resin, a thermoplastic resin, or the like, but may also include, for example, an epoxy resin. That is, the additive of one embodiment of the present invention may be an additive for an epoxy resin. Epoxy resins will be described later.

[0070] 3. Curable Resin Composition One aspect of the present invention provides a curable resin composition (hereinafter also referred to as "the composition of the present invention") containing the co-modified silicone described above in "1. Co-modified silicone." The composition of one embodiment of the present invention contains an epoxy resin (A), a curing agent (B), a filler (C), and a compound (D) of one embodiment of the present invention. Each component constituting the composition of the present invention will be described in detail below. Note that the matters described above in "1. Co-modified silicone" apply to the compound (D) of one embodiment of the present invention.

[0071] 3.1 Epoxy Resin (A) The composition of one embodiment of the present invention contains an epoxy resin (A). The epoxy resin (A) is a curable resin having an epoxy group, and specific examples thereof include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, and glycidylamine-type epoxy resins. Examples of epoxy resins include epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, isocyanurate type epoxy resins, phenolphthalimidine type epoxy resins, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

[0072] Furthermore, from the viewpoint of obtaining a cured product having excellent heat resistance, the epoxy resin (A) preferably contains an epoxy resin containing an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. Specific examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, bisphenolol type epoxy resins, and glycidylamine type epoxy resins having an aromatic structure. resins, glycidyl ester type epoxy resins having an aromatic structure, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins having an aromatic structure, epoxy resins having a butadiene structure having an aromatic structure, alicyclic epoxy resins having an aromatic structure, heterocyclic epoxy resins, spiro ring-containing epoxy resins having an aromatic structure, cyclohexanedimethanol type epoxy resins having an aromatic structure, naphthylene ether type epoxy resins, trimethylol type epoxy resins having an aromatic structure, tetraphenylethane type epoxy resins having an aromatic structure, and the like.

[0073] The content of the epoxy resin (A) is, for example, 1% by mass or more, preferably 2% by mass or more, relative to 100% by mass of the total solid content of the composition. This allows the fluidity of the composition during molding to be appropriately set, improving filling properties. The content of the epoxy resin (A) is, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, relative to 100% by mass of the total solid content of the composition. Typically, the thermal expansion coefficient of a resin is greater than that of the filler (C) described below. Therefore, it is believed that thermal shrinkage can be further reduced by relatively reducing the amount of the epoxy resin (A). In other words, it is believed that warpage of the substrate can be further reduced. The total solid content of the composition refers to the sum of all components contained in the composition of one embodiment of the present invention, excluding the solvent.

[0074] 3.2 Curing Agent (B) The composition of one embodiment of the present invention contains a curing agent (B). The curing agent (B) is not particularly limited as long as it has the property of curing an epoxy resin. The curing agent (B) preferably contains a phenolic curing agent. Phenol-based curing agents are preferred in terms of the balance of flame resistance, moisture resistance, electrical properties, curability, storage stability, etc. Phenolic curing agents include monomers, oligomers, polymers, etc. having two or more phenolic hydroxyl groups in the molecule. The molecular weight, molecular structure, etc. are not particularly limited. More specifically, the phenolic curing agent includes novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac, and phenol-biphenyl novolac resin; polyvinylphenol; multifunctional phenolic resins such as trisphenylmethane-type phenolic resin; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; phenol aralkyl-type phenolic resins such as phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton, and naphthol aralkyl resins having a phenylene and / or biphenylene skeleton; and bisphenol compounds such as bisphenol A and bisphenol F.

[0075] Examples of the curing agent (B) other than the phenol-based curing agent include amine-based curing agents, acid anhydride-based curing agents, mercaptan-based curing agents, and catalyst-based curing agents. Specific examples of the amine-based curing agents include aliphatic polyamines and aromatic polyamines. Specific examples of the acid anhydride-based curing agents include alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), and aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA). Specific examples of the mercaptan-based curing agents include polymercaptan compounds such as polysulfides, thioesters, and thioethers. Specific examples of the catalyst-based curing agents include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole; and BF ３ The curing agent (B) may be used singly or in combination of two or more kinds.

[0076] The content of the curing agent (B) is, for example, 0.5% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, based on 100% by mass of the total solid content of the composition. This provides excellent fluidity during molding, improving filling and moldability. The content of the curing agent (B) is, for example, 9% by mass or less, preferably 8% by mass or less, more preferably 7% by mass or less, based on 100% by mass of the total solid content of the composition. This can contribute to further suppressing warpage of the substrate.

[0077] 3.3 Filler (C) The composition of one embodiment of the present invention includes a filler (C). The filler (C) may be an inorganic filler or an organic filler. Specific examples of inorganic fillers include silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, titanium white, aluminum hydroxide, magnesium hydroxide, talc, clay, mica, glass fiber, diamond, graphite, carbon nanotubes, graphene, and other carbon allotropes. Specific examples of organic fillers include styrene-type, butadiene-type, and acrylic-type rubber powders, silicone resin powders, silicone elastomer particles, silicone elastomer composite particles, silicone resin-coated silicone elastomer particles, and acrylic core-shell particles. The filler (C) may be used alone or in combination of two or more types. Furthermore, the filler (C) may be a combination of an inorganic filler and an organic filler. By replacing a portion of the inorganic filler with an organic filler, the coefficient of linear expansion (CTE) and modulus of elasticity can be reduced while maintaining the strength of the cured product. The particle shape can be spherical, plate-like, granular, fibrous, or woven, but a nearly spherical shape is preferred. Furthermore, mixing particles of different sizes can increase the loading amount. Furthermore, when the filler (C) is an inorganic filler, from the viewpoint of heat dissipation, it is also possible to partially or completely replace silica with alumina, silicon nitride, aluminum nitride, boron nitride, or the like. Among these, the filler (C) preferably contains an inorganic filler, and more preferably contains silica. Examples of silica include fused crushed silica, fused spherical silica, crystalline silica, and secondary agglomerated silica.

[0078] As described above, the filler (C) is typically particulate, and the particle shape may be, but is not limited to, a spherical shape. The average particle size of the filler (C) is not particularly limited, but is typically 0.1 to 100 μm, preferably 0.5 to 50 μm, and more preferably 1 to 20 μm. By having the average particle size within the above range, it is possible to ensure appropriate fluidity during curing. Furthermore, by making the average particle size relatively small (e.g., 1 to 20 μm) and combining particles of different average particle sizes, it is possible to improve the filling ability into narrow gaps in cutting-edge wafer-level packages, for example. The average particle size of the filler (C) can be determined by acquiring volumetric particle size distribution data using a laser diffraction / scattering particle size distribution analyzer and processing the data. Measurement is typically performed wet.

[0079] When the filler (C) is an inorganic filler such as silica, it may be surface-modified with a coupling agent such as a silane coupling agent or a titanium-based coupling agent. This suppresses aggregation of the inorganic filler, resulting in better fluidity. Furthermore, the affinity between the inorganic filler and other components is increased, improving the dispersibility of the inorganic filler. This is thought to contribute to improving the mechanical strength of the cured product and suppressing the occurrence of microcracks. The coupling agent for surface modification will be described later in the section on coupling agent (E).

[0080] The content of the filler (C) is, for example, 45% by mass or more, 55% by mass or more, preferably 70% by mass or more, and more preferably 85% by mass or more, relative to 100% by mass of the total solid content of the composition. By appropriately increasing the content of the filler (C), warping of the substrate can be further reduced. In addition, by appropriately increasing the content of the filler (C) and relatively reducing the resin component, thermal expansion change after the composition is cured can be reduced. Small thermal expansion change makes it easier to suppress deterioration of warping. In addition, the content of the filler (C) is, for example, 98% by mass or less, preferably 95% by mass or less, and more preferably 92% by mass or less, relative to 100% by mass of the total solid content of the composition. By appropriately reducing the content of the filler (C), it is possible to suppress deterioration of moldability due to reduced fluidity during molding.

[0081] 3.4 Compound (D) of One Aspect of the Present Invention The composition of one aspect of the present invention contains compound (D) of one aspect of the present invention. The structure and the like of compound (D) of one aspect of the present invention are as described above in "1. Co-modified silicone."

[0082] The content of compound (D) in one embodiment of the present invention is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more, relative to 100% by mass of the total solids content of the composition. This allows the cured product of the composition to be endowed with excellent heat resistance, a favorable low modulus of elasticity, and / or a favorable low coefficient of thermal expansion. Furthermore, the content of compound (D) in one embodiment of the present invention is, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, relative to 100% by mass of the total solids content of the composition. Compound (D) is typically used in the range of 0.1 to 10% by mass, relative to 100% by mass of the total solids content of the composition. This allows the composition to maintain an appropriate modulus of elasticity without excessively reducing strength.

[0083] 3.5 Coupling Agent (E) The composition of one embodiment of the present invention may optionally contain a coupling agent. By including the coupling agent (E), for example, it is possible to further improve adhesion to the substrate and improve the dispersibility of the filler (C) in the composition. Improved dispersibility of the filler (C) improves the homogeneity of the final cured product, which can contribute to improving the mechanical strength of the cured product.

[0084] Examples of the coupling agent (E) include known coupling agents such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, alkenylsilane such as vinylsilane or hexenylsilane, various silane compounds such as acrylic silane and methacrylic silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. The coupling agent (E) may be used alone or in combination of two or more. Also, known surface treatment agents such as silazane may be used in combination.

[0085] The content of the coupling agent (E) is, for example, 0.1% by mass or more, preferably 0.2% by mass or more, based on the total mass of the composition. The coupling agent (E) is generally used in a treatment amount ranging from 0.01 to 2% by mass, based on the total mass of the filler (C) being 100% by mass. The content of the coupling agent (E) is, for example, 2.0% by mass or less, preferably 1.0% by mass or less, based on the total mass of the composition.

[0086] 3.6 Other Components The composition of one embodiment of the present invention may contain other optional components as needed. Examples of such optional components include various additives such as pH adjusters, ion scavengers, flame retardants, colorants, release agents, stress reducing agents (excluding those corresponding to compound (D) of one embodiment of the present invention), antioxidants, and heavy metal deactivators. Specific examples of these include the substances listed in Patent Document 2 (see paragraphs

[0070] to

[0075] ), WO 2024 / 202136 (

[0083] to

[0086] ), and WO 2021 / 149727 (

[0090] to

[0093] ). When these optional components are contained, the content of each component varies depending on the type and application, but may be within a range that does not interfere with the effects of the present invention, for example, 0.1 to 15.0% by mass, preferably 0.1 to 10.0% by mass, and more preferably 0.2 to 5.0% by mass.

[0087] 3.7 Methods for Producing the Composition of the Present Invention, Methods for Forming a Cured Product, and Uses The composition of one embodiment of the present invention can be produced by uniformly mixing components (A) to (D) and optional components such as component (E). Mixing can be performed using appropriate equipment such as a mixer or blender. The resulting mixture can be melt-kneaded using a kneader, heated rolls, or the like, preferably at a temperature of 40°C to 130°C, and then cooled and solidified to produce a composition of one embodiment of the present invention (specifically, a liquid, solid, or hot-melt (also known as B-stage) curable epoxy resin composition). The composition may be pulverized into powder or granules. Alternatively, a powder / granular composition may be compressed into tablets. Furthermore, a sheet-like composition can be produced by placing the mixture of the composition on a pallet, cooling it, and then applying a press roll, roll rolling, or coating it with a solvent mixture to form a sheet.

[0088] The composition of one embodiment of the present invention can be optionally melted by heating or the like, and then cured by a known curing method depending on the type of curable resin, to form a cured product of the composition of one embodiment of the present invention. For example, when the composition of one embodiment of the present invention contains an epoxy resin, the composition can be optionally melted by heating, and then finally cured by heating. In this case, the temperature of the curing reaction is, for example, in the range of 100 to 300°C, preferably 150 to 250°C, more preferably 150 to 200°C, and even more preferably 170 to 180°C.

[0089] The cured product of one embodiment of the present invention has properties such as heat resistance, a low modulus of elasticity, and / or a low coefficient of thermal expansion, and therefore can be suitably used in semiconductor devices. More specifically, the cured product can be suitably used, for example, as an encapsulant for semiconductor elements, IC chips, etc., a pressure-sensitive adhesive for semiconductor devices, an adhesive, an underfill agent, an insulating material, a build-up material for package substrates, etc.

[0090] 4. Semiconductor Device and Method for Producing a Semiconductor Device As one aspect, the present invention provides a semiconductor device (hereinafter also referred to as "semiconductor device of the present invention") comprising the cured product described above in "3.7 Method for Producing the Composition of the Present Invention, Method for Forming a Cured Product, and Uses." Specific examples of the semiconductor device include those described above in "3.7 Method for Producing the Composition of the Present Invention, Method for Forming a Cured Product, and Uses."

[0091] Furthermore, as one aspect, the present invention provides a method for manufacturing a semiconductor device (hereinafter also referred to as "the method for manufacturing a semiconductor device of the present invention"), which includes curing the composition of one embodiment of the present invention.

[0092] As described above, the curable resin composition of the present invention, particularly the curable epoxy resin composition (powder, tablet, granule, etc.), can be suitably used as a heat-melting (B-stage material) sealing material for sealing semiconductor elements. The method for sealing semiconductor elements is not particularly limited, and can be performed by known methods such as conventional transfer molding and compression molding. The semiconductor package to which the cured product of the present invention can be applied is also not particularly limited, and can be used to seal various semiconductor packages described, for example, in JP-A-2020-063338, JP-A-2019-085514, JP-A-2020-023643, etc.

[0093] The method for producing a semiconductor device of the present invention is not particularly limited as long as it includes a step of curing the composition of the present invention at any stage in the production process of the semiconductor device. The method for producing a semiconductor device of the present invention may also include a step of encapsulating a semiconductor element with the cured product of one aspect of the present invention.

[0094] For example, a laminate having a large number of semiconductor elements such as ICs mounted thereon is placed in a cavity of a mold, and then the cavity is filled with a composition according to one embodiment of the present invention, which is then heated and cured, thereby producing a semiconductor device in which the semiconductor elements are encapsulated with the cured product according to one embodiment of the present invention.

[0095] The molding conditions can be appropriately selected depending on the molding method, the curability of the curable resin composition, the mold temperature, and the like. For example, the conditions for transfer molding using the curable epoxy resin composition of the present invention can be appropriately set depending on the type of material in the composition of one embodiment of the present invention and the type of semiconductor device to be manufactured. Typically, the mold temperature is 170 to 180°C, and the molding time can be selected depending on the mold temperature and curability, but is generally set to 10 to 600 seconds, or 30 to 120 seconds. After the initial curing, post-curing or heat treatment can be carried out for a period ranging from several seconds to several hours to complete the curing reaction.

[0096] Furthermore, the sheet-like composition described above can be used to manufacture a semiconductor device by flip-chip mounting, for example, as follows: That is, the sheet-like composition is placed on the electrode surface side of a semiconductor element having bonding bumps or on the bump bonding side of a circuit board, and the semiconductor element and the circuit board are bump-bonded and adhesively sealed with a resin, thereby manufacturing a semiconductor device by flip-chip mounting.

[0097] The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples. In the composition formula below, Me represents methyl (—CH ３ ) group, Me ３ SiO group (or Me ３ (Si group) as “M”, Me ２ The SiO group is represented as "D ," and the MeHSiO group is represented as "D Ｈ " and a unit in which the methyl group in M ​​and D is modified by any of the substituents is represented as "M Ｒ " and "D Ｒ " was written.

[0098] <Synthesis of co-modified silicone> Each property was measured by the following method. [GPC peak top molecular weight] GPC analysis was performed using THF as the elution solvent, Waters ACQUITY APC XT Columns (#186007253 x 1 + #186007003 x 1 + #186006995 x 2) as the column, and RI as the detector, and the peak top molecular weight was determined using a calibration curve with standard polystyrene.

[0099] [Viscosity] The viscosity of the composition at 25°C was measured using a VISCOMIC EMD E-type viscometer manufactured by Tokyo Keiki Co., Ltd.

[0100] [Volatile content (105°C)] 1 g of a sample was weighed into an aluminum dish with a diameter of 6 cm, and heated at 105°C for 1 hour, after which the volatile content was determined from the sample remaining. [Volatile content (175°C)] 1 g of a sample was weighed into an aluminum dish with a diameter of 6 cm, and heated at 175°C for 3 hours, after which the volatile content was determined from the sample remaining. [ １３ C NMR and ２９ Si NMR Analysis] The analysis was carried out using ECA500 manufactured by JEOL and deuterated benzene as the measurement solvent.

[0101] Synthesis Example 1 (Example): Synthesis of phenol-polyether modified silicone Step 1: Add a compound of the average composition formula MD ６１．９ DH ５．８ 433.7 g of methylhydrogenpolysiloxane represented by M, average composition formula CH ２ =CH-CH ２ -O-(C ２ H ４ O) １８ (C ３ H ６ O) ２５ -CH ３ 712.9 g of an allyl polyether represented by the formula (I) and 120.0 g of toluene were charged, and 0.81 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration: 0.3 wt%) was added at 25°C while stirring under a nitrogen flow. The reaction solution was heated to 85-95°C and reacted for 5 hours, after which 2 g was sampled and confirmed to have no problems with the reaction rate using the alkali decomposition gas generation method. Step 2: 53.9 g of 2-allylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.39 g of the same platinum catalyst solution as above were added to the reaction solution. The reaction was allowed to proceed for 4 hours at 85-95°C, and the reaction was confirmed to be complete by the same method. Step 3: Low-boiling point components such as toluene and unreacted materials were distilled off under reduced pressure at 130-160°C. Further filtration yielded 1090 g of a composition containing phenol-polyether-modified silicone 1 represented by the following structure as a light brown, uniform liquid. The following structure is１３ C NMR and ２９ The molecular weight was determined from Si NMR and the peak top molecular weight from GPC.

[0102] Synthesis Example 2 (Example): Synthesis of phenol-polyether modified silicone Step 1: Add a compound of the average composition formula MD ５４．４ DH ７．７ 154.7 g of methylhydrogenpolysiloxane represented by M, 3.0 g of α-methylstyrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 22.1 g of vinyltristrimethylsiloxysilane represented by the average composition formula CH2=CH-Si(OSiMe3)3, and 500.0 g of toluene were charged, and while stirring under a nitrogen flow, 0.42 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.3 wt%) was added at 25°C. The reaction solution was heated to 70-80°C and reacted for 5 hours, after which 2 g was sampled and the reaction rate was confirmed to be satisfactory using an alkali decomposition gas generation method. Step 2: The reaction solution was added with the average composition formula CH ２ =CH-CH ２ -O-(C ２ H ４ O) １８ (C ３ H ６ O) ２５ -CH ３ An additional 311.1 g of allyl polyether represented by the formula (I) and 0.21 g of the same platinum catalyst solution as above were added. The reaction solution was heated to 80-100°C and reacted for 5 hours, after which 2 g was sampled and confirmed to have no problems with the reaction rate using the alkali decomposition gas generation method. Step 3: To the reaction solution, an additional 37.0 g of 2-allylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.26 g of the same platinum catalyst solution as above were added. The reaction was carried out at 90-120°C for 5 hours, and the reaction was confirmed to be complete by the same method. Step 4: Low-boiling point components such as toluene and unreacted materials were distilled off under reduced pressure at 130-175°C. Further filtration was carried out to obtain 896 g of a composition containing phenol-polyether-modified silicone 2 represented by the following structure as a brown, homogeneous liquid. The following structure is １３ C NMR and ２９The molecular weight was determined from Si NMR and the peak top molecular weight from GPC.

[0103] Synthesis Example 3 (Example): Synthesis of phenol-polyether modified silicone Step 1: Add a compound of the average composition formula MD ５４．４ DH ７．７ 154.3 g of methylhydrogenpolysiloxane represented by M, 22.1 g of vinyltristrimethylsiloxysilane represented by the average composition formula CH2=CH-Si(OSiMe3)3, and 500.0 g of toluene were charged, and while stirring under a nitrogen flow, 0.21 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.3 wt%) was added at 25°C. The reaction solution was heated to 70-80°C and reacted for 3 hours, after which 2 g was sampled and the reaction rate was confirmed to be satisfactory using an alkali decomposition gas generation method. Step 2: The reaction solution was added with the average composition formula CH ２ =CH-CH ２ -O-(C ２ H ４ O) １８ (C ３ H ６ O) ２５ -CH ３ An additional 308.0 g of allyl polyether represented by the formula (I) and 0.67 g of the same platinum catalyst solution as above were added. The reaction solution was heated to 70-80°C and reacted for 5 hours, after which 2 g was sampled and confirmed to have no problems with the reaction rate using the alkali decomposition gas generation method. Step 3: To the reaction solution, 40.0 g of 2-allylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.84 g of the same platinum catalyst solution as above were added. The reaction was carried out for 5 hours at 90-120°C, and the reaction was confirmed to be complete by the same method. Step 4: Low-boiling point components such as toluene and unreacted materials were distilled off under reduced pressure at 120-180°C. Further filtration was carried out to obtain 848 g of a composition containing phenol-polyether-modified silicone 3 represented by the following structure as a brown, homogeneous liquid. The following structure is １３ C NMR and ２９ The molecular weight was determined from Si NMR and the peak top molecular weight from GPC.

[0104] Synthesis Example 4 (Example): Synthesis of phenol-polyether modified silicone Step 1: Add a compound of the average composition formula MD ５４．４ DH ７．７ 153.4 g of methylhydrogenpolysiloxane represented by M, 21.9 g of vinyltristrimethylsiloxysilane represented by the average composition formula CH2=CH-Si(OSiMe3)3, and 500.0 g of toluene were charged, and while stirring under a nitrogen flow, 0.20 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration 0.3 wt%) was added at 25°C. The reaction solution was heated to 70-80°C and reacted for 3 hours, after which 2 g was sampled and confirmed to have no problems with the reaction rate using an alkali decomposition gas generation method. Step 2: The reaction solution was added with a toluene solution of the average composition formula CH ２ =CH-CH ２ -O-(C ２ H ４ O) １８ (C ３ H ６ O) ２５ -CH ３ An additional 308.0 g of allyl polyether represented by the formula (I) and 0.44 g of the same platinum catalyst solution as above were added. The reaction solution was heated to 70-80°C and reacted for 5 hours, after which 2 g was sampled and confirmed to have no problems with the reaction rate using the alkali decomposition gas generation method. Step 3: To the reaction solution, 40.0 g of eugenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1.53 g of the same platinum catalyst solution as above were added. The reaction was carried out for 5 hours at 90-120°C, and the reaction was confirmed to be complete by the same method. Step 4: Low-boiling point components such as toluene and unreacted materials were distilled off under reduced pressure at 120-190°C. Further filtration yielded 853 g of a composition containing phenol-polyether-modified silicone 4 represented by the following structure as a brown, homogeneous liquid. The following structure is １３ C NMR and ２９ The molecular weight was determined from Si NMR and the peak top molecular weight from GPC.

[0105] The structural information of the compounds synthesized in Synthesis Examples 1 to 4 is shown in Table 1. The volatile content of DOWSIL (registered trademark) FZ-3736 (epoxy polyether-modified silicone manufactured by Dow-Toray, viscosity 2,360 mPa s), which was prepared as a comparative compound, was 0.5% at 105°C and 66.1% at 175°C.

[0106] When the heat resistance of the compounds of Synthesis Examples 1 to 4 and the comparative compounds is compared, the volatile content (at 105°C) is close to 0% in all cases, meaning that the volatile component is low, but in Comparative Example 1, nearly 66% was lost at 175°C. On the other hand, the co-modified silicones of Synthesis Examples 1 to 4, which have phenolic hydroxyl groups, have a volatile content kept to around 15 to 20%, making them suitable for use in high temperature ranges.

[0107] <Preparation of Curable Resin Composition> Each component in the blending amount (parts by mass) shown in Table 2 was mixed at room temperature using a mixer to obtain a mixture. Next, the mixture was heated and kneaded at a temperature of 70°C or higher and 110°C or lower. Then, it was cooled to room temperature to obtain a curable resin composition. Details of each raw material component are as follows. (Epoxy resins) Epoxy resin 1: Biphenyl-type epoxy resin (Mitsubishi Chemical Corporation, product number: YX-4000H) Epoxy resin 2: Mixture of trisphenylmethane-type epoxy resin (75% by mass) and biphenyl-type epoxy resin (25% by mass) (Mitsubishi Chemical Corporation, product number: YL6677) (Curing agent) Curing agent 1: Trisphenylmethane-type phenolic resin (Air Water Inc., HE910-20) (Inorganic filler) Inorganic filler 1: Spherical silica with an average particle size of 19 μm (Nippon Steel Sumikin Materials Co., Ltd., Micron Company, product number: S430-5) Inorganic filler 2: Spherical silica with an average particle size of 0.5 μm (Admatechs Co., Ltd., product number: SC-2500-SQ) Inorganic filler 3: Spherical silica with an average particle size of 1.5 μm (Admatechs Co., Ltd., product number: SC-5500-SQ) (Curing accelerator) Curing accelerator 1: 2,3-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.) Curing accelerator 2: triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) (coupling agent) Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Dow-Toray Industries, Inc., Z-6883) (mold release agent) Mold release agent: glycerin trimontanic acid ester (Clariant Japan Co., Ltd., Ricorb WE-4) Co-modified silicone compound: As an example, the phenol-polyether-modified silicone of Synthesis Example 1 was used, and as a comparative example, DOWSIL (registered trademark) FZ-3736 (epoxy-polyether-modified silicone manufactured by Dow-Toray Industries, Inc.) of Comparative Example 1 was used.

[0108] <Evaluation of Mechanical Properties of Cured Products> Each prepared curable resin composition was cured by the following method, and the mechanical properties of the resulting cured products were evaluated. [Preparation of Cured Products] Cured products were prepared using each curable resin composition listed in Table 2. A mold consisting of upper, middle, and lower molds was used for molding. A mold with a cutout measuring 100 mm x 10 mm x 4 mm was used as the middle mold. An amount of curable resin composition corresponding to the volume of the cutout of the middle mold placed on the lower mold was placed and sandwiched between the upper mold and a manual hydraulic heating press was used to mold the cured product at a mold temperature of 175°C, 2.4 MPa, and a curing time of 10 minutes, yielding a test piece measuring 100 mm long, 10 mm wide, and 4 mm thick. The resulting test piece was then heat-treated at 175°C for 4 hours and then allowed to cool. In this manner, a cured product for evaluation was prepared.

[0109] [Linear expansion coefficient of cured product] The linear expansion coefficient of a 4 mm x 4 mm x 10 mm cured product was measured using a thermomechanical analyzer (TMA7100, manufactured by Hitachi High-Tech Science Corporation). The measurement was performed under conditions of a temperature rise rate of 5°C / min from -30°C to 300°C. The measurement data was analyzed, and the average linear expansion coefficient [ppm / °C] between 0°C and 140°C was designated CTE1, and the average linear expansion coefficient [ppm / °C] between 180°C and 220°C was designated CTE2.

[0110] [Flexural Modulus and Flexural Strength of Cured Product] The flexural modulus [MPa (N / mm2)] and flexural strength [MPa (N / mm2)] of a cured product measuring 100 mm long x 10 mm wide x 4 mm thick at 25°C were evaluated using a tensile tester (Shimadzu Corporation, AGS-X, 10N-10kN).

[0111] [Spiral Flow Evaluation] Using a transfer molding machine (manufactured by Takara Manufacturing Co., Ltd.), the resin composition of each example was injected into a spiral flow measurement mold conforming to ASTM D3123-09 under conditions of a mold temperature of 175°C, an injection pressure of 12 MPa, and a dwell time of 180 seconds, followed by curing, and the spiral flow was measured. The spiral flow is measured in cm. The curable resin composition containing a co-modified silicone compound not having a group with a phenolic hydroxyl group (Comparative Example 2) had a spiral flow of 141.0 cm, while the curable resin composition containing a phenol-polyether-modified silicone (Example 1) had a spiral flow of 162.6 cm.

[0112] As shown in Table 2 and the above results, evaluation using a curable resin composition containing a phenol-polyether-modified silicone (Example 1) yielded favorable results, including low modulus of elasticity, CTE1, and CTE2, and excellent fluidity (flowability) during molding. On the other hand, a curable resin composition not containing a co-modified silicone compound (Comparative Example 1) yielded high values ​​for modulus of elasticity, CTE1, and CTE2. Furthermore, evaluation of a curable resin composition containing a co-modified silicone compound not containing a group having a phenolic hydroxyl group (Comparative Example 2) yielded a lower modulus of elasticity, but the effect of reducing CTE1 and CTE2 was insufficient, resulting in poor fluidity during molding. The evaluation of Example 1 was intended to seal semiconductor packages, etc., but the evaluation can also be applied to underfills and other resin compositions.

[0113]

Claims

1. A copolymerized silicone containing a phenolic hydroxyl group-containing structure and a polyether structure in the molecule.

2. The copolymerized silicone according to claim 1, having a viscosity at 25°C in the range of 50 to 100,000 mPa·s.

3. Average compositional formula (1): R １ ａ R ２ ｂ R ３ ｃ R ４ ｄ SiO （４－ａ－ｂ－ｃ－ｄ）／２ A covariant silicone represented by the formula, wherein in the average compositional formula (1), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ２ each independently represents a group having a phenolic hydroxyl group represented by the following general formula (2), and R ３ each independently represents a group containing a polyether structure represented by the following general formula (3), and R ４ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a silicon-containing organic group; a, b, c, and d satisfy b > 0, c > 0, a ≥ 0, d ≥ 0, and a + b + c + d = 4. The covariant silicone according to claim 1. (In general formula (2), ２’ represents a divalent hydrocarbon group having 1 to 18 carbon atoms bonded to a silicon atom, and ２” each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that at least one of ２” is a hydroxyl group.) (In general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms, a represents a number from 5 to 100, and Z represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group having 1 to 12 carbon atoms.) 4. Average composition formula (2): (R １ ２ R'SiO １／２ ), ａ (R ２ R'SiO ２／２ ), ｂ (R ３ R'SiO ２／２ ), ｂ’ (R ４ R'SiO ２／２ ), ｂ” (R'SiO ３／２ ), ｃ (SiO ４／２ ), ｄ which is a covariant silicone represented by the formula: In the above average composition formula (2), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ２ each independently represents a group having a phenolic hydroxyl group represented by the following general formula (2), and R ３ each independently represents a group containing a polyether structure represented by the following general formula (3), and R ４ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a silicon-containing organic group, and R' each independently represents R １ , R ２ , R ３ or R ４ any one of them, where a, b, b', b", c and d satisfy b > 0, b' > 0, a ≥ 0, b" ≥ 0, c ≥ 0, d ≥ 0, and 20 ≤ a + b + b' + b" + c + d ≤ 1000. The covariant silicone according to claim 1. (In the general formula (2), R ２’ represents a divalent hydrocarbon group having 1 to 18 carbon atoms bonded to a silicon atom, and R ２” each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, provided that at least one of R ２” is a hydroxyl group.) (In general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms, a represents a number from 5 to 100, and Z represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group having 1 to 12 carbon atoms.) 5. The covariant silicone according to claim 1, having a structure represented by the following general formula (1). (In general formula (1), R １ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ２ each independently represents a group having a phenolic hydroxyl group represented by the following general formula (2), and R ３ each independently represents a group containing a polyether structure represented by the following general formula (3), and R ４ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a silicon-containing organic group. X each independently represents R １ , R ２ , R ３ or R ４ represents any one of them. m represents a number from 0 to 100, provided that when m = 0, at least one of X is R ２ . n represents a number from 0 to 100, provided that when n = 0, at least one of X is R ３ . When m = n = 0, two Xs in the molecule are R ２ and R ３ respectively. l represents a number from 0 to 1000.) (In general formula (2), R ２’ represents a divalent hydrocarbon group having 1 to 18 carbon atoms bonded to a silicon atom, and R ２” each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, provided that at least one of R ２” is a hydroxyl group.) (In general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms, a represents a number from 5 to 100, and Z represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms or an acyl group having 1 to 12 carbon atoms.) 6. An additive for an organic resin, comprising the copolymerized silicone according to any one of claims 1 to 5.

7. The additive for an organic resin according to claim 6, wherein the organic resin contains an epoxy resin.

8. A curable resin composition, comprising the copolymerized silicone according to any one of claims 1 to 5.

9. The curable resin composition according to claim 8, wherein the curable resin contains an epoxy resin.

10. A cured product obtained by curing the curable resin composition according to claim 8 or 9.

11. A semiconductor device, comprising the cured product according to claim 10.

12. A method for manufacturing a semiconductor device, comprising curing the curable resin composition according to claim 8 or 9.

Images