WO2015019767A1 - Curing resin composition and semiconductor device employing same - Google Patents

Abstract

　Provided are a curing resin composition which has transparency, heat resistance, and pliability, as well as having thermal shock resistance and reflow resistance, which moreover has barrier properties with respect to hydrogen sulfide (H₂S) gas and sulfur oxide (SO_X) gases, and which is useful in sealing applications for semiconductor elements (especially optical semiconductor elements); and a cured article, sealing material, and semiconductor device employing the same. Provided are a curing resin composition containing (A) a polyorganosiloxane, (B) a silsesquioxane, and (C) an isocyanurate compound, the polyorganosiloxane (A) being a polyorganosiloxane having an aryl group, and the curing resin composition having viscosity of 4,000-8,000 mPa·s; and a cured article, sealing material, and semiconductor device employing the same.

Description

Curable resin composition and semiconductor device using the same

The present invention relates to a curable resin composition, a cured product obtained using the curable resin composition, a sealing material, and a semiconductor device obtained using the sealing material. This application claims the priority of Japanese Patent Application No. 2013-163577 for which it applied to Japan on August 6, 2013, and uses the content here.

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

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

Patent Document 2 discloses a resin composition for sealing an optical element having excellent transparency, UV resistance, and heat resistance coloring property, which contains an aliphatic carbon-carbon unsaturated bond and does not contain an H—Si bond. At least selected from the group consisting of a liquid silsesquioxane of a type structure and a liquid silsesquioxane of a saddle type structure containing an H—Si bond and no aliphatic carbon-carbon unsaturated bond A resin composition for sealing an optical element containing one kind of silsesquioxane as a resin component is disclosed. However, since the cured product of the resin composition containing cage silsesquioxane is relatively hard and lacks flexibility, 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 having reactivity with SiH groups in one molecule, and at least two SiH groups in one molecule. A curable composition containing a chain-containing and / or cyclic polyorganosiloxane-containing compound and a hydrosilylation catalyst as an essential component is disclosed. However, the physical properties such as crack resistance of these materials are still not satisfactory.

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

Patent Document 4 discloses (A) a polysiloxane having at least two alkenyl groups bonded to silicon atoms, (B) a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms, and (C) hydrosilyl. And (D) a zinc compound, the component (D) is contained in an amount of 0.1 to 5 parts by mass relative to a total of 100 parts by mass of the component (A) and the component (B), A silicone resin composition having excellent sulfidation properties is disclosed. However, although corrosion resistance against hydrogen sulfide (H ₂ S) is disclosed, there is no description about corrosion resistance against other corrosive gases.

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

There are multiple types of corrosive gases that corrode semiconductor devices, and there are several types of corrosive gases such as hydrogen sulfide (H ₂ S) gas and sulfur oxide (SO _x ) gas, which are typical corrosive gases. A sealing material having a sufficient barrier property for any of them has not yet been disclosed.

Furthermore, 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 to improve the light extraction efficiency. Further, in the process of manufacturing an optical semiconductor device used as a white LED, a phosphor may be mixed and used as a sealing material for an optical semiconductor element, and the phosphor settles in the sealing material and is unevenly distributed. In order to prevent this, a sealing material having a high viscosity is required.

Accordingly, an object of the present invention, transparency, provided with a heat resistance, comprising a thermal shock resistance, and further, the barrier property to corrosive gases (in particular, barrier properties against hydrogen sulfide (H ₂ S) gas (resistant H ₂ S High refractive index and high viscosity useful for sealing of semiconductor devices (especially optical semiconductor devices), which have both corrosive properties and barrier properties against sulfur oxide (SO _X ) gas (SO _X corrosion resistance)) It is providing the curable resin composition which is. Another object of the present invention is to provide transparency, heat resistance, flexibility, thermal shock resistance and reflow resistance (crack resistance in the reflow process, adhesion to the package, etc.), and further corrosiveness. An object of the present invention is to provide a curable resin composition having a high refractive index and a high viscosity, which is useful for sealing a semiconductor element having a gas barrier property. Another object of the present invention is to provide a cured product and encapsulant having a high refractive index having excellent transparency, heat resistance, flexibility, thermal shock resistance, reflow resistance, and barrier properties against corrosive gases. There is to do. Still another object of the present invention is to provide a semiconductor device having such a cured product and / or a sealing material.

The present inventors added a silsesquioxane and an isocyanurate compound to a polyorganosiloxane having an aryl group, and a curable resin composition having a viscosity of 4000 to 8000 mPa · s has excellent transparency, The inventors have found that a cured product having heat resistance, in particular, a barrier property against corrosive gas and excellent thermal shock resistance can be formed, and the present invention has been completed.

That is, this invention is curable resin composition containing polyorganosiloxane (A), silsesquioxane (B), and isocyanurate compound (C), Comprising: Polyorganosiloxane (A) has an aryl group. Provided is a curable resin composition which is a polyorganosiloxane and has a viscosity of 4000 to 8000 mPa · s.

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

Further, in the present invention, the molecular weight dispersity (Mw / Mn) is 0.95 when the weight average molecular weight in terms of standard polystyrene according to gel permeation chromatography of the polyorganosiloxane (A) is Mw and the number average molecular weight is Mn. The curable resin composition described above, which is ˜4.00.

The present invention also provides the curable resin composition as described above, which contains a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond as the polyorganosiloxane (A).

The present invention also provides the above curable resin composition containing, as the polyorganosiloxane (A), a polyorganosiloxane (A2) having a Si—H bond.

Further, the present invention provides a polyorganosiloxane (A) as a formula (6)

[In Formula (6), R ²¹ to R ²⁶ are the same or different and each represents a hydrogen atom, an aryl group, a monovalent hydrocarbon group, a monovalent heterocyclic group, or an aliphatic carbon-carbon unsaturated bond. Including monovalent group. However, at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond. One or more of R ²¹ to R ²⁶ are an aryl group. R ²⁷ represents a divalent hydrocarbon group. r and s each represent an integer of 1 or more. ]
The curable resin composition comprising the polyorganosiloxane having the structure represented by:

Moreover, this invention provides said curable resin composition whose silsesquioxane (B) is ladder type silsesquioxane.

In the present invention, the isocyanurate compound (C) is 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).

[In Formula (2) and Formula (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
The curable resin composition is an isocyanurate compound represented by:

Moreover, this invention provides said curable resin composition in which any one or more among ^Rx , ^Ry , ^Rz in Formula (1) is group represented by Formula (3).

The present invention further includes a silane coupling agent (D), and the content of the silane coupling agent (D) is the total amount of polyorganosiloxane (A) and silsesquioxane (B) (100 parts by weight). The curable resin composition is 0.01 parts by weight or more and less than 1.0 part by weight.

In addition, the present invention provides the above curable resin composition, wherein the silane coupling agent (D) includes a partial condensate obtained by hydrolysis and partial condensation of one or more silane coupling agents. provide.

The present invention further includes a zinc compound (E), and the content of the zinc compound (E) is based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition is provided in an amount of 0.01 part by weight or more and less than 1.0 part by weight.

In the present invention, the content of the zinc compound (E) is 0.3 parts by weight or more and 0.000 parts by weight with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition is provided in an amount of less than 6 parts by weight.

The present invention also provides the curable resin composition as described above, wherein the zinc compound (E) is zinc carboxylate.

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

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

The present invention also provides a semiconductor device obtained using the above-described sealing material.

Moreover, the curable resin composition of this invention is related with the following.
[1] A curable resin composition containing a polyorganosiloxane (A), a silsesquioxane (B), and an isocyanurate compound (C), wherein the polyorganosiloxane (A) has an aryl group A curable resin composition having 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] A structure in which the polyorganosiloxane (A) is represented by the formula (6) (in particular, R ²⁷ is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, more preferably an ethylene group. The curable resin composition according to [1] or [2], comprising a polyorganosiloxane containing).
[4] The content (blending amount) of the polyorganosiloxane (A) is 60 to 99.7% by weight with respect to the total amount (100% by weight) of the curable resin composition [1] to [3] The curable resin composition as described in any one of these.
[5] The structure represented by the formula (6) with respect to the total amount (total content, 100% by weight) of the polyorganosiloxane (A) (particularly, R ²⁷ is a linear or branched chain having 1 to 5 carbon atoms) The curable resin composition according to [3] or [4], wherein the proportion of the polyorganosiloxane containing an alkylene group (preferably an ethylene group) is 60 to 100% by weight.
[6] The polyorganosiloxane (A) has an aliphatic carbon-carbon double bond, an aryl group-containing polyorganosiloxysilalkylene, an aliphatic carbon-carbon double bond, and a Si—H bond. The curable resin composition according to any one of [3] to [5], wherein two types of polyorganosiloxysilalkylene having an aryl group are used.
[7] The curable resin composition according to any one of [1] to [6], comprising 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] Any of [1] to [8], wherein the content of silsesquioxane (B) is 0.01 to 30% by weight relative to the total amount (100% by weight) of the curable resin composition The curable resin composition according to one.
[10] The content of silsesquioxane (B) is 0.01 to 30 parts by weight with respect to the total amount (100 parts by weight) of polyorganosiloxane (A) and silserkioxane (B). [1] The curable resin composition according to any one of [9].
[11] As the isocyanurate compound (C), the formula (1)
[In the formula (1), R ^x , R ^y and R ^z are the same or different and represent a group represented by the formula (2) or a group represented by the formula (3). [In Formula (2) and Formula (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
The curable resin composition according to any one of [1] to [10], comprising an isocyanurate compound represented by:
[12] The curable resin composition according to any one of [1] to [11], wherein the isocyanurate compound (C) is monoallyl diglycidyl isocyanurate.
[13] Any one of [1] to [12], wherein the content of the isocyanurate compound (C) is 0.01 to 10% by weight relative to the total amount (100% by weight) of the curable resin composition. The curable resin composition described in 1.
[14] The proportion of the isocyanurate compound (C) is 0.01 to 0.5 parts by weight with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). [1] The curable resin composition according to any one of [13].
[15] The curable resin composition according to any one of [1] to [14], further comprising a silane coupling agent (D).
[16] The curable resin composition according to [15], wherein the silane coupling (D) is 3-glycidoxypropyltrimethoxysilane.
[17] The content of the silane coupling (D) is 0.01 part by weight or more and 1.0 part by weight with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition according to [15] or [16], which is less than part.
[18] Any one of [15] to [17], wherein the content of the silane coupling (D) is 0.01 to 5 parts by weight with respect to the total amount of the curable resin composition (100 parts by weight). The curable resin composition described in 1.
[19] The silane coupling agent (D) includes any one of [15] to [18] including a partial condensate obtained by hydrolysis and partial condensation of one or more silane coupling agents. The curable resin composition described in 1.
[20] The proportion of the partial condensate obtained by hydrolysis and partial condensation of one or more silane coupling agents in the silane coupling agent (D) is the total amount of the silane coupling agent (D). [19] The curable resin composition according to [19], which is 50 to 100% by weight relative to (100% by weight).
[21] The proportion of the partial condensate obtained by hydrolysis and partial condensation of one or more silane coupling agents in the silane coupling agent (D) is the total amount of the curable resin composition (100 The curable resin composition according to [19] or [20], which is 0.01 to 5 parts by weight relative to (parts by weight).
[22] The ratio of the partial condensate obtained by hydrolyzing and partially condensing one or more silane coupling agents in the silane coupling agent (D) is such that the polyorganosiloxane (A) and the silyl The curing according to any one of [19] to [21], which is 0.01 part by weight or more and less than 1.0 part by weight relative to the total amount (100 parts by weight) of sesquioxane (B). Resin composition.
[23] The curable resin composition according to any one of [1] to [22], further comprising a zinc compound (E).
[24] The curable resin composition according to [23], wherein the zinc compound (E) is zinc carboxylate.
[25] The curable resin composition according to [23], wherein the zinc compound (E) is zinc octylate.
[26] The content of the zinc compound (E) is 0.01 parts by weight or more and 1.0 part by weight with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition according to any one of [23] to [25], which is less than
[27] The curable resin composition according to any one of [23] to [26], wherein the zinc content (100% by weight) in the compound of zinc compound (E) is 2 to 30% by weight.

Since the curable resin composition of the present invention has the above-described configuration, a cured product having excellent transparency and heat resistance can be formed. In particular, the cured product has excellent thermal shock resistance, more specifically, excellent peel resistance (adhesiveness to the LED package) and crack resistance under conditions where the temperature changes severely, and further, H ₂ S gas, SO _X gas, etc. Excellent barrier properties against multiple corrosive gases. Moreover, the cured | curing material obtained may be excellent also in a softness | flexibility and reflow resistance. For this reason, the curable resin composition of the present invention can be preferably used as a sealing material for an optical semiconductor element (for example, an LED element, a semiconductor laser element, a solar power generation element, a CCD element, etc.). An optical semiconductor device obtained by sealing an optical semiconductor element with a cured product of the curable resin composition has excellent 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 an unprecedented high temperature (for example, 180 ° C. or higher).

It is the schematic which shows one Embodiment of the optical semiconductor device which sealed the optical semiconductor element using the curable resin composition of this invention. The left figure (a) is a perspective view, and the right figure (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) is It is a polyorganosiloxane having an aryl group and a curable resin composition having 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 siloxane bonds (Si—O—Si), and an aryl group as a substituent in the main chain. It is a polyorganosiloxane having The polyorganosiloxane (A) may be a linear or branched polyorganosiloxane having a hydrosilyl group or a group having an aliphatic carbon-carbon unsaturated bond. Examples of the polyorganosiloxane (A) include well-known and commonly used silicone skeletons such as a phenyl silicone skeleton (polydiphenylsiloxane) and a phenylmethylsilicone skeleton (polymethylphenylsiloxane). The polyorganosiloxane (A) does not include silsesquioxane (B).

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

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

The aryl group in the polyorganosiloxane (A) may have one or more substituents. Examples of the substituent include halogen atoms, substituted or unsubstituted hydrocarbon groups, hydroxyl groups, alkoxy groups, alkenyloxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, mercapto groups (thiol groups), alkylthio groups, and alkenyls. Thio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group or substituted amino group (mono or dialkylamino group, acylamino group, etc.), epoxy group, cyano group An isocyanate group, a carbamoyl group, an isothiocyanate group, and the like.

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

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

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

As said aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned, for example.

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, examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded include, for example, C _7-18 aralkyl groups (particularly, C _7-10 aralkyl groups) such as benzyl group and phenethyl group, cinnamyl and the like. A C _6-10 aryl-C _2-6 alkenyl group such as a group, a C _1-4 alkyl-substituted aryl group such as a tolyl group, a C _2-4 alkenyl-substituted aryl group such as a styryl group, and the like.
As a substituent which the said substituted or unsubstituted hydrocarbon group (substituted hydrocarbon group) has, the thing similar to the substituent which the aryl group may have is mentioned, for example.

Moreover, as one or more substituents which the aryl group in polyorganosiloxane (A) has, group represented by Formula (4) is mentioned as another example.

A plurality of R ′ in the formula (4) may be the same or different. R ′ in formula (4) is 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, an acyloxy group, a mercapto group (thiol Group), alkylthio group, alkenylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group or substituted amino group (mono or dialkylamino group, acylamino group, etc.) ), Epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group and the like.

In the group represented by the formula (4), each R ′ is a hydrogen atom, a C _1-10 alkyl group (particularly a C _1-4 alkyl group), a C _2-10 alkenyl group (particularly a C ₂ group). _-4 alkyl group), C _3-12 cycloalkyl group, C _3-12 cycloalkenyl group, aromatic ring with C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. which may have a substituent C _6-14 aryl group, C _7-18 aralkyl groups, C _6-10 aryl -C _2-6 alkenyl group, a hydroxyl group, C _1-6 alkoxy group, a halogen atom .

The content of aryl group (converted to phenyl group) with respect to the total amount (100% by weight) of polyorganosiloxane (A) is not particularly limited, but is preferably 35% by weight or more (for example, 35 to 70% by weight), preferably 40% by weight. The above is more preferable, and 45% by weight or more is still more preferable. When content of the said aryl group is less than 35 weight%, the barrier property with respect to the corrosive gas of the hardened | cured material obtained may become low. Further, all of the substituents in the main chain composed of the siloxane bond (Si—O—Si) of the polyorganosiloxane (A) may be aryl groups, or some of the substituents are aryl groups. May be. The content of the aryl group can be measured, for example, by ¹ H-NMR.

Examples of the polyorganosiloxane (A) include polyorganosiloxane having a structure represented by the formula (6). In the present specification, a polyorganosiloxane having a structure represented by the formula (6) is referred to as “polyorganosiloxysilalkylene”.
The curable resin composition of the present invention preferably contains polyorganosiloxysilalkylene as the polyorganosiloxane (A), and more preferably the polyorganosiloxane (A) is only polyorganosiloxysilalkylene. Polyorganosiloxysilalkylene is less prone to form low-molecular-weight rings in the production process than polyorganosiloxanes whose main chain consists solely of siloxane bonds (Si—O—Si), and decomposes by heating to produce silanol groups. It is difficult to produce (-SiOH). Therefore, it becomes easy to obtain a cured product with low surface tackiness and little yellowing.

In formula (6), R ²¹ to R ²⁶ are the same or different and each represents a hydrogen atom, the above-described aryl group, a substituent of the above-described aryl group, a heterocyclic group, or an aliphatic carbon-carbon unsaturated bond described later. (Preferably the same or different, 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) Including monovalent groups). However, at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond.
It is preferable that all of R ²¹ to R ²⁶ are not monovalent groups containing an aliphatic carbon-carbon unsaturated bond. Further, at least one of R ²¹ to R ²⁶ is preferably an aryl group (C _6-14 aryl group such as a phenyl group or a naphthyl group (particularly a C _6-10 aryl group), particularly a phenyl group). . 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 aryl group in the polyorganosiloxane (A) described above.

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 and an alicyclic carbon group. And a monovalent group in which two or more of a hydrogen group and an aromatic hydrocarbon group are bonded. Examples of the monovalent heterocyclic group include a pyridyl group, a furyl group, a thienyl group, and the like.

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

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

As said monovalent | monohydric aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group, a naphthyl group, an anthryl group, etc. are mentioned, for example.

Examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include a C _7-18 aralkyl group (particularly a C _7-10 aralkyl group) such as a benzyl group and a phenethyl group, and a C _6-10 such as a cinnamyl group. Examples thereof include C _1-4 alkyl-substituted aryl groups such as aryl-C _2-6 alkenyl group and tolyl group, C _2-4 alkenyl-substituted aryl groups such as styryl group, and the like.

The monovalent hydrocarbon group may have a substituent. That is, the monovalent hydrocarbon group may be a monovalent hydrocarbon group in which at least one hydrogen atom of the monovalent hydrocarbon group exemplified above is replaced with a substituent. The substituent preferably has 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms. Specific examples of the substituent include, for example, a halogen atom; a hydroxyl group; an alkoxy group; an alkenyloxy group; an aryloxy group; an aralkyloxy group; an acyloxy group; a mercapto group; an alkylthio group; Aroxy group; carboxyl group; alkoxycarbonyl group; aryloxycarbonyl group; aralkyloxycarbonyl group; amino group; mono- or dialkylamino group; mono- or diphenylamino group; acylamino group; epoxy group-containing group; Group; oxo group; isocyanate group; a group in which two or more of these are bonded via a C _1-6 alkylene group, if necessary.

Examples of the alkoxy group include C _1-6 alkoxy groups (preferably C _1-4 alkoxy groups) such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group. Examples of the alkenyloxy group include a C _2-6 alkenyloxy group (preferably a C _2-4 alkenyloxy group) such as an allyloxy group. Examples of the aryloxy group include, for example, substitution of a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group, etc. on the aromatic ring, such as a phenoxy group, a tolyloxy group, and a naphthyloxy group. And a C _6-14 aryloxy group which may have a group. Examples of the aralkyloxy group include C _7-18 aralkyloxy groups such as benzyloxy group and phenethyloxy group. Examples of the acyloxy group include C _1-12 acyloxy groups such as an acetyloxy group, a propionyloxy group, a (meth) acryloyloxy group, and a benzoyloxy group.

Examples of the alkylthio group include C _1-6 alkylthio groups (preferably C _1-4 alkylthio groups) such as a methylthio group and an ethylthio group. Examples of the alkenylthio group include C _2-6 alkenylthio groups (preferably C _2-4 alkenylthio groups) such as an allylthio group. Examples of the arylthio group include a phenylthio group, a tolylthio group, a naphthylthio group, and the like, and a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, and a C _1-4 alkoxy group on the aromatic ring. Examples thereof include a C _6-14 arylthio group which may be present. Examples of the aralkylthio group include C _7-18 aralkylthio groups such as benzylthio group and phenethylthio group. Examples of the alkoxycarbonyl group include C _1-6 alkoxy-carbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Examples of the aryloxycarbonyl group include C _6-14 aryloxy-carbonyl groups such as a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group. Examples of the aralkyloxycarbonyl group include C _7-18 aralkyloxy-carbonyl groups such as benzyloxycarbonyl group. Examples of the mono- or dialkylamino group include mono- or di-C _1-6 alkylamino groups such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group. Examples of the acylamino group include C _1-11 acylamino groups such as an acetylamino group, a propionylamino group, and a benzoylamino group. Examples of the epoxy group-containing group include a glycidyl group, a glycidyloxy group, and a 3,4-epoxycyclohexyl group. As said oxetanyl group containing group, an ethyl oxetanyloxy group etc. are mentioned, for example. As said acyl group, an acetyl group, a propionyl group, a benzoyl group etc. are mentioned, for example. Examples of the 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 those in the monovalent hydrocarbon group.

As the monovalent hydrocarbon group and monovalent heterocyclic group, more specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, decyl group, Phenyl group, naphthyl group, anthryl group, benzyl group, phenethyl group, pyridyl group, furyl group, thienyl group, vinyl group, allyl group, styryl group (for example, p-styryl group), substituted hydrocarbon group (for example, 2- (3,4-epoxycyclohexyl) ethyl group, 3-glycidylpropyl group, 3-methacryloxypropyl group, 3-acryloxypropyl group, N-2- (aminoethyl) -3-aminopropyl group, 3 -Aminopropyl group, N-phenyl-3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, etc.)

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

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

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

The terminal structure of the polyorganosiloxysilalkylene is not particularly limited, and examples thereof include a silanol group, an alkoxysilyl group, and a trialkylsilyl group (for example, a trimethylsilyl group). Various groups such as a group containing an aliphatic carbon-carbon double bond and a hydrosilyl group may be introduced at the terminal of the polyorganosiloxysilalkylene.

As described above, the polyorganosiloxysilalkylene may have a linear or branched chain structure. As the polyorganosiloxysilalkylene, for example, polyorganosiloxysilalkylene having a branched chain and an aryl group is preferable.

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

As the polyorganosiloxane (A), it is preferable to use two or more (particularly two) polyorganosiloxysilalkylene. Among these, from the viewpoint of barrier properties against corrosive gas, a group having an aliphatic carbon-carbon double bond, a polyorganosiloxysilalkylene having an aryl group, a group having an aliphatic carbon-carbon double bond, Si— It is preferable to use two types, a group having an H bond and a polyorganosiloxysilalkylene having an aryl group.

When two or more types of polyorganosiloxane (A) are used, the ratio of polyorganosiloxysil alkylene to the total amount (total content, 100% by weight) of polyorganosiloxane (A) in the curable resin composition of the present invention is particularly Although not limited, it is preferably 60% by weight or more (for example, 60 to 100% by weight), more preferably 80% by weight or more (for example, 80 to 99.5% by weight), and still more preferably 88% by weight or more. If the ratio of polyorganosiloxysilalkylene is less than 60% by weight, the cured product tends to yellow, or the surface tends to have tackiness and the handleability tends to decrease.

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. Further, the weight average molecular weight (Mw) is preferably from 500 to 20,000, more preferably from 600 to 10,000, and still more preferably from 700 to 6,500. 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 4000 and / or the weight average molecular weight (Mw) exceeds 20000, the compatibility between the polyorganosiloxane (A) and other components may be reduced. When two or more organosiloxanes (A) are used in combination, the compatibility between the polyorganosiloxanes may be reduced. The polyorganosiloxane (A) may be a mixture of those having various number average molecular weights (Mn) and / or weight average molecular weights (Mw) within the above range. The number average molecular weight (Mn) and / or the weight average molecular weight (Mw) can be calculated, for example, as a molecular weight in terms of polystyrene by gel permeation chromatography.

The molecular weight dispersity (Mw / Mn) calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyorganosiloxane (A) is preferably 0.95 to 4.00, and preferably 1.00 to 3. 80 is more preferable, and 1.20 to 3.50 is still more preferable. When the molecular weight dispersity (Mw / Mn) exceeds 3.50, the resulting cured product may have low heat resistance and barrier properties against corrosive gas.

The content of the polyorganosiloxane (A) in the curable resin composition of the present invention is not particularly limited, but the total amount (100% by weight) of the curable resin composition is not particularly limited. ) Is preferably 60 to 99.7% by weight, more preferably 75 to 99.0% by weight, still more preferably 90 to 98.5% by weight. If the content is less than 60% by weight, the thermal shock resistance of the resulting cured product may be reduced. On the other hand, when 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 an aryl group, and the substituent other than the aryl group may be a substituent of a 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). , Hydroxyl group, alkoxy group, alkenyloxy group, acyloxy group, mercapto group (thiol group), alkylthio group, alkenylthio group, carboxyl group, alkoxycarbonyl group, amino group or substituted amino group (mono or dialkylamino group, acylamino group) Etc.), an epoxy group, a cyano group, an isocyanate group, a carbamoyl group, an isothiocyanate group, and the like.

Examples of the substituent other than the aryl group in the polyorganosiloxane (A) include a hydrogen atom, a group having a Si—H bond (hydrosilyl group, etc.), a substituted or unsubstituted hydrocarbon group (preferably an alkyl group or aliphatic carbon). —At least one substituent selected from a group having a carbon double bond (such as an alkenyl group) is particularly preferable. The polyorganosiloxane (A) includes, 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 a Si—H bond, an aryl group, an aliphatic group It may be a polyorganosiloxane having a group having a group carbon-carbon double bond and a group having a Si—H bond.

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

[Polyorganosiloxane having an aliphatic carbon-carbon double bond (A1)]
The curable resin composition of the present invention includes a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond as the polyorganosiloxane (A) (in this specification, simply “polyorganosiloxane (A1)”). May be included). Among these, the polyorganosiloxane (A) is preferably a polyorganosiloxane (A1) (only the polyorganosiloxane (A1)). The aliphatic carbon-carbon double bond may have any partial structure and / or component constituting the polyorganosiloxane (A1). The aliphatic carbon-carbon double bond may have a substituent (for example, a substituent that a silicon atom has) in the polyorganosiloxane (A1). The aliphatic carbon-carbon double bond is 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). May be.

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

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

[Polyorganosiloxane having Si—H bond (A2)]
The curable resin composition of the present invention may be referred to as a polyorganosiloxane (A2) having a Si—H bond as the polyorganosiloxane (A) (in this specification, simply referred to as “polyorganosiloxane (A2)”). ) May be included. The Si—H bond may have any partial structure and / or component constituting the polyorganosiloxane (A2). Note that the Si—H bond may have a substituent in the polyorganosiloxane (A2) (for example, a substituent that a silicon atom has). Further, 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 an Si—H bond is not particularly limited, and examples thereof include a group represented by formula (4), in which at least one of three R ′ is a hydrogen atom.

The content of the Si—H bond relative to the total amount of the polyorganosiloxane (A) (total content, 100% by weight) is not particularly limited, but is equivalent to a hydrogen atom or H (hydride) in the Si—H bond (H (Converted) is preferably 0.01 to 0.50% by weight, more preferably 0.05 to 0.30% by weight, still more preferably 0.08 to 0.20% by weight. By having the Si—H bond within the above range, there is a tendency that a cured product excellent in various physical properties such as heat resistance, crack resistance, and barrier property against corrosive gas is easily obtained. The content of the Si—H bond can be measured by, for example, ¹ H-NMR.

The content of the polyorganosiloxane (A2) with respect to the total amount (100% by weight) of the polyorganosiloxane (A) 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) within the above range, there is a tendency that a cured product excellent in various physical properties such as heat resistance of the obtained cured product, crack resistance, and barrier property against corrosive gas is easily obtained. .

Ratio of aliphatic carbon-carbon double bond content (in terms of vinyl group) a1 (mol / g) to Si—H bond content (in terms of H) a2 (mol / g) in polyorganosiloxane (A) a1 / A2 is preferably 0.80 to 1.10, more preferably 0.90 to 1.05, and still more preferably 0.95 to 1.00. By setting a1 / a2 to 1.10 or less, it is possible to improve the barrier property against corrosive gas. In addition, by setting a1 / a2 to 0.80 or more, strength such as crack resistance can be particularly enhanced.

The polyorganosiloxane (A1) may be a polyorganosiloxane (A2) having a Si—H bond at the same time, and the polyorganosiloxane (A2) may be a polyorganosiloxane having an aliphatic carbon-carbon double bond at the same time. Siloxane (A1) may be used.

Further, the polyorganosiloxane (A) may be composed of only one of the polyorganosiloxane (A1) and the polyorganosiloxane (A2), and the polyorganosiloxane (A) is two or more different from each other. The polyorganosiloxane (A1) and / or the polyorganosiloxane (A2) may be used.

The polyorganosiloxane (A) is composed of two or more different types of polyorganosiloxane, and at least one of the two or more types of polyorganosiloxane is polyorganosiloxane (A2). In this case, the two or more kinds of polyorganosiloxanes excluding the polyorganosiloxane (A2) are preferably polyorganosiloxanes (A1) having no Si—H bond.

The polyorganosiloxane (A) is a silsesquioxane (B), an isocyanurate compound (C), a silane coupling agent (D), a zinc compound (E), a hydrosilation catalyst, a hydrosilylation reaction inhibitor, which will be described later. In addition, some or all of other components such as other siloxane compounds, other silane compounds, solvents, additives, and the like may be included in advance. In that case, the polyorganosiloxane (A1) may include a part of the other component, and the polyorganosiloxane (A2) may include a remaining part of the other component. Further, only one of the polyorganosiloxane (A1) and the polyorganosiloxane (A2) may contain a part 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, and examples thereof include a silsesquioxane having a random structure, a cage structure, and a ladder structure (ladder-type silsesquioxane). The silsesquioxane having a ladder structure is a main component. Silsesquioxane is preferred. The silsesquioxane (B) preferably contains a ladder-type silsesquioxane as a main component. Especially, it is more preferable that silsesquioxane (B) is only ladder type silsesquioxane.

Silsesquioxane is a kind of polysiloxane. Polysiloxane is generally a compound having a main chain composed of siloxane bonds (Si—O—Si), and the basic structural unit thereof is a monovalent unit in which an M unit (a silicon atom is bonded to one oxygen atom). Units), D units (units composed of divalent groups in which silicon atoms are bonded to two oxygen atoms), T units (units composed of trivalent groups in which silicon atoms are bonded to three oxygen atoms) Unit) and Q unit (unit consisting of a tetravalent group in which a silicon atom is bonded to four oxygen atoms).
Silsesquioxane (B) is a polysiloxane of the T units and basic units, the 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 cage structure, and a ladder structure. The ladder-type silsesquioxane is a structure of the Si—O—Si skeleton having a ladder structure. Silsesquioxane having

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). Furthermore, the silsesquioxane (B) is not particularly limited, but is preferably liquid at room temperature. The said silsesquioxane (B) can be used individually by 1 type or in combination of 2 or more types.

By including silsesquioxane (B), the barrier property against a corrosive gas of a cured product formed by curing is improved, and further, toughness (particularly, crack resistance) tends to be improved. The content (blending amount) of silsesquioxane (B) in the curable resin composition of the present invention is not particularly limited, but is 0.01 to 0.1% with respect to the total amount (100 wt%) of the curable resin composition. 30 wt% is preferable, 0.1 to 20 wt% is more preferable, 0.5 to 15 wt% is further preferable, and 7 to 13 wt% is particularly preferable.

The content of silsesquioxane (B) is not particularly limited, but from the viewpoint of barrier properties against corrosive gases (particularly, corrosion resistance against H ₂ S gas), for example, polyorganosiloxane (A) and silsesquioxane. The amount is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, still more preferably 1 to 15 parts by weight, particularly preferably relative to the total amount (100 parts by weight) of oxan (B). 7 to 13 parts by weight.

[Isocyanurate Compound (C)]
The curable resin composition of the present invention contains an isocyanurate compound (C). By including the isocyanurate compound (C), the curable resin composition of the present invention particularly improves the barrier property against the corrosive gas of the cured product formed by curing, and further improves the adhesion to the adherend. To do. Especially, it is preferable that an isocyanurate compound (C) contains the isocyanurate compound represented by Formula (1). In particular, the isocyanurate compound (C) is preferably only the isocyanurate compound represented by the formula (1).

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

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

The isocyanurate compound (C) is not particularly limited. For example, monoallyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, triallyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, triglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methylpropenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5- Bis (2-methylepoxypropyl) isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3-bis (2-methylpropenyl) -5-glycidyl isocyanurate, 1,3 -Screw (2 Methyl propenyl) -5- (2-methyl-epoxypropyl) isocyanurate, tris (2-methyl-propenyl) isocyanurate. Of these, monoallyl diglycidyl isocyanurate is preferable. In addition, an isocyanurate compound (C) can be used individually by 1 type or in combination of 2 or more types.

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

The content of the isocyanurate compound (C) is not particularly limited, but is preferably 0.01 to 10% by weight, and 0.05 to 5% by weight with respect to the total amount (100% by weight) of the curable resin composition. More preferred is 0.1 to 3% by weight. When the content of the isocyanurate compound (C) is less than 0.01% by weight, the barrier property against the corrosive gas and the adhesion to the adherend may be deteriorated. On the other hand, when the content of the isocyanurate compound (C) exceeds 10% by weight, a solid may precipitate in the curable resin composition or the cured product may become cloudy. The ratio of the isocyanurate compound (C) is not particularly limited. From the viewpoint of the barrier property against the corrosive gas of the cured product, for example, the total amount of polyorganosiloxane (A) and silsesquioxane (B) (100 0.01 to 0.5 parts by weight is preferable with respect to parts by weight).

[Silane coupling agent (D)]
The curable resin composition of the present invention may contain a silane coupling agent (D). When the curable resin composition of the present invention contains the silane coupling agent (D), in particular, the adhesion to the adherend is improved 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), for example, the compatibility of the isocyanurate compound (C) with other components is improved. Therefore, when a composition of the isocyanurate compound (C) and the silane coupling agent (D) is formed in advance and then blended with other components, a uniform curable resin composition is easily obtained.

As the silane coupling agent (D), a known or conventional silane coupling agent can be used, and is not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxy group-containing silane coupling agent such as 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N- (1, -Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (β-aminoethyl) ) -Γ-aminopropylmethyldiethoxysilane and other amino group-containing silane coupling agents; tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltri Methoxysilane, vinyltris (methoxyethoxysilane), phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylto Examples include limethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, mercaptopropylenetrimethoxysilane, mercaptopropylenetriethoxysilane, and the like. 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 above 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 the corrosive gas and the thermal shock resistance can be improved.

The partial condensate can be obtained by hydrolyzing and partially condensing one type or two or more types of the silane coupling agents. Well-known or conventional methods can be used for hydrolysis and partial condensation. For example, a method of adding a solvent, water and, if necessary, a catalyst to the mixture of the silane coupling agent and stirring with heating can be mentioned. During the stirring, by-products (such as water and alcohols) may be removed by distillation as necessary.

The partial condensate is not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane oligomer, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane-tetramethoxysilane oligomer, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropyltriet Epoxy group-containing co-oligomer such as silane-tetraethoxysilane oligomer; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane-tetramethoxysilane oligomer, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane-tetraethoxysilane oligomer, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane-tetramethoxysilane oligomer, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane-tetraethoxy Silane oligomer, N-2- (aminoethyl) -3-aminopropyltriethoxysilane-tetramethoxysilane oligomer, N-2- (aminoethyl) -3-aminopropyltriethoxysilane-tetraethoxysilane oligomer, 3-a Nopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-aminopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetramethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetraethoxysilane oligomer, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine-tetramethoxysilane oligomer, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine-tetraethoxysilane oligomer, Amino groups such as N-phenyl-3-aminopropyltrimethoxysilane-tetramethoxysilane oligomer and N-phenyl-3-aminopropyltrimethoxysilane-tetraethoxysilane oligomer Containing oligomers: vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltris (methoxyethoxysilane) ) -Tetramethoxysilane oligomer, vinyltris (methoxyethoxysilane) -tetraethoxysilane oligomer, vinyltriacetoxysilane-tetramethoxysilane oligomer, vinyltriacetoxysilane-tetraethoxysilane oligomer, and other vinyl group-containing co-oligomers; phenyltrimethoxy Silane-tetramethoxysilane oligomer, phenyltrimethoxysilane-tetraethoxysilane oligomer, Phenyl group-containing co-oligomers such as phenyldimethoxysilane-tetramethoxysilane oligomer and diphenyldimethoxysilane-tetraethoxysilane oligomer; γ- (meth) acryloxypropyltriethoxysilane-tetramethoxysilane oligomer, γ- (meth) acryloxy Propyltriethoxysilane-tetraethoxysilane oligomer, γ- (meth) acryloxypropyltrimethoxysilane-tetramethoxysilane oligomer, γ- (meth) acryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, γ- (meth) acryl Roxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, γ- (meth) acryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, γ- (me (T) Acryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, γ- (meth) acryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer and other (meth) acryl group-containing co-oligomers; mercaptopropylenetrimethoxysilane- Examples thereof include mercapto group-containing co-oligomers such as tetramethoxysilane oligomer, mercaptopropylenetrimethoxysilane-tetraethoxysilane oligomer, mercaptopropylenetriethoxysilane-tetramethoxysilane oligomer, mercaptopropylenetriethoxysilane-tetraethoxysilane oligomer.

The silane coupling agent (D) may be synthesized or a commercially available product may be used. Commercially available silane coupling agents include, for example, Z-6610, Z-6011, Z-6020, Z-6094, Z-6683, Z-6032, Z-6040, Z-6044, Z-6043, Z- 6075, Z-6300, Z-6519, Z-6825, Z-6030, Z-6033, Z-6062, Z-6862, Z-6911, Z-6026, AZ-720, Z-6050 (all trade names , All manufactured by Toray Dow Corning Co., Ltd.), KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE -503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9 03, KBM-573, KBM-575, KBE-585, KBM-1003, KBE-1003, KBM-802, KBM-803, KBE-846, KBE-9007, X-41-1053, X-41-1056, X-41-1059A, X-41-1805, X-41-1808, X-41-1810, KR-513, X-40-2672B, X-40-9272B, X-40-2651, etc. Name, both of which are manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, the said silane coupling agent may be used independently and may be used in combination of 2 or more type.

The content of the silane coupling agent (D) is not particularly limited, but is preferably 0.01 to 5 parts by weight, preferably 0.03 to 1 part by weight with respect to the total amount (100 parts by weight) of the curable resin composition. Is more preferable, and 0.05 to 0.8 part by weight is still more preferable. By making content of a silane coupling agent (D) into said range, there exists an effect which improves the barrier property with respect to corrosive gas, and reflow resistance. In particular, when a partial condensate of a silane coupling agent is used, there is an effect of greatly improving the corrosion resistance (particularly H ₂ S corrosion resistance) and the thermal shock resistance. When the content of the silane coupling agent (D) is less than 0.01 parts by weight, the adhesion to the adherend is lowered, and particularly when the isocyanurate compound (C) is used in a compatible state. Curing may not be obtained. 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 a target range.

Although content of a silane coupling agent (D) is not specifically limited, From a viewpoint of the barrier property with respect to corrosive gas, and reflow resistance, for example, the total amount of polyorganosiloxane (A) and silsesquioxane (B) The amount is preferably 0.01 part by weight or more and less than 1.0 part by weight with respect to (100 parts by weight), more preferably 0.08 to 0.9 part by weight.

The ratio of the partial condensate of the silane coupling agent in the silane coupling agent (D) is not particularly limited. For example, it is 50 to 100 with respect to the total amount (100% by weight) of the silane coupling agent (D). % By weight is preferred, more preferably 80 to 100% by weight. Especially, it is preferable that the said silane coupling agent (D) is only the said partial condensate of a silane coupling agent. When the ratio of the partial condensate of the silane coupling agent is within the above range, the corrosion resistance (particularly H ₂ S corrosion resistance) and the thermal shock resistance are further improved.

The proportion of the above-mentioned partial condensate of the silane coupling agent in the curable resin composition is not particularly limited, but from the viewpoint of corrosion resistance (particularly corrosion resistance against H ₂ S gas) and thermal shock resistance, for example, The amount of the curable resin composition is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 1 part by weight, and still more preferably 0.05 to 0.8 parts by weight with respect to the total amount (100 parts by weight). .

Further, the ratio of the partial condensate of the silane coupling agent is not particularly limited, but from the viewpoint of corrosion resistance (particularly corrosion resistance against H ₂ S gas), thermal shock resistance, and reflow resistance, for example, The amount is preferably 0.01 parts by weight or more and less than 1.0 part by weight, and more preferably 0.08 to 0.000 parts by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). 9 parts by weight.

[Zinc compound (E)]
The curable resin composition of the present invention may contain a zinc compound (E). By the curable resin composition of the present invention contains the zinc compound, in particular, tends to barrier property against H ₂ S gas is improved.

Although it does not specifically limit as a zinc compound (E), For example, the complex, metal salt, etc. which contain zinc are mentioned. For example, zinc diketone complexes such as zinc bisacetylacetonate and bis (octane-2,4-dionato) zinc, and zinc carboxylates such as zinc naphthenate, zinc octylate, zinc acetoacetate, zinc (meth) acrylate, and zinc neodecanate And the like, and inorganic zinc compounds typified by zinc oxides such as zinc oxide and zinc stannate, 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 these, the zinc compound (E) is more preferably only zinc carboxylate (particularly zinc octylate).

The zinc compound (E) is not particularly limited, but from the viewpoint of barrier properties against corrosive gas, the zinc content in the compound (100% by weight) is preferably 2 to 30% by weight, for example. The amount is preferably 5 to 20% by weight, particularly preferably 6 to 17% by weight.

Although content of a zinc compound (E) is not specifically limited, 0.01 weight part or more 1 1 with respect to the total amount (100 weight part) of the said polyorganosiloxane (A) and the said silsesquioxane (B). Less than 0.0 part by weight is preferable, 0.1 part by weight or more and less than 0.8 part by weight is more preferable, and 0.3 part by weight or more and less than 0.6 part by weight is still more preferable. By setting the content of the zinc compound (E) within the above range, the thermal shock resistance and the reflow resistance can be maintained at a practically sufficient level. When the content of the zinc compound (E) is less than 0.01 parts by weight, the barrier property against H ₂ S gas may be deteriorated. On the other hand, when the content of the zinc compound (E) is 1.0 part by weight or more, the barrier property against SO _X gas may be lowered.

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

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

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

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

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

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

[Additive]
The curable resin composition of the present invention includes, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, Inorganic fillers such as carbon black, silicon carbide, silicon nitride, boron nitride, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; silicone resins, epoxy resins, Organic resin fine powders such as fluororesins; fillers such as conductive metal powders such as silver and copper, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorus) Flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents, lubricants Wax, plasticizer, mold release agent, impact resistance improver, hue improver, fluidity improver, colorant (dye, pigment, etc.), dispersant, defoamer, defoamer, antibacterial agent, preservative, viscosity Conventional additives such as regulators and thickeners may be included. These additives can 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 the aliphatic carbon-carbon double bond is 0.2 to 4 mol per 1 mol of hydrosilyl group present in the curable resin composition. It is preferable that the composition (formulation composition) be 0.5, more preferably 0.5 to 1.5 mol, still more preferably 0.8 to 1.2 mol. By controlling the ratio of hydrosilyl group and aliphatic carbon-carbon double bond within the above range, the heat resistance, transparency, flexibility, reflow resistance and barrier property against corrosive gas of the cured product are further improved. Tend.

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

The viscosity of the curable resin composition of the present invention at 25 ° C. is 4000 to 8000 mPa · s. 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 be difficult to disperse uniformly. 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 stable.

The viscosity of the curable resin composition of the present invention can be appropriately adjusted by a known or common method. For example, silsesquioxane (B), silane coupling agent (D), other siloxane compounds, other silane compounds, solvents, additives, and the like may be appropriately selected to adjust the desired viscosity. Alternatively, a commercially available polyorganosiloxane (A) may be appropriately selected and adjusted to a desired viscosity.
In this specification, the viscosity at 25 ° C. refers to a cone-plate rotational viscometer (cone plate viscometer) (for example, a rheometer (trade name “PhysicaUDS-200”, manufactured by Anton Paar)) and a cone plate (cone diameter). : 16 mm, taper angle = 0 °)), and the viscosity measured under the conditions of temperature: 25 ° C. and rotation speed: 5 rpm.

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

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

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

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

GD-1125A: manufactured by Changxing Chemical Industry Co., Ltd., vinyl group content 1.13 wt%, phenyl group content 42.79 wt%, SiH group content (hydride conversion) 0 wt%, number average molecular weight 2858, weight Average molecular weight 9598, viscosity 6300 mPa · s
GD-1125B: manufactured by Changxing Chemical Industry Co., Ltd., vinyl group content 3.71% by weight, phenyl group content 51.75% by weight, SiH group content (hydride conversion) 0.16% by weight, number average molecular weight 671 , Weight average molecular weight 1354, viscosity 5900 mPa · s
OE-6663A: manufactured by Toray Dow Corning Co., Ltd., vinyl group content 1.72% by weight, phenyl group content 54.20% by weight, SiH group content (hydride conversion) 0% by weight, number average molecular weight 3600, Weight average molecular weight 11000, viscosity 5100 mPa · s
OE-6631B: manufactured by Toray Dow Corning Co., Ltd., vinyl group content 3.81% by weight, phenyl group content 57.49% by weight, SiH group content (hydride conversion) 0.34% by weight, number average molecular weight 830, weight average molecular weight 2200, viscosity 13500 mPa · s

[Synthesis of Silsesquioxane (B)]
<Synthesis Example 1>
A reaction vessel was charged with 15.86 g of phenyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 6.16 g of methyl isobutyl ketone (MIBK), and the mixture was cooled to 10 ° C. To the above mixture, 4.32 g of water and 0.16 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) were added dropwise over 1 hour. After the addition, these mixtures were kept at 10 ° C. for 1 hour. Thereafter, 26.67 g of MIBK was added to dilute the reaction solvent.
Next, the temperature of the reaction vessel was raised to 70 ° C., and when the temperature reached 70 ° C., 0.16 g of 5N hydrochloric acid (25 mmol as hydrogen chloride) was added, and the polycondensation reaction was performed under nitrogen for 4 hours. .
Subsequently, 11.18 g of divinyltetramethyldisiloxane and 3.25 g of hexamethyldisiloxane were added to the reaction solution, and a silylation reaction was performed at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer solution became neutral, and then the upper layer solution was collected.
Next, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 40 ° C. to obtain a colorless and transparent liquid reaction product (ladder-type silsesquioxane having a vinyl group at the terminal, 13.0 g). .
The number average molecular weight (Mn) of the above reaction was 840, and the molecular weight dispersity was 1.06.

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

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

[Synthesis of Silane Coupling Agent (D)]
<Synthesis Example 2>
A reaction vessel was charged with 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). The mixture was heated to 50 ° C.
Next, 16.2 g of water and 16.2 g of ethanol were added dropwise over 30 minutes, the temperature was further raised, and a polycondensation reaction was performed under reflux for 4 hours.
Subsequently, the volatile components were distilled off while raising the temperature to 80 ° C. under normal pressure. Thereafter, the remaining volatile components were distilled off while raising the temperature to 100 ° C. under reduced pressure conditions (30 Torr) to obtain a colorless and transparent liquid reaction product (141.5 g).

[Zinc compound (E)]
The following products were used as the zinc compound (E).
Zinc octylate: manufactured by Nippon Chemical Industry Co., Ltd., trade name “Nikka Octix Zinc” (Zn: 15%)

<Examples and Comparative Examples>
Examples 1 to 5 and Comparative Examples 1 to 3 were carried out according to the following procedure.
According to Table 1, silsesquioxane (B), isocyanurate compound (C), silane coupling agent (D), and zinc compound (E) are mixed at a predetermined weight ratio (the amount of each component in Tables 1 and 2). The unit is parts by weight), and the mixture was stirred at 60 ° C. for 2 hours. Then, after cooling to room temperature, polyorganosiloxane (A) was mixed and further stirred at room temperature for 30 minutes to obtain a curable resin composition.
In Table 1, for zinc octylate, the amount obtained by removing mineral spirit from “Nikka Octix zinc” is shown.

[Measurement of viscosity]
Using the rheometer (trade name “PhysicaUDS-200”, manufactured by Anton Paar) and a cone plate (cone diameter: 16 mm, taper angle = 0 °), the above samples were subjected to conditions of temperature: 25 ° C. and rotation speed: 5 rpm. Under the conditions, the viscosity (mPa · s) at 25 ° C. was measured.

[Measurement of luminous intensity maintenance rate]
The curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were injected into the LED package (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. Then, it heated at 80 degreeC for 1 hour and 150 degreeC for 4 hours, and created the sample. In addition, after inject | pouring curable resin composition into a LED package, it may heat at 150 degreeC for 1 hour, and may produce a sample.
Using the total luminous flux measuring machine (manufactured by Optronic Laboratories, multi-spectral radiation measurement system “OL771”), the total luminous flux (unit: lm) when a current of 20 mA is passed is measured for each sample. The total luminous flux before the corrosivity test was used.
Next, each sample was subjected to the SO _X corrosion test and H ₂ S corrosion test described later, and the total luminous flux was measured in the same manner as described above, and this was defined as the total luminous flux after the corrosion test.
Then, the luminous intensity maintenance factor was calculated according to the following formula.
Luminance maintenance rate (%) = (total luminous flux before corrosion test / total luminous flux after corrosion test) × 100

[SO _X corrosion test]
Each of the above samples and 0.3 g of sulfur powder (manufactured by Kishida Chemical Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was further placed in an aluminum box. Subsequently, the aluminum box is put into an oven (manufactured by Yamato Kagaku Co., Ltd., model number “DN-64”), the oven temperature is set to 80 ° C., taken out after 24 hours, and the total luminous flux is measured as described above. did.

[H ₂ S corrosion test]
Each sample was placed in a gas corrosion tester (model number “GS-UV” manufactured by Suga Test Instruments 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 luminous flux was measured.

[Evaluation of corrosion resistance]
The evaluation standards for corrosion resistance were as follows.
A: The luminous intensity maintenance rate in the SO _X corrosion test is 85% or more, the luminous intensity maintenance rate in the H ₂ S corrosion test is 99% or more, and B: The luminous intensity maintenance rate in the SO _X corrosion test is 85% or more, and Luminance maintenance rate in H ₂ S corrosion test is less than 99% C: Luminance maintenance rate in SO _X corrosion test is less than 85%

[Thermal shock resistance test]
Using the thermal shock tester (manufactured by ESPEC Corporation, model number “TSB-21”) for each of the above samples, exposure to a temperature of −40 ° C. for 5 minutes, followed by a temperature of 100 ° C. for 5 minutes is 1 The application of thermal shock as a cycle was performed 1000 cycles. Then, using a digital microscope (manufactured by Keyence Co., Ltd., model number “VW-9000”), the number of samples where peeling and cracks were observed in the LED package sealing material was counted, and the peeling occurrence rate and crack occurrence rate were calculated. It calculated according to the following formula.
Peeling occurrence rate (%) = (number of samples in which peeling is recognized / total number of samples) × 100
Crack generation rate (%) = (number of samples with cracks / total number of samples) × 100

[Evaluation of thermal shock resistance]
The evaluation criteria for thermal shock resistance were as follows.
A: Peeling occurrence rate is 20% or less and crack occurrence rate is 10% or less B: Peeling occurrence rate is over 20% and 50% or less, and crack occurrence rate is 10% or less C: Crack occurrence rate is 10% Over

[Reflow resistance test]
Each of the above samples was placed in a constant temperature and humidity layer (manufactured by ESPEC Corp., model number “SH-641”) adjusted to a temperature of 30 ° C. and a humidity of 70% RH, and taken out after 192 hours. Subsequently, each sample was heat-treated twice at a temperature of 260 ° C. for 10 seconds using a reflow furnace (manufactured by ANTOM Co., Ltd., model number “UNI-5016F”). Thereafter, the peel occurrence rate and the crack occurrence rate were calculated in the same manner as in the thermal shock resistance test.

[Evaluation of reflow resistance]
The evaluation criteria for reflow resistance were as follows.
A: Peeling rate is 10% or less and cracking rate is 20% or less B: Peeling rate is 10% or less, and cracking rate is over 20% and 50% or less C: Peeling rate is 10% Over

In Comparative Examples 1 to 3, none of the corrosion resistance, thermal shock resistance, and reflow resistance was satisfactory.
On the other hand, in Example 1, by adding the silsesquioxane (B), the isocyanurate compound (C), and the silane coupling agent (D), the corrosion resistance (especially SO _X corrosion resistance) is improved. Along with a significant improvement, a dramatic improvement in reflow resistance (particularly the occurrence rate of peeling) was observed.
Further, in Example 2, by using the silane coupling agent (D) of Synthesis Example 2, the H ₂ S corrosion resistance is significantly improved as compared to Example 1, and a significant improvement in thermal shock resistance is recognized. It was.
Next, in Example 3, when the zinc compound (E) in the range described in Patent Document 4 was added, the H ₂ S corrosion resistance was improved, and the corrosion resistance was at a satisfactory level. On the other hand, the thermal shock resistance tended to be slightly lower than in Example 2.
Therefore, in Example 4, when the amount of the zinc compound (E) was further increased as compared with Example 3, surprisingly, the thermal shock resistance decreased in Example 3 was significantly improved in Example 4. Was recognized. In addition, reflow resistance has been dramatically improved.
In Example 5, when the amount of the silane coupling agent (D) was reduced as compared with Example 3, the thermal shock resistance tended to improve, but the reflow resistance slightly decreased.
As described above, a curable resin composition, a cured product, a sealing material, and light having both a sufficient level of thermal shock resistance and reflow resistance for practical use while satisfying both SO _X corrosion resistance and H ₂ S corrosion resistance. A semiconductor device was obtained.

The curable resin composition and the cured product of the present invention include heat-resistant, transparent, flexible, barrier property against corrosive gas, thermal shock resistance, reflow resistance, adhesives, coating agents, sealing materials, etc. Useful for applications. In particular, the curable resin composition and the cured product of the present invention are suitable as a sealing material for optical semiconductor elements (for example, LED elements, semiconductor laser elements, solar power generation elements, CCD elements, etc.).

100: Reflector (resin composition for light reflection)
101: Metal wiring 102: Optical semiconductor element 103: Bonding wire 104: Hardened material (sealing material)

Claims (17)

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

   

   [In Formula (6), R ²¹ to R ²⁶ are the same or different and each represents a hydrogen atom, an aryl group, a monovalent hydrocarbon group, a monovalent heterocyclic group, or an aliphatic carbon-carbon unsaturated bond. Including monovalent group. However, at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond. One or more of R ²¹ to R ²⁶ are an aryl group. R ²⁷ represents a divalent hydrocarbon group. r and s each represent an integer of 1 or more. ]
   The curable resin composition according to any one of claims 1 to 5, comprising a polyorganosiloxane having a structure represented by:
7. The curable resin composition according to any one of claims 1 to 6, wherein the silsesquioxane (B) is a ladder-type silsesquioxane.
8. The isocyanurate compound (C) has the formula (1)
   

   

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

   

   

   [In Formula (2) and Formula (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
   The curable resin composition according to any one of claims 1 to 7, which is an isocyanurate compound represented by the formula:
9. The curable resin composition according to claim 8, wherein any one or more of R ^x , R ^y , and R ^z in the formula (1) is a group represented by the formula (3).
10. Further, a silane coupling agent (D) is contained, and the content of the silane coupling agent (D) is 0.00 with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition according to any one of claims 1 to 9, wherein the content is 01 parts by weight or more and less than 1.0 part by weight.
11. The curable resin composition according to claim 10, wherein the silane coupling agent (D) contains a partial condensate obtained by hydrolysis and partial condensation of one or more silane coupling agents.
12. Furthermore, the zinc compound (E) is contained, and the content of the zinc compound (E) is 0.01 parts by weight or more with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition according to any one of claims 1 to 11, which is less than 1.0 part by weight.
13. The content of the zinc compound (E) is 0.3 parts by weight or more and less than 0.6 parts by weight with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (B). The curable resin composition according to claim 12.
14. The curable resin composition according to claim 12 or 13, wherein the zinc compound (E) is zinc carboxylate.
15. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 14.
16. A sealing material obtained using the curable resin composition according to any one of claims 1 to 14.
17. A semiconductor device obtained using the sealing material according to claim 16.

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