KR20150135531A - Curing resin composition and semiconductor device employing same - Google Patents

Abstract

Disclosed is a semiconductor device which has transparency, heat resistance, flexibility, thermal shock resistance and fl ow resistance, and has barrier properties against hydrogen sulfide (H ₂ S) gas and barrier properties against sulfur oxide (SO _x ) A curable resin composition useful for sealing applications of elements (particularly optical semiconductor elements), a cured product using the composition, a sealing material, and a semiconductor device.
The present invention relates to a curable resin composition containing a polyorganosiloxane (A), a silsesquioxane (B) and an isocyanurate compound (C), wherein the polyorganosiloxane (A) is a polyorganosiloxane And has a viscosity of 4000 to 8000 mPa · s, a cured product using the same, a sealing material, and a semiconductor device.

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. The present application claims priority of Japanese Patent Application No. 2013-163577 filed on August 6, 2013, the contents of which are 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 sealing that is excellent in transparency, UV resistance, and heat resistant coloring property. The resin composition of the present invention is a resin composition for optical- Containing at least one silsesquioxane selected from the group consisting of a liquid silsesquioxane of a cage structure containing an aliphatic carbon-carbon unsaturated bond and containing an H-Si bond and containing no aliphatic carbon-carbon unsaturated bond as a resin component A resin composition for sealing a device is disclosed. 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 a branched chain containing at least two SiH groups in one molecule, Or a cyclic polyorganosiloxane, and a hydrosilylation catalyst as essential components. However, the physical properties such as crack resistance of these materials are not yet satisfactory.

On the other hand, a metal material such as an electrode in an optical semiconductor device is likely to be corroded by a corrosive gas, and there is a problem that conduction characteristics (for example, conduction characteristics in a high temperature environment) deteriorate 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 can not be said to have a sufficient barrier property to corrosive gas.

Patent Document 4 discloses a catalyst 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, and (D) a 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) have. However, although corrosion resistance against hydrogen sulfide (H ₂ S) is disclosed, there is no description about corrosion resistance against other corrosive gases.

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

There are a plurality of types of corrosive gases that corrode the semiconductor device and those having sufficient barrier properties against any of a plurality of corrosive gases such as hydrogen sulfide (H ₂ S) gas and sulfur oxide (SO _x ) gas, which are typical corrosive gases The same sealing material has not been disclosed yet.

In addition, in an optical semiconductor device used as a white LED (Light Emitting Diode) for illumination or backlight, a sealing material having a high refractive index is required in order to improve the light extraction efficiency. Further, in the step of manufacturing the optical semiconductor device used as a white LED, the sealing material of the optical semiconductor element may be mixed with a fluorescent material in some cases. In order to prevent the fluorescent material from being unevenly distributed in the sealing material, Materials are required.

It is therefore an object of the present invention and at the same time having the transparency, heat resistance, and a thermal shock resistance, and barrier properties against the corrosive gases (in particular, the barrier properties of the hydrogen sulfide (H ₂ S) gas (in the H ₂ S corrosion) (Particularly an optical semiconductor element), which is excellent in heat resistance and barrier property (SO _X corrosion resistance) against sulfur oxides (SO _X ) gas, and which has high refractive index and high viscosity . Another object of the present invention is to provide a resin composition which is excellent in transparency, heat resistance and flexibility, and which has thermal shock resistance and downflow resistance (crack resistance in a reflow process, adhesion to a package, etc.) Which has high refractive index and high viscosity, which is useful for sealing applications of semiconductor elements having barrier properties. Another object of the present invention is to provide a cured product and a sealing material having a high refractive index with excellent transparency, heat resistance, flexibility, thermal shock resistance, downflow resistance and barrier property against corrosive gas. Still another object of the present invention is to provide a semiconductor device having such a cured product and / or a sealing material.

The inventors of the present invention have found that a curable resin composition having a viscosity of 4000 to 8000 mPa · s is excellent in transparency and heat resistance by adding silsesquioxane and isocyanurate compounds to polyorganosiloxane having an aryl group, Barrier properties and thermal shock resistance can be formed. Thus, the present invention has been completed.

That is, the present invention relates to a curable resin composition containing a polyorganosiloxane (A), a silsesquioxane (B) and an isocyanurate compound (C), wherein the polyorganosiloxane (A) And a viscosity of 4000 to 8000 mPa · s.

The present invention also provides the above-mentioned curable resin composition, wherein the number average molecular weight (Mn) of the polyorganosiloxane (A) in terms of standard polystyrene by gel permeation chromatography is 500 to 4000.

Further, the present invention relates to a polyorganosiloxane (A) having a weight average molecular weight in terms of standard polystyrene by gel permeation chromatography as Mw and a molecular weight dispersion degree (Mw / Mn) as a number average molecular weight in Mn of from 0.95 to 4.00 The above-mentioned curable resin composition.

Further, the present invention provides the above-mentioned curable resin composition containing a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond as the polyorganosiloxane (A).

Further, the present invention provides the above-mentioned curable resin composition containing a polyorganosiloxane (A2) having Si-H bonds as the polyorganosiloxane (A).

Further, the present invention relates to a polyorganosiloxane (A)

[In the formula (6), R ²¹ to R ²⁶ are the same or different and each represents a monovalent group containing a hydrogen atom, an aryl group, a monovalent hydrocarbon group, a monovalent heterocyclic group, or an aliphatic carbon- Provided that at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond, at least one of R ²¹ to R ²⁶ is an aryl group, R ²⁷ is a divalent hydrocarbon group, r and s each represent an integer of 1 or more;

The present invention provides a curable resin composition containing the polyorganosiloxane as described above.

Further, the present invention provides the above-mentioned curable resin composition wherein the silsesquioxane (B) is a ladder-type silsesquioxane.

The present invention also relates to a process for producing an 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]].

Wherein the isocyanurate compound is an isocyanurate compound represented by the following formula (1).

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

The present invention further provides a process for producing a silane coupling agent which further comprises a silane coupling agent (D) and wherein the content of the silane coupling agent (D) is 0.01 (parts by weight) to 100 parts by weight of the polyorganosiloxane (A) By weight or more and less than 1.0 part by weight, based on the weight of the curable resin composition.

The present invention also provides the above-mentioned curable resin composition containing a partial condensate obtained by hydrolyzing and partially condensing one or more silane coupling agents of the silane coupling agent (D).

The present invention further provides a process for producing a zinc compound (E), which further contains a zinc compound (E) and contains 0.01 part by weight per 100 parts by weight of the total amount of the zinc compound (E) And less than 1.0 part by weight based on 100 parts by weight of the curable resin composition.

The present invention also provides a curable resin composition comprising the curable resin composition (A) and the silsesquioxane (B) in an amount of 0.3 part by weight or more and less than 0.6 part by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) .

Further, the present invention provides the curable resin composition described above wherein the zinc compound (E) is a carboxylic acid resin.

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

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

Further, the present invention provides a semiconductor device obtained by using the above-mentioned 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) and an isocyanurate compound (C), wherein the polyorganosiloxane (A) is a polyorganosiloxane having an aryl group And a viscosity of 4000 to 8000 mPa · s.

[2] The curable resin composition according to [1], wherein the polyorganosiloxane (A) is a polyorganosiloxane having a branched chain.

[3] The polyorganosiloxane (A) is 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] A curable resin composition according to [1] or [2], wherein the curable resin composition contains a polyorganosiloxane.

[4] The curable resin composition according to any one of [1] to [3], wherein the content (amount) of the polyorganosiloxane (A) is 60 to 99.7% by weight based on the total amount (100% by weight) of the curable resin composition.

[5] The structure represented by the formula (6) (in particular, R ²⁷ represents a linear or branched alkylene group having 1 to 5 carbon atoms) relative to the total amount of the polyorganosiloxane (A) , More preferably 60 to 100% by weight of the polyorganosiloxane containing an ethylene group) is contained in the curable resin composition according to [3] or [4].

[6] The polyorganosiloxane composition according to any one of [1] to [5], wherein the polyorganosiloxane (A) is a polyorganosiloxane compound having an aliphatic carbon-carbon double bond and having an aryl group and having an aliphatic carbon- The curable resin composition according to any one of [3] to [5], wherein two kinds of polyorganosiloxysilylenes are used.

[7] The curable resin composition according to any one of [1] to [6], which contains silsesquioxane (B).

[8] The curable resin composition according to any one of [1] to [7], wherein the silsesquioxane (B) is a ladder-type silsesquioxane.

[9] The curable resin composition according to any one of [1] to [8], wherein the content of the silsesquioxane (B) is 0.01 to 30% by weight with respect to the total amount (100% by weight) of the curable resin composition.

[10] A process for producing a silsesquioxane resin as described in any one of [1] to [9], wherein the content of silsesquioxane (B) is 0.01 to 30 parts by weight relative to the total amount (100 parts by weight) of the polyorganosiloxane (A) Wherein the curable resin composition according to any one of < 1 >

As the isocyanurate compound (C), a compound represented by the formula (1)

Wherein R ^x , R ^y and R ^z are the same or different and represent a group represented by the formula (2) or a group represented by the formula (3) (in 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]]

The curable resin composition according to any one of [1] to [10], wherein the curable resin composition contains an isocyanurate compound represented by the following formula:

[12] The curable resin composition according to any one of [1] to [11], wherein the isocyanurate compound (C) is monoallyldiglycidyl isocyanurate.

[13] The curable resin composition according to any one of [1] to [12], 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 [13], wherein the proportion of the isocyanurate compound (C) is 0.01 to 0.5 parts by weight relative 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.

[15] The curable resin composition according to any one of [1] to [14], which further contains a silane coupling agent (D).

[16] The curable resin composition according to [15], wherein the silane coupling (D) is 3-glycidoxypropyltrimethoxysilane.

(15) or (16) wherein the content of the silane coupling (D) is 0.01 part by weight or more and less than 1.0 part by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane Wherein the curable resin composition is a curable resin composition.

[18] The curable resin composition according to any one of [15] to [17], wherein the content of the silane coupling agent (D) is 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the curable resin composition.

[19] The curable resin composition according to any one of [15] to [18], wherein the silane coupling agent (D) contains a partial condensate obtained by hydrolysis and partial condensation of one or two or more silane coupling agents.

[20] The method for producing a silane coupling agent according to any one of [1] to [20], wherein the proportion of the partial condensate obtained by hydrolysis and partial condensation of one or two or more silane coupling agents in the silane coupling agent (D) To 100% by weight of the curable resin composition.

The proportion of the partial condensate obtained by hydrolyzing and partially condensing one or two or more kinds of silane coupling agents in the silane coupling agent (D) is 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the curable resin composition The curable resin composition according to [19] or [20].

[22] The method for producing a silanol coupling agent according to any one of [1] to [4], wherein the proportion of the partial condensate obtained by hydrolyzing and partially condensing one or more silane coupling agents in the silane coupling agent (D) The curable resin composition according to any one of [19] to [21], wherein the amount is 0.01 part by weight or more and less than 1.0 part by weight with respect to the total amount (100 parts by weight).

[23] The curable resin composition according to any one of [1] to [22], which further contains a zinc compound (E).

[24] The curable resin composition according to [23], wherein the zinc compound (E) is a carboxylic acid acylate.

[25] The curable resin composition according to [23], wherein the zinc compound (E) is octylic acid.

[26] to [25], wherein the content of the zinc compound (E) is 0.01 part by weight or more and less than 1.0 part by weight based on 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.

[27] The curable resin composition according to any one of [23] to [26], wherein the zinc content of the compound (100% by weight) in the zinc compound (E) is 2 to 30% by weight.

Since the curable resin composition of the present invention has the above-described structure, a cured product having excellent transparency and heat resistance can be formed. Particularly, the cured product is excellent in heat-resisting impact resistance, more specifically, in terms of peel resistance (adhesion to LED package) and crack resistance under the condition of severe temperature change, and also has excellent heat resistance such as H ₂ S gas, SO _x gas, Barrier properties against a plurality of corrosive gases are also excellent. In addition, the obtained cured product may be excellent in flexibility and flowability. Therefore, it can be suitably used as a sealing material for the curable resin optical semiconductor element (for example, an LED element, a semiconductor laser element, a photovoltaic element, a CCD element, etc.) of the present invention, An optical semiconductor device obtained by sealing an optical semiconductor element with a high quality and durability. In particular, the curable resin composition of the present invention is useful as a sealing material for a next-generation light source that requires heat resistance to a high temperature (for example, 180 DEG C or higher) which has not been available.

1 is a schematic view showing an embodiment of a photosemiconductor device in which an optical semiconductor element is sealed using the curable resin composition of the present invention. The left side view (a) is a perspective view, and the right side view (b) is a sectional view.

The curable resin composition of the present invention is a curable resin composition containing a polyorganosiloxane (A), a silsesquioxane (B) and an isocyanurate compound (C), wherein the polyorganosiloxane (A) Polyorganosiloxane, and a viscosity of 4000 to 8000 mPa · s.

[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 a polyorganosiloxane having an aryl group as a substituent in the main chain . The polyorganosiloxane (A) may be a straight-chain or branched polyorganosiloxane having a hydrosilyl group or a group having an aliphatic carbon-carbon unsaturated bond. Examples of the polyorganosiloxane (A) include silicone skeletons such as phenyl silicon skeleton (polydiphenylsiloxane) and phenylmethyl silicone skeleton (polymethylphenylsiloxane). The polyorganosiloxane (A) does not contain silsesquioxane (B).

The polyorganosiloxane (A) may be a straight-chain and / or branched-chain polyorganosiloxane. Among them, polyorganosiloxane having branched chains (branched-chain polyorganosiloxane) is preferable from the viewpoint of the strength of the cured product.

The aryl group in the polyorganosiloxane (A) is not particularly limited, and for example, a C _{6- 14} aryl group (particularly a C _{6- 10} aryl group) such as a phenyl group or a naphthyl group may, for example, be mentioned. These aryl groups may be substituents (groups bonded directly to silicon atoms) of the silicon atom in the polyorganosiloxane (A).

The aryl group in the polyorganosiloxane (A) may have at least one substituent. Examples of the substituent include a halogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, a mercapto group (thiol group) An amino group or a substituted amino group (such as a mono or dialkylamino group or an acylamino group), an epoxy group, a cyano group, an isocyanate group, an isocyanato group, A carbamoyl group, and an isothiocyanate group.

Examples of the substituted or unsubstituted hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups in which two or more thereof are bonded.

Examples of the aliphatic hydrocarbon group 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 vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 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) . As the alkynyl group may be mentioned, for example, ethynyl group, a propynyl group such as a C _{2- 20} alkynyl group (preferably a C _{2- 10} alkynyl group, more preferably C _{2- 4} alkynyl group), and the like.

Examples of the alicyclic hydrocarbon group 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.

The aromatic hydrocarbon group includes, for example, a phenyl group, a naphthyl group of the C _{6- 14} aryl group (in particular, C _{6- 10} aryl group), and the like.

Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Further, as the group bonded group of the aliphatic hydrocarbon group and the 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- 6} and the like can be mentioned an 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.

Examples of the substituent of the substituted or unsubstituted hydrocarbon group (substituted hydrocarbon group) include the same substituents as the substituent which the aryl group may have.

As another example of the substituent of the aryl group in the polyorganosiloxane (A), a group represented by the formula (4) is exemplified.

 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 substituted or unsubstituted hydrocarbon group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, (Mono or dialkylamino group, acylamino group and the like), an alkylthio 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.

Formula (4) in the group represented by each R 'each represent a hydrogen atom, C _{1- 10} alkyl groups (particularly, C _1-4 alkyl group) include, C _{2- 10} alkenyl group (particularly, C _{2- 4} alkyl), C _3-12 cycloalkyl, C _3-12 cycloalkyl in the alkenyl group, the aromatic ring C _{1- 4} alkyl, C _{2- 4} alkenyl group, a halogen atom, C _1- C _{4 6-} which may have a substituent such as an alkoxy group ₁₄ aryl group, C _{7- 18} aralkyl group, C _{6- 10} aryl -C _{2- 6} alkenyl group, a hydroxyl group, C _1-6 alkoxy group is preferable, a halogen atom.

The content of the aryl group (in terms of phenyl group) relative to the total amount (100% by weight) of the polyorganosiloxane (A) is not particularly limited, but is preferably 35% by weight or more (for example, 35 to 70% by weight) By weight or more, and more preferably 45% by weight or more. If the content of the aryl group is less than 35% by weight, the barrier property against the corrosive gas of the resulting cured product may be lowered. Further, all the substituents in the main chain composed of the siloxane bond (Si-O-Si) of the polyorganosiloxane (A) may be aryl groups, or a part of the substituents may be aryl groups. The content of the aryl group can be measured by, for example, ¹ H-NMR.

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 " polyorganosiloxysilylalkane ".

The curable resin composition of the present invention preferably contains a polyorganosiloxysilane (A) as the polyorganosiloxane (A), more preferably the polyorganosiloxysilane (A) is only a polyorganosiloxysilane Do. The polyorganosiloxysilylalkylene is less likely to generate a low molecular weight ring in the production process as compared with the polyorganosiloxane in which the main chain is composed only of a siloxane bond (Si-O-Si), and decomposes by heating to produce a silanol group -SiOH). ≪ / RTI > As a result, a cured product having a low surface stickiness and a low yellowing tendency is apt to be obtained.

In the formula (6), R ²¹ to R ²⁶ are the same or different and each represents a hydrogen atom, the above-mentioned aryl group, a substituent of the above-mentioned aryl group, a heterocyclic group, or an aliphatic carbon-carbon unsaturated bond (Preferably a monovalent group containing a hydrogen atom, the above-mentioned aryl group, a monovalent hydrocarbon group, a monovalent heterocyclic group, or an aliphatic carbon-carbon unsaturated bond described later) . Provided that at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond.

It is also preferable that all of R ²¹ to R ²⁶ are not monovalent groups containing an aliphatic carbon-carbon unsaturated bond. It is also, R ²¹ to R ²⁶ of the at least one or more of the aryl group (phenyl group, a naphthyl group, etc. C _{6- 14} aryl group (particularly C _{6- 10} aryl group), in particular phenyl group) are preferred. The aryl group in R ²¹ to R ²⁶ may have one or more substituents. Examples of the substituent of the aryl group in R ²¹ to R ²⁶ include the same substituents as the substituent of the aryl group in the above-mentioned polyorganosiloxane (A).

Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group; A monovalent alicyclic hydrocarbon group; A monovalent aromatic hydrocarbon group; An aliphatic hydrocarbon group, a monovalent group in which two or more of an alicyclic hydrocarbon group and an aromatic 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, decyl group, dodecyl group, such as straight chain or C _{1- 20} alkyl group branched (preferably Advantageously there may be mentioned a 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 metallyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, 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) . 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).

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

Examples of the group bonded with the aliphatic hydrocarbon group and the alicyclic hydrocarbon group include a cyclohexylmethyl group and a methylcyclohexyl group. A combination of aliphatic hydrocarbon group and aromatic hydrocarbon group, a benzyl group, a phenethyl group, etc. C _{7- 18} aralkyl group (particularly, C _{7- 10} aralkyl group), such as thinner push the C _{6- 10} aryl -C _{2- 6} alkenyl group there may be mentioned C _{1- 4} alkyl-substituted aryl group, styryl group, etc. C _2-4 alkenyl substituted with aryl groups such as tolyl group.

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 of 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; An aryloxy group; Aralkyloxy groups; An acyloxy group; A mercapto group; An alkylthio group; Alkenylthio; Arylthio group; An aralkylthio group; A carboxyl group; An alkoxycarbonyl group; An aryloxycarbonyl 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; These two or more according to need, and the like groups bonded by interposing an C _{1- 6} alkylene.

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} alkoxycarbonyl 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. As the aryloxy group, for example, a phenoxy group, tolyl rilok group, a naphthyloxy group, C _{1- 4} alkyl group on the aromatic ring at the time, such as, _2- C ₄ alkenyl group, a halogen atom, a substituent such as a C _{1- 4} alkoxy group the and the like _6- C ₁₄ aryloxy group which may optionally have. 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. As the arylthio group, for example, such as phenylthio, tolyl rilti come, naphthyl, aromatic ring and a C _{1- 4} alkyl group such as tilti come, _2- C ₄ alkenyl group, a halogen atom, C _{1- 4} alkoxy group A C _{6- 14} arylthio group which may have a substituent, 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. As said aryloxycarbonyl group, for example, phenoxy group, tolyloxy group, naphthyloxy group, etc. C _{6- 14} aryloxy-carbonyl group, and the like. 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 in the heterocyclic group include the same substituents as the above-mentioned substituent of the monovalent hydrocarbon group.

More specific examples of the monovalent hydrocarbon group and the monovalent heterocyclic group include the methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, decyl group, phenyl group, naphthyl group, A substituted or unsubstituted hydrocarbon group (for example, 2- (3 (thienyl)), a benzyl group, a phenethyl group, a pyridyl group, a furyl group, a thienyl group, Acryloxypropyl group, N-2- (aminoethyl) -3-aminopropyl group, 3-aminocyclohexyl group, Propyl group, N-phenyl-3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group and the like).

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

In the formula (6), R ²⁷ represents a divalent hydrocarbon group. Examples of the divalent monovalent hydrogen group include a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Examples of the linear or branched alkylene group include a linear or branched alkylene group having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group and a trimethylene group. . 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. Examples of the divalent aromatic hydrocarbon group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 4,4'-biphenylene group and a naphthylene 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 the brackets attached with r may be the same or different. When the structures in the parentheses attached with 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 appended may be the same or different. When the structures in parentheses to which s is attached 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. The addition form of the structure in parentheses with r in equation (6) and the structure in parentheses with s attached is not particularly limited and may be random or block. 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 polyorganosiloxysilylene.

As described above, the polyorganosiloxysilane may have either straight chain or branched chain structure. As the polyorganosiloxy alkylene, for example, a polyorganosiloxysilane having a branched chain and an aryl group is preferable.

Examples of the polyorganosiloxysilkylene include GD-1125A (manufactured by Chokko Chemical Industry Co., Ltd.) and GD-1125B (manufactured by Chokko Chemical Industry Co., Ltd.).

As the polyorganosiloxane (A), it is preferable to use two or more (especially two) kinds of the above-mentioned polyorganosiloxysilylenes. Among them, from the viewpoint of barrier property against corrosive gas, it is preferable to use a polyorganosiloxysilylene having a group having an aliphatic carbon-carbon double bond and an aryl group, a group having an aliphatic carbon-carbon double bond, And polyorganosiloxysilylenes having an aryl group are preferably used.

When two or more kinds of polyorganosiloxane (A) are used, it is preferable that the total amount (100% by weight) of the polyorganosiloxysilane (A) in the curable resin composition of the present invention The ratio is not particularly limited, but is preferably 60 wt% or more (for example, 60 to 100 wt%), more preferably 80 wt% or more (for example, 80 to 99.5 wt%), 88% by weight or more. When the proportion of the polyorganosiloxysilylalkylene is less than 60% by weight, the cured product tends to become yellowish, or the surface tends to have tackiness, and the handling property tends to deteriorate.

The number average molecular weight (Mn) of the polyorganosiloxane (A) is preferably 500 to 4000, more preferably 550 to 2800, and still more preferably 600 to 1500. The weight average molecular weight (Mw) is preferably from 500 to 20,000, more preferably from 600 to 10000, and even more preferably from 700 to 6500. When the number average molecular weight (Mn) and / or the weight average molecular weight (Mw) is less than 500, the heat resistance of the resulting cured product may be lowered. On the other hand, if the number average molecular weight (Mn) exceeds 4,000 and / or the weight average molecular weight (Mw) exceeds 20,000, the compatibility of the polyorganosiloxane (A) When two or more kinds of the organosiloxane (A) are used in combination, the compatibility of the polyorganosiloxanes with each other may be lowered. The polyorganosiloxane (A) may have a number average molecular weight (Mn) and / or a weight average molecular weight (Mw) in the above range, but may be a mixture thereof. The number average molecular weight (Mn) and / or the weight average molecular weight (Mw) can be calculated, for example, as molecular weight in terms of polystyrene by gel permeation chromatography.

The molecular weight dispersion (Mw / Mn) calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyorganosiloxane (A) is preferably from 0.95 to 4.00, more preferably from 1.00 to 3.80, 3.50 is more preferable. When the molecular weight dispersion degree (Mw / Mn) is more than 3.50, the heat resistance of the obtained cured product and the barrier property against corrosive gas may be lowered.

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 is preferably 60 to 100 parts by weight based on 100 parts by weight of the curable resin composition. 99.7% by weight, more preferably 75 to 99.0% by weight, and still more preferably 90 to 98.5% by weight. When the content is less than 60% by weight, the heat-resistant impact resistance of the resulting cured product may be lowered. On the other hand, if the content exceeds 99.5% by weight, the barrier property against the corrosive gas of the obtained cured product may be lowered.

The polyorganosiloxane (A) may have a substituent other than the aryl group, and the substituent other than the aryl group may be a substituent of the silicon atom in the polyorganosiloxane (A). Examples of the substituent other than the aryl group include a hydrogen atom, a halogen 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 cycloalkenyl group) 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 isocyanate group, a carbamoyl group, and an isothiocyanate group.

Examples of the substituent other than the aryl group in the polyorganosiloxane (A) include a hydrogen atom, a group having a Si-H bond (such as a hydrosilyl group), a substituted or unsubstituted hydrocarbon group (preferably an alkyl group or an aliphatic- And a group having a carbon-carbon double bond (an alkenyl group and the like)) is particularly preferable. The polyorganosiloxane (A) may be, for example, a polyorganosiloxane having an aryl group and a group having an aliphatic carbon-carbon double bond, a polyorganosiloxane having an aryl group and a group having an Si-H bond, an aryl group, an aliphatic A polyorganosiloxane having a group having a carbon-carbon double bond and a group having a Si-H bond, or the like.

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

[Polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond]

The curable resin composition of the present invention is a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond as the polyorganosiloxane (referred to simply as " polyorganosiloxane (A1) ). Among them, the polyorganosiloxane (A) is preferably a polyorganosiloxane (A1) (only a polyorganosiloxane (A1)). The aliphatic carbon-carbon double bond may have any of the partial structures and / or constituents of the polyorganosiloxane (A1). The aliphatic carbon-carbon double bond may have a substituent (for example, a substituent having a silicon atom) in the polyorganosiloxane (A1). The aliphatic carbon-carbon double bond may be present at the end of the main chain (straight chain and / or branched chain) composed of the siloxane bond (Si-O-Si) of the polyorganosiloxane (A1).

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 the formula (4) at least one of the three R 'in the group represented by the C _{2- 20} alkenyl group, a cycloalkenyl group of C _3-12, C _{4 -15} crosslinked cyclic unsaturated hydrocarbon group, include C _{2- 4} alkenyl substituted aryl group, or the like thinner push airway. Among them, preferably an alkenyl, more preferably C _{2- 20} alkenyl group, more preferably a vinyl group.

The content of the aliphatic carbon-carbon double bond (in terms of the vinyl group) relative to the total amount (100 wt%) of the polyorganosiloxane (A) is not particularly limited, but is preferably 1.5 to 15.0 wt%, more preferably 2.0 to 13.0 wt% By weight, and still more preferably 3.0 to 12.0% by weight. By having the aliphatic carbon-carbon double bond in the above range, there is a tendency that a cured product having excellent physical properties such as heat resistance, crack resistance and barrier property against corrosive gas of the resulting cured product tends to be obtained. The content of the aliphatic carbon-carbon double bond can be measured, for example, by ¹ H-NMR.

[Polyorganosiloxane (A2) having Si-H bond]

The curable resin composition of the present invention is a polyorganosiloxane (A2) having Si-H bonds (sometimes referred to simply as "polyorganosiloxane (A2)" in this specification) as the polyorganosiloxane (A) . The Si-H bond may have any of the partial structures and / or constituents of the polyorganosiloxane (A2). The Si-H bond may have a substituent (for example, a substituent having a silicon atom) in the polyorganosiloxane (A2). The Si-H bond may be present at the end of the main chain (straight chain and / or branched chain) composed of the siloxane bond (Si-O-Si) of the polyorganosiloxane (A2).

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 content of the Si-H bond relative to the total amount of the polyorganosiloxane (A) (the total content, 100 wt%) is not particularly limited, but the weight conversion of H (hydride) in a hydrogen atom or a Si- H), more preferably 0.05 to 0.30% by weight, and still more preferably 0.08 to 0.20% by weight. By having the Si-H bond in the above-mentioned range, a cured product having excellent physical properties such as heat resistance, crack resistance and barrier property against corrosive gas tends to be obtained of the obtained cured product. The content of the Si-H bond can be measured by, for example, ¹ H-NMR.

The content of the polyorganosiloxane (A2) relative to the total amount of the polyorganosiloxane (A) (100% by weight) is not particularly limited, but is preferably 50% by weight or more, and more preferably 80% by weight or more. By containing the polyorganosiloxane (A2) in the above range, a cured product having excellent physical properties such as heat resistance, crack resistance and barrier property against corrosive gas of the cured product obtained tends to be easily obtained.

A ratio a1 / a2 (mol / g) of the content of aliphatic carbon-carbon double bond (in terms of vinyl groups) a1 (mol / g) in the polyorganosiloxane (A) and the content of Si- Is preferably 0.80 to 1.10, more preferably 0.90 to 1.05, still more preferably 0.95 to 1.00. By setting the ratio a1 / a2 to be 1.10 or less, the barrier property against the corrosive gas in particular can be enhanced. By setting a1 / a2 to 0.80 or more, the strength such as crack resistance can be increased.

The polyorganosiloxane (A1) may be a polyorganosiloxane (A2) having Si-H bonds at the same time, and the polyorganosiloxane (A2) may be a polyorganosiloxane having an aliphatic carbon- A1).

The polyorganosiloxane (A) may be composed of only one of the polyorganosiloxane (A1) or the polyorganosiloxane (A2), and the polyorganosiloxane (A) may be composed of two or more different kinds of polyorganosiloxane Or may be composed of the organosiloxane (A1) and / or the polyorganosiloxane (A2).

When the polyorganosiloxane (A) is composed of two or more different kinds of polyorganosiloxanes, when at least one of the two or more kinds of polyorganosiloxanes is a polyorganosiloxane (A2), the poly It is preferable that the two or more kinds of polyorganosiloxanes except for the organosiloxane (A2) are polyorganosiloxane (A1) having no Si-H bond.

The polyorganosiloxane (A) can be obtained by reacting a silsesquioxane (B), an isocyanurate compound (C), a silane coupling agent (D), a zinc compound (E), a hydrosilylation catalyst, A reaction inhibitor, other siloxane compounds, other silane compounds, solvents, additives, and the like. In that case, the polyorganosiloxane (A1) may contain a part of the other component and the polyorganosiloxane (A2) may contain the remaining part of the other component. Further, only either one of the polyorganosiloxane (A1) or the polyorganosiloxane (A2) may contain some or all of the other components.

[Silsesquioxane (B)]

The curable resin composition of the present invention contains silsesquioxane (B). The silsesquioxane is not particularly limited, but silsesquioxane (ladder silsesquioxane) having a random structure, a basket structure and a ladder structure can be given, and silsesquioxane having a ladder structure as a main component It is preferably silsesquioxane. The silsesquioxane (B) preferably contains ladder-type silsesquioxane as a main component. Among them, silsesquioxane (B) is more preferably ladder-type silsesquioxane.

Silsesquioxane is a polysiloxane. The polysiloxane is generally 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), Q unit (unit consisting of a tetravalent group in which a silicon atom is bonded to four oxygen atoms) .

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

The silsesquioxane (B) may have two or more aliphatic carbon-carbon double bonds in the molecule (in one molecule). The silsesquioxane (B) may have a group having two or more Si-H bonds in the molecule (in one molecule). The silsesquioxane (B) is not particularly limited, but is preferably liquid at room temperature. The silsesquioxane (B) may be used singly or in combination of two or more.

The inclusion of the silsesquioxane (B) tends to improve the barrier properties to the corrosive gas of the cured product formed by curing in particular, and to improve the toughness (particularly, crack resistance). The content (blend amount) of silsesquioxane (B) 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 entire amount of the curable resin composition (100% By weight, more preferably from 0.5 to 15% by weight, and particularly preferably from 7 to 13% by weight.

The content of the silsesquioxane (B) is not particularly limited, but from the viewpoint of the barrier property against the corrosive gas (in particular, the corrosion resistance against the H ₂ S gas), for example, the polyorganosiloxane (A) More preferably from 0.1 to 20 parts by weight, still more preferably from 1 to 15 parts by weight, particularly preferably from 7 to 13 parts by weight, based on 100 parts by weight of the total amount (100 parts by weight) Wealth.

[Isocyanurate compound (C)]

The curable resin composition of the present invention contains an isocyanurate compound (C). By containing the isocyanurate compound (C), the curable resin composition of the present invention improves the barrier property to the corrosive gas of the cured product formed by curing in particular, and improves the adhesion to the adherend. Among them, the isocyanurate compound (C) preferably contains an isocyanurate compound represented by the formula (1). In particular, the isocyanurate compound (C) is preferably 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). Among them, it is preferable that at least one (preferably one or two, and more preferably one) of R ^x , R ^y and R ^z in the formula (1) is a group represented by the formula (3) Do.

In the formulas (2) and (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a pentyl group, a hexyl group, An ethylhexyl group, and the like. Among these alkyl groups, straight or branched alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group and isopropyl group are preferable. 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 isocyanurate 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methylpropenyl) isocyanurate, diallyl monoglycidyl isocyanurate, triglycidyl isocyanurate, ) -3,5-diglycidylisocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, Bis (2-methylpropenyl) -5-glycidylisocyanurate, 1,3-bis (2-methylpropenyl) - (2-methylepoxypropyl) isocyanurate, and tris (2-methylpropenyl) isocyanurate. Among them, monoallyldiglycidylisocyanurate is preferable. The isocyanurate compound (C) may be used singly or in combination of two or more.

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

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, more preferably 0.1 to 3% by weight based on the whole amount of the curable resin composition (100% By weight is more preferable. 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 be precipitated in the curable resin composition or the cured product may be clouded. 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, for example, the total amount of the polyorganosiloxane (A) and the silsesquioxane (B) 0.01 part by weight to 0.5 part by weight is preferable.

[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 adhesion to an adherend is improved in particular, and the barrier property against the corrosive gas of the cured product is further improved.

Since the silane coupling agent (D) has good compatibility with the polyorganosiloxane (A) and the isocyanurate compound (C), the silane coupling agent (D) is excellent in compatibility with other components of the isocyanurate compound (C) and the 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.

As the silane coupling agent (D), a partial condensate of the silane coupling agent may be used. By using the partial condensate, the viscosity of the curable resin composition of the present invention can be improved, and the barrier property against corrosive gas and thermal shock resistance can be improved.

The partial condensate is obtained by hydrolyzing and partially condensing one or more silane coupling agents. For the hydrolysis and partial condensation, well-known or common methods can be used. For example, there can be mentioned a method of adding a solvent, water and, if necessary, a catalyst to the mixture of the silane coupling agent, followed by heating and stirring. During the stirring, by-products (water, alcohols and the like) may be removed by distillation as necessary.

Examples of the partial condensate include, but are not limited to, 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane oligomer, 2- ( (3,4-epoxycyclohexyl) ethyltrimethoxysilane-tetramethoxysilane oligomer, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropylmethyl Tetramethoxysilane oligomer, 3-glycidoxypropylmethylethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropylmethyldiethoxysilane- A co-oligomer containing an epoxy group such as triethoxysilane-tetraethoxysilane oligomer; (Aminoethyl) -3-aminopropylmethyldimethoxysilane-tetraethoxysilane oligomer, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane-tetramethoxysilane oligomer, N- (Aminoethyl) -3-aminopropyltrimethoxysilane-tetraethoxysilane oligomer, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane-tetramethoxysilane oligomer, N- (Aminoethyl) -3-aminopropyltriethoxysilane-tetramethoxysilane oligomer, N-2- (aminoethyl) -3-aminopropyltriethoxysilane-tetraethoxysilane oligomer, Aminopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetramethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetraethoxysilane-tetramethoxysilane oligomer, Ethoxysilane oligomer, 3-triethoxysilyl-N- (1,3-dimethyl-butyl ) Propylamine-tetramethoxysilane oligomer, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine-tetraethoxysilane oligomer, N-phenyl- Silanol-tetramethoxysilane oligomer, N-phenyl-3-aminopropyltrimethoxysilane-tetraethoxysilane oligomer, and the like; Vinyltriethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane- (Methoxyethoxysilane) -tetramethoxysilane oligomer, vinyltris (methoxyethoxysilane) -tetraethoxysilane oligomer, vinyltriacetoxysilane-tetramethoxysilane oligomer, vinyltriacetoxysilane-tetra Vinyl group-containing co-oligomers such as methoxy silane oligomers; Phenyl trimethoxysilane-tetramethoxysilane oligomer, phenyl trimethoxysilane-tetraethoxysilane oligomer, phenyl trimethoxysilane-tetraethoxysilane oligomer, phenyl trimethoxysilane-tetraethoxysilane oligomer, diphenyl dimethoxysilane-tetramethoxysilane oligomer and diphenyl dimethoxysilane- Containing oligomers; (meth) acryloxypropyltriethoxysilane-tetramethoxysilane oligomer, γ- (meth) acryloxypropyltriethoxysilane-tetraethoxysilane oligomer, γ- (meth) acryloxypropyltrimethoxysilane (Meth) acryloxypropyltrimethoxysilane-tetraethoxysilane oligomer,? - (meth) acryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer,? - (meth) Acryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, γ- (meth) acryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, γ- (meth) acryloxypropylmethyldiethoxysilane-tetraethoxysilane A (co) oligomer containing a (meth) acryl group such as an oligomer; Mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, And a mercapto group-containing co-oligomer such as tetraethoxysilane oligomer.

The silane coupling agent (D) may be synthesized, or a commercially available product may be used. Examples of commercially available products of the silane coupling agent include Z-6610, Z-6011, Z-6020, Z-6094, Z-6883, Z-6032, Z-6040, Z- Z-6000 (all trade names, all of Toray Industries, Inc.), Z-6300, Z-6519, Z-6825, Z-6030, Z-6033, Z-6062, Z-6862, Z- KBM-403, KBM-402, KBM-403, KBM-403, KBM-1403, KBM-502, KBM-503, KBE- 603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-1003, KBE-1003, KBM- KBM-803, KBE-846, KBE-9007, X-41-1053, X-41-1056, X-41-1059A, X-41-1805, X-41-1808, 513, X-40-2672B, X-40-9272B and X-40-2651 (all trade names, all manufactured by Shin-Etsu Chemical Co., Ltd.). The silane coupling agents may be used alone 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 5 parts by weight, more preferably 0.03 to 1 part by weight, further preferably 0.05 to 0.8 part by weight, relative to 100 parts by weight of the total amount of the curable resin composition Do. When the content of the silane coupling agent (D) is within the above range, the barrier property and the flow resistance to the corrosive gas are improved. Particularly, when a partial condensate of a silane coupling agent is used, there is an effect of significantly improving the corrosion resistance (particularly, the H ₂ S corrosion resistance in the interior) and the thermal shock resistance. If the content of the silane coupling agent (D) is less than 0.01 parts by weight, the adhesion to an adherend is reduced, and in some cases, sufficient curing may not be obtained when the isocyanurate compound (C) is used in common. On the other hand, when the content of the silane coupling agent (D) exceeds 5% by weight, it may be difficult to adjust the viscosity of the curable resin composition within the desired range.

The content of the silane coupling agent (D) is not particularly limited, but from the viewpoint of the barrier property against the corrosive gas and the flow resistance, the total amount of the polyorganosiloxane (A) and the silsesquioxane (B) 0.01 part by weight or more and less than 1.0 part by weight, and more preferably 0.08 to 0.9 part by weight, based on 100 parts by weight of the resin (A).

The proportion of the partial condensate of the silane coupling agent in the silane coupling agent (D) is not particularly limited, but is preferably 50 to 100% by weight based on the total amount (100% by weight) of the silane coupling agent (D) Preferably 80 to 100% by weight. Among them, the silane coupling agent (D) is preferably only the partial condensate of the silane coupling agent. When the ratio of the partial condensate of the silane coupling agent is in the above range, the corrosion resistance (especially H ₂ S corrosion resistance in particular) and thermal shock resistance are further improved.

The proportion of the partial condensate of the silane coupling agent in the curable resin composition is not particularly limited. However, from the viewpoint of corrosion resistance (in particular, corrosion resistance against internal H ₂ S gas) and thermal shock resistance, the total amount of the curable resin composition More preferably from 0.03 to 1 part by weight, still more preferably from 0.05 to 0.8 part by weight, based on 100 parts by weight of the resin (A).

The proportion of the partial condensate of the silane coupling agent is not particularly limited. However, from the viewpoint of corrosion resistance (in particular, corrosion resistance against internal H ₂ S gas), thermal shock resistance and floatability, for example, polyorganosiloxane A ) And silsesquioxane (B) is preferably 0.01 parts by weight or more and less than 1.0 part by weight, more preferably 0.08 to 0.9 parts by weight, based on the total amount (100 parts by weight) of the silsesquioxane (B).

[Zinc compound (E)]

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

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 decanoate, an inorganic zinc compound represented by zinc oxide such as zinc oxide and zinc stearate, and mixtures thereof. Of these, zinc carboxylate is preferable, and zinc octylate is particularly preferable. The zinc compound (E) preferably contains at least zinc carboxylate (particularly, zinc octylate). Among them, it is more preferable that the zinc compound (E) is only zinc carboxylate (particularly, zinc octylate).

The zinc compound (E) is not particularly limited, but from the viewpoint of the barrier property to the corrosive gas, the zinc content of the compound (100% by weight) is preferably 2 to 30% by weight, 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 or more and less than 1.0 part by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B) , More preferably from 0.1 part by weight to less than 0.8 part by weight, and still more preferably from 0.3 part by weight to less than 0.6 part by weight. By setting the content of the zinc compound (E) within the above range, it becomes possible to maintain the heat-resistant impact resistance and the down flow resistance at a level sufficient for practical use. 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) 1.0 parts by weight or more, there is a case in which the barrier gas for SO _X decreases.

[Hydrosilylation catalyst]

The curable resin composition of the present invention may further contain a hydrosilylation catalyst. By containing the hydrosilylation catalyst, the curing resin composition of the present invention can efficiently advance the curing reaction (hydrosilylation reaction). Examples of the hydrosilylation catalyst include known hydrosilylation catalysts such as platinum catalysts, rhodium catalysts, and palladium catalysts. Specific examples of the catalyst include platinum fine particles such as platinum fine powder, platinum black, platinum supported silica fine powder, platinum supported activated carbon, chloroplatinic acid, chloroplatinic acid and complex with alcohol, aldehyde, ketone, platinum olefin complex, platinum-carbonylvinylmethyl complex A platinum-based catalyst such as a platinum-phosphine complex, a platinum-phosphite complex, etc., and a platinum-based catalyst such as a platinum-based catalyst such as a platinum-based catalyst such as a platinum-vinylidene- A palladium-based catalyst or a rhodium-based catalyst containing a palladium atom or a rhodium atom in place of the platinum atom in the catalyst. 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 amount 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% by weight.

[Other siloxane compounds]

The curable resin composition of the present invention may further contain a cyclic siloxane compound having two or more aliphatic carbon-carbon double bonds in the molecule (in one molecule) as another siloxane compound. The curable resin composition of the present invention may further contain a cyclic siloxane compound having a group having two or more Si-H bonds in the molecule (in one molecule) as another siloxane compound. These cyclic siloxanes may be used singly or in combination of two or more. 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 entire amount of the curable resin composition (100% By weight, more preferably 0.5 to 10% by weight.

[Other silane compounds]

The curable resin composition of the present invention may contain other silane compounds (for example, a compound 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, 1,1,3,5,5,7,7,9,9- And straight chain or branched chain siloxanes having Si-H groups such as 1,3,5,5,7,7,9,9,9-undecamethylpentasiloxane. 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, calcined 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, May contain an additive for generators. 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 (composition 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, bottom flowability and barrier property against the 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-liquid composition in which each component is mixed in advance, or two or more components which are stored separately may be mixed at a predetermined ratio before use (For example, two-liquid system) composition.

The curable resin composition of the present invention has a viscosity at 25 占 폚 of 4000 to 8000 mPa 占 퐏. The viscosity is preferably 4500 to 7000 mPa · s, more preferably 5000 to 6000 mPa · s. When the viscosity is less than 4000 mPa.s, for example, when the curable resin composition contains a phosphor, the phosphor may not be uniformly dispersed in some cases. On the other hand, when the viscosity exceeds 8000 mPa · s, for example, when the curable resin composition is injected into the LED package, the injection amount may not be stabilized.

The viscosity of the curable resin composition of the present invention can be suitably adjusted by methods known to those skilled in the art. For example, silsesquioxane (B), silane coupling agent (D), other siloxane compounds, other silane compounds, solvents, additives and the like may be appropriately selected and adjusted to a desired viscosity. Alternatively, a commercially available polyorganosiloxane (A) may be suitably selected and adjusted to a desired viscosity.

The viscosity at 25 캜 as used herein refers to a viscosity at 25 캜 of a cone-plate type rotational viscometer (cone plate type viscometer) (for example, Rheometer (trade name "PhysicaUDS-200", manufactured by AntonPaar) : 16 mm, taper angle = 0 DEG)) at a temperature of 25 DEG C and a rotation speed of 5 rpm.

[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 may be appropriately selected from conventionally known conditions. For example, from the viewpoint of the reaction rate, the temperature (curing temperature) is preferably from 25 to 180 캜 (more preferably from 60 to 150 캜 ), 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.

<Examples>

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 product was carried out 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 x 2 (Manufactured by TOSOH CORPORATION), guard column: Tskgel guardcolumn H _HR L (manufactured by TOSOH CORPORATION), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, .

[Polyorganosiloxane (A)]

As the polyorganosiloxane (A), the following products were used.

GD-1125A, manufactured by Chokko Chemical Industry Co., Ltd., having a vinyl group content of 1.13 wt%, a phenyl group content of 42.79 wt%, a SiH group content (in terms of hydride) of 0 wt%, a number average molecular weight of 2858, a weight average molecular weight of 9598, · S

GD-1125B manufactured by Chokko Chemical Industry Co., Ltd., having a vinyl group content of 3.71 wt%, a phenyl group content of 51.75 wt%, a SiH group content of 0.16 wt% (in terms of hydride), a number average molecular weight of 671, a weight average molecular weight of 1354, · S

OE-6631A: manufactured by Toray-Dow Corning Incorporated, having a vinyl group content of 1.72 wt%, a phenyl group content of 54.20 wt%, a SiH group content (in terms of hydride) of 0 wt%, a number average molecular weight of 3600, a weight average molecular weight of 11000, · S

OE-6631B: manufactured by Toray-Dow Corning Incorporated, having a vinyl group content of 3.81 wt%, a phenyl group content of 57.49 wt%, a SiH group content (in terms of hydride) of 0.34 wt%, a number average molecular weight of 830, a weight average molecular weight of 2200, · S

[Synthesis of silsesquioxane (B)] [

&Lt; Synthesis Example 1 &

15.86 g of phenyltriethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd.) and 6.16 g of methyl isobutyl ketone (MIBK) were added to the reaction vessel, and the mixture was cooled to 10 占 폚. To the mixture was added dropwise 4.32 g of water and 0.16 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) over 1 hour. After the dropwise addition, the mixture was kept at 10 DEG C for 1 hour. Thereafter, 26.67 g of MIBK was added, and the reaction solvent was diluted.

Subsequently, the temperature of the reaction vessel was raised to 70 캜, and at the time when the temperature reached 70 캜, 0.16 g of 5N hydrochloric acid (25 mmol as hydrogen chloride) was added, and the polycondensation reaction was carried out under nitrogen for 4 hours.

Subsequently, 11.18 g of divinyltetramethyldisiloxane and 3.25 g of hexamethyldisiloxane were added to the reaction solution, and the silylation reaction was carried out at 70 DEG C for 4 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 and 40 占 폚 to obtain a colorless transparent liquid phase reaction product (ladder silsesquioxane having vinyl group at the terminal, 13.0 g).

The number average molecular weight (Mn) of the reaction was 840 and the molecular weight dispersion degree was 1.06.

[Isocyanurate compound (C)]

As the isocyanurate compound (C), the following products were used.

Monoallyl diglycidyl isocyanurate: manufactured by Shikoku Kasei Kogyo Co., Ltd.

[Silane coupling agent (D)]

As the silane coupling agent (D), the following products were used.

3-glycidyloxypropyltrimethoxysilane: manufactured by Dow Corning Toray Co., Ltd.

[Synthesis of silane coupling agent (D)] [

&Lt; Synthesis Example 2 &

210.9 g of 3-glycidoxypropyltrimethoxysilane, 20.8 g of tetraethoxysilane, 210.9 g of methanol, 20.8 g of ethanol and 17.4 g of potassium fluoride (1% ethanol solution) were charged in a reaction vessel, The temperature was raised to 50 占 폚.

Subsequently, 16.2 g of water and 16.2 g of ethanol were added dropwise over 30 minutes, and after the temperature was raised again, the polycondensation reaction was carried out for 4 hours under reflux.

Subsequently, the volatile components were removed by distillation while raising the temperature to 80 ° C under atmospheric pressure. Thereafter, the remaining volatile components were distilled off by raising the temperature to 100 캜 under reduced pressure (30 Torr) to obtain a colorless transparent liquid phase reaction product (141.5 g).

[Zinc compound (E)]

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

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

&Lt; Examples and Comparative Examples &

Examples 1 to 5 and Comparative Examples 1 to 3 were carried out according to the following procedure.

(B), the isocyanurate compound (C), the silane coupling agent (D) and the zinc compound (E) were mixed in a predetermined weight ratio (unit amount of each component in Table 1 and Table 2 Were weighed), followed by stirring at 60 DEG C for 2 hours. Thereafter, after cooling to room temperature, the polyorganosiloxane (A) was mixed and further stirred at room temperature for 30 minutes to obtain a curable resin composition.

In addition, zinc octylate in Table 1 indicates the amount excluding mineral spirit from &quot; nikkaitith zinc &quot;.

[Measurement of viscosity]

Each of the samples was measured under the conditions of a temperature of 25 ° C and a rotation speed of 5 rpm using a rheometer (trade name "PhysicaUDS-200", manufactured by Antonfarza Co.) and a cone plate (cone diameter: 16 mm, taper angle = The viscosity (mPa · s) at 25 ° C was measured.

[Measurement of brightness retention rate]

The curable resin composition obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was injected into the LED package (InGaN element, 3.5 mm x 2.8 mm) shown in Fig. 1, and the curable resin composition was heated at 60 DEG C for 1 hour, then at 80 DEG C And heated at 150 DEG C for 4 hours to prepare a sample. Further, after the curable resin composition is injected into the LED package, the sample may be prepared by heating at 150 DEG C for 1 hour.

The total luminous flux (unit: 1 m) when a current of 20 mA was passed was measured for each of the above samples using a total luminous flux measuring instrument (OL771, manufactured by Optronics Laboratories, Inc.) And the total flux before the corrosion test was set.

Subsequently, each of the above-mentioned samples was subjected to a SO _X corrosion test and an H ₂ S corrosion test, which will be described later, and the total luminous flux was measured in the same manner as described above, and this was used as a total luminous flux after the causticity test.

Thereafter, the luminosity retention ratio was calculated according to the following formula.

Light Retention Rate (%) = (total flux before corrosion test / total flux after corrosion test) x 100

[SO _X Corrosivity Test]

0.3 g of each of the samples and sulfur powder (manufactured by Kishida Chemical Co., Ltd.) was 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 &quot; DN-64 &quot;, manufactured by Yamato Kagaku Kogyo Co., Ltd.), the oven temperature was set at 80 캜 and taken out after 24 hours, The luminous flux was measured.

[H ₂ S Corrosion Test]

Each of the above samples was placed in a gas corrosion tester (model number "GS-UV", manufactured by Suga Shikoku Co., Ltd.) adjusted to a hydrogen sulfide concentration of 25 ppm, a temperature of 50 ° C. and a humidity of 80% RH and taken out after 96 hours, The total flux was measured as described above.

[Evaluation of corrosion resistance]

The corrosion resistance evaluation criteria were as follows.

A: SO _X corrosive test brightness retention ratio is 85% or more in, and H ₂ S corrosion test stand of brightness maintenance rate is 99% or more in

B: SO brightness retention ratio in the _X-corrosion test is less than 85% and less than 99% brightness retention ratio in the H ₂ S corrosion test

C: Light retention ratio of less than 85% in SO _X corrosion test

[Thermal shock resistance test]

Each of the samples was subjected to thermal shock test using a thermal shock tester (product number: TSB-21, manufactured by Espec Co., Ltd.) at a temperature of -40 ° C for 5 minutes and then at a temperature of 100 ° C for 5 minutes. The application was carried out for 1000 cycles. Thereafter, the number of samples in which peeling and cracks were recognized in the sealing material of the LED package was counted using a digital microscope (model number &quot; VW-9000 &quot;, manufactured by KENENCE CORPORATION) Therefore, it is calculated.

Peeling occurrence rate (%) = (number of samples to be peeled / total number of samples) × 100

Crack incidence (%) = (number of samples with cracks / total number of samples) × 100

[Evaluation of thermal shock resistance]

Evaluation criteria of thermal shock resistance were as follows.

A: The peeling occurrence rate is 20% or less, and the crack occurrence rate is 10% or less

B: The peeling occurrence rate is more than 20% and not more than 50%, and the crack occurrence rate is not more than 10%

C: Cracking rate exceeds 10%

[Flow test for downward flow]

Each of the above samples was placed in a thermo-hygrostat (SH-641, manufactured by Espec Co., Ltd.) adjusted to a temperature of 30 ° C and a humidity of 70% RH and taken out after 192 hours. Subsequently, each sample was subjected to heat treatment at 260 DEG C for 10 seconds twice using reflow furnace (ANTOM Co., Ltd., model number &quot; UNI-5016F &quot;). Thereafter, the peeling occurrence rate and the crack occurrence rate were calculated in the same manner as in the thermal shock resistance test.

[Evaluation of Flowability]

The criteria for evaluation of the flowability were as follows.

A: The peel occurrence rate is 10% or less, and the crack occurrence rate is 20% or less

B: the peeling occurrence rate is 10% or less, and the crack occurrence rate is more than 20% and not more than 50%

C: The rate of peeling exceeds 10%

In Comparative Examples 1 to 3, it was not a result that the corrosion resistance, the thermal shock resistance, and the flow resistance were both satisfactory.

On the other hand, in Example 1, corrosion resistance (especially SO _x corrosion resistance) was remarkably improved by adding silsesquioxane (B), isocyanurate compound (C) and silane coupling agent (D) A dramatic improvement in the flowability (in particular, the peeling occurrence rate) was recognized.

Further, in Example 2, by using the silane coupling agent (D) of Synthesis Example 2, H ₂ S corrosion resistance was remarkably improved as compared with Example 1, and a significant improvement in thermal shock resistance was recognized.

Next, in Example 3, the addition of the zinc compound (E) in the range described in Patent Document 4 resulted in improvement of the inner H ₂ S corrosion resistance, and the corrosion resistance was satisfactory. On the other hand, the thermal shock resistance tended to be slightly lower than that of Example 2.

Therefore, in Example 4, the zinc compound (E) was further increased in comparison with Example 3, and as a result, it was surprisingly found that in Example 4, the lowered thermal shock resistance was significantly improved in Example 4. Not only that, however, it was recognized that the flow performance was improved dramatically.

Further, in Example 5, as a result of reducing the silane coupling agent (D) in comparison with Example 3, the thermal shock resistance tended to be improved, but the down flow property was slightly lowered.

From the above, it was possible to obtain a curable resin composition, a cured product, a sealing material, and an optical semiconductor device which combine both the SO _X corrosion resistance and the H ₂ S corrosion resistance in the interior, and have sufficient heat shock resistance and down flow resistance for practical use.

The curable resin composition and the cured product of the present invention are useful in applications such as adhesives, coating agents, and sealing materials that require heat resistance, transparency, flexibility, barrier properties against corrosive gases, thermal shock resistance, and flow resistance. Particularly, the curable resin composition and the cured product of the present invention are suitable as a sealing material for an optical semiconductor element (for example, an LED element, a semiconductor laser element, a photovoltaic element, a CCD element, and the like).

100 reflector (light-reflecting resin composition)
101 metal wiring
102 optical semiconductor element
103 bonding wire
104 Hardened cargo (seal material)

Claims (17)

A curable resin composition comprising a polyorganosiloxane (A), silsesquioxane (B), and an isocyanurate compound (C)
Wherein the polyorganosiloxane (A) is a polyorganosiloxane having an aryl group,
And a viscosity of 4000 to 8000 mPa · s. The curable resin composition according to claim 1, wherein the number average molecular weight (Mn) of the polyorganosiloxane (A) in terms of standard polystyrene by gel permeation chromatography is 500 to 4000. 3. The polyorganosiloxane (A) according to claim 1 or 2, wherein the weight average molecular weight of the polyorganosiloxane (A) in terms of standard polystyrene by gel permeation chromatography is Mw, the molecular weight dispersion degree (Mw / Mn ) Is from 0.95 to 4.00. The curable resin composition according to any one of claims 1 to 3, wherein the polyorganosiloxane (A) contains a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond. The curable resin composition according to any one of claims 1 to 4, wherein the polyorganosiloxane (A) contains a polyorganosiloxane (A2) having Si-H bonds. 6. The polyorganosiloxane (A) according to any one of claims 1 to 5, wherein the polyorganosiloxane (A)

[In the formula (6), R ²¹ to R ²⁶ are the same or different and each represents a monovalent group containing a hydrogen atom, an aryl group, a monovalent hydrocarbon group, a monovalent heterocyclic group, or an aliphatic carbon- Provided that at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond, at least one of R ²¹ to R ²⁶ is an aryl group, R ²⁷ is a divalent hydrocarbon group, r and s each represent an integer of 1 or more;
Wherein the polyorganosiloxane has a structure represented by the following formula (1). The curable resin composition according to any one of claims 1 to 6, wherein the silsesquioxane (B) is a ladder-type silsesquioxane. 8. The method according to any one of claims 1 to 7, wherein 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]].
Wherein the isocyanurate compound is an isocyanurate compound. The curable resin composition according to claim 8, wherein at least one of R ^x , R ^y and R ^z in the formula (1) is a group represented by formula (3). The positive resist composition according to any one of claims 1 to 9, further comprising a silane coupling agent (D), wherein the content of the silane coupling agent (D) 0.01 to less than 1.0 part by weight based on the total amount (100 parts by weight) of the curable resin composition. The curable resin composition according to claim 10, wherein the silane coupling agent (D) contains a partial condensate obtained by hydrolyzing and partially condensing one or more silane coupling agents. The polyimide resin composition according to any one of claims 1 to 11, which further contains a zinc compound (E), and the content of the zinc compound (E) is in a total amount of polyorganosiloxane (A) and silsesquioxane (B) 100 parts by weight) is less than 0.01 parts by weight and less than 1.0 parts by weight. The curable resin composition according to claim 12, wherein the content of the zinc compound (E) is 0.3 parts by weight or more and 0.6 parts by weight or less based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition according to claim 12 or 13, wherein the zinc compound (E) is a carboxylic acid acyclic resin composition. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 14. A sealing material obtained by using the curable resin composition according to any one of claims 1 to 14. A semiconductor device obtained by using the sealing material according to claim 16.

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