KR20150028368A - Curable resin composition and semiconductor device obtained using same - Google Patents

Abstract

The invention seals the use of with also having transparency, heat resistance, flexibility, and hydrogen sulfide (H ₂ S) barrier performance SOx for gas (SO _X) combines the barrier properties of the gas, the semiconductor device (particularly an optical semiconductor element) A cured product using the same, a sealing material, and a semiconductor device.
A curable resin composition comprising a polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C) and a zinc compound (E), wherein the polyorganosiloxane (A) (A) and silsesquioxane (B), and the total amount of the polyorganosiloxane (A) and the silsesquioxane (B) 100 parts by weight), and a cured product, a sealing material and a semiconductor device using the curable resin composition.

Description

Technical Field [0001] The present invention relates to a curable resin composition and a semiconductor device using the same,

The present invention relates to a curable resin composition, a cured product obtained by using the curable resin composition, a sealing material, and a semiconductor device obtained by using the sealing material. This application claims priority of Japanese Patent Application No. 2013-160291, filed in Japan on Aug. 1, 2013, the content of which is incorporated herein by reference.

In a semiconductor device requiring a high heat resistance and a high withstand voltage, a material covering the semiconductor element is generally required to have a heat resistance of about 150 캜 or more. Particularly, a material (sealing material) for covering 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. Presently, for example, as a sealing material in a backlight unit of a liquid crystal display, an epoxy resin material or a silicone resin material is used.

Patent Document 1 discloses a material having a high heat resistance and a good heat dissipation property and containing at least one first organosilicon polymer having a crosslinking structure of siloxane (Si-O-Si bond) and at least one first organosilicon polymer having a linear structure of a siloxane Discloses a synthetic polymer compound containing at least one kind of a third organosilicon polymer having a molecular weight of 20,000 to 800,000 linked by a siloxane bond. However, the physical properties of these materials are not yet satisfactory.

Patent Document 2 discloses a resin composition for optical device encapsulation that is excellent in transparency, UV resistance, and heat resistance and color fastness. It is a resin composition for optical device encapsulation, which comprises a liquid silsesquioxane having a cage structure containing an aliphatic carbon-carbon unsaturated bond and containing no H- , And liquid silsesquioxane of a cage-like structure containing an H-Si bond and containing no aliphatic carbon-carbon unsaturated bond as a resin component, wherein the silsesquioxane is at least one selected from the group consisting of Discloses a resin composition for sealing. However, the cured product of the resin composition containing cage-like silsesquioxane is relatively hard and has a low flexibility, so that there is a problem that cracks and cracks are likely to occur.

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, a chain-like and / or branched chain containing at least two SiH groups in one molecule A compound such as cyclic polyorganosiloxane, and a curing composition containing a hydrosilylation catalyst as an essential component. However, the physical properties such as crack resistance of these materials are not yet satisfactory.

On the other hand, in the optical semiconductor device, a metal material such as an electrode is likely to be corroded by corrosive gas, and there is a problem that the electrification characteristic (for example, the electrification characteristic in a high temperature environment) deteriorates over time. Therefore, sealing materials for optical semiconductors are required to have high barrier properties against corrosive gases. However, sealing materials using conventional silicone-based resin materials disclosed in Patent Documents 1 to 3 and the like can not be said to have sufficient barrier property to corrosive gas.

Patent Document 4 discloses a resin composition comprising (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, (C) a hydrosilylation reaction catalyst, ) Zinc compound and 0.1 to 5 parts by mass of the component (D) relative to 100 parts by mass of the total of the component (A) and the component (B) . However, although corrosion resistance against hydrogen sulfide (H ₂ S) is disclosed, no corrosion resistance against other corrosive gases has been described at all.

Japanese Patent Application Laid-Open No. 2006-206721 Japanese Patent Laid-Open No. 2007-031619 Japanese Patent Application Laid-Open No. 2002-314140 Japanese Patent Laid-Open No. 11-178983

Corrosive gas that corrodes the semiconductor device has a plurality of types exist, a typical corrosive gas hydrogen sulfide (H ₂ S) sealed with a sufficient barrier property even as the gas or sulfur oxides (SO _X) gas or the like, a plurality of corrosive gases, which The material has not yet been disclosed.

Therefore, an object of the present invention is to provide a gas barrier film which has transparency, heat resistance and flexibility and is excellent in barrier properties against corrosive gases (in particular, barrier properties against hydrogen sulfide (H ₂ S) gas (H ₂ S corrosion resistance) (For example, a cured product useful for sealing applications of a semiconductor element (in particular, an optical semiconductor element)) excellent in barrier property (SO _X corrosion resistance) against SO _X gas I have to.

Another object of the present invention is to provide a cured product obtained by curing the curable resin composition. It is another object of the present invention to provide a sealing material obtained using the curable resin composition. Another object of the present invention is to provide a semiconductor device obtained by using the sealing material.

In the present specification, no deterioration is caused even when high-temperature heat is applied in the reflow process during the production of the optical semiconductor device. Specifically, cracks are unlikely to occur in the sealing material, and peeling or the like A property that does not cause the problem of " flowability " In the present specification, the property that the sealing material is less prone to cracking is sometimes referred to as " crack resistance ".

The present inventors have found that a curable resin composition obtained by adding a silsesquioxane, an isocyanurate compound and a zinc compound to a polyorganosiloxane having no aryl group has excellent heat resistance, transparency, flexibility, and flowability, It is possible to form a cured product having excellent barrier properties against gas (in particular, H ₂ S corrosion resistance and SO _x corrosion resistance), and thus the present invention has been completed.

That is, the present invention provides a curable resin composition comprising a polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C) and a zinc compound (E) (B) is a polyorganosiloxane having no aryl group and the ladder-type silsesquioxane is contained as the silsesquioxane (B), and the content of the zinc compound (E) is less than the content of the polyorganosiloxane (A) and the silsesquioxane B) is not less than 0.01 parts by weight and less than 0.1 parts by weight based on the total amount (100 parts by weight) of the curable resin composition.

The present invention also provides the curable resin composition comprising ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule as silsesquioxane (B).

Further, the present invention provides the above curable resin composition comprising ladder-type silsesquioxane having Si-H bonds in its molecule as silsesquioxane (B).

Further, the present invention provides the curable resin composition comprising ladder-type silsesquioxane having an aryl group in the molecule as silsesquioxane (B).

The present invention also provides the curable resin composition comprising the isocyanurate compound represented by the formula (1) as the isocyanurate compound (C).

[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).

[Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom or a straight or branched alkyl group having 1 to 8 carbon atoms]

The present invention also provides the curable resin composition wherein at least one of R ^x , R ^y and R ^z in the formula (1) is a group represented by the formula (3).

Further, the present invention provides the curable resin composition containing zinc carboxylate as the zinc compound (E).

The present invention also provides the curable resin composition comprising a polyorganosiloxane having a structure represented by formula (6) as the polyorganosiloxane (A).

[In the 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. Provided that at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond. R ²⁷ represents a divalent hydrocarbon group. r and s each represent an integer of 1 or more.

Further, the present invention provides the curable resin composition further comprising a silane coupling agent (D).

The present invention also provides a cured product obtained by curing the curable resin composition.

Further, the present invention provides a sealing material obtained by using the curable resin composition.

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

Further, the curable resin composition of the present invention relates to the following.

[1] A curable resin composition comprising a polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C) and a zinc compound (E), wherein the polyorganosiloxane (A) (A) and silsesquioxane (B), wherein the content of the zinc compound (E) is at least one kind selected from the group consisting of a polyorganosiloxane (A) and a silsesquioxane Is not less than 0.01 parts by weight and less than 0.1 parts by weight based on the total amount (100 parts by weight) of the curing resin composition.

[2] The curable resin composition according to [1], wherein the polyorganosiloxane (A) has a branched chain and is a polyorganosiloxane having no aryl group.

[3] The polyorganosiloxane (A) contains a structure represented by the formula (6) (particularly, R ²⁷ is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, more preferably an ethylene group) 1] or [2], wherein the polyorganosiloxane is a polyorganosiloxane having a branched chain and no aryl group.

[4] The polyorganosiloxane (A) is a polyorganosiloxane having a structure represented by the formula (6) (R ²⁷ is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, more preferably an ethylene group) (Mw / Mn) of 1.0 to 7.0 (more preferably 2.0 to 6.5, still more preferably 3.0 to 6.0, particularly preferably 4.0 or more but not more than 5.5) having a branched chain, a branched chain, , Wherein the polyorganosiloxane is at least one selected from the group consisting of a polyorganosiloxane and a polyorganosiloxane. The curable resin composition according to any one of [1] to [3]

[5] The curable resin composition according to any one of [1] to [4], wherein the content (amount) of the polyorganosiloxane (A) is 55 to 95% by weight based on the total amount (100% .

[6] A process for producing a silsesquioxane resin composition according to any one of [1] to [5], wherein the silsesquioxane (B) is a ladder-type silsesquioxane having an aliphatic carbon- [1] to [5], which is at least one ladder-type silsesquioxane selected from the group consisting of ladder-type silsesquioxane in which T is a trimethylsilyl group and ladder-type silsesquioxane having an aryl group in the molecule, Wherein the curable resin composition is a curable resin composition.

[7] The curable resin composition according to any one of [1] to [6], wherein the content (amount) of the silsesquioxane (B) is 5 to 45% by weight relative to the total amount (100% .

[8] The curable resin composition according to any one of [1] to [7], wherein the ratio of the silsesquioxane (B) to the polyorganosiloxane (A) is 1 to 40 parts by weight.

(1) wherein R ^x , R ^y and R ^z are the same or different and are a group represented by the formula (2) or a group represented by the formula (3) (2) and (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a straight or branched alkyl group having 1 to 8 carbon atoms] The curable resin composition according to any one of [1] to [8], which contains a cyanurate compound.

[10] The process according to any one of [1] to [9], wherein the isocyanurate compound (C) is monoallyldiglycidylisocyanurate, triallyl isocyanurate, or monomethyl diglycidylisocyanurate Wherein the curable resin composition according to any one of < 1 >

[11] The curable resin composition according to any one of [1] to [10], wherein the content of the isocyanurate compound (C) is 0.01 to 10% by weight based on the total amount (100% by weight) of the curable resin composition.

[1] to [11], wherein the ratio of the isocyanurate compound (C) to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B) Wherein the curable resin composition is a curable resin composition.

[13] The curable resin composition according to any one of [1] to [12], further comprising a silane coupling agent (D).

[14] The curable resin composition according to [13], wherein the silane coupling agent (D) is 3-glycidoxypropyltrimethoxysilane.

[15] The curable resin composition according to any one of [1] to [14], wherein the zinc compound (E) is zinc bisacetylacetonate, zinc naphthenate or zinc octylate.

[16] The curable resin composition according to any one of [1] to [15], wherein the content of the zinc compound (E) is 0.05 to 0.085% by weight based on the total amount (100% by weight) of the curable resin composition.

[17] The curable resin composition according to any one of [1] to [16], wherein the zinc content of the total amount of the zinc compound (E) compound (100% by weight) is 2 to 30% by weight.

As the curable resin composition of the present invention having the above structure, heat resistance, transparency, flexibility, reflow property, adhesion, etc. it is excellent, and H ₂ S gas and SO _X gas or the like, a plurality of corrosive gases (in particular, in H ₂ S corrosion resistance and SO _x corrosion resistance) can be formed. Therefore, the cured product of the curable resin composition of the present invention is useful as a sealing material for a semiconductor device, particularly as a sealing material for an optical semiconductor element such as an LED. Further, the curable resin composition of the present invention can obtain a next-generation light source sealing material which requires heat resistance in a high temperature (for example, 180 DEG C or higher) environment. Further, the optical semiconductor device is sealed by the cured product of the curable resin composition of the present invention, so that an optical semiconductor device excellent in quality and durability can be obtained.

The curable resin composition of the present invention is a curable resin composition comprising as essential components a polyorganosiloxane (A), silsesquioxane (B), isocyanurate compound (C) and zinc compound (E) Wherein the organosiloxane (A) is a polyorganosiloxane having no aryl group and the ladder-type silsesquioxane as the silsesquioxane (B), the content of the zinc compound (E) Is not less than 0.01 parts by weight and less than 0.1 parts by weight based on the total amount (100 parts by weight) of silsesquioxane (B).

[Polyorganosiloxane (A)]

The polyorganosiloxane (A) in the curable resin composition of the present invention is a polyorganosiloxane having a main chain composed of a siloxane bond (Si-O-Si), and is a polyorganosiloxane having no aryl group. Among them, the polyorganosiloxane (A) is preferably a polyorganosiloxane having branched chains (branched-chain polyorganosiloxane) in view of the strength of the cured product. The polyorganosiloxane (A) is a linear or branched polyorganosiloxane having a hydrosilyl group and / or a group having an aliphatic carbon-carbon unsaturated bond (preferably, a hydrosilyl group and / or an aliphatic carbon-carbon unsaturated bond Or a branched polyorganosiloxane having a group having a group represented by the following formula (1). Examples of the silicon skeleton (main chain) in the polyorganosiloxane (A) include silicone skeletons such as dimethyl silicone skeleton (polydimethylsiloxane). Further, the polyorganosiloxane (A) does not contain silsesquioxane (B).

The polyorganosiloxane having no aryl group is a polyorganosiloxane having substantially no aryl group in the molecule. Specifically, the content of the aryl group relative to the total amount (100% by weight) of the polyorganosiloxane (A) is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, more preferably 0.1% , And it is particularly preferable that no aryl group is present in the polyorganosiloxane (A). If the content of the aryl group exceeds 0.5% by weight, desired properties (heat resistance, refractive index, etc.) of the cured product may not be obtained. The aryl group includes, for example, and the like can be mentioned C _{6- 14} aryl group, a phenyl group, a naphthyl group or the like. The aryl group also includes those having a substituent.

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

The alkyl group as the C _{1- 10} alkyl group and more preferably C _{1- 4} alkyl group. Examples of the alkenyl group preferably a C _{2- 10} alkenyl Al, and more preferably alkenyl groups are C _{2- 4} Al. Examples of the cycloalkyl group is preferably a C _{3- 12} cycloalkyl group. As the cycloalkenyl group is preferably a _3- C ₁₂ cycloalkenyl. Examples of the alkoxy group is preferably a C _{1- 6} alkoxy. As the alkenyloxy group is preferably a C _{1- 6} alkenyloxy. As the acyloxy group is preferably a C _{1- 6} acyloxy. Examples of the alkylthio group is preferably a C _{1- 6} alkylthio. Examples of the alkenyl groups are preferred nilti come C _{1- 6} alkenyl thio. The alkoxycarbonyl group is preferably a C _1-6 alkoxycarbonyl group.

As the above-mentioned polyorganosiloxane (A), at least one or more selected from a hydrogen atom, a group having an Si-H bond, a substituted or unsubstituted hydrocarbon group (preferably an alkyl group or an alkenyl group) Particularly preferred are polyorganosiloxanes having a substituent.

The position of the substituent in the polyorganosiloxane (A) is not particularly limited, and may be located on the side chain or on the end with respect to the main chain composed of the siloxane bond (Si-O-Si).

The number average molecular weight of the polyorganosiloxane (A) is preferably 500 to 20,000, more preferably 1,000 to 10,000, and still more preferably 2,000 to 8,000. The weight average molecular weight is preferably 500 to 50,000, more preferably 5,000 to 40,000, and still more preferably 10,000 to 30,000. The number average molecular weight and / or the weight average molecular weight can be calculated, for example, as molecular weight in terms of polystyrene by gel permeation chromatography.

In the curable resin composition of the present invention, the polyorganosiloxane (A) may be used singly or in combination of two or more. When two or more polyorganosiloxanes (A) are used in combination, at least one of them has a hydrosilyl group, and at least one of them preferably has an aliphatic carbon-carbon unsaturated bond. As the polyorganosiloxane (A) having a hydrosilyl group in the case of using two or more kinds of the polyorganosiloxane (A) in combination, a polyorganosiloxylalkylene having a hydrosilyl group, a branched poly An organosiloxane, and a branched chain polyorganosiloxylalkylene having a hydrosilyl group are preferable. Examples of the polyorganosiloxane (A) having an aliphatic carbon-carbon unsaturated bond in the case of using two or more kinds of the polyorganosiloxane (A) in combination include polyorganosiloxanes having an aliphatic carbon- , Branched-chain polyorganosiloxanes having aliphatic carbon-carbon unsaturated bonds, and branched-chain polyorganosiloxysilanes having aliphatic carbon-carbon unsaturated bonds are preferable.

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

The polyorganosiloxane (A) includes, for example, a polyorganosiloxane having a structure represented by the formula (6). In the present specification, the polyorganosiloxane containing the structure represented by the formula (6) is referred to as " polyorganosiloxysilylene. &Quot;

The polyorganosiloxane (A) preferably contains a polyorganosiloxysilane, more preferably a polyorganosiloxysilane alone. The polyorganosiloxysilylenes may be used singly or in combination of two or more.

In the 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. Provided that 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, and the like. 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. The group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, yisook group, a decyl group, straight or branched dodecyl group, such as C _{1- 20} alkyl group (preferably there may be mentioned C _{1- 10} alkyl group, more preferably an alkyl group such as C _{1- 4).} Examples of the alkenyl group include a vinyl group, an allyl group, a methallyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, , and 3-pentenyl group, 4-pentenyl group, 5-hexenyl group and the like of C _{2- 20} alkenyl group (preferably a C _{2- 10} alkenyl group, more preferably C _{2- 4} alkenyl group) have. As the alkynyl group, for example, ethynyl group, a propynyl group such as a C _{2- 20} alkynyl group, and the like (it is preferably C _2-10 alkynyl groups, more preferably C _2-4 alkynyl group).

The monovalent alicyclic hydrocarbon group includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl _3- C ₁₂ cycloalkyl group such as a group, a cyclohexyl group, a cycloalkyl dodecyl group; Cyclohexenyl group, and the like of _3- C ₁₂ cycloalkenyl group; And a C _4-15 bridged cyclic hydrocarbon group such as a bicycloheptanyl group and a bicycloheptenyl group.

Further, examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group, a methylcyclohexyl group, and the like.

The monovalent hydrocarbon group may have a substituent. That is, the monovalent hydrocarbon group may be a monovalent hydrocarbon group in which at least one hydrogen atom among the monovalent hydrocarbon groups exemplified above is substituted with a substituent. The number of carbon atoms of the substituent is preferably 0 to 20, more preferably 0 to 10. Specific examples of the substituent include a halogen atom; A hydroxyl group; An alkoxy group; An alkenyloxy group; Aralkyloxy groups; An acyloxy group; A mercapto group; An alkylthio group; Alkenylthio; An aralkylthio group; A carboxyl group; An alkoxycarbonyl group; An aralkyloxycarbonyl group; An amino group; A mono or dialkylamino group; A mono or diphenylamino group; An acylamino group; An epoxy group-containing group; An oxetanyl group-containing group; Acyl; An oxo group; Isocyanate group; Two or more thereof is necessary, and the like groups bonded via an _1- C ₆ alkylene group.

The alkoxy group includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropyl oxy group, a butoxy group, C _{1- 6} alkoxy group such as isobutyl-oxy group (preferably C _{1- 4} alkoxy group), etc. . Examples of the alkenyloxy group, for example, allyl (preferably _2- C ₄ alkenyloxy group) _2- C ₆ alkenyloxy group such as oxy, and the like. The aralkyl oxy group as the example, there may be mentioned a benzyloxy group, C _{7- 18} aralkyl oxy group such as a phenethyl tilok time. Examples of the acyloxy group include C _1-12 acyloxy groups such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group and benzoyloxy group.

Examples of the alkylthio group, for example, there may be mentioned a methyl thio group, ethyl come C _{1- 6} alkylthio, such as importing tea (preferably C _{1- 4} alkylthio group) and the like. The alkenyl nilti come as, for example, there may be mentioned the allyl-thio group such as C _{2- 6} alkenyl nilti come (preferably C _{2- 4} alkenyl nilti come), and the like. The aralkyl there may be mentioned an alkylthio as for example, benzyl-thio, phenethyl, etc. tilti import of C _{7- 18} aralkyl thio group and the like. And the like can be mentioned groups wherein the alkoxy group as, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, such as a C _{1- 6} alkoxy. The aralkyloxycarbonyl groups as, for example, benzyloxy-C _{7- 18} aralkyl group such as oxy-carbonyl group, and the like. Examples of the mono or dialkylamino group include a mono or di-C _1-6 alkylamino group such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group. Examples of the acylamino group, for example, there may be mentioned an acetyl group, a propionyl group, a C _{1- 11} acylamino group such as benzoylamino group and the like. Examples of the epoxy group-containing group include a glycidyl group, a glycidyloxy group and a 3,4-epoxycyclohexyl group. Examples of the oxetanyl group-containing group include ethyloxetanyloxy group and the like. Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.

The monovalent heterocyclic group may have a substituent. Examples of the substituent include the same substituents as the substituent that the monovalent hydrocarbon group may have.

More specific examples of the monovalent hydrocarbon group and the monovalent heterocyclic group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a pyridyl group, (For example, p-styryl group), a hydrocarbon group having a substituent (for example, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidyl Propyl group, 3-methoxypropyl group, 3-acryloxypropyl group, N-2- (aminoethyl) -3-aminopropyl group, 3- Anisopropylpropyl, etc.) and the like.

In the formula (6), R ²⁷ represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a linear or branched alkylene group and a divalent alicyclic hydrocarbon group. Examples of the linear or branched alkylene group include straight chain or branched alkylene groups 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. have. Examples of the bivalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3- And a divalent cycloalkylene group (including a cycloalkylidene group) such as a 1,4-cyclohexylene group and a cyclohexylidene group. Among them, R ²⁷ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms (particularly 1 to 5 carbon atoms), more preferably an ethylene group.

In the formula (6), r represents an integer of 1 or more. When r is an integer of 2 or more, the structures in parentheses attached with r may be the same or different from each other. When the structures in parentheses attached to r are different from each other, the addition form of each structure is not particularly limited and may be a random type or a block type. In the formula (6), s represents an integer of 1 or more. 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 attached to s are different from each other, the addition form of each structure is not particularly limited and may be a random type or a block type. In the formula (6), the addition form of the structure in parentheses to which r is appended and the structure in parentheses to which s is appended is not particularly limited, and may be a random type or a block type. 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 polyorganosiloxysilylene is not particularly limited, and examples thereof include a silanol group, an alkoxysilyl group, and a trialkylsilyl group (e.g., trimethylsilyl group). Various groups such as a group containing an aliphatic carbon-carbon double bond and a hydrosilyl group may be introduced into the terminal of the polyorganosiloxane having the structure represented by the formula (6).

As described above, the polyorganosiloxysilane may have either straight chain or branched chain structure, and particularly preferably has a branched chain. As the polyorganosiloxy alkylene, for example, a polyorganosiloxysilane having a branched chain and no aryl group is preferable.

The polyorganosiloxane (A) is not particularly limited, but may be a polyorganosiloxane having two or more (particularly, two) polyorganosiloxanes (particularly preferably two or more (particularly, two) Alkylene) is preferably used. Among them, it is preferable to use a compound having a molecular weight distribution (Mw / Mn) of 1.0 to 7.0 (more preferably 2.0 to 6.5, still more preferably 3.0 to 6.0, particularly preferably 4.0 or more and 5.5 or less) (Particularly preferably, at least two kinds of the above-mentioned polyorganosiloxysilylenes) is preferably used as the polyorganosiloxane. Particularly, the polyorganosiloxane (A) is preferably a polyorganosiloxane having a molecular weight dispersion degree (Mw / Mn) of 4.4 to 5.0 and having no aryl group (in particular, a polyorganosiloxane Preferably, two kinds of the above-mentioned polyorganosiloxy alkylene) are used.

The polyorganosiloxane (A) is not particularly limited, but from the viewpoint of better barrier property to corrosive gas, for example, two kinds of polyorganosiloxane (A) having different aliphatic carbon-carbon double bond content It is preferable to use a polyorganosiloxane (particularly preferably two kinds of polyorganosiloxysilylenes). Specifically, a polyorganosiloxane having an aliphatic carbon-carbon double bond content of 1.55 wt% or less (for example, 0.1 to 1.55 wt%, preferably 0.5 to 1.4 wt%) (preferably, And polyorganosiloxanes having a content of aliphatic carbon-carbon double bonds of more than 1.55% by weight (for example, greater than 1.55% by weight and less than 10% by weight, preferably 1.6 to 8% by weight) Preferably, polyorganosiloxysilkylene) is used.

Examples of the polyorganosiloxysilylenes include GD-1012A (manufactured by Choko Chemical Industry Co., Ltd.) and GD-1012B (manufactured by Choko Chemical Industry Co., Ltd.).

The content (blending amount, the total content when two or more kinds) of the polyorganosiloxane (A) in the curable resin composition of the present invention is not particularly limited, but the content of the polyorganosiloxane (A) in the curable resin composition of the present invention To 95% by weight, more preferably 60% to 92% by weight, and still 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, when the content exceeds 95% by weight, the gas barrier property against the corrosive gas may not be sufficiently obtained.

When two or more polyorganosiloxanes (A) are used, the proportion of the polyorganosiloxysilane to the total amount (100 wt%) of the polyorganosiloxane (A) in the curable resin composition of the present invention is (For example, 60 to 100% by weight), more preferably 80% by weight or more (for example, 80 to 99.5% by weight), more preferably 90% %. If the proportion of the polyorganosiloxysilylene is less than 60% by weight, the cured product tends to become yellowish or tends to have adhesiveness on the surface, so that the handling property tends to deteriorate.

[Silsesquioxane (B)]

The curable resin composition of the present invention comprises silsesquioxane (B) containing ladder type silsesquioxane as a main component. Ladder-type silsesquioxanes are polysiloxanes having a crosslinked three-dimensional structure.

The polysiloxane is a compound having a main chain composed of a siloxane bond (Si-O-Si), and its basic constitutional unit is an M unit (a unit comprising a monovalent group in which a silicon atom is bonded to one oxygen atom), a D 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).

Silsesquioxane is a polysiloxane of the T unit to the main unit, its empirical formula (Basic Structure) is represented by RSiO _{1 .5.} The Si-O-Si skeleton structure of silsesquioxane includes a random structure, a basket structure and a ladder structure, and the ladder silsesquioxane is silsesquioxane having a Si-O-Si skeleton structure of ladder structure .

A ladder-type silsesquioxane of the present invention the empirical formula (Basic Structure) RSiO _0.5 is represented by _1, with R containing a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent group containing 1 oxygen atom, a monovalent nitrogen atom Or a monovalent sulfur atom-containing group, and at least a part of R is a monovalent organic group. Each R 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, , An alkenylthio group, an arylthio group, an aralkylthio group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an epoxy group, a cyano group, an isocyanate group, a carbamoyl group and an isothiocyanate group .

Examples of the hydrocarbon group for R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups obtained by bonding two or more thereof.

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

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

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

Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group in R are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. The group bonded aliphatic hydrocarbon group and an aromatic hydrocarbon, for example, benzyl group, phenethyl group and so on of the C _{7- 18} aralkyl group (particularly, C _{7- 10} aralkyl group), such as thinner push the C _{6- 10} aryl -C _{2 -,} and the like ₆ alkenyl group, a tolyl group such as a C _{1- 4} alkyl-substituted aryl group, styryl group and so on in the C _{2- 4} alkenyl substituted aryl group.

The hydrocarbon group in R may have a substituent. The number of carbon atoms of the substituent in the hydrocarbon group is preferably 0 to 20, more preferably 0 to 10. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; A hydroxyl group; A methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, a butoxy group, an alkoxy group such as iso-butyl-oxy group (preferably a C _{1- 6} alkoxy group, more preferably C _{1- 4} alkoxy group); Alkenyloxy group such as allyloxy groups (preferably C _{2- 6} alkenyl group, preferably a C _{2- 4} alkenyloxy group than); To the aromatic ring, such as a phenoxy group, tolyl rilok group, a naphthyloxy group C _{1- 4} alkyl, C _{2- 4} alkenyl group, a halogen atom, C _{1- 4} alkoxy group, an aryloxy group which may have a substituent such as a (preferably is C _{6- 14} aryl group); Aralkyl oxy group such as a benzyloxy group, a phenethyl tilok group (preferably a C _{7- 18} aralkyl group); Acetyl-oxy group, propionyl oxy group, a (meth) acyloxy group such as acryloyloxy group acryloyl, benzoyl oxy group (preferably a C _{1- 12} acyloxy group); A mercapto group; Methyl get tea, alkylthio groups, such as ethyl thio group (preferably a C _{1- 6} alkylthio, get more preferably C _{1- 4} alkyl group); Import nilti alkenyl such as allyl come tea (preferably C _{2- 6} alkenyl nilti get, get more preferably C _{2- 4} alkenyl nilti); Phenylthio, tolyl rilti come, naphthyl tilti C _{1- 4} alkyl group on the aromatic ring, such as importing, _2- C ₄ alkenyl group, a halogen atom, C _{1- 4} alkoxy group came may have a substituent such as an aryl tee (preferably Advantageously _6- C ₁₄ arylthio); Benzyl come tea, phenethyl tilti come aralkyl tea such as import (preferably a C _{7- 18} aralkyl alkylthio); A carboxyl group; Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, such as an alkoxycarbonyl group (preferably a C _{1- 6} alkoxy-carbonyl group); Phenoxy group, a tolyloxy group, naphthyloxy group etc. of the aryloxycarbonyl group (preferably a C _{6- 14} aryloxy-carbonyl group); Aralkyloxycarbonyl groups, such as benzyloxycarbonyl group (preferably a C _{7- 18} aralkyloxy-carbonyl group); An amino group; A mono or dialkylamino group (preferably a mono or di-C _1-6 alkylamino group) such as a methylamino group, an ethylamino group, a dimethylamino group or a diethylamino group; Acylamino group such as acetylamino group, propionylamino group, a benzoyl group (preferably a C _{1- 11} acylamino group); An epoxy group-containing group such as a glycidyloxy group; An oxetanyl group-containing group such as an ethyloxetanyloxy group; Acyl groups such as acetyl, propionyl and benzoyl; An oxo group; Two or more thereof is necessary, and the like groups bonded via an _1- C ₆ alkylene group.

Examples of the monovalent oxygen atom-containing group in R include a hydroxyl group, a hydroperoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an isocyanate group, a sulfo group, . Examples of the monovalent nitrogen atom-containing group include an amino group or a substituted amino group (such as a mono or dialkylamino group or an acylamino group), a cyano group, an isocyanate group, an isothiocyanate group or a carbamoyl group. Examples of the monovalent sulfur atom-containing group include a mercapto group (thiol group), a sulfo group, an alkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, and an isothiocyanate group have. The above-mentioned monovalent organic group, monovalent oxygen atom-containing group, monovalent nitrogen atom-containing group and monovalent sulfur atom-containing group may be overlapped with each other.

Examples of R include a group represented by the following formula (4).

A plurality of R 'in formula (4) may be the same or different. R 'in the formula (4) represents 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, And the like.

In groups represented by the formula (4), respectively, as each of R ', a hydrogen atom, C _{1- 10} alkyl groups (particularly, C _{1- 4} alkyl), C _{2- 10} alkenyl group (particularly, C _{2- 4} alkenyl ), C _{3- 12} cycloalkyl, C _3-12 cycloalkenyl group, to the aromatic ring C _{1- 4} alkyl, C _{2- 4} alkenyl group, a halogen atom, which may have a substituent such as a C _{1- 4} alkoxy group, C _6-14 aryl, C _{7- 18} aralkyl group, C _{6- 10} aryl -C _{2- 6} alkenyl group, a hydroxyl group, it is preferably C _{1- 6} alkoxy group, a halogen atom.

Of the above, R is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group, more preferably an aliphatic hydrocarbon group (particularly an alkyl group, an alkenyl group), an aromatic A hydrocarbon group (particularly, a phenyl group).

Examples of the ladder-type silsesquioxane in the present invention include ladder-type silsesquioxane represented by the following formula (5).

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). The formula (5) in that R represents the same as the R in RSiO _{1 .5} (that is hereinafter, referred to as "side chain"), T represents an end group. Examples of T in the formula (5) group is the same and the like as exemplified as the R in RSiO _{1 .5.} Among them, T in the formula (5) is preferably a trimethylsilyl group, a vinyl group or an SiH-containing group.

The ratio of the substituted or unsubstituted hydrocarbon group to the total amount of R (100 mol%) in the formula (5) in the formula (5) is not particularly limited, but it is preferably 50 mol% , More preferably 80 mol% or more, and still more preferably 90 mol% or more. Particularly, a substituted or unsubstituted alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms such as a methyl group or ethyl group) to the total amount (100 mol% The total amount of the aryl group (preferably an aryl group having 6 to 10 carbon atoms, particularly a phenyl group), a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms (preferably an aralkyl group having 7 to 10 carbon atoms, particularly a benzyl group) Mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more. Particularly, from the viewpoint of the barrier property to the corrosive gas of the cured product, it is preferable that a part or the whole of R is an aryl group which is substituted or unsubstituted. That is, the ladder-type silsesquioxane may be a ladder-type silsesquioxane having at least a substituent or an unsubstituted aryl group in the molecule.

The number average molecular weight and / or the weight average molecular weight of the silsesquioxane (B) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 30,000, Particularly preferred. If the molecular weight is less than 100, the heat resistance of the cured product may be lowered. On the other hand, when the molecular weight exceeds 80,000, compatibility with other components of the silsesquioxane (B) may be lowered. Further, the silsesquioxane (B) may be a mixture of those having various molecular weights in the above-mentioned range. The number average molecular weight and the weight average molecular weight can be calculated, for example, as molecular weight in terms of polystyrene by gel permeation chromatography.

The silsesquioxane (B), particularly the ladder silsesquioxane, in the present invention can be produced by a known production method (for example, a hydrolysis and condensation method using a trifunctional silane compound as a raw material).

In the curable resin composition of the present invention, the silsesquioxane (B) may be used singly or in combination of two or more.

The content (blend amount) of silsesquioxane (B) in the curable resin composition of the present invention is not particularly limited, but is preferably 5 to 45% by weight, more preferably 7 to 20% by weight based on the total amount (100% More preferably 40% by weight, and still more preferably 10% by weight to 35% by weight. When the content is less than 5% by weight, there is a case where the gas barrier property against the corrosive gas, such as SO _X does not sufficiently obtained. On the other hand, if the content exceeds 45% by weight, the crack resistance of the cured product may deteriorate or the heat resistance may not be sufficiently obtained. The ratio of silsesquioxane (B) in the curable resin composition of the present invention is not particularly limited, but from the viewpoints of heat resistance, barrier properties to corrosive gases, and crack resistance of the cured product, for example, polyorganosiloxane (A ) Is preferably 1 to 40 parts by weight, more preferably 5 to 35 parts by weight, and particularly preferably 10 to 30 parts by weight, based on 100 parts by weight of the resin (A).

[Ladder-like silsesquioxane (B1)]

The curable resin composition of the present invention comprises, as the silsesquioxane (B), a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule (in the present specification, simply "ladder-type silsesquioxane (B1)" ) May be included. As the silsesquioxane (B), only ladder-type silsesquioxane (B1) may be used, and ladder-type silsesquioxane (B1) other than ladder-type silsesquioxane For example, ladder-type silsesquioxane (B2), ladder-type silsesquioxane having an aryl group in the molecule, and the like may be used. 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 at a side chain and / or an end group and includes, for example, an aliphatic carbon- Bond and a Si-H bond. The ladder-type silsesquioxane (B1) may be used singly or in combination of two or more.

Examples of the group having an aliphatic carbon-carbon double bond include a vinyl group, an allyl group, a metallyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, such as a pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 5-hexenyl group C _{2- 20} alkenyl group (preferably C ₂ to ₁₀ alkenyl group, more preferably C _{2 - 4} Alkenyl group); A C _3-12 cycloalkenyl group such as a cyclohexenyl group; A C _4-15 bridged cyclic unsaturated hydrocarbon group such as a bicycloheptenyl group; C _{2- 4} alkenyl substituted with aryl groups such as a styryl group; Thinning, and the like. Further, the aliphatic carbon-carbon double bond, groups having, in groups represented by the formula (4), the three R 'at least one of the C _{2- 20} alkenyl group, a cycloalkenyl group of C _3-12, C crosslinked cyclic unsaturated hydrocarbon group of _4-15, C _{2- 4} alkenyl substituted aryl group, it includes airway thinner bran or the like. Of these, preferably an alkenyl group, more preferably C _{2- 20} alkenyl group, more preferably a vinyl group.

The number of the aliphatic carbon-carbon double bonds in the molecule (in one molecule) in ladder silsesquioxane (B1) is not particularly limited, but is preferably 2 or more (for example, 2 to 50) , And more preferably 2 to 30 carbon atoms. By having the aliphatic carbon-carbon double bond in the above-mentioned range, a cured product excellent in various physical properties such as heat resistance, crack resistance, and barrier property 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, more preferably 1.1 to 4.4 mmol / g. The ratio (by weight) of the aliphatic carbon-carbon double bonds contained in the ladder silsesquioxane (B1) is not particularly limited, but is preferably 2.0 to 15.0% by weight, more preferably 3.0 to 12.0% % By weight is more preferable.

The ladder-type silsesquioxane (B1) is not particularly limited, but it is preferably liquid at room temperature (about 25 ° C). More specifically, the viscosity of the ladder-type silsesquioxane (B1) at 23 캜 is preferably 100 to 100000 mPa 占 퐏, more preferably 500 to 10,000 mPa 占 퐏, and further preferably 1000 to 8000 mPa 占 퐏. If the viscosity is less than 100 mPa.s, the heat resistance of the cured product may be lowered. On the other hand, if the viscosity exceeds 100000 mPa · s, it may become difficult to manufacture or handle the curable resin composition. The viscosity at 23 캜 was measured with a cone plate (conical diameter: 16 mm, taper angle = 0 °) with a rheometer (trade name "Physica UDS-200", manufactured by Anton Paar) At a temperature of 23 DEG C and a rotation speed of 20 rpm.

Although the ladder-type silsesquioxane (B1) is not particularly limited, ladder-type silsesquioxane (solid at 25 占 폚 which is solid at normal temperature (about 25 占 폚) and ladder- May be referred to as " ladder-type silsesquioxane (S1) "). In the case where the curable resin composition of the present invention contains ladder-type silsesquioxane (S1) (for example, when ladder-type silsesquioxane (S1) and (S2) are included) The barrier property against the corrosive gas of the cured product is improved, and the toughness (particularly, crack resistance) tends to be improved.

The ladder-type silsesquioxane (S1) can be used in combination with ladder-type silsesquioxane (B1), ladder-type silsesquioxane (B2) which is liquid at room temperature, ladder-type silsesquioxane having an aryl group in the molecule .

[Ladder-like silsesquioxane (B2)]

The curable resin composition of the present invention is characterized in that ladder silsesquioxane having Si-H bonds in the molecule (hereinafter referred to simply as " ladder silsesquioxane (B2) " In some cases). As the silsesquioxane (B), ladder-type silsesquioxane (B2) may be used alone or ladder-type silsesquioxane (B2) other than ladder-type silsesquioxane (For example, ladder-type silsesquioxane (B1), ladder-type silsesquioxane having an aryl group in the molecule, etc.) may be used. The ladder-type silsesquioxane (B2) is not particularly limited as long as it is a compound having a group having a hydrogen atom or a Si-H bond in a side chain and / or a terminal group. The ladder-type silsesquioxane (B2) may be used singly or in combination of two or more.

The group having the Si-H bond is not particularly limited, and examples thereof include groups in which at least one of the three R 's in the group represented by the formula (4) is a hydrogen atom.

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

The content of the hydrogen atom or the group having Si-H bond in the ladder silsesquioxane (B2) is not particularly limited, but is preferably 0.01 to 0.50 mmol / g, more preferably 0.08 to 0.28 mmol / g Do. The ratio (by weight) of the hydrogen atom or the group having Si-H bond contained in ladder silsesquioxane (B2) is not particularly limited, but hydrogen atoms or H (hydra (In terms of H) of 0.01 to 0.50% by weight, more preferably 0.08 to 0.28% by weight. When the content of the hydrogen atom or the group having the Si-H bond is too small (for example, less than 0.01 mmol / g and less than 0.01% by weight in terms of H), the curing of the curable resin composition does not proceed sufficiently There is a case. On the other hand, when the content of the hydrogen atom or the group having the Si-H bond is too large (for example, exceeding 0.50 mmol / g and exceeds 0.50% by weight in terms of H), the hardness of the cured product becomes high, It may be easy. The content of the hydrogen atom or the group having Si-H bond in the ladder-type silsesquioxane (B2) can be measured, for example, by ¹ H-NMR.

The content of the group having Si-H bonds with respect to the total amount (100 mol%) of the hydrogen atom or the group having Si-H bonds in the ladder silsesquioxane (B2) is not particularly limited Is preferably from 50 to 100 mol%, more preferably from 80 to 100 mol% from the viewpoint of the degree of curing.

The ladder-type silsesquioxane (B2) is not particularly limited, but is preferably a liquid at room temperature (about 25 캜). More specifically, the viscosity at 23 캜 of the ladder-type silsesquioxane (B2) is preferably 100 to 100000 mPa · s, more preferably 500 to 10000 mPa · s, and even more preferably 1000 to 8000 mPa · s. If the viscosity is less than 100 mPa.s, the heat resistance of the cured product may be lowered. On the other hand, if the viscosity exceeds 100000 mPa · s, it may become difficult to manufacture or handle the curable resin composition. The viscosity at 23 캜 can be measured by, for example, the same method as the viscosity of the ladder-type silsesquioxane (B1).

Although the ladder-type silsesquioxane (B2) is not particularly limited, ladder-type silsesquioxane which is solid at room temperature (about 25 ° C) (solid at 25 ° C and ladder silsesquioxane having a hydrosilyl group as " Ladder type silsesquioxane (S2) "). When the curable resin composition of the present invention contains ladder type silsesquioxane (S2) (for example, when it contains ladder type silsesquioxane (S1) and (S2)), The barrier property against the corrosive gas of the cured product is improved, and the toughness (particularly, crack resistance) tends to be improved.

The ladder-type silsesquioxane (S2) can be obtained by mixing ladder-type silsesquioxane (B2), ladder-type silsesquioxane (B1) and ladder-type silsesquioxane having an aryl group in the molecule May be used.

[Other ladder type silsesquioxane]

As the ladder type silsesquioxane in the curable resin composition of the present invention, ladder type silsesquioxane (B1), ladder type silsesquioxane (B2), ladder type silsesquioxane having an aryl group in the molecule Type silsesquioxane (hereinafter sometimes referred to as " other ladder-type silsesquioxane ") may also be used. In particular, the other ladder-type silsesquioxane is at least one ladder type silsesquioxane selected from ladder type silsesquioxane (B1), ladder type silsesquioxane (B2) and ladder type silsesquioxane having an aryl group in the molecule Type silsesquioxane is preferable.

[Isocyanurate compound (C)]

The curable resin composition of the present invention comprises an isocyanurate compound (C). By containing the isocyanurate compound (C), the curable resin composition of the present invention has an improved barrier property to the corrosive gas of the cured product formed by curing, and further tends to improve the adhesion to the adherend. The isocyanurate compound (C) preferably contains an isocyanurate compound represented by the formula (1). Among them, the isocyanurate compound (C) is preferably only the isocyanurate compound represented by 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). Among them, any one or more (preferably one or two, more preferably one) of R ^x , R ^y and R ^z in the formula (1) is a group represented by the formula (3) desirable.

In the formulas (2) and (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a straight or branched alkyl group having 1 to 8 carbon atoms. Examples of the straight or branched chain 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 sec-butyl group, a pentyl group, a hexyl group, a heptyl group, , Ethylhexyl group and the like. Among these alkyl groups, straight or branched alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl and isopropyl groups are preferred. It is particularly preferable that R ¹ and R ² in the formulas (2) and (3) are each a hydrogen atom.

Examples of the isocyanurate compound (C) include, but are not limited to, monoallyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, triallyl isocyanurate, monoallyl diglycidyl Allyl-3-isocyanurate, dicyanomonoglycidyl isocyanurate, triglycidyl isocyanurate, monomethyl diglycidyl isocyanurate, dimethyl monoglycidyl isocyanurate, 1-allyl- (2-methylpropenyl) isocyanurate, 1- (2-methylpropenyl) -3,5-diglycidyl isocyanurate, 1- Bis (2-methylpropenyl) isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3- -Glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate, tris There may be mentioned acrylate and the like. Of these, monoallyldiglycidylisocyanurate, triallyl isocyanurate, and monomethyl diglycidyl isocyanurate are preferable. Each of the isocyanurate compounds (C) may be used alone or in combination of two or more.

The isocyanurate compound (C) may be mixed with other components after mixing with the silane coupling agent (D), as described later, from the viewpoint of improving compatibility with other components.

The content of the isocyanurate compound (C) is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight based on the total amount (100% by weight) of the curable resin composition, By weight to 3% by weight. If the content of the isocyanurate compound (C) is less than 0.01% by weight, the barrier property to the corrosive gas of the cured product and the adhesion to the adherend may be lowered. On the other hand, when the content of the isocyanurate compound (C) exceeds 10% by weight, a solid may precipitate in the curable resin composition or the cured product may become cloudy. The ratio of the isocyanurate compound (C) is not particularly limited, but from the viewpoint of the barrier property to the corrosive gas of the cured product, the ratio of the polyorganosiloxane (A) to the silsesquioxane (B) Is preferably 0.01 to 0.5 parts by weight based on the total amount (100 parts by weight).

[Silane coupling agent (D)]

The curable resin composition of the present invention may contain a silane coupling agent (D). When the curable resin composition of the present invention contains the silane coupling agent (D), the barrier property to the corrosive gas of the cured product is further improved, and in particular, the adhesion to the adherend tends to be improved.

Since the silane coupling agent (D) has good compatibility with the silsesquioxane (B) and the isocyanurate compound (C), it is preferable to use, for example, (C) and a silane coupling agent (D) are formed in advance and then mixed with other components, a uniform curable resin composition is likely to be obtained.

As the silane coupling agent (D), there may be used a publicly known silane coupling agent or a generic silane coupling agent. Examples thereof include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- -Aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, N- (p-aminoethyl) - gamma -aminopropylmethyldiethoxysilane and the like An amino group-containing silane coupling agent; Vinyltriethoxysilane, vinyltris (methoxyethoxysilane), phenyltriethoxysilane, dimethyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (Meth) acryloxypropyltriethoxysilane,? - (meth) acryloxypropyltrimethoxysilane,? - (meth) acryloxypropyltrimethoxysilane, (Meth) acryloxypropylmethyldiethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and the like can be given. Among them, an epoxy group-containing silane coupling agent (particularly 3-glycidoxypropyltrimethoxysilane) can be preferably used. Among them, 3-glycidoxypropyltrimethoxysilane is preferable. The silane coupling agent (D) may be used singly or in combination of two or more.

The content of the silane coupling agent (D) is not particularly limited, but is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight based on the total amount (100% By weight is more preferable. If the content of the silane coupling agent (D) is less than 0.01% by weight, the adhesiveness to the adherend is lowered. In particular, when the isocyanurate compound (C) is used in an aqueous medium, sufficient effect (for example, Gas barrier property, etc.) may not be obtained in some cases. On the other hand, if the content of the silane coupling agent exceeds 15% by weight, the curing becomes insufficient and the toughness, heat resistance and barrier property of the cured product may be lowered.

[Zinc compound (E)]

The curable resin composition of the present invention comprises a zinc compound (E). When the curable resin composition of the present invention contains the zinc compound (E), the barrier property to H ₂ S gas tends to be improved in particular.

The zinc compound (E) is not particularly limited, and examples thereof include a complex containing zinc and a metal salt. For example, zinc diketone complexes such as zinc bisacetylacetonate and bis (octane-2,4-dionate) zinc, zinc zinc naphthenate, zinc octylate, zinc acetoacetate, zinc (meth) An organic zinc compound represented by zinc carboxylate such as neodecanate, an inorganic zinc compound represented by zinc oxide such as zinc oxide and zinc stearate, and mixtures thereof. Among them, a zinc diketone complex (especially zinc bisacetylacetonate) or zinc carboxylate is preferable, and zinc carboxylate is more preferable, and zinc acrylate and zinc octylate are particularly preferable. The zinc compound (E) preferably contains at least zinc carboxylate (in particular, zinc naphthenate, zinc octylate). Among them, it is more preferable that the zinc compound (E) is only zinc carboxylate (particularly, zinc naphthenate, zinc octylate). The zinc compound (E) may be used singly or in combination of two or more.

The zinc compound (E) is not particularly limited, but it is preferable that the zinc content with respect to the total amount (100 wt%) of the compound is, for example, 2 to 30 wt% Is 5 to 20% by weight, particularly preferably 6 to 17% by weight.

The content of the zinc compound (E) is not particularly limited, but is preferably 0.01 part by weight to less than 0.1 part by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B) More preferably 0.05 part by weight or more and less than 0.1 part by weight, and more preferably 0.07 part by weight or more and less than 0.1 part by weight. If the content of the zinc compound (E) is less than 0.01 part by weight, the barrier property against the H ₂ S gas may be lowered. On the other hand, if the content of the zinc compound (E) 0.1 parts by weight or more, there is a case in which the barrier gas for SO _X decreases. When the content of the zinc compound (E) is within the above range, the H ₂ S corrosion resistance and SO _x corrosion resistance are excellent. In particular, the use of the zinc compound (E) octylate zinc (in particular, the zinc content is from 2 to 30% by weight octylate zinc) as in the above-described range, and within the SO _X corrosion resistance is excellent, in H ₂ S corrosion is considerably It is possible to obtain an excellent cured product.

The content of the zinc compound (E) in the curable resin composition of the present invention is not particularly limited, but is preferably 0.05 to 0.085 wt%, more preferably 0.05 to 0.085 wt%, based on the total amount (100 wt%) of the curable resin composition 0.06 to 0.08% by weight.

[Hydrosilylation catalyst]

The curable resin composition of the present invention may further comprise a hydrosilylation catalyst. The curable resin composition of the present invention contains a hydrosilylation catalyst, so that the curing reaction (hydrosilylation reaction) can proceed efficiently. Examples of the hydrosilylation catalyst include known hydrosilylation catalysts such as platinum catalysts, rhodium catalysts, and palladium catalysts. Specific examples thereof include carbon black of platinum such as platinum fine powder, platinum black, platinum-supported fine silica powder, platinum-supported activated carbon, chloroplatinic acid, chloroplatinic acid and a complex with alcohol, aldehyde, ketone and the like, platinum olefin complex and platinum- A platinum-based catalyst such as a platinum-phosphine complex, a platinum-phosphite complex or the like, a platinum-based catalyst such as a platinum-divinyltetramethyldisiloxane complex or a platinum-cyclvinylmethylsiloxane complex, A palladium-based catalyst or a rhodium-based catalyst containing a palladium atom or a rhodium atom instead of a platinum atom. The hydrosilylation catalyst may be used singly or in combination of two or more.

The content of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited. For example, the content of platinum, palladium or rhodium in the hydrosilylation catalyst is preferably in the range of 0.01 to 1,000 ppm by weight , And more preferably in the range of 0.1 to 500 ppm. When the content of the hydrosilylation catalyst is within this range, the crosslinking speed is not remarkably slowed, and it is preferable because there is little possibility of occurrence of problems such as coloring in the cured product.

[Hydrosilylation reaction inhibitor]

The curable resin composition of the present invention may contain a hydrosilylation reaction inhibitor in order to adjust the rate 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-pentene-1-yne, and 3,5-dimethyl-3-hexene-1-yne; Thiazole, benzothiazole, benzotriazole, and the like. The hydrosilylation reaction inhibitor may be used singly or in combination of two or more. The content of the hydrosilylation reaction inhibitor differs depending on the crosslinking conditions of the curable resin composition. In practice, the content of the hydrosilylation reaction inhibitor in the curable resin composition is preferably in the range of 0.00001 to 5 wt%.

[Other siloxane compound]

The curable resin composition of the present invention may further include a cyclic siloxane compound having two or more aliphatic carbon-carbon double bonds in the molecule (in one molecule) as the other siloxane compound. The curable resin composition of the present invention may further comprise a cyclic siloxane having a group having two or more Si-H bonds in the molecule (in one molecule) as the other siloxane compound. The cyclic siloxane may be used singly or in combination of two or more kinds. The content (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, more preferably 0.1 to 20% by weight based on the total amount (100% by weight) of the curable resin composition , More preferably 0.5 to 10 wt%.

[Other silane compound]

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 , And 3,5,5,7,7,9,9,9-undecamethylpentasiloxane, and the like, and the like. The silane compounds may be used singly or in combination of two or more. The content of the silane compound is not particularly limited, but is preferably 0 to 5% by weight, more preferably 0 to 1.5% by weight based on the total amount (100% by weight) of the curable resin composition.

[menstruum]

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, propylene glycol monomethyl ether acetate and the like. These solvents may be used singly or in combination of two or more.

[additive]

The curable resin composition of the present invention may contain other optional components such as precipitated silica, wet silica, fumed silica, fired silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, Inorganic fillers such as silicon, silicon nitride and boron nitride; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; Organic resin fine powder such as silicone resin, epoxy resin and fluorine resin; (Phosphorus-based flame retardant, halogen-based flame retardant, inorganic flame retardant, etc.), a flame-retarding auxiliary agent, a reinforcing material (other additives), a filler such as a conductive metal powder such as copper Coloring agent (dye, pigment, etc.), dispersant, defoaming agent, defoaming agent, antimicrobial agent, preservative, viscosity adjusting agent, thickening agent, etc., etc.), nucleating agent, coupling agent, lubricant, wax, plasticizer, mold release agent, The additive may be included. These additives may be used alone or in combination of two or more.

[Curable resin composition]

The curable resin composition of the present invention is not particularly limited, but is preferably a composition (compounding composition) such that the aliphatic carbon-carbon double bond is 0.2 to 4 moles relative to 1 mole of the hydrosilyl group present in the curable resin composition, Preferably 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles. By controlling the ratio of the hydrosilyl group and the aliphatic carbon-carbon double bond within the above range, the heat resistance, transparency, flexibility, dripping resistance and barrier property against corrosive gas of the cured product are more likely to be improved.

The curable resin composition of the present invention is not particularly limited, but it can be produced by stirring and mixing the above components at room temperature. Further, the curable resin composition of the present invention may be used as a one-component composition in which each component is mixed in advance, or may be used, for example, as a multi-component composition in which two or more components, which are separately stored, (For example, a two-liquid system) composition.

The curable resin composition of the present invention is not particularly limited, but it is preferably liquid at room temperature (about 25 캜). More specifically, the curable resin composition of the present invention preferably has a viscosity at 23 占 폚 of 300 to 20,000 mPa 占 퐏, more preferably 500 to 10,000 mPa 占 퐏, and still more preferably 1000 to 8,000 mPa 占 퐏. When the viscosity is less than 300 mPa.s, the heat resistance of the cured product may be lowered. On the other hand, when the viscosity exceeds 20,000 mPa · s, it becomes difficult to manufacture and handle the curable resin composition, and bubbles may easily remain in the cured product. The viscosity of the curable resin composition can be measured, for example, by the same method as the viscosity of the above-described ladder-type silsesquioxane (B1).

[Cured goods]

By curing the curable resin composition of the present invention by a curing reaction (hydrosilylation reaction), a cured product (hereinafter sometimes referred to as "the 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 the reaction rate, the temperature (curing temperature) is 25 to 180 캜 (more preferably 60 to 150 ° 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, and flexibility, and is excellent in resistance to down flow such as crack resistance in a reflow process, adhesion to a package, and excellent barrier property to corrosive gas .

[Seal material 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 curing the curable resin composition of the present invention is excellent in various physical properties such as heat resistance, transparency and flexibility, and is excellent in flow resistance and barrier property against corrosive gas. Therefore, the sealing material of the present invention can be preferably used as a sealing material for a semiconductor device in a semiconductor device, particularly as a sealing material for an optical semiconductor element (particularly, a high-luminance and short-wavelength optical semiconductor element) in an optical semiconductor device. By sealing the semiconductor element (particularly, the 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.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

The ¹ H-NMR analysis of the reaction product and the product was carried out by using JEOL ECA500 (500 MHz). The measurement of the number average molecular weight and the weight average molecular weight of the reaction product and the product was carried out by using an Alliance HPLC system 2695 (manufactured by Waters), a refractive index detector 2414 (manufactured by Waters), a column: Tskgel GMH _HR- M × (Manufactured by TOSOH CO., LTD.), Guard column: Tskgel guard column H _HR L (manufactured by TOSOH CORPORATION), column oven: column heater U-620 (manufactured by Sugai) Measurement was carried out at 40 캜.

[Polyorganosiloxane (A)]

The following products were used as the polyorganosiloxane (A).

GD-1012A, manufactured by Choko Chemical Industry Co., Ltd., vinyl group content 1.33 wt%, phenyl group content 0 wt%, SiH group content (in terms of hydride) 0 wt%, number average molecular weight 5108,

GD-1012B manufactured by Choko Chemical Industry Co., Ltd., a vinyl group content of 1.65 wt%, a phenyl group content of 0 wt%, a SiH group content (in terms of hydride) of 0.19 wt%, a number average molecular weight of 4563,

KER-2500A, manufactured by Shin-Etsu Chemical Co., Ltd., having a vinyl group content of 1.53 wt%, a phenyl group content of 0 wt%, a SiH group content of 0.03 wt% (in terms of hydride), a number average molecular weight of 4453,

KER-2500B, manufactured by Shin-Etsu Chemical Co., Ltd., having a vinyl group content of 1.08 wt%, a phenyl group content of 0 wt%, a SiH group content (in terms of hydride) of 0.13 wt%, a number average molecular weight of 4636,

[Synthesis of silsesquioxane (B)] [

≪ Synthesis Example 1 &

30.06 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 21.39 g of vinyltriethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 17.69 g of methyl isobutyl ketone (MIBK) And the mixture was cooled to 10 占 폚. 281 mmol (5.06 g) of water and 0.48 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) were added dropwise to the mixture over 1 hour. After the dropwise addition, the mixture was kept at 10 DEG C for 1 hour. Thereafter, 80.0 g of MIBK was added, and the reaction solution was diluted.

Subsequently, the temperature of the reaction vessel was raised to 70 占 폚, 703 millimoles (12.64 g) of water was added at 70 占 폚, and the polycondensation reaction was carried out under nitrogen for 12 hours.

Subsequently, 15.0 g of hexamethyldisiloxane was added to the reaction solution, and the silylation reaction was carried out at 70 占 폚 for 3 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer became neutral, and then the supernatant was collected. Subsequently, the solvent was distilled off from the supernatant under the conditions of 1 mmHg at 60 ° C to obtain 22.0 g of ladder silsesquioxane having a terminal trimethylsilyl group as a colorless transparent solid.

The ladder silsesquioxane had a weight average molecular weight (Mw) of 5000, a vinyl group content (average content) per molecule of 11.68 wt%, and a methyl group / vinyl group (molar ratio) of 60/40.

The ¹ H-NMR spectrum of the ladder-type silsesquioxane was as follows.

¹ H-NMR (JEOL _{ECA500 (500MHz, CDCl 3))} δ: 0-0.3ppm (br), 5.8-6.1ppm (br)

≪ Synthesis Example 2 &

To the reaction vessel were added 34.07 g of methyltriethoxysilane, 11.49 g of phenyltriethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd.) and 17.69 g of methyl isobutyl ketone (MIBK), and the mixture was heated to 10 Lt; 0 > C. 240 mmol (4.33 g) of water and 0.48 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) were added dropwise to the mixture over one hour. After the dropwise addition, the mixture was kept at 10 DEG C for 1 hour. Thereafter, 80.0 g of MIBK was added, and the reaction solution was diluted.

Subsequently, the temperature of the reaction vessel was raised to 70 DEG C, and 60 DEG C (10.91 g) of water was added at 70 DEG C, and the polycondensation reaction was carried out under nitrogen for 9 hours. Further, 6.25 g of vinyltriethoxysilane was added, and the reaction was carried out for 3 hours.

Subsequently, 15.0 g of hexamethyldisiloxane was added to the reaction solution, and the silylation reaction was carried out at 70 占 폚 for 3 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer became neutral, and then the supernatant was collected. Subsequently, the solvent was distilled off from the supernatant under the conditions of 1 mmHg at 60 캜 to obtain ladder-type silsesquioxane (equivalent to the ladder-type silsesquioxane (B1) described above) having a vinyl group and a trimethylsilyl group at the terminal thereof, The product was obtained as a transparent liquid product.

The ladder silsesquioxane had a weight average molecular weight (Mw) of 3,400, a vinyl group content (average content) per molecule of 3.96% by weight, and a phenyl group / methyl group / vinyl group (molar ratio) of 17/68/15 .

The ¹ H-NMR spectrum of the ladder-type silsesquioxane was as follows.

¹ H-NMR (JEOL _{ECA500 (500MHz, CDCl 3))} δ: -0.3-0.3ppm (br), 5.7-6.2ppm (br), 7.1-7.7ppm (br)

≪ Synthesis Example 3 &

31.06 g of methyltriethoxysilane, 2.38 g of phenyltriethoxysilane and 93.00 g of methyl isobutyl ketone (MIBK) were charged into the reaction vessel, and the mixture was cooled to 10 캜. 240 mmol (4.33 g) of water and 0.24 g of 5N hydrochloric acid (1.2 mmol as hydrogen chloride) were added dropwise to the mixture over 1 hour. After the dropwise addition, the mixture was kept at 10 DEG C for 1 hour.

Subsequently, the temperature of the reaction vessel was raised to 50 DEG C, 120 millimoles (2.16 g) of water was added at 50 DEG C, and the polycondensation reaction was carried out under nitrogen for 4 hours. Further, 11.18 g of vinyltriethoxysilane was added and the reaction was carried out for 4 hours.

Subsequently, 19.5 g of hexamethyldisiloxane was added to the reaction solution, and the silylation reaction was carried out at 50 占 폚 for 1 hour. Thereafter, the reaction solution was cooled, washed with water until the lower layer became neutral, and then the supernatant was collected. Subsequently, the solvent was distilled off from the supernatant under the conditions of 1 mmHg at 60 캜 to obtain ladder-type silsesquioxane (equivalent to the ladder-type silsesquioxane (B1) described above) having a vinyl group and a trimethylsilyl group at the terminal thereof, The product was obtained as a transparent liquid product.

The ladder silsesquioxane had a number average molecular weight (Mn) of 879 and a weight average molecular weight (Mw) of 1116.

≪ Synthesis Example 4 &

12 g of the ladder-type silsesquioxane obtained in Synthesis Example 2, 24 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Tokyo Kasei Kogyo K.K.) and 2.0 g of a 2.0% platinum-cyclovinylsiloxane complex And 10 μl of a vinylcyclosiloxane solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. Subsequently, the reaction was terminated by heating at 70 占 폚 for 8 hours. Subsequently, the mixture was concentrated in an evaporator, and then subjected to a reduced pressure at 0.2 Torr for 3 hours using a vacuum pump to obtain ladder-type silsesquioxane (the ladder-like silsesquioxane (B2) having SiH- and trimethylsilyl groups at the ends thereof Was obtained as a liquid product.

The weight average molecular weight (Mw) of the ladder type silsesquioxane was 3700, and the content (average content) of SiH groups per molecule was 0.11% by weight on the basis of H (hydride) in SiH groups.

The ¹ H-NMR spectrum of the ladder-type silsesquioxane was as follows.

¹ H-NMR (JEOL _{ECA500 (500MHz, CDCl 3))} δ: -0.3-0.3ppm (br), 4.7ppm (s), 7.1-7.7ppm (br)

[Zinc compound (E)]

As the zinc compound (E), the following products were used.

Zinc naphthenate: manufactured by Nihon Kagaku Sangyo Co., Ltd., trade name "Naphtex Zinc" (Zn: 8%)

(Zinc: 15%) manufactured by Nihon Kagaku Sangyo Co., Ltd., trade name "Nitacoxitics Zinc"

Acetyl acetone Zinc: manufactured by Nihon Kagaku Sangyo Co., Ltd., trade name "Nasem Zinc"

≪ Examples and Comparative Examples &

Examples 1 to 9 and Comparative Examples 1 to 9 were carried out in the following order.

The isocyanurate compound (C) and the silane coupling agent (D) were mixed in a predetermined weight ratio (the unit of the blending amount of each component in Table 1 and Table 2 was in parts by weight) according to Tables 1 and 2, Compound (E) and silsesquioxane (B) were mixed and stirred at 60 占 폚 for 2 hours. Thereafter, the mixture was cooled to room temperature, mixed with the polyorganosiloxane (A), and stirred at room temperature for 30 minutes to obtain a curable resin composition.

In Table 1 and Table 2, the amounts of zinc naphthenate and zinc octylate represent amounts excluding mineral spirits from " naphtex zinc " and " nikkaitix zinc ", respectively.

[H ₂ S Corrosion Test]

The curable resin composition obtained in Examples 1 to 9 and Comparative Examples 1 to 9 was injected into an LED package (trade name: "SMD LED (Top View Type 3528 Pre Mold Lead Frame)", manufactured by SDI Corporation) And heated at 100 占 폚 for 1 hour and then at 150 占 폚 for 5 hours to prepare a sample.

The sample was placed in a gas corrosion tester (model number "GS-UV" manufactured by Suga Shikoku Co., Ltd.) adjusted to a hydrogen sulfide concentration of 12 ppm, a temperature of 40 ° C. and a humidity of 80% RH, and after 48 hours, The corrosion condition of the electrode was observed. The color of the electrode was silver-white before the test, and changed to dark brown and black as the corrosion progressed.

The evaluation criteria of the corrosivity test were "A" when no discoloration was mostly seen on the silver electrode, "B" when slightly discolored to black or black, and "C" when completely discolored to dark brown or black.

[SO _X Corrosivity Test]

The curable resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 9 were injected into an LED package (product name: "SMD LED (Top View Type 3528 Pre Mold Lead Frame)" manufactured by SDI Corporation) Hour, followed by heating at 150 DEG C for 5 hours to prepare a sample.

0.3 g of the sample and sulfur powder (manufactured by Kishida Chemical Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was placed in an aluminum box. Subsequently, the aluminum box was placed in an oven (model number " DN-64 ", manufactured by Yamato Kagaku Co., Ltd.) and the oven temperature was set at 80 캜. After 24 hours, The corrosion condition was observed. The color of the electrode was silver white before the test, but changed to dark brown and then black as the corrosion progressed.

The evaluation criteria for the corrosion test were the same as those for the H ₂ S corrosion test.

[Corrosion test result]

In Comparative Example 1, according to Patent Document 4, when a small amount of the zinc compound (E) was added, the corrosion resistance effect was not recognized.

On the other hand, in Comparative Example 2 and Comparative Example 3, the effect of H ₂ S corrosion was recognized even when a small amount of the zinc compound (E), which was below the range described in Patent Document 4, was added. However, the effects of SO _X in corrosion was observed.

On the other hand, in Comparative Examples 4 and 5, when the isocyanurate compound (C) was added, the effect of SO _x corrosion resistance was recognized, but the effect of H ₂ S corrosion resistance was not recognized.

On the other hand, in Comparative Example 6 and Comparative Example 7, when the isocyanurate compound (C) was added and a zinc compound (E) in the range described in Patent Document 4 was further added, the effect of the internal H ₂ S corrosion It was given, surprisingly, in SO _X corrosion resistance has become even reduced.

Thus, Examples 1 and 2 In Comparative Example 6, and adjusting the zinc compound (E) toward a small amount compared to the bars 7, while maintaining the corrosion resistance was observed in H ₂ S to SO _X in the corrosion resistance is improved.

From the above, it was recognized that by adding a zinc compound (E) in a limited range to the system to which the isocyanurate compound (C) was added, a composition having both SO _x corrosion resistance and internal H ₂ S corrosion resistance could be obtained.

Further, from the comparison of Examples 4 and 5 with other Examples, the zinc compound (E) is superior to the acetylacetone zinc in that the saturated fatty acid zinc such as zinc naphthenate or zinc octylate is superior in corrosion resistance particularly to H ₂ S It was acknowledged.

Further, from the comparison of Example 3 and other Examples, it was recognized that the polyorganosiloxane (B) was superior to the KER-2500 system in the GD-1012 system especially in the inner H ₂ S corrosion resistance.

The curable resin composition and the cured product of the present invention are useful in applications such as adhesives, coatings, and sealants that require 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 (12)

A curable resin composition comprising a polyorganosiloxane (A), silsesquioxane (B), an isocyanurate compound (C) and a zinc compound (E)
Wherein the polyorganosiloxane (A) is a polyorganosiloxane having no aryl group,
Type silsesquioxane as the silsesquioxane (B)
Wherein the content of the zinc compound (E) is 0.01 part by weight or more and less than 0.1 part by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition according to claim 1, wherein the silsesquioxane (B) comprises ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule. The curable resin composition according to any one of claims 1 to 3, wherein the silsesquioxane (B) comprises a ladder-type silsesquioxane having Si-H bonds in its molecule. The curable resin composition according to any one of claims 1 to 3, wherein the silsesquioxane (B) comprises ladder-type silsesquioxane having an aryl group in the molecule. The curable resin composition according to any one of claims 1 to 4, wherein the isocyanurate compound (C) comprises an isocyanurate compound represented by 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).

[Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom or a straight or branched alkyl group having 1 to 8 carbon atoms] The curable resin composition according to claim 5, wherein at least one of R ^x , R ^y , and R ^z in formula (1) is a group represented by formula (3). The curable resin composition according to any one of claims 1 to 6, wherein the zinc compound (E) comprises zinc carboxylate. The curable resin composition according to any one of claims 1 to 7, wherein the polyorganosiloxane (A) is a polyorganosiloxane having a structure represented by formula (6).

[In the 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. Provided that at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond. R ²⁷ represents a divalent hydrocarbon group. r and s each represent an integer of 1 or more. The curable resin composition according to any one of claims 1 to 8, 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 9. A sealing material obtained by using the curable resin composition according to any one of claims 1 to 9. A semiconductor device obtained by using the sealing material according to claim 11.