KR101563472B1 - Curable resin composition and semiconductor device using same - Google Patents

Abstract

The present invention relates to a semiconductor device which has transparency, heat resistance and flexibility and which has a bottom flow property and also has a barrier property against a hydrogen sulfide (H ₂ S) gas and a barrier property against a sulfur oxide (SO _x ) Particularly optical semiconductor elements), a cured product using the same, a sealing material, and a semiconductor device.
A curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B) and a zinc compound (E), wherein the polyorganosiloxane (A) is a polyorganosiloxane having an aryl group, (D), and the content of the zinc compound (E) is 0.01 part by weight or more and 0.1 part by weight or less based on 100 parts by weight of the total amount of the polyorganosiloxane (A) and the silsesquioxane (D) , A cured product using the same, a sealing material, and a semiconductor device.

Description

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

The present invention relates to a curable resin composition, a cured product obtained by using the curable resin composition, a sealing material, and a semiconductor device obtained by using the sealing material. This application claims priority of Japanese Patent Application No. 2013-161865, filed in Japan on Aug. 2, 2013, the content of which is incorporated herein by reference.

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

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

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

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

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

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

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

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

It is therefore an object of the present invention, transparency, with also having a thermal resistance, barrier properties (in particular, the barrier properties of the hydrogen sulfide (H ₂ S) gas for a corrosive gas (in the H ₂ S corrosion) and sulfur oxides (SO _X (Particularly, an optical semiconductor element), which has barrier properties (gas resistance to SO _X ) to gas). Another object of the present invention is to provide a semiconductor device which has transparency, heat resistance and flexibility and has a bottom flowability (crack resistance in a reflow process, adhesion to a package, etc.) The present invention provides a curable resin composition useful for sealing applications of a semiconductor device having a high heat resistance. Another object of the present invention is to provide a cured product and a sealing material which have excellent heat resistance, transparency and flexibility, and which are excellent in flow resistance and barrier property against corrosive gas. Still another object of the present invention is to provide a semiconductor device having the cured product and / or the sealing material.

The present inventors have found that a curable resin composition obtained by adding an isocyanurate compound and a zinc compound to an aryl group-containing polyorganosiloxane has excellent heat resistance and transparency, and is capable of forming a cured product excellent in barrier property against corrosive gas And the present invention has been completed.

That is, the present invention provides a curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B) and a zinc compound (E), wherein the polyorganosiloxane (A) is a polyorganosiloxane (D), and the content of the zinc compound (E) is preferably 0.01 to 100 parts by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (D) By weight or more and less than 0.1 part by weight.

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

The present invention also relates to a polyorganosiloxane (A) having a weight average molecular weight in terms of standard polystyrene by gel permeation chromatography as Mw and a molecular weight dispersion (Mw / Mn) as a number average molecular weight in terms of Mn of from 0.95 to 6.00 By weight of the curable resin composition.

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

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

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

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

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

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

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

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

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

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

Further, the present invention provides the above curable resin composition comprising ladder type silsesquioxane as silsesquioxane (D).

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

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

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

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

[1] A curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B) and a zinc compound (E), wherein the polyorganosiloxane (A) is a polyorganosiloxane having an aryl group, (D), and the content of the zinc compound (E) relative to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (D) To less than 0.1 part by weight.

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

[3] The polyorganosiloxane (A) contains a structure represented by the formula (6) (particularly, R ²⁷ is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, more preferably an ethylene group) Is a polyorganosiloxane, which is a polyorganosiloxane.

[4] The curable resin composition according to any one of [1] to [3], wherein the content (amount) of the polyorganosiloxane (A) is 60 to 99.5% by weight based on the total amount (100% .

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

[6] A method for producing a polyorganosiloxane (A), which comprises reacting a polyorganosiloxysilane having an aliphatic carbon-carbon double bond and an aryl group with a polyorganosiloxane having an aliphatic carbon-carbon double bond and an Si- The curable resin composition according to any one of [3] to [5], wherein two kinds of organosiloxane alkylenes are used.

(1) wherein R ^x , R ^y and R ^z are the same or different and are a group represented by formula (2) or a group represented by formula (3) (2) and (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a straight or branched alkyl group having 1 to 8 carbon atoms] The curable resin composition according to any one of [1] to [6], which contains a cyanurate compound.

[8] The curable resin composition according to any one of [1] to [7], wherein the isocyanurate compound (B) is monoallyldiglycidyl isocyanurate.

[9] The curable resin composition according to any one of [1] to [8], wherein the content of the isocyanurate compound (B) is 0.01 to 10% by weight relative to the total amount (100% by weight) of the curable resin composition.

[1] to [9], wherein the proportion of the isocyanurate compound (B) is 0.01 to 0.5 parts by weight based on the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (D) Wherein the curable resin composition is a curable resin composition.

[11] The curable resin composition according to any one of [1] to [10], further comprising a silane coupling agent (C).

[12] The curable resin composition according to [11], wherein the silane coupling agent (C) is 3-glycidoxypropyltrimethoxysilane.

[13] The curable resin composition according to any one of [1] to [12], which contains silsesquioxane (D).

[14] The curable resin composition according to any one of [1] to [13], wherein the silsesquioxane (D) is a ladder-type silsesquioxane.

[15] The curable resin composition according to any one of [1] to [14], wherein the content of silsesquioxane (D) is 0.01 to 30% by weight relative to the total amount (100% by weight) of the curable resin composition.

[16] The curable resin composition according to any one of [1] to [15], wherein the zinc compound (E) is zinc carboxylate.

[17] The curable resin composition according to any one of [1] to [16], wherein the zinc compound (E) is zinc naphthenate or zinc octylate.

[18] The curable resin composition according to any one of [1] to [17], wherein the content of the zinc compound (E) is 0.02 to 0.085% by weight based on the total amount (100% by weight) of the curable resin composition.

[19] The curable resin composition according to any one of [1] to [18], wherein the zinc content of the total amount of the zinc compound (E) compound (100% by weight) is 2 to 30% by weight.

Since the curable resin composition of the present invention has the above-described structure, a cured product having excellent heat resistance and transparency can be formed. Particularly, the cured product has excellent barrier properties against a plurality of corrosive gases such as H ₂ S gas and SO _x gas. In addition, the obtained cured product may be excellent in flexibility and flowability. Therefore, 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 photovoltaic element, a CCD element or the like), and the curable resin composition of the present invention An optical semiconductor device obtained by sealing an optical semiconductor element with a cured product has excellent quality and durability. Particularly, the curable resin composition of the present invention is useful as a sealing material for a next-generation light source that requires heat resistance against a high temperature (for example, 180 DEG C or higher) which has not been available.

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

The curable resin composition of the present invention is a curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B) and a zinc compound (E), wherein the polyorganosiloxane (A) (D), and the content of the zinc compound (E) is in the range of 100 parts by weight based on the total amount of the polyorganosiloxane (A) and the silsesquioxane (D) Is not less than 0.01 parts by weight and less than 0.1 parts by weight.

[Polyorganosiloxane (A)]

The polyorganosiloxane (A) in the curable resin composition of the present invention is a polyorganosiloxane having a main chain composed of a siloxane bond (Si-O-Si), and a polyorganosiloxane having an aryl group as a substituent in the main chain . The polyorganosiloxane (A) may be a straight-chain or branched polyorganosiloxane having a hydrosilyl group or a group having an aliphatic carbon-carbon unsaturated bond. Examples of the polyorganosiloxane (A) include silicone skeletons such as phenyl silicon skeleton (polydiphenylsiloxane) and phenylmethyl silicone skeleton (polymethylphenylsiloxane). The polyorganosiloxane (A) does not contain silsesquioxane (D).

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

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

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

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

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

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

The aromatic hydrocarbon group includes, for example, a phenyl group, a naphthyl group of the C _{6- 14} aryl group (particularly, C _6-10 aryl group), and the like.

Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Further, as the group bonded group of the aliphatic hydrocarbon group and the aromatic hydrocarbon, for example, benzyl group, phenethyl group and so on of the C _{7- 18} aralkyl group (particularly, C _{7- 10} aralkyl group), such as thinner push the C _{6- 10} aryl -C _2-6 alkenyl group such as, a tolyl group such as a C _{1- 4} alkyl-substituted aryl group, a styryl group in the _2- C ₄ alkenyl group and the like can be mentioned substituted aryl groups. Examples of the substituent possessed by the substituted hydrocarbon group (substituted hydrocarbon group) include the same substituents as the above-mentioned substituents the aryl group may have.

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

A plurality of R 'in formula (4) may be the same or different. R 'in the formula (4) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, (Mono or dialkylamino group, acylamino group and the like), an alkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, An epoxy group, a cyano group, an isocyanate group, a carbamoyl group, and an isothiocyanate group.

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

The content of the aryl group (in terms of the phenyl group) to the total amount (100% by weight) of the polyorganosiloxane (A) is not particularly limited, but is preferably 35% by weight or more (for example, 35 to 70% by weight) More preferably 40% by weight or more, and still more preferably 44% by weight or more. If the content of the aryl group is less than 35% by weight, the barrier property against the corrosive gas of the resulting cured product may be lowered. Further, all of the substituents in the main chain composed of the siloxane bond (Si-O-Si) of the polyorganosiloxane (A) may be an aryl group, or a part of the substituents may be an aryl group. The content of the aryl group can be measured by, for example, ¹ H-NMR.

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

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

The molecular weight dispersion degree (Mw / Mn) calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyorganosiloxane (A) is not particularly limited but is preferably 0.95 to 6.00, more preferably 0.95 to 4.00 More preferably 1.00 to 3.80, and particularly preferably 1.20 to 3.50. When the molecular weight dispersion degree (Mw / Mn) is more than 3.50, the heat resistance of the obtained cured product and the barrier property against corrosive gas may be lowered.

The content (blending amount, the total content when two or more kinds) of the polyorganosiloxane (A) in the curable resin composition of the present invention is not particularly limited, but the content of the polyorganosiloxane (A) in the curable resin composition of the present invention To 99.5% by weight, more preferably 70% to 99.0% by weight, and still more preferably 85% to 98.5% by weight. When the content is less than 55% by weight, crack resistance of the obtained cured product may be lowered. On the other hand, if the content exceeds 99.5% by weight, the barrier property against the corrosive gas of the obtained cured product may be lowered.

The polyorganosiloxane (A) may have a substituent other than an aryl group, and the substituent other than the aryl group may be a substituent possessed by the silicon atom in the polyorganosiloxane (A). Examples of the substituent other than the aryl group include a hydrogen atom, a halogen atom, a group having a Si-H bond, a substituted or unsubstituted hydrocarbon group (preferably an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group) An alkoxy group, an alkenyloxy group, an acyloxy group, a mercapto group (thiol group), an alkylthio group, an alkenylthio group, a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group (mono- or dialkylamino group, An isocyanate group, a carbamoyl group, and an isothiocyanate group.

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

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

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

Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group; A monovalent alicyclic hydrocarbon group; A monovalent aromatic hydrocarbon group; An aliphatic hydrocarbon group, a monovalent group in which two or more of alicyclic hydrocarbon groups and aromatic hydrocarbon groups are bonded, and the like. Examples of the monovalent heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

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

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

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

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

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

The alkoxy group includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropyl oxy group, a butoxy group, C _{1- 6} alkoxy group such as isobutyl-oxy group (preferably C _{1- 4} alkoxycarbonyl group), etc. . Examples of the alkenyloxy group, for example, allyl (preferably _2- C ₄ alkenyloxy group) _2- C ₆ alkenyloxy group such as oxy, and the like. A substituent such as the aryloxy group as, for example, a phenoxy group, tolyl rilok group, a naphthyloxy group to the aromatic ring at the time of such as C _{1- 4} alkyl, C _{2- 4} alkenyl group, a halogen atom, C _{1- 4} alkoxy group which may have, and the like _6- C ₁₄ aryloxy group. The aralkyl oxy group as the example, there may be mentioned a benzyloxy group, C _{7- 18} aralkyl oxy group such as a phenethyl tilok time. Examples of the acyloxy group include C _1-12 acyloxy groups such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group and benzoyloxy group.

Examples of the alkylthio group, for example, there may be mentioned a methyl thio group, ethyl come C _{1- 6} alkylthio, such as importing tea (preferably C _{1- 4} alkylthio group) and the like. The alkenyl nilti come as, for example, there may be mentioned the allyl-thio group such as C _{2- 6} alkenyl nilti come (preferably C _{2- 4} alkenyl nilti come), and the like. As the arylthio group, for example, phenylthio, tolyl rilti came, to the aromatic ring, such as naphthyl tilti come C _{1- 4} alkyl, C _{2- 4} alkenyl group, a halogen atom, a substituent such as a C _{1- 4} alkoxy group which may have a C _{6- 14,} and the like arylthio. The aralkyl there may be mentioned an alkylthio as for example, benzyl-thio, phenethyl, etc. tilti import of C _{7- 18} aralkyl thio group and the like. And the like can be mentioned groups wherein the alkoxy group as, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, such as a C _{1- 6} alkoxy. As said aryloxycarbonyl group, for example, phenoxy group, tolyloxy group, naphthyloxy group, etc. C _{6- 14} aryloxy-carbonyl group, and the like. Examples of the aralkyloxycarbonyl group include a C _7-18 aralkyloxy-carbonyl group such as benzyloxycarbonyl group and the like. Examples of the mono or dialkylamino group include a mono or di-C _1-6 alkylamino group such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group. Examples of the acylamino group, for example, there may be mentioned an acetyl group, a propionyl group, a C _{1- 11} acylamino group such as benzoylamino group and the like. Examples of the epoxy group-containing group include a glycidyl group, a glycidyloxy group and a 3,4-epoxycyclohexyl group. Examples of the oxetanyl group-containing group include ethyloxetanyloxy group and the like. Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.

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

More specific examples of the monovalent hydrocarbon group and monovalent heterocyclic group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a decyl group, (For example, a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, a benzyl group, a phenethyl group, a pyridyl group, Acryloxypropyl group, N-2- (aminoethyl) -3-aminopropyl group, 3- (methoxycyclohexyl) ethyl group, 3-glycidylpropyl group, 3- Aminopropyl group, N-phenyl-3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group and the like).

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

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

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

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

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

Examples of the polyorganosiloxysilylenes include GD-1130A (manufactured by Choko Chemical Industry Co., Ltd.) and GD-1130B (manufactured by Choko Chemical Industry Co., Ltd.).

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

When two or more kinds of polyorganosiloxane (A) are used, the total amount (total content, 100% by weight) of the polyorganosiloxane (A) in the curable resin composition of the present invention Is preferably not less than 60% by weight (for example, from 60 to 100% by weight), more preferably not less than 80% by weight (for example, from 80 to 99.5% by weight) Is at least 90% by weight. If the proportion of the polyorganosiloxysilylene is less than 60% by weight, the cured product tends to become yellowish or tends to have adhesiveness on the surface, so that the handling property tends to deteriorate.

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

The curable resin composition of the present invention comprises a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond as the polyorganosiloxane (A) (referred to simply as " polyorganosiloxane (A1) May be included. The aliphatic carbon-carbon double bond may have any partial structure and / or constituent component constituting the polyorganosiloxane (A1). The aliphatic carbon-carbon double bond may have a substituent (for example, a substituent having a silicon atom) in the polyorganosiloxane (A1). The aliphatic carbon-carbon double bond may be present at the end of the main chain (straight chain and / or branched chain) composed of the siloxane bond (Si-O-Si) of the polyorganosiloxane (A1).

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

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

[Polyorganosiloxane (A2) having Si-H bond]

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

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

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

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

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

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

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

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

[Isocyanurate compound (B)]

The curable resin composition of the present invention comprises an isocyanurate compound (B). By including the isocyanurate compound (B) in the curable resin composition of the present invention, the barrier property to the corrosive gas of the cured product formed by curing in particular is improved, and the adhesion to the adherend is improved. Among them, the isocyanurate compound (B) preferably contains an isocyanurate compound represented by the formula (1). In particular, the isocyanurate compound (B) is preferably the isocyanurate compound represented by the formula (1) alone.

In the formula (1), R ^x , R ^y and R ^z are the same or different and represent a group represented by the formula (2) or a group represented by the formula (3). Among them, it is preferable that at least one (preferably one or two, more preferably one) of R ^x , R ^y and R ^z in the formula (1) is a group represented by the formula (3) .

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

Examples of the isocyanurate compound (B) include, but are not limited to, monoallyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, triallyl isocyanurate, monoallyl diglycidyl isocyanurate (2-methylpropoxy) isocyanurate, diallyl monoglycidyl isocyanurate, triglycidyl isocyanurate, 1-allyl-3,5-bis Phenyl) -3,5-diglycidylisocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, Bis (2-methylpropenyl) - isocyanurate, 1,3-bis (2-methylpropenyl) 5- (2-methylepoxypropyl) isocyanurate, and tris (2-methylpropenyl) isocyanurate. Among them, monoallyldiglycidylisocyanurate is preferable. Each of the isocyanurate compounds (B) may be used alone or in combination of two or more.

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

The content of the isocyanurate compound (B) is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, more preferably 0.1 to 5% by weight based on the total amount (100% by weight) of the curable resin composition. More preferably 3% by weight. When the content of the isocyanurate compound (B) is less than 0.01% by weight, the barrier property to the corrosive gas of the cured product and the adhesion to the adherend may be lowered. On the other hand, when the content of the isocyanurate compound (B) 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 (B) is not particularly limited, but from the viewpoint of the barrier property to the corrosive gas of the cured product, for example, the total amount of the polyorganosiloxane (A) and the silsesquioxane (D) 100 parts by weight).

[Silane coupling agent (C)]

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

The silane coupling agent (C) has good compatibility with the polyorganosiloxane (A) and the isocyanurate compound (B), and therefore, for example, the silane coupling agent (C) (B) and the silane coupling agent (C) are formed in advance to improve the properties of the resin composition, it is easy to obtain a uniform curable resin composition.

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

The content of the silane coupling agent (C) is not particularly limited, but is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight based on the total amount (100% % Is more preferable. If the content of the silane coupling agent (C) is less than 0.01% by weight, the adhesiveness to the adherend is lowered. In particular, when the isocyanurate compound (B) Or the like) may not be obtained in some cases. On the other hand, if the content of the silane coupling agent (C) exceeds 15% by weight, the curing becomes insufficient and the toughness, heat resistance and barrier property against the corrosive gas of the cured product may be lowered.

[Silsesquioxane (D)]

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

Silsesquioxane is a polysiloxane. The polysiloxane is generally a compound having a main chain composed of a siloxane bond (Si-O-Si), and its basic constituent unit is an M unit (a unit comprising a monovalent group in which a silicon atom is bonded to one oxygen atom), a D unit (A unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms), a T unit (a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms), and a Q unit .

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

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

When the curable resin composition of the present invention contains silsesquioxane (D), the barrier property to the corrosive gas of the cured product formed by curing in particular is improved, and the toughness (especially crack resistance) There is a tendency to improve. The content (amount) of silsesquioxane (D) in the curable resin composition of the present invention is not particularly limited, but is preferably 0.01 to 30% by weight, more preferably 0.1 to 30% by weight based on the total amount (100% More preferably 20% by weight, and still more preferably 0.5% by weight to 10% by weight.

[Zinc compound (E)]

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

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

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

The content of the zinc compound (E) is not particularly limited, but the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (D) (the silsesquioxane (D) , More preferably from 0.03 part by weight to less than 0.1 part by weight, more preferably from 0.05 part by weight to less than 0.1 part by weight, based on the total weight of the polyorganosiloxane (A) Particularly preferably 0.07 part by weight or more and less than 0.1 part by weight. If the content of the zinc compound (E) is less than 0.01 part by weight, the barrier property against the H ₂ S gas may be lowered. On the other hand, if the content of the zinc compound (E) 0.1 parts by weight or more, there is a case in which the barrier gas for SO _X decreases.

The content of the zinc compound (E) in the curable resin composition of the present invention is not particularly limited, but is preferably 0.01 to 0.1 wt%, more preferably 0.01 to 0.1 wt%, based on the total amount (100 wt%) of the curable resin composition By weight is 0.05 to 0.085% by weight.

[Hydrosilylation catalyst]

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

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

[Hydrosilylation reaction inhibitor]

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

[Other siloxane compound]

The curable resin composition of the present invention may further include a cyclic siloxane compound having two or more aliphatic carbon-carbon double bonds in the molecule (in one molecule) as the other siloxane compound. The curable resin composition of the present invention may further comprise a cyclic siloxane having a group having two or more Si-H bonds in the molecule (in one molecule) as the other siloxane compound. The cyclic siloxane may be used singly or in combination of two or more kinds. The content (amount) of the cyclic siloxane in the curable resin composition of the present invention is not particularly limited, but is preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight based on the total amount (100% by weight) of the curable resin composition , More preferably 0.5 to 10 wt%.

[Other silane compound]

The curable resin composition of the present invention may contain other silane compounds (for example, compounds having a hydrosilyl group). Examples of the other silane compounds include methyl (trisdimethylsiloxy) silane, tetrakis (dimethylsiloxy) silane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5, 5-hexamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1, , 1,3,5,5,7,7,7-nonamethyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,1,1 , And 3,5,5,7,7,9,9,9-undecamethylpentasiloxane, and the like, and the like. The silane compounds may be used singly or in combination of two or more. The content of the silane compound is not particularly limited, but is preferably 0 to 5% by weight, more preferably 0 to 1.5% by weight based on the total amount (100% by weight) of the curable resin composition.

[menstruum]

The curable resin composition of the present invention may contain a solvent. Examples of the solvent include conventionally known solvents such as toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate and the like. These solvents may be used singly or in combination of two or more.

[additive]

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

[Curable resin composition]

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

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

The curable resin composition of the present invention is not particularly limited, but it is preferably liquid at room temperature (about 25 캜). More specifically, the curable resin composition of the present invention preferably has a viscosity at 23 占 폚 of 300 to 20,000 mPa 占 퐏, more preferably 500 to 10,000 mPa 占 퐏, and still more preferably 1000 to 8,000 mPa 占 퐏. When the viscosity is less than 300 mPa.s, the heat resistance of the cured product may be lowered. On the other hand, when the viscosity exceeds 20,000 mPa · s, it becomes difficult to manufacture and handle the curable resin composition, and bubbles may easily remain in the cured product. The viscosity at 23 캜 was measured with a cone plate (conical diameter: 16 mm, taper angle = 0 °) with a rheometer (trade name "Physica UDS-200", manufactured by Anton Paar) At a temperature of 23 DEG C and a rotation speed of 20 rpm.

[Cured goods]

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

[Seal material and semiconductor device]

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

Example

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

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

[Polyorganosiloxane (A)]

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

GD-1130A, manufactured by Choko Chemical Industry Co., Ltd., a vinyl group content of 4.32 wt%, a phenyl group content of 44.18 wt%, a SiH group content (in terms of hydride) of 0 wt%, a number average molecular weight of 1107,

GD-1130B manufactured by Choko Chemical Industry Co., Ltd., a vinyl group content of 3.45 wt%, a phenyl group content of 50.96 wt%, a SiH group content (in terms of hydride) of 0.17 wt%, a number average molecular weight of 631,

OE-6630A, manufactured by Toray Dow Corning Incorporated, having a vinyl group content of 2.17 wt%, a phenyl group content of 51.94 wt%, a SiH group content (in terms of hydride) of 0 wt%, a number average molecular weight of 2532,

OE-6630B manufactured by TORAY DOW CORNING CO., LTD. Having a vinyl group content of 3.87 wt%, a phenyl group content of 50.11 wt%, a SiH group content (in terms of hydride) of 0.17 wt%, a number average molecular weight of 783,

[Isocyanurate compound (B)]

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

Monoallyldiglycidylisocyanurate: manufactured by Shikoku Chemical Industry Co., Ltd.

[Silane coupling agent (C)]

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

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

[Synthesis of silsesquioxane (D)] [

≪ Synthesis Example 1 &

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

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

Subsequently, 11.18 g of divinyltetramethyldisiloxane and 3.25 g of hexamethyldisiloxane were added to the reaction solution, and the silylation reaction was carried out at 70 占 폚 for 4 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer became neutral, and then the supernatant was collected. Subsequently, the solvent was distilled off from the supernatant under the conditions of 1 mmHg at 40 占 폚 to obtain a colorless transparent liquid reaction product (ladder silsesquioxane having a vinyl group at the terminal, 13.0 g). The number average molecular weight (Mn) of the reaction was 840 and the molecular weight dispersion degree was 1.06.

[Zinc compound (E)]

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

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

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

≪ Examples and Comparative Examples &

Examples 1 to 7 and Comparative Examples 1 to 6 were carried out in the following order.

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

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

[Measurement of brightness retention rate]

The curable resin composition obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was injected into the LED package (InGaN element, 3.5 mm x 2.8 mm) shown in Fig. 1 and heated at 60 DEG C for 1 hour, then at 80 DEG C For 1 hour and 150 ° C for 4 hours to prepare a sample. Further, the curable resin composition may be injected into the LED package, and then heated at 150 占 폚 for one hour to prepare a sample.

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

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

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

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

[SO _X Corrosivity Test]

0.3 g of each of the samples and sulfur powder (manufactured by Kishida Chemical Co., Ltd.) was placed in a 450 ml glass bottle, and the glass bottle was placed in an aluminum box. Subsequently, the aluminum box was placed in an oven (model number " DN-64 ", manufactured by Yamato Kagaku Kogyo), the oven temperature was set at 80 占 폚 and taken out after 24 hours, The luminous flux was measured.

[H ₂ S Corrosion Test]

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

[Evaluation of corrosion resistance]

The corrosion resistance evaluation criteria were as follows.

A: SO yet brightness retention ratio is 85% or more of the corrosion test in the _X, H ₂ S than the brightness retention ratio of 99% in corrosion test

B: SO yet brightness retention ratio is 85% or more of the corrosion test in the _X, H ₂ S is less than 99% brightness retention ratio in a corrosion test

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

In Comparative Examples 1 to 3 in SO _X corrosion resistance was not sufficient enough to, in H ₂ S corrosion.

On the other hand, in Comparative Examples 4 to 6, when the zinc compound (E) in the range described in Patent Document 4 was added, the H ₂ S corrosion resistance was improved, but the SO _X corrosion resistance was rather lowered unexpectedly.

Accordingly, the embodiment and Comparative Examples 4 and adjusting the zinc compound (E) toward the small bar relative to to 6, while maintaining the H ₂ S within the corrosive SO _X in corrosion resistance was observed to be improved.

Further, from the comparison of Examples 2, 4 and 6, it was recognized that the increase of the silsesquioxane (B) improves the SO _X corrosion resistance without lowering the H ₂ S corrosion resistance.

Further, from the comparison between Example 5 and Example 4, it was recognized that the addition of the silane coupling agent (D) improves the SO _x corrosion resistance without lowering the H ₂ S corrosion resistance.

From the above, by adding a zinc compound (E) in a limited range, a curable resin composition having both SO _x corrosion resistance and H ₂ S corrosion resistance can be obtained.

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

100: Reflector (light-use resin composition)
101: metal wiring
102: optical semiconductor element
103: Bonding wire
104: Hardened product (sealing material)

Claims (15)

A curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B) and a zinc compound (E), wherein the polyorganosiloxane (A) is a polyorganosiloxane having an aryl group, E) is less than 0.01 part by weight and less than 0.1 part by weight with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A). The curable resin composition according to claim 1, wherein the number average molecular weight (Mn) of the polyorganosiloxane (A) in terms of standard polystyrene by gel permeation chromatography is 500 to 4000. The polyorganosiloxane (A) according to claim 1, wherein the weight average molecular weight of the polyorganosiloxane (A) in terms of standard polystyrene by gel permeation chromatography is Mw and the molecular weight dispersion degree (Mw / Mn) of the number average molecular weight is Mn 6.00. The curable resin composition according to claim 1, wherein the polyorganosiloxane (A) is a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond. The curable resin composition according to claim 1, wherein the polyorganosiloxane (A) is a polyorganosiloxane (A2) having Si-H bonds. The curable resin composition according to claim 1, wherein the isocyanurate compound (B) comprises an isocyanurate compound represented by 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 the formulas (2) and (3), R ¹ and R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.]] The curable resin composition according to claim 6, wherein at least one of R ^x , R ^y and R ^z in the formula (1) is a group represented by the formula (3). The curable resin composition according to claim 1, wherein the zinc compound (E) comprises zinc carboxylate. The curable resin composition according to claim 1, wherein the polyorganosiloxane (A) is a polyorganosiloxane having a structure represented by formula (6).

[In the formula (6), R ²¹ to R ²⁶ are the same or different and each represents a hydrogen atom, an aryl group, a monovalent hydrocarbon group, or a monovalent heterocyclic group. Provided that at least one of R ²¹ to R ²⁶ is a monovalent group containing an aliphatic carbon-carbon unsaturated bond. Further, at least one of R ²¹ to R ²⁶ is 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 claim 1, further comprising a silane coupling agent (C). The positive resist composition according to claim 1, further comprising silsesquioxane (D), wherein the content of the zinc compound (E) relative to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (D) 0.01 to less than 0.1 part by weight of the curable resin composition. The curable resin composition according to claim 11, wherein the silsesquioxane (D) is a ladder-type silsesquioxane. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 12. A sealing material obtained by using the curable resin composition according to any one of claims 1 to 12. A semiconductor device obtained by using the sealing material according to claim 14.

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