WO2015186722A1

WO2015186722A1 - Curable resin composition, cured product, sealing material, and semiconductor device

Info

Publication number: WO2015186722A1
Application number: PCT/JP2015/065989
Authority: WO
Inventors: 中川泰伸; 板谷亮
Original assignee: 株式会社ダイセル
Priority date: 2014-06-06
Filing date: 2015-06-03
Publication date: 2015-12-10
Also published as: CN106459584A; JPWO2015186722A1; JP6474801B2; KR20170016432A; TW201604240A

Abstract

　The purpose of the present invention is to provide a curable resin composition useful for sealing semiconductor elements (particularly optical semiconductor elements), said curable resin composition having both heat resistance and corrosion resistance against corrosive gases.　This curable resin composition is characterized by including a polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C), and a carboxylate (E) of a rare-earth metal element, wherein a polyorganosiloxane not containing an aryl group is included as the polyorganosiloxane (A), and a ladder-type silsesquioxane is included as the silsesquioxane (B).

Description

Curable resin composition, cured product, sealing material, and semiconductor device

The present invention relates to a curable resin composition, a cured product obtained using the curable resin composition, a sealing material, and a semiconductor device obtained using the sealing material. This application claims the priority of Japanese Patent Application No. 2014-117841 for which it applied to Japan on June 6, 2014, and uses the content here.

In a semiconductor device that requires high heat resistance and high withstand voltage, a material covering a semiconductor element is generally required to have a heat resistance of about 150 ° C. or higher. In particular, a material (encapsulant) that covers an optical material such as an optical semiconductor element is required to have excellent physical properties such as transparency and flexibility in addition to heat resistance. Currently, for example, as a sealing material in a backlight unit of a liquid crystal display, silicone-based resin materials such as Patent Documents 1 to 4 are used.

JP 2006-206721 A JP 2007-031619 A JP 2002-314140 A JP 2011-177893 A

In Patent Document 1, as a material having high heat resistance and good heat dissipation, at least one first organosilicon polymer having a crosslinked structure of siloxane (Si—O—Si conjugate) and a linear shape of siloxane are disclosed. A synthetic polymer compound containing at least one kind of a third organosilicon polymer having a molecular weight of 20,000 to 800,000, which is linked to at least one second organosilicon polymer having a linking structure by a siloxane bond. Is disclosed. However, the physical properties of cured products of these compounds are not yet satisfactory.

Patent Document 2 discloses an optical element sealing resin composition excellent in transparency, UV resistance, and heat resistance colorability, which contains an aliphatic carbon-carbon unsaturated bond and does not contain an Si—H bond. At least selected from the group consisting of a liquid silsesquioxane of a type structure and a liquid silsesquioxane of a saddle type structure containing an Si—H bond and no aliphatic carbon-carbon unsaturated bond A resin composition for sealing an optical element containing one kind of silsesquioxane as a resin component is disclosed. And it describes that the transmittance | permeability fall after heating at 150 degreeC for 100 hours becomes comparatively small. However, the heat resistance is not yet satisfactory, and the cured product of the resin composition containing a cage silsesquioxane is relatively hard and lacks flexibility, so that there is a problem that cracks and cracks are likely to occur. is there.

Patent Document 3 discloses an organic compound such as triallyl isocyanurate containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and at least two SiH groups in one molecule. A curable composition containing a chain-containing and / or cyclic polyorganosiloxane-containing compound and a hydrosilylation catalyst as an essential component is disclosed. However, physical properties such as heat resistance and crack resistance of these materials are still not satisfactory.

On the other hand, metal materials such as electrodes in an optical semiconductor device are easily corroded by corrosive gas, and there is a problem that current-carrying characteristics (for example, current-carrying characteristics in a high-temperature environment) deteriorate with time. Therefore, the sealing material for optical semiconductors is required to have a high barrier property against corrosive gas (corrosion resistance against corrosive gas). However, sealing materials using conventional silicone resin materials disclosed in Patent Documents 1 to 3 and the like cannot be said to have sufficient barrier properties against corrosive gases.

Patent Document 4 discloses (A) a polysiloxane having at least two alkenyl groups bonded to silicon atoms, (B) a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms, and (C) hydrosilyl. And (D) a zinc compound, the component (D) is contained in an amount of 0.1 to 5 parts by mass relative to a total of 100 parts by mass of the component (A) and the component (B), A silicone resin composition having excellent sulfidation properties is disclosed. However, although corrosion resistance against hydrogen sulfide (H ₂ S) is disclosed, there is no description about corrosion resistance against other corrosive gases. Also, the heat resistance was not satisfactory.

As a sealing material for next-generation light sources, higher heat resistance has been demanded. In addition, with the miniaturization and thinning of equipment, a material that covers a semiconductor element has been required to have better heat resistance.
Furthermore, since there are a plurality of types of corrosive gases that corrode semiconductor devices, it has been required to have barrier properties against a wide variety of corrosive gases. In particular, the present inventors have at least a barrier property against hydrogen sulfide (H ₂ S) gas (H ₂ S corrosion resistance) and a barrier property against sulfur oxide (SO _x ) gas as a material covering the semiconductor element. It has been found that it is important to combine (SO _x corrosion resistance).

Accordingly, the object of the present invention is to provide heat resistance (especially heat resistance of 180 ° C. or more) and corrosion resistance against corrosive gases (particularly barrier properties against hydrogen sulfide (H ₂ S) gas (H ₂ S corrosion resistance). ) and sulfur oxides (combines SO _x) barrier properties against gases (resistance SO _x corrosion)), to provide a useful cure resin composition for the sealing purpose of the semiconductor device (particularly an optical semiconductor element) It is in. Another object of the present invention is to provide a curable resin composition useful for sealing semiconductor devices (especially optical semiconductor devices), which has transparency and flexibility, and also has heat resistance and corrosion resistance against corrosive gases. To provide things.

When the present inventors add a carboxylate of a rare earth metal atom to a specific silicone resin, an increase in hardness after heating of the cured product is suppressed, and in addition to a remarkable improvement in heat resistance, H ₂ S corrosion resistance Also found to improve. Furthermore, by adding a silsesquioxane containing a silsesquioxane ladder and an isocyanurate compound to a specific silicone resin and a carboxylate of a rare earth metal atom, heat resistance, H ₂ S corrosion resistance (H ₂ S gas barrier property) without reducing, it found that excellent resistance to SO _x corrosion (SO _x gas barrier properties), thereby completing the present invention.

That is, the present invention includes a polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C), and a carboxylate (E) of a rare earth metal atom. There is provided a curable resin composition comprising a polyorganosiloxane having no group and a ladder-type silsesquioxane as the silsesquioxane (B).

It is preferable that the ladder-type silsesquioxane includes a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule.

It is preferable that the ladder-type silsesquioxane includes a ladder-type silsesquioxane having a Si—H bond in the molecule.

It is preferable that the ladder-type silsesquioxane includes a ladder-type silsesquioxane having an aryl group in the molecule.

As the isocyanurate compound (C), the formula (1)

[In the formula (1), R ^x , R ^y and R ^z are the same or different and represent a group represented by the formula (2) or a group represented by the formula (3).

[In Formula (2) and Formula (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
It is preferable that the isocyanurate compound represented by these is included.

The compound represented by the formula (1) is preferably a compound in which at least one of R ^x , R ^y and R ^z is a group represented by the formula (3).

As the carboxylate (E) of the rare earth metal atom, it is preferable to contain yttrium carboxylate.

The carboxylate (E) of the rare earth metal atom is preferably a mixture of cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, and neodymium carboxylate.

Of Si—H groups present in the compound contained in the curable resin composition relative to the total number of aliphatic carbon-carbon double bonds bonded to silicon atoms present in the compound contained in the curable resin composition The ratio of the total number is preferably less than 1.

Furthermore, it is preferable that a silane coupling agent (D) is included.

Furthermore, the present invention provides a cured product obtained by curing the curable resin composition.

Furthermore, this invention provides the sealing material obtained using the said curable resin composition.

Furthermore, the present invention provides a semiconductor device obtained using the sealing material.

That is, the present invention relates to the following.
[1] A polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C), and a carboxylate (E) of a rare earth metal atom. The polyorganosiloxane (A) has an aryl group. A curable resin composition comprising a polyorganosiloxane that does not contain a ladder-type silsesquioxane as silsesquioxane (B).
[2] The curable resin composition according to [1], wherein the ladder-type silsesquioxane includes a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule.
[3] The curable resin composition according to [1] or [2], wherein the ladder-type silsesquioxane includes a ladder-type silsesquioxane having a Si—H bond in the molecule.
[4] The curable resin composition according to any one of [1] to [3], wherein the ladder-type silsesquioxane includes a ladder-type silsesquioxane having an aryl group in the molecule.
[5] The curable resin composition according to any one of [1] to [4], which contains an isocyanurate compound represented by the formula (1) as the isocyanurate compound (C).
[6] The isocyanurate compound represented by the formula (1) is an isocyanurate compound in which one or more of R ^x , R ^y , and R ^z are groups represented by the formula (3) [ [5] The curable resin composition according to [5].
[7] The curable resin composition according to any one of [1] to [6], wherein the carboxylate (E) of the rare earth metal atom contains yttrium carboxylate.
[8] The rare earth metal carboxylate (E) is a mixture of cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, and neodymium carboxylate, [1] to [6] Curable resin composition.
[9] Si— present in the compound contained in the curable resin composition relative to the total number of aliphatic carbon-carbon double bonds bonded to silicon atoms present in the compound contained in the curable resin composition The curable resin composition according to any one of [1] to [8], wherein the ratio of the total number of H groups is less than 1.
[10] The curable resin composition according to any one of [1] to [9], further including a silane coupling agent (D).
[11] The polyorganosiloxane contained in the polyorganosiloxane (A) is a linear or branched polyorganosiloxane having a hydrosilyl group or a group having an aliphatic carbon-carbon unsaturated bond [1] ] The curable resin composition according to any one of [10] to [10].
[12] The curable resin composition according to any one of [1] to [11], wherein the polyorganosiloxysilalkylene is a polyorganosiloxysilalkylene having a structure represented by the formula (6).
[13] The curing according to any one of [1] to [12], wherein the proportion of the polyorganosiloxane having no aryl group is 50% by weight or more based on the total amount of the polyorganosiloxane (A). Resin composition.
[14] The curable property according to any one of [1] to [13], wherein the content of the polyorganosiloxane (A) is 55 to 95% by weight based on the total amount of the curable resin composition. Resin composition.
[15] The curability according to any one of [1] to [14], wherein the content of the ladder-type silsesquioxane is 50% by weight or more based on the total amount of the silsesquioxane (B). Resin composition.
[16] The content of the ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule is 20% by weight or more based on the total amount of the silsesquioxane (B) [2] The curable resin composition according to any one of [15] to [15].
[17] The content of the ladder-type silsesquioxane having a Si—H bond in the molecule is 10% by weight or more based on the total amount of the silsesquioxane (B) [3] to [16] The curable resin composition as described in any one of these.
[18] The curing according to any one of [1] to [17], wherein the content of the silsesquioxane (B) is 5 to 45% by weight with respect to the total amount of the curable resin composition. Resin composition.
[19] The content of the isocyanurate compound (C) is 0.01 to 10% by weight based on the total amount of the curable resin composition, according to any one of [1] to [18] Curable resin composition.
[20] The content of the silane coupling agent (D) is 0.01 to 15% by weight, based on the total amount of the curable resin composition, [1] to [19] Curable resin composition.
[21] Any of [1] to [20], wherein the content of the carboxylate (E) of the rare earth metal atom is 0.008 to 1.000% by weight with respect to the total amount of the curable resin composition. The curable resin composition according to claim 1.
[22] A cured product obtained by curing the curable resin composition according to any one of [1] to [21].
[23] A sealing material obtained using the curable resin composition according to any one of [1] to [21].
[24] A semiconductor device obtained using the sealing material according to [23].

Since the curable resin composition of the present invention has the above-described configuration, it has heat resistance and barrier properties against a plurality of corrosive gases such as H ₂ S gas and SO _x gas (H ₂ S corrosion resistance, SO resistance). _x Excellent corrosion resistance. Moreover, it is excellent also in transparency, a softness | flexibility, reflow resistance, adhesiveness, etc. Therefore, the curable resin composition of the present invention is useful as a sealing material for semiconductor devices, particularly as a sealing material for optical semiconductor elements such as LEDs. Further, the curable resin composition of the present invention is useful as a sealing material for next-generation light sources that are required to have heat resistance in an environment of an unprecedented high temperature (for example, 180 ° C. or higher). Furthermore, an optical semiconductor device excellent in quality, durability, and the like can be obtained by sealing the optical semiconductor element with a cured product of the curable resin composition of the present invention.

The curable resin composition of the present invention includes at least a polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C), and a carboxylate (E) of a rare earth metal atom. The polyorganosiloxane (A) contains at least a polyorganosiloxane having no aryl group. The silsesquioxane (B) includes at least a ladder-type silsesquioxane.

[Polyorganosiloxane (A)]
The polyorganosiloxane (A) in the curable resin composition of the present invention is a polyorganosiloxane having a main chain composed of siloxane bonds (Si—O—Si) and having no aryl group. Including at least.
In this specification, a polyorganosiloxane having a main chain composed of siloxane bonds (Si—O—Si) may be simply referred to as “polyorganosiloxane”.

The polyorganosiloxane contained in the polyorganosiloxane (A) is not particularly limited. For example, polyorganosiloxane having no aryl group, polyorganosiloxane having an aryl group, -Si-O- group ( In addition to a siloxy group), a polyorganosiloxane having an —Si—A— group [silalkylene group; A represents a divalent hydrocarbon group (for example, an alkylene group)] and no aryl group (hereinafter referred to as the “siloxy group”). Polyorganosiloxane is referred to as “polyorganosiloxysilalkylene”).
The polyorganosiloxane contained in the polyorganosiloxane (A) may be a linear or branched polyorganosiloxane having a hydrosilyl group or a group having an aliphatic carbon-carbon unsaturated bond. Examples of the polyorganosiloxane contained in the polyorganosiloxane (A) include polyorganosiloxanes having a well-known and commonly used silicone skeleton such as a dimethyl silicone skeleton (polydimethylsiloxane).
In addition, silsesquioxane (B) is not contained in the polyorganosiloxane contained in polyorganosiloxane (A).

The polyorganosiloxane contained in the polyorganosiloxane (A) may be a polyorganosiloxane having a straight chain and / or a branched chain.

The aryl group in the polyorganosiloxane having an aryl group is not particularly limited, and examples thereof include C _6-14 aryl groups (particularly C _6-10 aryl groups) such as a phenyl group and a naphthyl group. These aryl groups may be substituents (groups directly bonded to silicon atoms) possessed by silicon atoms in the polyorganosiloxane (A).

The polyorganosiloxane having no aryl group is preferably a polyorganosiloxane that does not substantially contain an aryl group in the molecule. Specifically, the content of the aryl group in the polyorganosiloxane having no aryl group (100% by weight) is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, The content is more preferably 0.1% by weight or less, and particularly preferably no aryl group is present in the polyorganosiloxane (A). When the content of the aryl group is 0.5% by weight or less (particularly due to the absence of the aryl group), desired physical properties (such as heat resistance and refractive index) are easily obtained in the cured product. The content of aryl groups in the polyorganosiloxane can be measured by ¹ H-NMR.

Examples of the substituent of the silicon atom in the polyorganosiloxane contained in the polyorganosiloxane (A) include a group having a Si—H bond, a substituted or unsubstituted hydrocarbon group (preferably an alkyl group, an alkenyl group). , Cycloalkyl group or cycloalkenyl group), hydroxyl group, alkoxy group, alkenyloxy group, acyloxy group, mercapto group (thiol group), alkylthio group, alkenylthio group, carboxyl group, alkoxycarbonyl group, amino group or substituted amino group Examples include a group (mono or dialkylamino group, acylamino group, etc.), an epoxy group, a halogen atom, and the like.

As the alkyl group, a C _1-10 alkyl group is preferable, and a C _1-4 alkyl group is more preferable. The alkenyl group is preferably a C _2-10 alkenyl group, and more preferably a C _2-4 alkenyl group. The cycloalkyl group is preferably a C _3-12 cycloalkyl group. As the cycloalkenyl group, a C _3-12 cycloalkenyl group is preferable. As the alkoxy group, a C _1-6 alkoxy group is preferable. The alkenyloxy group is preferably a C _1-6 alkenyloxy group. As the acyloxy group, a C _1-6 acyloxy group is preferable. As the alkylthio group, a C _1-6 alkylthio group is preferable. As the alkenylthio group, a C _1-6 alkenylthio group is preferable. The alkoxycarbonyl group is preferably a C _1-6 alkoxycarbonyl group. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are preferable.

As the substituent, at least one substituent selected from a group having a Si—H bond and a substituted or unsubstituted hydrocarbon group (preferably an alkyl group or an alkenyl group) is preferable.

The position of the substituent in the polyorganosiloxane is not particularly limited, and may be located in the side chain or at the terminal with respect to the main chain composed of the siloxane bond (Si—O—Si). May be.

The polyorganosiloxane having a hydrosilyl group may be a polyorganosiloxane having an aliphatic carbon-carbon unsaturated bond at the same time. Further, the polyorganosiloxane having an aliphatic carbon-carbon unsaturated bond may be a polyorganosiloxane having a hydrosilyl group at the same time.

Examples of the divalent hydrocarbon group (A) in the silalkylene group of the polyorganosiloxysilalkylene include, for example, an alkylene group (such as a linear or branched alkylene group having 1 to 18 carbon atoms), divalent The alicyclic hydrocarbon group is preferably a linear or branched alkylene group having 2 to 4 carbon atoms (particularly an ethylene group).

Examples of the polyorganosiloxysilalkylene include polyorganosiloxysilalkylene having a structure represented by the following formula (6).

In formula (6), R ²¹ to R ²⁶ are the same or different and each represents a hydrogen atom, a monovalent hydrocarbon group, or a monovalent heterocyclic group. However, at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond.

Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group; a monovalent alicyclic hydrocarbon group; a monovalent group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded to each other. Etc.

Examples of the monovalent heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

Examples of the monovalent aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include straight chain or branched chain C _1- such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group. ₂₀ alkyl group (preferably C _1-10 alkyl group, more preferably C _1-4 alkyl group) and the like. Examples of the alkenyl group include vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group and 2-pentenyl group. C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-4 alkenyl groups) such as 3-pentenyl group, 4-pentenyl group and 5-hexenyl group. Examples of the alkynyl group include C _2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C _2-10 alkynyl group, more preferably C _2-4 alkynyl group).

Examples of the monovalent alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group; and a C ₃₋ group such as a cyclohexenyl group. ₁₂ cycloalkenyl groups; C _4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl group and bicycloheptenyl group.

In addition, examples of the monovalent group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group.

The monovalent hydrocarbon group and the monovalent heterocyclic group may have a substituent.
That is, in the monovalent hydrocarbon group or the monovalent heterocyclic group, at least one hydrogen atom of the monovalent hydrocarbon group or monovalent heterocyclic group exemplified above is replaced with a substituent. Further, it may be a monovalent hydrocarbon group or a monovalent heterocyclic group. The substituent preferably has 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms. Specific examples of the substituent include a halogen atom; a hydroxyl group; an alkoxy group; an alkenyloxy group; an acyloxy group; an mercapto group; an alkylthio group; an alkenylthio group; a carboxyl group; Or a dialkylamino group; an acylamino group; an epoxy group-containing group; an oxetanyl group-containing group; an acyl group; an oxo group; an isocyanate group; a group in which two or more of these are bonded via a C _1-6 alkylene group, if necessary. Can be mentioned.

Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group include C _1-6 alkoxy groups (preferably C _1-4 alkoxy groups) such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group. Examples of the alkenyloxy group include a C _2-6 alkenyloxy group (preferably a C _2-4 alkenyloxy group) such as an allyloxy group. Examples of the acyloxy group include C _1-12 acyloxy groups such as an acetyloxy group, a propionyloxy group, and a (meth) acryloyloxy group.

Examples of the alkylthio group include C _1-6 alkylthio groups (preferably C _1-4 alkylthio groups) such as a methylthio group and an ethylthio group. Examples of the alkenylthio group include C _2-6 alkenylthio groups (preferably C _2-4 alkenylthio groups) such as an allylthio group. Examples of the alkoxycarbonyl group include C _1-6 alkoxy-carbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Examples of the mono- or dialkylamino group include mono- or di-C _1-6 alkylamino groups such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group. Examples of the acylamino group include C _1-11 acylamino groups such as an acetylamino group and a propionylamino group. Examples of the epoxy group-containing group include a glycidyl group, a glycidyloxy group, and a 3,4-epoxycyclohexyl group. As said oxetanyl group containing group, an ethyl oxetanyloxy group etc. are mentioned, for example. As said acyl group, an acetyl group, a propionyl group, a benzoyl group etc. are mentioned, for example.

Examples of the monovalent hydrocarbon group and monovalent heterocyclic group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, decyl group, pyridyl group, furyl group, and thienyl group. Vinyl group, allyl group, substituted hydrocarbon group (for example, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidylpropyl group, 3-methacryloxypropyl group, 3-acryloxypropyl group, N-2- (aminoethyl) -3-aminopropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, etc.) are preferred.

R ²¹ to R ²⁶ in the above formula (6) may be the same or different.

In the formula (6), R ²⁷ represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group include a linear or branched chain group having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Of the alkylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. And divalent cycloalkylene groups (including cycloalkylidene groups) such as a silene group, 1,4-cyclohexylene group, and cyclohexylidene group. Among them, R ²⁷ is a linear or branched alkylene group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 2 to 4 carbon atoms). Is more preferable, and an ethylene group is more preferable.

In formula (6), r represents an integer of 1 or more. When r is an integer of 2 or more, the structures in parentheses to which r is attached may be the same or different. When the structures in parentheses marked with r are different from each other, the addition form of the structures is not particularly limited, and may be a random type or a block type. Moreover, in Formula (6), s shows an integer greater than or equal to 1. When s is an integer of 2 or more, the structures in parentheses to which s is attached may be the same or different. When the structures in parentheses with s are different from each other, the addition form of the structures is not particularly limited, and may be a random type or a block type. Furthermore, in the formula (6), the structure in parentheses with r and the structure in parentheses with s are not particularly limited, and may be a random type or a block type. May be. R and s may be the same or different. That is, in formula (6), r and s are the same or different and each represents an integer of 1 or more.

The terminal structure of the polyorganosiloxysilalkylene is not particularly limited. For example, a group containing an aliphatic carbon-carbon double bond, hydrosilyl group, silanol group, alkoxysilyl group, trialkylsilyl group (for example, trimethylsilyl group) Etc.

As described above, the polyorganosiloxysilalkylene may have a linear or branched chain structure.

The above polyorganosiloxysilalkylene can be produced, for example, by the method described in JP2012-140617A.

The polyorganosiloxane contained in the polyorganosiloxane (A) can be used singly or in combination of two or more.

The ratio of the polyorganosiloxane having no aryl group in the polyorganosiloxane (A) (for example, polyorganosiloxysilalkylene) is not particularly limited, but from the viewpoint of flexibility, for example, the total amount of polyorganosiloxane (A) ( 100% by weight) is preferably 50% by weight or more, more preferably 80% by weight or more, and still more preferably 95% by weight or more. Among these, from the viewpoint of obtaining more excellent flexibility, the polyorganosiloxane (A) is particularly preferably only a polyorganosiloxane having no aryl group. In addition, when 2 or more types of polyorganosiloxane which does not have an aryl group is included, the ratio of total content (weight) is said.

When two or more polyorganosiloxanes are used in combination, it is preferable that at least one has a hydrosilyl group and at least one has an aliphatic carbon-carbon unsaturated bond.

The number average molecular weight (Mn) of the polyorganosiloxane (particularly polyorganosiloxane having no aryl group) contained in the polyorganosiloxane (A) is preferably 500 to 20000, more preferably 1000 to 10,000, and 2000 to 8000. Is more preferable. The weight average molecular weight (Mw) is preferably from 500 to 50,000, more preferably from 5,000 to 40,000, and even more preferably from 10,000 to 30,000. When the number average molecular weight and / or the weight average molecular weight is 500 or more, the resulting cured product is excellent in heat resistance. When the number average molecular weight is 20000 or less and / or the weight average molecular weight is 50000 or less, the compatibility between the polyorganosiloxane (A) and other components is excellent.
In addition, the number average molecular weight and the weight average molecular weight in the present specification are, for example, Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), as a molecular weight in terms of polystyrene by gel permeation chromatography. Column: Tskel GMH _HR -M × 2 (manufactured by Tosoh Corporation), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corporation), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF Measurement conditions: measured under the conditions of 40 ° C.
Therefore, even if the number average molecular weight and the weight average molecular weight are included in different ranges when other analytical instruments are used, the number average molecular weight and / or the weight average molecular weight are within the above range depending on the measurement conditions. Then, it corresponds to the polyorganosiloxane contained in the polyorganosiloxane (A) which is one component constituting the curable resin composition of the present invention.

Molecular weight dispersity (Mw / Mn) calculated from weight average molecular weight (Mw) and number average molecular weight (Mn) of polyorganosiloxane (particularly polyorganosiloxane having no aryl group) contained in polyorganosiloxane (A) ) Is not particularly limited, but is preferably 1.0 to 7.0, more preferably 2.0 to 6.5, and still more preferably 3. from the viewpoint of heat resistance and compatibility with other components. It is 0 to 6.0, particularly preferably 4.0 to 5.5.

The content (in terms of vinyl group) of aliphatic carbon-carbon double bond in the molecule of polyorganosiloxane (particularly polyorganosiloxane having no aryl group) contained in polyorganosiloxane (A) is not particularly limited. However, from the viewpoint that it is easy to adjust the number of aliphatic carbon-carbon double bonds bonded to the silicon atom present in the compound contained in the curable resin composition, and that a cured product having excellent flexibility and strength can be easily obtained. For example, it is preferably 3.0% by weight or less (eg 0.5 to 3.0% by weight). The content of the aliphatic carbon-carbon double bond in the molecule can be measured by ¹ H-NMR, for example.

The content (blending amount) of the polyorganosiloxane (A) in the curable resin composition of the present invention is not particularly limited, but is 55 to 95% by weight with respect to the total amount (100% by weight) of the curable resin composition. It is preferably 60 to 92% by weight, more preferably 65 to 90% by weight. If the content is less than 55% by weight, the crack resistance of the cured product may be lowered. On the other hand, if the content exceeds 90% by weight, gas barrier properties against corrosive gas may not be sufficiently obtained.

[Silsesquioxane (B)]
The curable resin composition of the present invention contains at least a ladder-type silsesquioxane as the silsesquioxane (B). The ladder-type silsesquioxane is a polysiloxane having a crosslinked three-dimensional structure.

Polysiloxane is a compound having a main chain composed of siloxane bonds (Si—O—Si), and the basic structural unit thereof is an M unit (a monovalent group in which a silicon atom is bonded to one oxygen atom). Unit), D unit (unit consisting of a divalent group in which a silicon atom is bonded to two oxygen atoms), T unit (unit consisting of a trivalent group in which a silicon atom is bonded to three oxygen atoms) , And Q unit (unit consisting of a tetravalent group in which a silicon atom is bonded to four oxygen atoms). Further, examples of the structure of the Si—O—Si skeleton include a random structure, a cage structure, and a ladder structure.
Silsesquioxane (B) contained in silsesquioxane is a polysiloxane represented by the empirical formula (basic structural formula) SiO _1.5 having the T unit as a basic structural unit, for example, Si having a random structure. Silsesquioxane having a structure of —O—Si skeleton, silsesquioxane having a structure of Si—O—Si skeleton of cage structure, silsesquioxane having a structure of Si—O—Si skeleton of ladder structure ( Ladder type silsesquioxane) and the like. The silsesquioxane (for example, ladder-type cissesquioxane) contained in cissesquioxane (B) can be used individually by 1 type or in combination of 2 or more types.

In the empirical formula (basic structural formula) RSiO _1.5 of the ladder-type silsesquioxane, the R includes, for example, a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group (not including a carbon atom) Monovalent oxygen atom-containing group), monovalent nitrogen atom-containing group (carbon atom, monovalent nitrogen atom-containing group not containing oxygen atom), or monovalent sulfur atom-containing group (including carbon atom, oxygen atom) Non-monovalent sulfur atom-containing groups). At least a part of R is preferably a monovalent organic group. The Rs may be the same or different.

Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent organic group in R include a substituted or unsubstituted hydrocarbon group (monovalent hydrocarbon group), an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, and an alkylthio group. Groups, alkenylthio groups, arylthio groups, aralkylthio groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, epoxy groups, cyano groups, isocyanate groups, carbamoyl groups, isothiocyanate groups, etc. It is done.

Examples of the hydrocarbon group in R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

Examples of the aliphatic hydrocarbon group for R include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include C _1-20 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, dodecyl group (preferably C _{1- 10} alkyl group, more preferably C _1-4 alkyl group). Examples of the alkenyl group include a vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, Examples thereof include C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-4 alkenyl groups) such as 3-pentenyl group, 4-pentenyl group, and 5-hexenyl group. Examples of the alkynyl group include C _2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C _2-10 alkynyl group, more preferably C _2-4 alkynyl group).

Examples of the alicyclic hydrocarbon group in the R include C _3-12 cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a _cyclododecyl group; and a C ₃₋ group such as a cyclohexenyl group. ₁₂ cycloalkenyl groups; C _4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl group and bicycloheptenyl group.

Examples of the aromatic hydrocarbon group in R include C _6-14 aryl groups (particularly, C _6-10 aryl groups) such as phenyl group and naphthyl group.

In addition, examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group in R are bonded to each other include a cyclohexylmethyl group and a methylcyclohexyl group. Examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded include, for example, C _7-18 aralkyl groups such as benzyl group and phenethyl group (particularly C _7-10 aralkyl groups), and C such as cinnamyl group. _Examples thereof include C _1-4 alkyl-substituted aryl groups such as _6-10 aryl-C _2-6 alkenyl groups and tolyl groups, and C _2-4 alkenyl-substituted aryl groups such as styryl groups.

The hydrocarbon group in R may have a substituent. The number of carbon atoms of the substituent in the hydrocarbon group is preferably 0-20, more preferably 0-10. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group and isooctyl group. C _1-20 alkyl group such as decyl group, dodecyl group (preferably C _1-10 alkyl group, more preferably C _1-4 alkyl group); vinyl group, allyl group, methallyl group, 1-propenyl group, iso C _2-20 alkenyl groups such as propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and 5-hexenyl group (Preferably C _2-10 alkenyl group, more preferably C _2-4 alkenyl group); methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy Alkoxy groups (preferably C _1-6 alkoxy groups, more preferably C _1-4 alkoxy groups) such as cis groups and isobutyloxy groups; Alkenyloxy groups such as allyloxy groups (preferably C _2-6 alkenyloxy groups, more Preferably a C _2-4 alkenyloxy group); a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group, etc. on the aromatic ring, such as a phenoxy group, a tolyloxy group, a naphthyloxy group, etc. An aryloxy group (preferably a C _6-14 aryloxy group) which may have the following substituents; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group (preferably a C _7-18 aralkyloxy group); Acyloxy groups such as oxy group, propionyloxy group, (meth) acryloyloxy group, benzoyloxy group (preferably C _1-12 acyloxy group); Luccapto group; alkylthio group such as methylthio group and ethylthio group (preferably C _1-6 alkylthio group, more preferably C _1-4 alkylthio group); alkenylthio group such as allylthio group (preferably C _2-6 alkenylthio group) More preferably a C _2-4 alkenylthio group); a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group on the aromatic ring, such as phenylthio group, tolylthio group, naphthylthio group, etc. An arylthio group (preferably a C _6-14 arylthio group) which may have a substituent such as aralkylthio group (preferably a C _7-18 aralkylthio group) such as a benzylthio group or a phenethylthio group; a carboxyl group; Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group (preferably C _{1 -6} alkoxy-carbonyl group); aryloxycarbonyl group such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group (preferably C _6-14 aryloxy-carbonyl group); aralkyloxycarbonyl such as benzyloxycarbonyl group Group (preferably C _7-18 aralkyloxy-carbonyl group); amino group; mono- or dialkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (preferably mono- or di-C _1-6 Alkylamino group); acylamino group such as acetylamino group, propionylamino group, benzoylamino group (preferably C _1-11 acylamino group); epoxy group-containing group such as glycidyloxy group; oxetanyl group such as ethyloxetanyloxy group Group; acetyl group, group Oxo group; Pioniru group, an acyl group such as benzoyl group, etc. bonded groups via a C _1-6 alkylene group, depending These demands have 2 or more thereof.

Examples of the alkoxy group, the alkenyloxy group, the acyloxy group, the alkylthio group, the alkenylthio group, and the alkoxycarbonyl group in R include those exemplified as R ²¹ to R ²⁶ in Formula (6). It is done.

Examples of the aryloxy group in R include a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, and a C _1-4 alkoxy group on the aromatic ring, such as a phenoxy group, a tolyloxy group, and a naphthyloxy group. And a C _6-14 aryloxy group which may have a substituent such as Examples of the aralkyloxy group include C _7-18 aralkyloxy groups such as benzyloxy group and phenethyloxy group. Examples of the arylthio group include a phenylthio group, a tolylthio group, a naphthylthio group, and the like, and a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, and a C _1-4 alkoxy group on the aromatic ring. Examples thereof include a C _6-14 arylthio group which may be present. Examples of the aralkylthio group include C _7-18 aralkylthio groups such as benzylthio group and phenethylthio group. Examples of the aryloxycarbonyl group include C _6-14 aryloxy-carbonyl groups such as a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group. Examples of the aralkyloxycarbonyl group include C _7-18 aralkyloxy-carbonyl groups such as benzyloxycarbonyl group.

Examples of the monovalent oxygen atom-containing group in R include a hydroxyl group, a hydroperoxy group, and a sulfo group. Examples of the monovalent nitrogen atom-containing group include an amino group or a substituted amino group (mono- or dialkylamino group, acylamino group, etc.). Moreover, as said monovalent | monohydric sulfur atom containing group, a mercapto group (thiol group) etc. are mentioned, for example.

Furthermore, examples of R in the empirical formula (basic structural formula) RSiO _1.5 include a group represented by the following formula (4).

A plurality of R ′ in the above formula (4) may be the same or different. Examples of R ′ in the formula (4) include a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom-containing group. Is mentioned. These groups include the same groups as those exemplified as R in the above empirical formula (Basic Structure) RSiO _1.5.

In the group represented by the above formula (4), each R ′ is a hydrogen atom, a C _1-10 alkyl group (especially a C _1-4 alkyl group), a C _2-10 alkenyl group (especially C 1 _2-4 alkenyl groups), C _3-12 cycloalkyl groups, C _3-12 cycloalkenyl groups, C _1-4 alkyl groups on aromatic rings, C _2-4 alkenyl groups, halogen atoms, C _1-4 alkoxy groups, etc. A C _6-14 aryl group, a C _7-18 aralkyl group, a C _6-10 aryl-C _2-6 alkenyl group, a hydroxyl group, a C _1-6 alkoxy group, or a halogen atom, which may have a substituent of preferable.

Among them, the R in the empirical formula (basic structural formula) RSiO _1.5 is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group, and still more preferably a fatty acid. An aromatic hydrocarbon group (particularly an alkyl group) and an aromatic hydrocarbon group (particularly a phenyl group).

As said ladder type silsesquioxane, the ladder type silsesquioxane represented by following formula (5) may be sufficient, for example.

In the above formula (5), p is an integer of 1 or more (preferably 1 to 5000, more preferably 1 to 2000, still more preferably 1 to 1000). T in the above formula (5) represents a terminal group. Examples of R in the formula (5) (hereinafter sometimes referred to as “side chain”) include those exemplified as R in the empirical formula RSiO _1.5 . The T in the above formula (5), for example, those exemplified as R of the empirical formula RSiO _1.5. Among them, R or T in the above formula (5) is preferably a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a group represented by formula (4), more preferably a hydrogen atom or aliphatic carbonization. A hydrogen group (especially an alkyl group or an alkenyl group) or an aromatic hydrocarbon group (especially a phenyl group). In particular, T in the formula (5) preferably includes a trimethyl group, and more preferably includes a trimethyl group and a vinyl group, or a trimethyl group and a SiH-containing group.

The ratio of the substituted or unsubstituted hydrocarbon group to the total amount (100 mol%) of R in the formula (5) is not particularly limited, but is preferably 50 mol% or more, more preferably 80 mol% or more, 90 More preferably, it is at least mol%. In particular, a substituted or unsubstituted alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, particularly a methyl group or an ethyl group, etc., having 1 to 4 carbon atoms, based on the total amount (100 mol%) of R in formula (5). Alkyl groups), substituted or unsubstituted aryl groups (preferably aryl groups having 6 to 10 carbon atoms, particularly phenyl groups), substituted or unsubstituted aralkyl groups having 7 to 10 carbon atoms (preferably 7 to 10 carbon atoms). The total amount of aralkyl groups, particularly benzyl groups, is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more. In particular, from the viewpoint of the barrier property against the corrosive gas of the cured product, a part or all of R is preferably a substituted or unsubstituted aryl group.

[Ladder-type silsesquioxane (B1)]
Examples of the ladder-type silsesquioxane include a ladder-type silsesquioxane (B1) having an aliphatic carbon-carbon double bond in the molecule (hereinafter simply referred to as “ladder-type silsesquioxane (B1)”). May be included). The ladder-type silsesquioxane is preferably a ladder-type silsesquioxane (B1). The ladder-type silsesquioxane (B1) is not particularly limited as long as it is a compound having a group having an aliphatic carbon-carbon double bond in the side chain or the terminal group.

Examples of the group having an aliphatic carbon-carbon double bond include a vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, C _2-20 alkenyl groups such as 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and 5-hexenyl group (preferably C _2-10 alkenyl group, more preferably C _2-4 alkenyl group) Group); C _3-12 cycloalkenyl group such as cyclohexenyl group; C _4-15 bridged cyclic unsaturated hydrocarbon group such as bicycloheptenyl group; C _2-4 alkenyl-substituted aryl group such as styryl group; cinnamyl Group and the like. In the group having an aliphatic carbon-carbon double bond, in the group represented by the above formula (4), at least one of three R ′ has an aliphatic carbon-carbon double bond ( For example, C _2-20 alkenyl group, C _3-12 cycloalkenyl group, C _4-15 bridged cyclic unsaturated hydrocarbon group, C _2-4 alkenyl substituted aryl group, cinnamyl group, etc. It is. Among them, an alkenyl group is preferable, a C _2-20 alkenyl group is more preferable, and a vinyl group is more preferable.

In the ladder-type silsesquioxane (B1), the number of the aliphatic carbon-carbon double bonds in the molecule (in one molecule) is not particularly limited, but is preferably 2 or more (for example, 2 to 50). 2 to 30 are more preferable. By having the aliphatic carbon-carbon double bond within the above-mentioned range, a cured product excellent in various physical properties such as heat resistance, crack resistance, and barrier properties against corrosive gas tends to be obtained.

The content of the aliphatic carbon-carbon double bond in the ladder-type silsesquioxane (B1) is not particularly limited, but is preferably 0.7 to 5.5 mmol / g, and 1.1 to 4.4 mmol / g is more preferable. The ratio (by weight) of the aliphatic carbon-carbon double bond contained in the ladder-type silsesquioxane (B1) is not particularly limited, but is 2.0 to 15.0% by weight in terms of vinyl group. Is preferable, and 3.0 to 12.0% by weight is more preferable.

The ladder-type silsesquioxane (B1) is not particularly limited, but may be liquid at room temperature (about 25 ° C.) or may be solid. Among these, it is preferably liquid at room temperature. More specifically, the viscosity of the ladder-type silsesquioxane (B1) at 25 ° C. is preferably 100 to 100,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1000 to 8000 mPa · s. If the viscosity is less than 100 mPa · s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 100,000 mPa · s, it may be difficult to prepare and handle the curable resin composition. The viscosity at 25 ° C. is, for example, a temperature: 25 ° C., rotation using a rheometer (trade name “PhysicaUDS-200”, manufactured by Anton Paar) and a cone plate (cone diameter: 16 mm, taper angle = 0 °). Number: It can be measured under the condition of 20 rpm.
When the silsesquioxane (B) contains silsesquioxane (B1) that is solid at room temperature, the corrosion resistance against corrosive gas and toughness (particularly crack resistance) tend to be improved.

[Ladder-type silsesquioxane (B2)]
Examples of the ladder-type silsesquioxane include a ladder-type silsesquioxane (B2) having a Si—H bond in the molecule (hereinafter, simply referred to as “ladder-type silsesquioxane (B2)”). ) May be included. The ladder-type silsesquioxane may be a ladder-type silsesquioxane (B2). The ladder-type silsesquioxane (B2) is not particularly limited as long as it is a compound having a hydrogen atom or a group having a Si—H bond in the side chain or the terminal group.

The group having an Si—H bond is not particularly limited, and examples thereof include a hydrosilyl group and a group represented by the above formula (4), in which at least one of three R ′ is a hydrogen atom. It is done.

In the ladder-type silsesquioxane (B2), the number of the hydrogen atom or the group having the Si—H bond in the molecule (in one molecule) is not particularly limited, but two or more (for example, 2 to 50) ) Is preferred, and 2 to 30 are more preferred. By having the hydrogen atom or the group having Si-H in the above range, the heat resistance of the cured product of the curable resin composition tends to be improved.

The ratio (weight basis) of the hydrogen atom or the SiH group contained in the ladder-type silsesquioxane (B2) is not particularly limited, but is in terms of weight (H conversion) of H (hydride) in the hydrogen atom or SiH group. 0.01 to 0.50 wt% is preferable, and 0.08 to 0.28 wt% is more preferable. When there is too little content of the said hydrogen atom or the said SiH group (for example, when less than 0.01 weight% in conversion of H), hardening of curable resin composition may not fully advance. On the other hand, when there is too much content of the said hydrogen atom or the said SiH group (for example, when exceeding 0.50 weight% in H conversion), the hardness of hardened | cured material will become high and it may become easy to crack. The content of the hydrogen atom or the SiH group in the ladder-type silsesquioxane (B2) can be measured, for example, by ¹ H-NMR.

The proportion of SiH groups present in the ladder-type silsesquioxane (B2) is not particularly limited, but from the viewpoint of flexibility, for example, all of the compounds present in the curable resin composition of the present invention are present. The amount is preferably 0 to 80 mol%, more preferably 0 to 50 mol%, based on the SiH group (100 mol%).

The ladder-type silsesquioxane (B2) is not particularly limited, but may be liquid at normal temperature (about 25 ° C.) or may be solid. Among these, it is preferably liquid at normal temperature. More specifically, the viscosity of the ladder-type silsesquioxane (B2) at 25 ° C. is preferably 100 to 100,000 mPa · s, more preferably 500 to 10000 mPa · s, and still more preferably 1000 to 8000 mPa · s. If the viscosity is less than 100 mPa · s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 100,000 mPa · s, it may be difficult to prepare and handle the curable resin composition. The viscosity at 25 ° C. can be measured, for example, by the same method as that for ladder type silsesquioxane (B1).
When the silsesquioxane (B) contains silsesquioxane (B2) that is solid at room temperature, the corrosion resistance against corrosive gas and the toughness (particularly crack resistance) tend to be improved.

[Other ladder-type silsesquioxanes]
The ladder-type silsesquioxane may contain, for example, a ladder-type silsesquioxane having an aryl group in the molecule. Examples of the aryl group in the ladder-type silsesquioxane having an aryl group in the molecule include a C _6-14 aryl group (particularly a C _6-10 aryl group) such as a phenyl group and a naphthyl group. These aryl groups may be substituents (groups directly bonded to silicon atoms) possessed by silicon atoms in the polyorganosiloxane (A).
The ladder-type silsesquioxane is a ladder-type silsesquioxane (B1), a ladder-type silsesquioxane (B2), or a ladder-type silsesquioxane other than a ladder-type silsesquioxane having an aryl group in the molecule. Sesquioxane (hereinafter may be referred to as “other ladder-type silsesquioxane”) may be included. In particular, the other ladder-type silsesquioxane is preferably used in combination with ladder-type silsesquioxane (B1) or ladder-type silsesquioxane (B2).

The ladder-type silsesquioxane is not particularly limited. For example, the ladder-type silsesquioxane includes a ladder-type polyorganosiloxane (B1), a ladder-type polyorganosiloxane (B2), and a ladder-type silsesquioxane having an aryl group in the molecule. It preferably contains at least one silsesquioxane selected from the group, and more preferably contains ladder-type silsesquioxane (B1) and / or ladder-type silsesquioxane (B2).

The content of the ladder-type silsesquioxane in the silsesquioxane (B) is not particularly limited. For example, the content is 50% by weight or more with respect to the total amount of the silsesquioxane (B) (100% by weight). More preferably, it is 70 weight% or more, More preferably, it is 90 weight% or more. Especially, it is preferable that silsesquioxane (B) is only the said ladder type silsesquioxane. That is, the silsesquioxane (B) is preferably the ladder-type silsesquioxane. When the content of the ladder-type silsesquioxane is within the above range, more excellent in SO _x corrosion.

The content of the ladder-type silsesquioxane (B1) in the silsesquioxane (B) is not particularly limited, but is, for example, 20% by weight with respect to the total amount (100% by weight) of the silsesquioxane (B). The above is preferable, more preferably 40% by weight or more, still more preferably 50% by weight or more, and particularly preferably 90% by weight or more. As an upper limit, 100 weight% is preferable, for example, and 95 weight%, 80 weight%, and 60 weight% may be sufficient. Especially, it is preferable that silsesquioxane (B) is only the said ladder type silsesquioxane (B1). That is, the ladder-type silsesquioxane (B1) may be used as the silsesquioxane (B).

The content of the ladder-type silsesquioxane (B2) in the silsesquioxane (B) is not particularly limited. For example, the content is 10% by weight with respect to the total amount (100% by weight) of the silsesquioxane (B). The above is preferable, more preferably 20% by weight or more, and still more preferably 40% by weight or more. The upper limit is, for example, preferably 100% by weight, more preferably 80% by weight, still more preferably 60% by weight, and particularly preferably 50% by weight. The silsesquioxane (B) may be only the ladder-type silsesquioxane (B2).
Silsesquioxane (B2) is preferably used in combination with silsesquioxane (B1) from the viewpoint of easy control of the number of SiH groups contained in the curable resin composition. Among them, the ratio of silsesquioxane (B1) to silsesquioxane (B2) (silsesquioxane (B1): silsesquioxane (B2)) is preferably 2 to 8: 8 to 2, more preferably. Is 4-6: 6-4.

The ladder type silsesquioxane can be produced by a known production method (for example, a hydrolytic condensation method using a trifunctional silane compound as a raw material).

The number average molecular weight and / or weight average molecular weight of the silsesquioxane contained in the silsesquioxane (B) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, and 300 to 3 Is more preferable, and 500 to 20000 is particularly preferable. If it is less than 100, the heat resistance of the cured product may be reduced, and if it exceeds 800,000, the compatibility of the silsesquioxane (B) with other components may be reduced. Silsesquioxane (B) may be a mixture having various molecular weights within the above range.

The content of the aliphatic carbon-carbon double bond in the molecule of silsesquioxane (particularly ladder-type silsesquioxane) contained in the silsesquioxane (B) (weight basis, in terms of vinyl group) is: Although not particularly limited, it is preferably 15.0% by weight or less (for example, 1.0 to 15.0% by weight), more preferably 1.2% from the viewpoint that a cured product excellent in flexibility and strength is easily obtained. ˜12.0% by weight. The content of the aliphatic carbon-carbon double bond in the molecule can be measured, for example, by ¹ H-NMR.

Content of SiH group in the molecule of silsesquioxane (particularly ladder-type silsesquioxane) contained in silsesquioxane (B) (weight conversion of H (hydride) in SiH group) is particularly limited. However, from the viewpoint of easily obtaining a cured product excellent in flexibility and strength, for example, 0.50% by weight or less (for example, 0.01 to 0.50% by weight) is preferable, and more preferably 0.03 to 0%. .28% by weight. The SiH group content can be measured, for example, by ¹ H-NMR.

Silsesquioxane (particularly ladder type silsesquioxane) contained in silsesquioxane (B) is not particularly limited, but from the viewpoint of compatibility with organosiloxane (A), a methyl group and a vinyl group Preferably, the ratio of methyl group to vinyl group (molar ratio, methyl group: vinyl group) is in the range of 5: 5 to 9.5: 0.5. A range of 5: 4.5 to 9: 1 is more preferable. The contents of the methyl group and vinyl group can be measured, for example, by ¹ H-NMR.

Silsesquioxane (B) is not particularly limited, but is preferably colorless and transparent, for example. Specifically, it is preferable that the light transmittance at 400 nm measured with an ultraviolet-visible light spectrophotometer is 90% or more.

Although silsesquioxane (B) is not specifically limited, For example, it can be manufactured by mixing the said ladder type silsesquioxane etc. uniformly.

The content (blending amount) of silsesquioxane (B) in the curable resin composition of the present invention is not particularly limited, but is 5 to 45 wt% with respect to the total amount (100 wt%) of the curable resin composition. %, More preferably 7 to 40% by weight, still more preferably 10 to 35% by weight. When the content is less than 5 wt%, the gas barrier property to corrosive gases such as SO _x is not sufficiently obtained. On the other hand, if the content exceeds 45% by weight, the crack resistance of the cured product may be lowered, or the heat resistance may not be sufficiently obtained.

Although content of silsesquioxane (B) in the curable resin composition of this invention is not specifically limited, For example, the total amount (100 weight part) of polyorganosiloxane (A) and silsesquioxane (B) The amount is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, still more preferably 8 to 30 parts by weight. When the content is in the above range, the corrosion resistance against a corrosive gas (especially SO _x corrosion resistance) is excellent.

The total content of the polyorganosiloxane (A) and the silsesquioxane (B) in the curable resin composition of the present invention is not particularly limited. For example, the total amount (100% by weight) of the curable resin composition Is preferably 60.000 to 100% by weight, more preferably 70.000 to 99.000% by weight. The total content of the polyorganosiloxane (A) and silsesquioxane (B) is in the above range, excellent corrosion resistance against corrosive gas (in particular resistance to SO _x corrosion). In particular, by being 99% by weight or less, the heat resistance and the corrosion resistance against corrosive gas are further improved.

[Isocyanurate Compound (C)]
The curable resin composition of the present invention contains an isocyanurate compound (C). By including the isocyanurate compound (C), the curable resin composition of the present invention particularly improves the barrier property against a corrosive gas of a cured product formed by curing, and further improves the adhesion to an adherend. Tend to.

The isocyanurate compound (C) preferably includes an isocyanurate compound represented by the formula (1). In particular, the isocyanurate compound (C) is preferably only the isocyanurate compound represented by the formula (1).

In the above formula (1), R ^x , R ^y and R ^z are the same or different and represent a group represented by the above formula (2) or a group represented by the above formula (3). Among them, any one or more (preferably one or two, more preferably one) of R ^x , R ^y and R ^{z in} the above formula (1) is a group represented by the above formula (3). Preferably there is.

In the above formulas (2) and (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a pentyl group, a hexyl group, A heptyl group, an octyl group, an ethylhexyl group, etc. are mentioned. Among the above alkyl groups, linear or branched alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. In the above formula (2) and the above formula (3), R ¹ and R ² are each particularly preferably a hydrogen atom.

The isocyanurate compound contained in the isocyanurate compound (C) is not particularly limited. For example, monoallyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, triallyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate , Triglycidyl isocyanurate, monomethyl diglycidyl isocyanurate, dimethyl monoglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methylpropenyl) -3,5- Diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, 1,3-diallyl-5- (2-methylepoxy Pyr) isocyanurate, 1,3-bis (2-methylpropenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate, tris (2 -Methylpropenyl) isocyanurate and the like. Of these, monoallyl diglycidyl isocyanurate is preferable. In addition, the isocyanurate compound in an isocyanurate compound (C) can be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of improving compatibility with other components, the isocyanurate compound (C) may be blended with other components after previously mixed with a silane coupling agent as described later.

The content of the isocyanurate compound (C) is not particularly limited, but is preferably 0.01 to 10% by weight, and 0.05 to 5% by weight with respect to the total amount (100% by weight) of the curable resin composition. More preferred is 0.1 to 3% by weight. If the content of the isocyanurate compound is less than 0.01% by weight, the barrier property against corrosive gas and the adhesion to the adherend may be lowered. On the other hand, when the content of the isocyanurate compound exceeds 10% by weight, solids may precipitate in the curable resin composition or the cured product may become cloudy.

[Silane coupling agent (D)]
The curable resin composition of the present invention may contain a silane coupling agent (D). By including a silane coupling agent (D), there exists a tendency for the adhesiveness with respect to a to-be-adhered body to improve.

Since the silane coupling agent (D) has good compatibility with the silsesquioxane (B), the isocyanurate compound (C) and the like, for example, to improve the compatibility of the isocyanurate compound with other components. When a composition of the isocyanurate compound (C) and the silane coupling agent (D) is previously formed and then blended with other components, a uniform curable resin composition is easily obtained.

As the silane coupling agent (D), a known or conventional silane coupling agent can be used, and is not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxy group-containing silane coupling agents such as 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N- (1 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (β-amino Amino group-containing silane coupling agents such as ethyl) -γ-aminopropylmethyldiethoxysilane; tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (Methoxyethoxysilane), phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- Meth) acryloxypropylmethyldimethoxysilane, .gamma. (meth) acryloxy propyl methyl diethoxy silane, mercapto propylene trimethoxysilane, and the like mercapto propylene triethoxysilane. Among them, an epoxy group-containing silane coupling agent (particularly 3-glycidoxypropyltrimethoxysilane) is preferable. In addition, a silane coupling agent (D) can be used individually by 1 type or in combination of 2 or more types.

The content of the silane coupling agent (D) is not particularly limited, but is preferably 0.01 to 15% by weight, preferably 0.1 to 10% by weight with respect to the total amount (100% by weight) of the curable resin composition. Is more preferable, and 0.5 to 5% by weight is still more preferable. When the content of the silane coupling agent is less than 0.01% by weight, the adhesion to the adherend is lowered, and particularly when the isocyanurate compound (C) is used in a compatible state, sufficient curing is achieved. May not be obtained. On the other hand, when content of a silane coupling agent (D) exceeds 15 weight%, hardening will become inadequate and the toughness of a hardened | cured material, heat resistance, and barrier property may fall.

[Carboxylate of rare earth metal atom (E)]
The curable resin composition of the present invention contains a carboxylate (E) of a rare earth metal atom. By including the carboxylate (E) of the rare earth metal atom, the H ₂ S corrosion resistance and the heat resistance tend to be improved. 1 type may be sufficient as the rare earth metal atom contained in the carboxylate of a rare earth metal atom, and 2 or more types may be sufficient as it.
In the present specification, a carboxylate of a rare earth metal atom is sometimes referred to as a rare earth carboxylate.

Examples of the rare earth metal atom in the carboxylate of the rare earth metal atom contained in the carboxylate (E) of the rare earth metal atom include yttrium, cerium, lanthanum, praseodymium, neodymium and the like. Examples of the carboxylate in the carboxylate of the rare earth metal atom include a carboxylate of a carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 12, more preferably 4 to 10, more preferably 5 to 7). And more preferably hexanoate such as 2-ethylhexanoate. Among them, the rare earth metal atom carboxylates include yttrium carboxylate, cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, neodymium carboxylate (particularly yttrium carboxylate having 1 to 20 carbon atoms, 1 to 20 carbon atoms). Cerium carboxylate, lanthanum carboxylate having 1 to 20 carbon atoms, praseodymium carboxylate having 1 to 20 carbon atoms, neodymium carboxylate having 1 to 20 carbon atoms, more preferably yttrium 2-ethylhexanoate, 2-ethyl (Cerium hexanoate, lanthanum 2-ethylhexanoate, praseodymium 2-ethylhexanoate, neodymium 2-ethylhexanoate) are preferred.
The rare earth metal atom carboxylates in the rare earth metal atom carboxylates (E) can be used alone or in combination of two or more.

The carboxylate (E) of the rare earth metal atom is, for example, a carboxylate of the rare earth metal atom containing cerium (for example, at least selected from the group consisting of cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, and neodymium carboxylate) A mixture of carboxylates of two or more rare earth metal atoms (such as a mixture of cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, and neodymium carboxylate), or only cerium carboxylate (single compound)), or carboxyl It is preferably a carboxylate of a rare earth metal atom containing yttrium acid (for example, yttrium carboxylate alone), and a 2-ethylhexanoate of a rare earth metal atom containing cerium (eg, cerium 2-ethylhexanoate, 2 -Lanthanum ethylhexanoate, 2 A mixture of 2-ethylhexanoate of at least two rare earth metal atoms selected from the group consisting of praseodymium ethylhexanoate and neodymium 2-ethylhexanoate (cerium 2-ethylhexanoate, lanthanum 2-ethylhexanoate, A mixture of praseodymium 2-ethylhexanoate and neodymium 2-ethylhexanoate), or only cerium 2-ethylhexanoate (single compound), or yttrium 2-ethylhexanoate is more preferable.
As the carboxylate (E) of the rare earth metal atom, for example, a commercial product such as a trade name “Octop® R” (manufactured by Hope Pharmaceutical Co., Ltd.) may be used.

The content of the rare earth metal atom in the curable resin composition of the present invention is not particularly limited, but is preferably 5 ppm or more and less than 5000 ppm, for example, 7 ppm or more and 1000 ppm with respect to the total amount of the curable resin composition (100 wt%). Is more preferably 10 ppm or more and less than 300 ppm. When the content of the rare earth metal atom is less than 5 ppm, the effect of the carboxylate (E) of the rare earth metal atom is not sufficiently exhibited, and the barrier property against the H ₂ S gas or the heat resistance may be lowered. . On the other hand, the transmittance | permeability of hardened | cured material may fall that it is 5000 ppm or more.
Content of the said rare earth metal atom in curable resin composition can be measured by the method as described in the below-mentioned evaluation (rare earth metal atom content (ppm)).

The content of the rare earth metal atom in the curable resin composition of the present invention is not particularly limited. For example, relative to the total content (100% by weight) of polyorganosiloxane (A) and silsesquioxane (B). 5 ppm or more and less than 5000 ppm is preferable, 7 ppm or more and less than 1000 ppm is more preferable, and 10 ppm or more and less than 300 ppm is still more preferable. When the content of the rare earth metal atoms is in the above range, the heat resistance and the corrosion resistance against a corrosive gas (particularly, the H ₂ S corrosion resistance) are further improved.

The content of the carboxylate (E) of the rare earth metal atom is not particularly limited, but is preferably 0.008 to 1.000% by weight with respect to the total amount (100% by weight) of the curable resin composition, for example. The amount is preferably 0.010 to 0.500% by weight, more preferably 0.015 to 0.400% by weight. Particularly, when the content of the rare earth metal atom is in the above range and the content of the carboxylate of the rare earth metal atom is in the above range, the heat resistance and the corrosion resistance against corrosive gas are further improved.

[Hydrosilylation catalyst]
The curable resin composition of the present invention may further contain a hydrosilylation catalyst. By including the hydrosilylation catalyst, the curable resin composition of the present invention can efficiently advance the curing reaction (hydrosilylation reaction). Examples of the hydrosilylation catalyst include well-known hydrosilylation catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Specifically, platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum olefin complexes, platinum-carbonylvinylmethyl Platinum-based catalysts such as platinum carbonyl complexes such as complexes, platinum-vinylmethylsiloxane complexes such as platinum-divinyltetramethyldisiloxane complexes and platinum-cyclovinylmethylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, and the like Examples of the platinum catalyst include a palladium catalyst or a rhodium catalyst containing a palladium atom or a rhodium atom instead of a platinum atom. In addition, the said hydrosilylation catalyst can be used individually by 1 type or in combination of 2 or more types.

The content of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited. For example, platinum, palladium, or rhodium in the hydrosilylation catalyst is in a range of 0.01 to 1,000 ppm by weight. The amount is preferably within the range of 0.1 to 500 ppm. It is preferable for the content of the hydrosilylation catalyst to be in such a range because the crosslinking rate will not be remarkably slowed and the cured product is less likely to cause problems such as coloring.

[Hydrosilylation reaction inhibitor]
The curable resin composition of the present invention may contain a hydrosilylation reaction inhibitor in order to adjust the speed of the curing reaction (hydrosilylation reaction). Examples of the hydrosilylation reaction inhibitor include alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol; 3-methyl-3 -Enyne compounds such as pentene-1-yne and 3,5-dimethyl-3-hexen-1-yne; and thiazole, benzothiazole, benzotriazole and the like. The said hydrosilylation reaction inhibitor can be used individually by 1 type or in combination of 2 or more types. The content of the hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the curable resin composition, but practically, the content in the curable resin composition is preferably in the range of 0.00001 to 5% by weight. .

[Other siloxane compounds]
The curable resin composition of the present invention may further contain a cyclic siloxane having two or more aliphatic carbon-carbon double bonds in the molecule (in one molecule) as another siloxane compound. The curable resin composition of the present invention may further contain a cyclic siloxane having two or more SiH groups in the molecule (in one molecule) as the other siloxane compound. The said cyclic siloxane can be used individually by 1 type or in combination of 2 or more types. The content (blending amount) of the cyclic siloxane in the curable resin composition of the present invention is not particularly limited, but is preferably 0.01 to 30% by weight with respect to the total amount (100% by weight) of the curable resin composition. 0.1 to 20% by weight is more preferable, and 0.5 to 10% by weight is still more preferable.

[Other silane compounds]
The curable resin composition of the present invention may contain other silane compounds (for example, compounds having a hydrosilyl group). Examples of the other silane compounds include methyl (trisdimethylsiloxy) silane, tetrakis (dimethylsiloxy) silane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5- Hexamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1, 1,3,5,5,7,7,7-nonamethyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,1,1, Examples thereof include linear or branched siloxanes having SiH groups such as 3,5,5,7,7,9,9,9-undecamethylpentasiloxane. In addition, the said silane compound can be used individually by 1 type or in combination of 2 or more types. The content of the silane compound is not particularly limited, but is preferably 0 to 5% by weight and more preferably 0 to 1.5% by weight with respect to the total amount (100% by weight) of the curable resin composition.

[solvent]
The curable resin composition of the present invention may contain a solvent. Examples of the solvent include conventionally known solvents such as toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, and propylene glycol monomethyl ether acetate. The said solvent can be used individually by 1 type or in combination of 2 or more types.

[Additive]
The curable resin composition of the present invention includes, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, Inorganic fillers such as carbon black, silicon carbide, silicon nitride, boron nitride, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; silicone resins, epoxy resins, Organic resin fine powders such as fluororesins; fillers such as conductive metal powders such as silver and copper, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorus) Flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents Lubricant, wax, plasticizer, release agent, impact resistance improver, hue improver, fluidity improver, colorant (dye, pigment, etc.), dispersant, defoamer, defoamer, antibacterial agent, preservative Conventional additives such as a viscosity modifier and a thickener may be included. These additives can be used alone or in combination of two or more.

[Curable resin composition]
Although the curable resin composition of the present invention is not particularly limited, the curable resin composition with respect to the total number of aliphatic carbon-carbon double bonds bonded to silicon atoms present in the compound contained in the curable resin composition. The ratio of the total number of hydrosilyl groups present in the compound contained in the product (also the molar ratio) is less than 1 (preferably 0.20 or more and less than 1.00, more preferably 0.50 to 0.98, even more preferably Is preferably 0.70 to 0.95) (formulation composition). By setting the ratio of the hydrosilyl group and the aliphatic carbon-carbon double bond within the above range, the hardness of the cured product decreases, so the load on the wire when used as an LED sealing material is reduced, and the reliability against thermal shock is reduced. Tend to improve.
In this specification, an aliphatic carbon-carbon double bond bonded to a silicon atom means an aliphatic carbon-carbon double bond contained in a substituent of the silicon atom. The aliphatic carbon-carbon double bond bonded to the silicon atom includes the terminal of the substituent of the silicon atom and the aliphatic carbon-carbon double bond other than the terminal.

The curable resin composition of the present invention is not particularly limited, but can be prepared, for example, by stirring and mixing the above components at room temperature. In addition, the curable resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately. It can also be used as a multi-component (for example, two-component) composition in which the components are mixed at a predetermined ratio before use.

The curable resin composition of the present invention is not particularly limited, but is preferably liquid at room temperature (about 25 ° C.). More specifically, the curable resin composition of the present invention has a viscosity at 25 ° C. of preferably 300 to 20000 mPa · s, more preferably 500 to 10000 mPa · s, and still more preferably 1000 to 8000 mPa · s. If the viscosity is less than 300 mPa · s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 20000 mPa · s, it is difficult to prepare and handle the curable resin composition, and bubbles may remain in the cured product. In addition, the viscosity of curable resin composition can be measured by the method similar to the viscosity of the above-mentioned ladder type silsesquioxane (B1), for example.

[Cured product]
By curing the curable resin composition of the present invention by a curing reaction (hydrosilylation reaction), a cured product (hereinafter sometimes referred to as “cured product of the present invention”) can be obtained. The conditions for the curing reaction are not particularly limited and can be appropriately selected from conventionally known conditions. For example, from the viewpoint of reaction rate, the temperature (curing temperature) is 25 to 180 ° C. (more preferably 60 ° C. to 150 ° C.). ° C), and the time (curing time) is preferably 5 to 720 minutes. The cured product of the present invention is excellent in various physical properties such as heat resistance, transparency, flexibility and the like, and further excellent in reflow resistance such as crack resistance in a reflow process and adhesion to a package, and in barrier properties against corrosive gas. Also excellent.

The A hardness before aging of the cured product of the present invention is not particularly limited, but is preferably less than 70, more preferably 30 to 69, still more preferably 40 to 68, and particularly preferably 45 or more and less than 60. When the A hardness before aging is within the above range, the hardness tends to hardly increase even after heating (for example, after heating at 200 ° C. for 500 hours). In particular, when the A hardness is less than 60, an increase in hardness after heating tends to be further suppressed. The A hardness before aging specifically refers to a value measured by the method described in “(A hardness before aging, A hardness after aging)” in (Evaluation) described later.
The A hardness before aging is bonded to, for example, silicon atoms present in all compounds contained in the curable resin composition with respect to hydrosilyl groups present in all compounds contained in the curable resin composition before curing. Adjusted by the ratio of aliphatic carbon-carbon double bond, vinyl weight ratio of polyorganosiloxane (A) and silsesquioxane (B), Si-H weight ratio, and blend amount of silsesquioxane (B) can do.

The A hardness after aging of the cured product of the present invention (after aging at 200 ° C. for 500 hours) is not particularly limited, but is preferably, for example, less than 90, more preferably 50 to 89, still more preferably 60 to 85, and particularly preferably. Is 65-75. When the A hardness after aging is in the above range, the heat resistance and the reliability against thermal shock are excellent. In particular, by being 85 or less, the heat resistance and the reliability against thermal shock are further improved. The A hardness after aging specifically refers to a value measured by the method described in “A hardness before aging, A hardness after aging” in (Evaluation) described later.
The A hardness after the aging is bonded to, for example, silicon atoms present in all compounds contained in the curable resin composition with respect to hydrosilyl groups present in all compounds contained in the curable resin composition before curing. It can be adjusted by the ratio of the aliphatic carbon-carbon double bond, the vinyl weight percentage contained in the polyorganosiloxane (A) or silsesquioxane (B), the SiH weight percentage, the amount of hydrosilylation catalyst, and the like.

[Encapsulant and semiconductor device]
The sealing material of the present invention is a sealing material containing the curable resin composition of the present invention as an essential component. The sealing material (cured product) obtained by using (for example, curing) the sealing material of the present invention is excellent in various physical properties such as heat resistance, transparency and flexibility, and further, reflow resistance and corrosion resistance. Excellent barrier to gas. Therefore, the sealing material of the present invention is preferably used as a sealing material for a semiconductor element in a semiconductor device, particularly as a sealing material for an optical semiconductor element (particularly, a high-luminance, short-wavelength optical semiconductor element) in an optical semiconductor device. Can be used. By sealing a semiconductor element (especially an optical semiconductor element) using the sealing material of the present invention, a semiconductor device (particularly an optical semiconductor device) excellent in durability and quality can be obtained.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these.

¹ H-NMR analysis of the reaction product and product was performed by JEOL ECA500 (500 MHz).
In addition, the number average molecular weight and the weight average molecular weight of the reaction product and the product are measured by Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR -M × 2 (Tosoh Corporation) )), Guard column: Tskel guard column H _HR L (manufactured by Tosoh Corp.), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C., polystyrene conversion .

[Polyorganosiloxane (A)]
The following products were used as the polyorganosiloxane (A).
GD-1012A: manufactured by Changxing Chemical Industry Co., Ltd., vinyl group content 1.33% by weight, phenyl group content 0% by weight, SiH group (hydride conversion) content 0% by weight, number average molecular weight 5108, weight average molecular weight 23385
GD-1012B: manufactured by Changxing Chemical Industry Co., Ltd., vinyl group content 1.65% by weight, phenyl group content 0% by weight, SiH group (in terms of hydride) content 0.19% by weight, number average molecular weight 4563, weight average molecular weight 21873
KER-2500A: manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.53% by weight, phenyl group content 0% by weight, SiH group (hydride conversion) content 0.03% by weight, number average molecular weight 4453, weight Average molecular weight 19355
KER-2500B: manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.08% by weight, phenyl group content 0% by weight, SiH group (hydride conversion) content 0.13% by weight, number average molecular weight 4636, weight Average molecular weight 18814

[Synthesis of Silsesquioxane (B)]
<Synthesis Example 1>
In a reaction vessel, 30.06 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 21.39 g of vinyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 17.69 g of methyl isobutyl ketone (MIBK) are charged. These mixtures were cooled to 10 ° C. To the above mixture, 281 mmol (5.06 g) of water and 0.48 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) were added dropwise over 1 hour. After the addition, these mixtures were kept at 10 ° C. for 1 hour. Thereafter, 80.0 g of MIBK was added to dilute the reaction solution.
Next, the temperature of the reaction vessel was raised to 70 ° C., and when the temperature reached 70 ° C., 703 mmol (12.64 g) of water was added, and the polycondensation reaction was performed under nitrogen for 12 hours.
Subsequently, 15.0 g of hexamethyldisiloxane was added to the reaction solution after the polycondensation reaction, and a silylation reaction was performed at 70 ° C. for 3 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer solution became neutral, and then the upper layer solution was collected. Next, the solvent was distilled off from the upper layer solution under the conditions of 1 mmHg and 60 ° C. to obtain 22.0 g of ladder-type silsesquioxane having a trimethylsilyl group at the terminal as a colorless and transparent solid product.
The ladder-type silsesquioxane has a weight average molecular weight (Mw) of 5000, a vinyl group content (average content) per molecule of 11.68% by weight, and a methyl group / vinyl group (molar ratio) is 60/40.
The ¹ H-NMR spectrum of the ladder-type silsesquioxane was as follows.
¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )) δ: 0 to 0.3 ppm (br), 5.8 to 6.1 ppm (br)

<Synthesis Example 2>
A reaction vessel was charged with 34.07 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 11.49 g of phenyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and 17.69 g of methyl isobutyl ketone (MIBK). The mixture was cooled to 10 ° C. To the above mixture, 240 mmol (4.33 g) of water and 0.48 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) were added dropwise over 1 hour. After the addition, these mixtures were kept at 10 ° C. for 1 hour. Thereafter, 80.0 g of MIBK was added to dilute the reaction solution.
Next, the temperature of the reaction vessel was raised to 70 ° C., and when the temperature reached 70 ° C., 606 mmol (10.91 g) of water was added, and the polycondensation reaction was performed under nitrogen for 9 hours. Furthermore, 6.25 g of vinyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and reacted for 3 hours.
Subsequently, 15.0 g of hexamethyldisiloxane was added to the reaction solution after the polycondensation reaction, and a silylation reaction was performed at 70 ° C. for 3 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer solution became neutral, and then the upper layer solution was collected. Next, the solvent is distilled off from the upper layer solution under conditions of 1 mmHg and 60 ° C., and a ladder-type silsesquioxane having a vinyl group and a trimethylsilyl group at the terminal (the above-described ladder-type silsesquioxane (B1) is used. Was obtained as a colorless and transparent liquid product.
The ladder type silsesquioxane has a weight average molecular weight (Mw) of 3400, a vinyl group content per molecule (average content) of 3.96% by weight, and a phenyl group / methyl group / vinyl group (moles). Ratio) was 17/68/15.
The ¹ H-NMR spectrum of the ladder-type silsesquioxane was as follows.
¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )) δ: -0.3-0.3 ppm (br), 5.7-6.2 ppm (br), 7.1-7.7 ppm (br)

<Synthesis Example 3>
A reaction vessel was charged with 31.06 g of methyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.), 2.38 g of phenyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.), and 93.00 g of methyl isobutyl ketone (MIBK). The mixture was cooled to 10 ° C. To the above mixture, 240 mmol (4.33 g) of water and 0.24 g of 5N hydrochloric acid (1.2 mmol as hydrogen chloride) were added dropwise over 1 hour. After the addition, these mixtures were kept at 10 ° C. for 1 hour.
Next, the temperature of the reaction vessel was raised to 50 ° C., and when the temperature reached 50 ° C., 120 mmol (2.16 g) of water was added, and the polycondensation reaction was performed under nitrogen for 4 hours. Furthermore, 11.18 g of vinyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and reacted for 4 hours.
Subsequently, 19.5 g of hexamethyldisiloxane was added to the reaction solution after the polycondensation reaction, and the silylation reaction was performed at 50 ° C. for 1 hour. Thereafter, the reaction solution was cooled, washed with water until the lower layer solution became neutral, and then the upper layer solution was collected. Next, the solvent is distilled off from the upper layer solution under conditions of 1 mmHg and 60 ° C., and a ladder-type silsesquioxane having a vinyl group and a trimethylsilyl group at the terminal (the above-described ladder-type silsesquioxane (B1) is used. Was obtained as a colorless and transparent liquid product.
The ladder type silsesquioxane had a number average molecular weight (Mn) of 879 and a weight average molecular weight (Mw) of 1116.

<Synthesis Example 4>
In a reaction vessel, 12 g of ladder-type silsesquioxane obtained in Synthesis Example 2, 24 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.0% platinum- 10 μl of a cyclovinylsiloxane complex vinylcyclosiloxane solution (manufactured by Wako Pure Chemical Industries, Ltd.) was charged. Subsequently, the reaction was completed by heating at 70 ° C. for 8 hours. Subsequently, after concentrating with an evaporator, the pressure is reduced at 0.2 Torr for 3 hours using a vacuum pump, and a ladder-type silsesquioxane having a SiH-containing group and a trimethylsilyl group at the terminal (the above-described ladder-type silsesquioxane ( Equivalent to B2) was obtained as a liquid product.
The ladder-type silsesquioxane has a weight average molecular weight (Mw) of 3700, and the SiH group content (average content) per molecule is 0.11% by weight in terms of the weight of H (hydride) in the SiH group. there were.
The ¹ H-NMR spectrum of the ladder-type silsesquioxane was as follows.
¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )) δ: -0.3-0.3 ppm (br), 4.7 ppm (s), 7.1-7.7 ppm (br)

[Isocyanurate Compound (C)]
The following products were used as the isocyanurate compound (C).
Monoallyl diglycidyl isocyanurate: manufactured by Shikoku Chemicals Co., Ltd.

[Silane coupling agent (D)]
The following products were used as the silane coupling agent (D).
3-Glycidyloxypropyltrimethoxysilane: manufactured by Toray Dow Corning

[Carboxylate of rare earth metal atom (E)]
The following products were used as carboxylate (E) of rare earth metal atoms.
Octope R: 2-ethylhexanoic acid rare earth (manufactured by Hope Pharmaceutical Co., Ltd .; rare earths include cerium, lanthanum, neodymium, praseodymium. As solvent, 2-ethylhexanoic acid: 8 wt%, mineral spirit 68% Including)
Yttrium 2-ethylhexanoate (Wako Pure Chemical Industries, Ltd .; Yttrium 2-ethylhexanoate (III), 49% toluene solution)
Cerium 2-ethylhexanoate (Wako Pure Chemical Industries, Ltd .; cerium (III) 2-ethylhexanoate, 49% 2-ethylhexanoic acid solution)

<Examples and Comparative Examples>
Examples 1 to 9 and Comparative Examples 1 to 4 were carried out according to the following procedure.
According to Table 1, the isocyanurate compound (C) and the silane coupling agent (D) were mixed at a predetermined weight ratio, and then the rare earth metal atom carboxylate (E) and silsesquioxane (B) were mixed. Stir for 2 hours at ° C. Then, it cooled to room temperature, mixed polyorganosiloxane (A), and stirred for 10 minutes at room temperature, and obtained curable resin composition.

[Evaluation]
About the sample obtained by the Example and the comparative example, it evaluated by the following measuring method or evaluation method.

(Rare earth metal atom content (ppm))
The content of rare earth metal atoms relative to the curable resin compositions (100% by weight) obtained in Examples 1 to 9 and Comparative Examples 1 to 4 was determined using the rare earth metal atoms contained in the sample using ICP-MS. It was measured by quantitative analysis.
Device: Product name “Agilent 7500cs” (manufactured by Yokogawa Analytical Systems)
A sample prepared by diluting with a solvent was used as a test solution for ICP-MS measurement. The standard solution for the calibration curve was used by adding a solution obtained by appropriately diluting the standard solution for atomic absorption of each element to the above test solution.

(SiH / Vinyl (molar ratio))
Curable resin composition with respect to 1 mol of an aliphatic carbon-carbon double bond bonded to a silicon atom present in the compounds contained in the curable resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 4. The ratio (molar ratio) of the number of moles of hydrosilyl groups present in the compound contained in the product was measured by ¹ H-NMR under the following conditions.
In addition, the ratio (weight basis) of the hydrosilyl group was calculated | required by the weight conversion (H conversion) of H (hydride) in SiH group.
Measuring condition apparatus: JEOL ECA500 (500 MHz, solvent: CDCl ₃ ) δ: 5.7-6.2 ppm, δ: 4.6-4.8 ppm

(A hardness before aging, A hardness after aging)
The curable resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were each poured into an aluminum cup having a diameter of 6 cm, and heated at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours. The obtained cured product was taken out from the aluminum cup and used as a sample for a 200 ° C. aging test. The thickness of the obtained sample was 6 mm.
Based on JIS K6253, A hardness (A hardness before aging) of the obtained sample was measured.
The obtained sample was put in an oven (model number “DN4101” manufactured by Yamato Scientific Co., Ltd.) at a temperature of 200 ° C. and taken out after 500 hours. According to JIS K6253, A hardness after aging at 200 ° C. for 500 hours (A after aging) Hardness).

(H ₂ S corrosion test)
The curable resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were injected into an LED package (trade name “SMD LED (Top View Type 3528 Pre Mold Lead Frame)” manufactured by SDI Corporation). Samples were prepared by heating at 100 ° C. for 1 hour, followed by heating at 150 ° C. for 5 hours.
The above sample was put in a gas corrosion tester (model number “GS-UV” manufactured by Suga Test Instruments Co., Ltd.) adjusted to a hydrogen sulfide concentration of 12 ppm, a temperature of 40 ° C., and a humidity of 80% RH. The state of electrode corrosion was observed. The color of the electrode is silver white before the test, but changes to brown and black as corrosion progresses.
The evaluation criteria for the corrosivity test are “A” when the silver electrode shows almost no discoloration, “B” when the discoloration is slightly brown or black, and “B” when the discoloration is completely brown or black. C ”.

(SO _x corrosion test)
The curable resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were injected into an LED package (trade name “SMD LED (Top View Type 3528 Pre Mold Lead Frame)” manufactured by SDI Corporation). Samples were prepared by heating at 100 ° C. for 1 hour, followed by heating at 150 ° C. for 5 hours.
The sample and 0.3 g of sulfur powder (manufactured by Kishida Chemical Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was further placed in an aluminum box. Subsequently, the aluminum box was put in an oven (manufactured by Yamato Scientific Co., Ltd., model number “DN-64”), and after 24 hours at 80 ° C., the corrosion state of the silver electrode in the LED package was observed. The color of the electrode is silver white before the test, but changes to brown and further black as corrosion progresses.
The evaluation standard of the corrosivity test was the same as that of the above H ₂ S corrosion test method.

[Test results]
In Comparative Example 1, since the rare earth metal atom carboxylate (E) was not added, the hardness increased significantly after thermal aging, and the heat resistance of the cured product was not recognized. Further, no H ₂ S corrosion resistance was observed.
In Comparative Example 2, a small amount of a rare earth metal atom carboxylate (E) was added, but the hardness increased significantly after thermal aging, and the heat resistance of the cured product was not recognized. Further, no H ₂ S corrosion resistance was observed.
In Comparative Example 3 and Comparative Example 4, since the rare earth metal atom carboxylate (E) was not added, the hardness significantly increased after thermal aging, and the heat resistance of the cured product was not recognized. Moreover, the effect of H ₂ S corrosion resistance was not recognized. Furthermore, since no silsesquioxane (B) and isocyanurate compound (C) were added, no SO _x corrosion resistance was observed.

In Examples 1 to 9, by adding a sufficient amount of the carboxylate (E) of a rare earth metal atom to Comparative Examples 1 and 2, the increase in hardness is small even after aging at 200 ° C. for 500 hours. Improved heat resistance. Furthermore, it was recognized that the H ₂ S corrosion resistance was also improved.
From comparison between Examples 4 to 5 and other examples, as the rare earth metal carboxylate (E), Octopo R, yttrium 2-ethylhexanoate and cerium 2-ethylhexanoate had the same heat resistance, It was found to exhibit resistance to H ₂ S corrosion.

(About SiH / Vinyl)
In Comparative Example 1 and Comparative Example 2, the compound contained in the curable resin composition with respect to 1 mol of an aliphatic carbon-carbon double bond bonded to the silicon atom present in the compound contained in the curable resin composition Since the number of moles (molar ratio) of hydrosilyl groups present was less than 1, the A hardness before aging was low and less than 60. However, the increase in the A hardness due to aging at 200 ° C. for 500 hours was relatively larger than those in Comparative Examples 3 and 4, and the heat resistance of the cured product was not recognized.
On the other hand, in Examples 1 to 7, all compounds contained in the curable resin composition with respect to 1 mol of an aliphatic carbon-carbon double bond bonded to a silicon atom present in the compound contained in the curable resin composition. Since the number of moles (molar ratio) of the hydrosilyl group present in is less than 1, the A hardness before aging was low and less than 60. In Examples 1 to 7, by adding a sufficient amount of the carboxylate (E) of a rare earth metal atom, the increase in A hardness by aging at 200 ° C. for 500 hours is the same as in Examples 8 to 9. It was about.
From the above, it was confirmed that a composition having heat resistance and H ₂ S corrosion resistance can be obtained by adding a sufficient amount of the carboxylate (E) of the rare earth metal atom to the silicone resin. . Further, by adding silsesquioxane (B), and isocyanurate compound (C), the composition having a resistance to SO _x corrosion was observed that the obtained.

The curable resin composition and cured product of the present invention are useful for applications such as adhesives, coating agents, and sealing materials that are required to have heat resistance, transparency, flexibility, and barrier properties against corrosive gases. In particular, the curable resin composition and the cured product of the present invention are suitable as a sealing material for an optical semiconductor element (LED element).

Claims

A polyorganosiloxane containing polyorganosiloxane (A), silsesquioxane (B), isocyanurate compound (C), and carboxylate (E) of a rare earth metal atom, and having no aryl group as polyorganosiloxane (A) A curable resin composition comprising siloxane and ladder-type silsesquioxane as silsesquioxane (B).
The curable resin composition according to claim 1, wherein the ladder-type silsesquioxane includes a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule.
3. The curable resin composition according to claim 1, wherein the ladder-type silsesquioxane includes a ladder-type silsesquioxane having a Si—H bond in the molecule.
The curable resin composition according to any one of claims 1 to 3, wherein the ladder-type silsesquioxane includes a ladder-type silsesquioxane having an aryl group in a molecule.
As the isocyanurate compound (C), the formula (1)

[In the formula (1), R x , R y and R z are the same or different and represent a group represented by the formula (2) or a group represented by the formula (3).

[In Formula (2) and Formula (3), R 1 and R 2 are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
The curable resin composition according to any one of claims 1 to 4, comprising an isocyanurate compound represented by the formula:
The isocyanurate compound represented by the formula (1) is an isocyanurate compound in which one or more of R x , R y , and R z are groups represented by the formula (3). Curable resin composition.
The curable resin composition according to any one of claims 1 to 6, comprising yttrium carboxylate as the rare earth metal atom carboxylate (E).
The curable resin composition according to any one of claims 1 to 6, wherein the rare-earth metal atom carboxylate (E) is a mixture of cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, and neodymium carboxylate. .
Of Si—H groups present in the compound contained in the curable resin composition relative to the total number of aliphatic carbon-carbon double bonds bonded to silicon atoms present in the compound contained in the curable resin composition The curable resin composition according to any one of claims 1 to 8, wherein the ratio of the total number is less than 1.
The curable resin composition according to any one of claims 1 to 9, further comprising a silane coupling agent (D).
A cured product obtained by curing the curable resin composition according to any one of claims 1 to 10.
A sealing material obtained using the curable resin composition according to any one of claims 1 to 10.
A semiconductor device obtained using the sealing material according to claim 12.