TW201512309A - Curable resin composition and semiconductor device using same - Google Patents

Abstract

Provided are: a curable resin composition provided with transparency, heat resistance, and flexibility, as well as with re-flow resistance, and also barrier properties with respect to hydrogen sulfide (H2S) gas and barrier properties with respect to sulfur oxide (SOX) gas, and that is useful in sealing applications for semiconductor elements (particularly optical semiconductor elements); a cured product using the same; a sealing material; and a semiconductor device.; A curable resin composition, and a cured product, sealing material, and semiconductor device using the same, the curable resin composition including a polyorganosiloxane (A), an isocyanurate compound (B), and a zinc compound (E), the polyorganosiloxane (A) being a polyorganosiloxane having an aryl group, the curable resin composition potentially further including a silsesquioxane (D), and the content of the zinc compound (E) being less than 0.01 part by weight to 0.1 part by weight with respect to the total amount (100 parts by weight) of the polyorganosiloxane (A) and the silsesquioxane (D).

Description

Curable resin composition and semiconductor device using the same

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

In need of high heat resistance. In a semiconductor device having a high withstand voltage, heat resistance of about 150 ° C or higher is generally required for a material covering a semiconductor element. In particular, in the material (sealing material) of the optical material such as the optical semiconductor element, the physical properties such as transparency and flexibility are required in addition to heat resistance. For example, as a sealing material for a backlight unit of a liquid crystal display, an epoxy resin material or an anthrone resin material is currently used.

In Patent Document 1, as a material having high heat resistance and good heat dissipation property, one or more synthetic polymer compounds containing a third organic ruthenium polymer having a molecular weight of 20,000 to 800,000 are disclosed, wherein the third organic oxime The polymer is a second type of at least one of a first organic ruthenium polymer having at least one crosslinked structure of a decane (Si-O-Si bond) and a linear connection structure having a siloxane. An organic ruthenium polymer linked by a decane bond. However, the physical properties of these materials are still not met.

Further, in Patent Document 2, transparency and UV resistance are exhibited. And a resin composition for optical element sealing which is excellent in heat-resistant coloring property, and a resin composition for optical element sealing containing a silsesquioxane as a resin component, wherein the sesquiterpene oxide is selected from the group consisting of a liquid sesquioxane having an aliphatic carbon-carbon unsaturated bond and a cage structure not containing an H-Si bond, and a cage containing an H-Si bond and not containing an aliphatic carbon-carbon unsaturated bond At least one of the group of liquid sesquiterpene oxides of the structure. However, since the cured product of the resin composition containing the cage type sesquiterpene oxide is hard and lacks flexibility, there is a problem that cracks or cracks easily occur.

Further, Patent Document 3 discloses an organic compound such as triallyl isocyanurate containing at least two carbon-carbon double bonds reactive with an SiH group in one molecule, in one molecule. A curable composition containing at least two SiH-based chain-like and/or cyclic polyorganosiloxanes and a hydroquinone-forming catalyst as essential components. However, the physical properties such as the crack resistance of these materials are still unsatisfactory.

On the other hand, a metal material such as an electrode of an optical semiconductor device is likely to be corroded by a corrosive gas, and there is a problem that electric conduction characteristics (for example, energization characteristics of a high-temperature environment) deteriorate with time. Therefore, in the sealing material for an optical semiconductor, high barrier property with respect to a corrosive gas is required. However, the sealing material of the conventional anthrone-based resin material disclosed in Patent Documents 1 to 3 and the like cannot be said to be sufficiently sufficient for the barrier property of the corrosive gas.

Patent Document 4 discloses a fluorenone resin composition comprising (A) a polyoxyalkylene having at least two alkenyl groups bonded to a ruthenium atom, and (B) having at least two bonded to a ruthenium atom. The hydrogen-based polyoxyalkylene crosslinking agent, the (C) hydroalkylation reaction catalyst, and the (D) zinc compound are contained in the above-mentioned (A) component and the total amount of the component (B) in an amount of 100 parts by mass. The component (D) is 0.1 to 5 parts by mass, and the sulfur resistance is good. However, although the corrosion resistance to hydrogen sulfide (H ₂ S) has been disclosed, there is no description about the corrosion resistance to other corrosive gases.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-206721

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-031619

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-314140

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-178983

There are many types of corrosive gases that corrode semiconductor devices, and there is still no disclosure of a plurality of corrosive properties such as hydrogen sulfide (H ₂ S) gas or sulfur oxide (SO _X ) gas as a representative corrosive gas. Any of the gases has a sealing material that is sufficiently barrier.

Therefore, an object of the present invention is to provide a cured product which is useful for sealing applications of a semiconductor element (particularly an optical semiconductor element), which has transparency, heat resistance, flexibility, and also has barrier properties against corrosive gases. (especially the barrier property against hydrogen sulfide (H ₂ S) gas (H ₂ S corrosion resistance) and the barrier property against sulfur oxide (SO _X ) gas (SO _X corrosion resistance). Moreover, another object of the present invention is to provide a curable resin composition useful for sealing applications of a semiconductor element, which has transparency, heat resistance, flexibility, and reflow resistance (resistance to a reflow step) It has crack resistance, adhesion to the package, etc., and also has barrier properties against corrosive gases. Further, 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 particularly have excellent reflow resistance and good barrier properties against corrosive gases. Still another object of the present invention is to provide a semiconductor device having the cured product and/or the sealing material.

The inventors of the present invention have found that a polycyanate compound having an aryl group and a curable resin composition of a zinc compound have excellent heat resistance and transparency, and in particular, can form corrosive properties. The cured product excellent in gas barrier properties further completes the present invention.

That is, the present invention provides a curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B), and a zinc compound (E), which is a curable resin composition. The polyorganosiloxane (A) is a polyorganosiloxane having an aryl group, and may further comprise a sesquiterpene oxide (D), and the content of the zinc compound (E) is relative to the polyorganosiloxane. The total amount (100 parts by weight) of the alkane (A) and the sesquioxane (D) is 0.01 parts by weight or more and less than 0.1 parts by weight.

Further, the present invention provides the curable resin composition as described above, wherein the polyorganosiloxane (A) has a number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography of 500 to 4,000.

Further, the present invention provides a curable resin composition as described above, The molecular weight dispersion (Mw/Mn) when the weight average molecular weight of the polyorganosiloxane (A) by gel permeation chromatography is Mw and the number average molecular weight is Mn is 0.95 to 6.00.

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

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

Further, the present invention provides the curable resin composition as described above, wherein the isomeric isocyanate compound (B) comprises an isomeric cyanurate compound represented by the formula (1); [In the formula (1), R ^x , R ^y , and R ^z may be the same or different, and represent a group represented by the formula (2) or a group represented by the formula (3);

In the formulae (2) and (3), R ¹ and R ² may be the same or different and each represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms]].

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

Moreover, the present invention provides the curable resin composition as described above, wherein the zinc compound (E) contains zinc carboxylate.

Furthermore, the present invention provides a curable resin composition as described above, wherein the polyorganosiloxane (A) comprises a polyorganooxynitane having a structure represented by the formula (6); [In the formula (6), R ²¹ to R ²⁶ may be the same or different and each represents a hydrogen atom, an aryl group, a monovalent hydrocarbon group or a monovalent heterocyclic group; however, one or more of R ²¹ to R ²⁶ are a monovalent group containing an aliphatic carbon-carbon unsaturated bond; further, one or more of R ²¹ to R ²⁶ is an aryl group; R ²⁷ represents a divalent hydrocarbon group; and r and s each represent an integer of 1 or more].

Further, the present invention provides a curable resin composition as described above, which further comprises a decane coupling agent (C).

Moreover, the present invention provides the curable resin composition as described above, wherein the sesquiterpene oxide (D) system contains a ladder type sesquiterpene alkane.

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

Moreover, the present invention provides a sealing material obtained by using the curable resin composition described above.

Moreover, the present invention provides a semiconductor device obtained by using the above-described sealing material.

Further, the curable resin composition of the present invention is as follows turn off.

[1] A curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B), and a curable resin composition of a zinc compound (E), which is characterized by: The polyorganosiloxane (A) is a polyorganosiloxane having an aryl group, and may further contain a sesquioxane (D), and the content of the zinc compound (E) is relative to the polyorganosiloxane (A). And the total amount (100 parts by weight) of the sesquioxane (D) is 0.01 parts by weight or more and less than 0.1 parts by weight.

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

[3] The curable resin composition according to [1] or [2] wherein the polyorganosiloxane (A) comprises a structure represented by the formula (6) (particularly, R ²⁷ is a carbon number of 1 to 5). A linear or branched chain alkyl group is preferred, and a polyethyl oxane of an ethyl group is more preferred.

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

[5] The curable resin composition according to [3] or [4], wherein the total amount (total content, 100% by weight) of the polyorganosiloxane (A) is contained in the structure represented by the formula (6) ( In particular, R ²⁷ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably an ethyl group having a polyorganosiloxane having a ratio of 60 to 100% by weight.

[6] The curable resin composition according to any one of [3] to [5] wherein polyorganosiloxane having an aliphatic carbon-carbon double bond and having an aryl group is used as the polyorganosiloxane (A) Alkoxyalkylalkylene, with aliphatic Two kinds of polyorganophosphonylalkylene alkylenes having a carbon-carbon double bond and a Si-H bond and having an aryl group.

[7] The curable resin composition according to any one of [1] to [6] wherein the isocyanurate compound (C) contains the isomeric cyanurate represented by the formula (1) a compound; [in the formula (1), R ^x , R ^y , and R ^z may be the same or different, and represent a group represented by the formula (2) or a group represented by the formula (3); [formula (2) and formula In (3), R ¹ and R ² may be the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]

[8] The curable resin composition according to any one of [1] to [7] wherein the isocyanurate compound (B) is monoallyl digoxypropyl isomeric cyanurate .

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

[10] The curable resin composition according to any one of [1] to [9] wherein the ratio of the isocyanurate compound (B) is relative to the polyorganosiloxane (A) and the half The total amount (100 parts by weight) of the decane (D) is 0.01 to 0.5 parts by weight.

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

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

[13] The curable resin composition according to any one of [1] to [12] wherein a sesquioxane (D) is contained.

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

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

[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 octoate.

[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 based on the total amount (100% by weight) of the curable resin composition. weight%.

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

Since the curable resin composition of the present invention has the above-described configuration, it is possible to form a cured product having excellent heat resistance and transparency. In particular, the cured product is excellent in barrier properties against various corrosive gases such as H ₂ S gas or SO _X gas. Further, the obtained cured product may have good flexibility or reflow resistance. Therefore, the curable resin composition of the present invention can be used particularly as a sealing material for a semiconductor element (for example, an LED element, a semiconductor laser element, a solar power generation element, a CCD element, etc.), and is composed of the curable resin of the present invention. The optical semiconductor device obtained by sealing the optical semiconductor element with the cured material 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 which requires heat resistance at a high temperature (for example, 180 ° C or higher) which has not been hitherto.

100‧‧‧Reflector (resin composition for light reflection)

101‧‧‧Metal wiring

102‧‧‧Optical semiconductor components

103‧‧‧bonding wire

104‧‧‧ hardened material (sealing material)

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

[Formation of the Invention]

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) is a polyorganosiloxane having an aryl group, and may further contain a sesquioxane (D), and the content of the zinc compound (E) is relative to the polyorganooxane (A) and sesquiterpene The total amount (100 parts by weight) of the oxyalkylene (D) is 0.01 parts by weight or more and less than 0.1 parts by weight.

[polyorganooxane (A)]

The polyorganosiloxane (A) of the curable resin composition of the present invention is a polyorganosiloxane having a main chain composed of a siloxane chain (Si-O-Si), and has an aryl group as the aforementioned A polyorganosiloxane having a substituent of the main chain. The polyorganosiloxane (A) may also be a linear or branched polyorganosiloxane containing a hydroquinone group or a group having an aliphatic carbon-carbon unsaturated bond. Examples of the polyorganosiloxane (A) include a phenyl fluorenone skeleton (polydiphenyl siloxane) and a phenyl methyl fluorenone skeleton (polymethyl phenyl siloxane). A well-known fluorenone skeleton. Further, in the polyorganosiloxane (A), sesquioxane (D) is not contained.

The polyorganosiloxane (A) may also be a polyorganosiloxane having a linear chain and/or a branched chain. Among them, from the viewpoint of the strength of the cured product, a polyorganosiloxane (branched polyorganosiloxane) having a branched chain is preferred.

The aryl group of the polyorganosiloxane (A) is not particularly limited, and examples thereof include a C _6-14 aryl (particularly a C _6-10 aryl) group such as a phenyl group or a naphthyl group. The aryl group may also be a substituent possessed by a ruthenium atom of the polyorganosiloxane (A) (a group directly bonded to a ruthenium atom).

The aryl group of the polyorganosiloxane (A) may have one or more substituents. 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, a decyloxy group, a decyl group (thiol group), and an alkyl sulfide. Alkyl, arylthio, arylthio, aralkylthio, carboxy, alkoxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, amine or substituted amine (mono or dialkylamino, guanylamino, etc.), An epoxy group, a cyano group, an isocyanate group, an amine formazan group, an isothiocyanate group or 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 bond of two or more kinds.

The aliphatic hydrocarbon group may, for example, be an alkyl group, an alkenyl group or an alkynyl group. The alkyl group may, for example, be a C _1-20 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group or a dodecyl group. Preferably, it is a C _1-10 alkyl group, more preferably a C _1-4 alkyl group). 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, and 1 a C _2-20 alkenyl group having a pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 5-hexenyl group or the like (preferably a C _2-10 alkenyl group, more preferably C _2-4 alkenyl) and the like. The alkynyl group may, for example, be a C _2-20 alkynyl group such as an ethynyl group or a propynyl group (preferably a C _2-10 alkynyl group, more preferably a C _2-4 alkynyl group).

Examples of the alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cyclododecyl group; and a C ₃ such as a cyclohexenyl group; a cycloalkenyl group of _-12 ; a C _4-15 crosslinked cyclic hydrocarbon group such as a bicycloheptyl group or a bicycloheptenyl group; and the like.

The aromatic hydrocarbon group may, for example, be a C _6-14 aryl group (particularly, a C _6-10 aryl group) such as a phenyl group or a naphthyl group.

In addition, examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded to each other include a cyclohexylmethyl group and a methylcyclohexyl group. In addition, examples of the group in which the aliphatic hydrocarbon group is bonded to the aromatic hydrocarbon group include a C _7-18 aralkyl group such as a benzyl group or a phenethyl group (particularly a C _7-10 aralkyl group). , cinnamyl, etc. C _6-10 aryl -C _2-6 alkenyl group, a tolyl group, etc. C _1-4 alkyl substituted aryl group, a styryl group, etc. C _2-4 alkenyl group substituted with an aryl group. The substituent which the above-mentioned substituted aryl group (substituted hydrocarbon group) has may be, for example, the same as the substituent which the aryl group may have.

In addition, as the aryl group of the polyorganosiloxane (A), one or more substituents may be mentioned, and a group represented by the formula (4) may be mentioned as another example.

The plurality of R ' in the formula (4) may be the same or different. R ' in the formula (4) may, for example, be 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, a decyloxy group or a fluorenyl group ( Thiol group), alkylthio group, alkenylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amine group or substituted amine group (mono or dialkylamino group) , amidino group, etc.), an epoxy group, a cyano group, an isocyanate group, an amine formazan group, an isothiocyanate group, and the like.

In the group represented by the formula (4), each R ' is each a hydrogen atom, a C _1-10 alkyl group (particularly a C _1-4 alkyl group), a C _2-10 alkenyl group (particularly C _{2 ). -4} alkenyl), C _3-12 cycloalkyl, C _3-12 cycloalkenyl, may have C _1-4 alkyl, C _2-4 alkenyl, halogen atom, C _1-4 alkoxy in the aromatic ring A C _6-14 aryl group, a C _7-18 aralkyl group, a C _6-10 aryl-C _2-6 alkenyl group, a hydroxyl group, a C _1-6 alkoxy group or a halogen atom of a substituent such as a group is preferable.

The content of the total amount (100% by weight) of the aryl group (in terms of phenyl group) 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 most preferably 44% by weight or more. When the content of the aryl group is less than 35% by weight, the obtained cured product may have a low barrier property against a corrosive gas. Further, all of the substituents of the main chain composed of the siloxane chain (Si-O-Si) of the polyorganosiloxane (A) may be an aryl group, or one of the substituents may be an aryl group. Further, the content of the aryl group can be measured, for example, by ¹ H-NMR or the like.

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

The polyorganosiloxane (A) has a number average molecular weight (Mn) of preferably from 500 to 4,000, more preferably from 550 to 2,800, and particularly preferably from 600 to 1,500. also, The weight average molecular weight (Mw) is preferably from 500 to 20,000, more preferably from 600 to 10,000, and particularly 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 obtained 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 is lowered, or a polyorganosiloxane (A) is combined. When two or more types are used, the compatibility of the polyorganosiloxanes may be lowered. Further, the polyorganosiloxane (A) may be a mixture of various number average molecular weights (Mn) and/or weight average molecular weights (Mw) having the above-mentioned ranges. Further, the number average molecular weight (Mn) and/or the weight average molecular weight (Mw) can be calculated, for example, as a polystyrene-converted molecular weight by gel permeation chromatography.

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

The content of the polyorganosiloxane (A) of the curable resin composition of the present invention (the total amount of the compounding amount when two or more kinds are used) is not particularly limited, and the total amount of the curable resin composition (100) The weight %) is preferably 55 to 99.5% by weight, more preferably 70 to 99.0% by weight, and particularly preferably 85 to 98.5% by weight. When the content is less than 55% by weight, the crack resistance of the obtained cured product may be lowered. On the other hand, when the content exceeds 99.5% by weight, the barrier properties of the obtained cured product with respect to the corrosive gas may be lowered.

The polyorganosiloxane (A) may have a substituent other than the aryl group, and the substituent other than the aryl group may be a substituent of a ruthenium atom of the polyorganosiloxane (A). Examples of the substituent other than the above 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). ), hydroxy, alkoxy, alkenyloxy, decyloxy, decyl (thiol), alkylthio, alkylthio, carboxy, alkoxycarbonyl, amine or substituted amine (mono or dialkylamino) , amidino group, etc.), an epoxy group, a cyano group, an isocyanate group, an amine formazan group, an isothiocyanate group, and the like.

The substituent other than the aforementioned aryl group of the polyorganosiloxane (A) is selected from a hydrogen atom, a group having a Si-H bond (hydroalkylene group, etc.), a substituted or unsubstituted hydrocarbon group (preferably an alkyl group). At least one or more substituents of a group having an aliphatic carbon-carbon double bond (alkenyl group or the like) are particularly preferred. The polyorganosiloxane (A) may, for example, be a polyorganosiloxane containing an aryl group and a group having an aliphatic carbon-carbon double bond; a polyorganoquinone containing an aryl group and a group having a Si-H bond; An oxane; a polyorganosiloxane containing an aryl group, a group having an aliphatic carbon-carbon double bond, and a group having a Si-H bond.

The polyorganosiloxane (A) is, for example, a polyorganosiloxane containing 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 "polyorganophosphonylalkylene alkylene".

In the formula (6), R ²¹ to R ²⁶ may be the same or different and each represent a hydrogen atom, the above aryl group, a substituent other than the above aryl group, a monovalent hydrocarbon group, or a monovalent heterocyclic group. However, one or more of R ²¹ to R ²⁶ are monovalent groups containing an aliphatic carbon-carbon unsaturated bond. Further, it is preferable that all of R ²¹ to R ²⁶ are monovalent groups containing an aliphatic carbon-carbon unsaturated bond. Further, at least one of R ²¹ to R ²⁶ is preferably an aryl group (a 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). Further, the aryl group of R ²¹ to R ²⁶ may have one or more substituents. The substituent of the aryl group of R ²¹ to R ²⁶ may be the same as the substituent of the aryl group of the polyorganosiloxane (A).

Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group; a monovalent alicyclic hydrocarbon group; a monovalent aromatic hydrocarbon group; and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. One price base and so on. Examples of the monovalent heterocyclic group include a pyridyl group, a furyl group, a thienyl group and the like.

The monovalent aliphatic hydrocarbon group may, for example, be an alkyl group, an alkenyl group or an alkynyl group. The alkyl group may, for example, be a linear or branched chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group or a dodecyl group. A C _1-20 alkyl group (preferably a C _1-10 alkyl group, more preferably a C _1-4 alkyl group) or the like. 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, and a 3-butenyl group. C _2-20 alkenyl group (preferably C _2-10 alkenyl group), preferably 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-hexenyl or the like Is C _2-4 alkenyl) and the like. The alkynyl group may, for example, be a C _2-20 alkynyl group such as an ethynyl group or a propynyl group (preferably a C _2-10 alkynyl group, more preferably a 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 or a cyclododecyl group; a cyclohexenyl group; a C _4-12 cycloalkenyl group; a C _4-15 crosslinked cyclic hydrocarbon group such as a bicycloheptyl group or a bicycloheptenyl group; and the like.

The monovalent aromatic hydrocarbon group may, for example, be a C _6-14 aryl group (particularly a C _6-10 aryl group) such as a phenyl group, a naphthyl group or a fluorenyl group.

In addition, 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. Examples of the group bonded to the aromatic hydrocarbon group and the aromatic hydrocarbon group include a C _7-18 aralkyl group (particularly a C _7-10 aralkyl group) such as a benzyl group or a phenethyl group, and a C ₆ such as a cinnamyl group. _a C _2-4 alkenyl-substituted aryl group such as a C _1-4 alkyl group-substituted aryl group such as _-10 aryl-C _2-6 alkenyl group or a tolyl group;

The aforementioned monovalent hydrocarbon group may have a substituent. That is, the monovalent hydrocarbon group may be substituted with at least one hydrogen atom of the monovalent hydrocarbon group listed above as a one-valent hydrocarbon group of the substituent. The carbon number of the above substituent is preferably from 0 to 20, more preferably from 0 to 10. 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; a decyloxy group; an anthracenyl group; an alkylthio group; Arylthio; arylalkylthio; carboxy; alkoxycarbonyl; aryloxycarbonyl; aralkyloxycarbonyl; amine; mono or dialkylamino; mono or diphenylamino; decylamino; A group containing an oxetane group; a fluorenyl group; a pendant oxy group; an isocyanate group; and two or more groups which are bonded via a C _1-6 alkyl group as needed.

The alkoxy group may, for example, be a C _1-6 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group (preferably C). _1-4 alkoxy) and the like. The above-mentioned alkenyloxy group may, for example, be a C _2-6 alkenyloxy group (preferably a C _2-4 alkenyloxy group) such as an allyloxy group. The aryloxy group may, for example, be a phenoxy group, a tolyloxy group or a naphthyloxy group, and may have a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom or a C _1-4 in the aromatic ring. A C _6-14 aryloxy group or the like which is a substituent of an alkoxy group or the like. Examples of the aralkyloxy group include a C _7-18 aralkyloxy group such as a benzyloxy group or a phenethyloxy group. Examples of the above-mentioned decyloxy group include a C _1-12 decyloxy group such as an ethoxycarbonyl group, a propyl decyloxy group, a (meth) acryloxy group, or a benzyl methoxy group.

The alkylthio group may, for example, be a C _1-6 alkylthio group such as a methylthio group or an ethylthio group (preferably a C _1-4 alkylthio group). The above-mentioned olefinyl group may, for example, be a C _2-6 olefinyl group (preferably a C _2-4 olefinyl group) such as an allylthio group. The arylthio group may, for example, be a phenylthio group, a tolylthio group or a naphthylthio group, and may have a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, or a C _1-4 in the aromatic ring. A C _6-14 arylthio group or the like of a substituent such as an alkoxy group. Examples of the aralkylthio group include a C _7-18 aralkylthio group such as a phenylmethylthio group or a phenethylthio group. The alkoxycarbonyl group may, for example, be a C _1-6 alkoxy-carbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group or a butoxycarbonyl group. Examples of the aryloxycarbonyl group include a C _6-14 aryloxy-carbonyl group such as a phenoxycarbonyl group, a tolyloxycarbonyl group or a naphthyloxycarbonyl group. The aralkyloxycarbonyl group may, for example, be a C _7-18 aralkyloxy-carbonyl group such as a benzyloxycarbonyl group. The mono- or dialkylamino group may, for example, be a mono- or di-C _1-6 alkylamino group such as a methylamino group, an ethylamino group, a dimethylamino group or a diethylamino group. Examples of the guanamine group include a C _1-11 guanamine group such as an acetamino group, a acrylamide group, or a benzylamino group. Examples of the epoxy group-containing group include a glycidyl group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. The oxetane group-containing group may, for example, be an ethyloxetaneoxy group or the like. Examples of the thiol group include an ethyl fluorenyl group, a propyl fluorenyl group, and a benzamidine group. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

The above monovalent heterocyclic group may have a substituent. The substituent may be the same as the substituent which the above-mentioned monovalent hydrocarbon group may have.

Specific examples of the monovalent hydrocarbon group and the monovalent heterocyclic group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and a phenyl group. Naphthyl, anthracenyl, benzyl, phenethyl, pyridyl, furyl, thienyl, vinyl, allyl, styryl (eg, p-styryl), substituted hydrocarbyl (eg , 2-(3,4-epoxycyclohexyl)ethyl, 3-epoxypropylpropyl, 3-methylpropenyloxypropyl, 3-propenyloxypropyl, N-2-(amine B ))-3-aminopropyl, 3-aminopropyl, N-phenyl-3-aminopropyl, 3-mercaptopropyl, 3-isocyanatepropyl, 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 hydrocarbon group include a linear or branched alkyl group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Examples of the linear alkyl group or the branched alkyl group include a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group, and a trimethylene group. It is a linear or branched chain alkyl group of 1 to 18. The divalent alicyclic hydrocarbon group may, for example, be a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-cyclohexylene group, or a 1,3-extension ring. A divalent cycloalkylene group (including a cycloalkylene group) of a hexyl group, a 1,4-cyclohexylene group, a cyclohexylene group or the like. 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'-linked phenyl group, an extended naphthyl group, and the like. . Among them, as R ²⁷ , a linear or branched alkyl group having 1 to 8 carbon atoms (particularly, a carbon number of 1 to 5) is preferred, and an ethyl group is more preferred.

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

The terminal structure of the polyorganophosphonylalkylene alkylene is not particularly limited, and examples thereof include a decyl alcohol group, an alkoxyalkyl group, and a trialkylalkyl group (for example, trimethyl fluorenyl group). At the terminal of the polyorganophosphonylalkylene alkylene, various groups including an aliphatic carbon-carbon double bond group or a hydroalkylene group may be introduced.

The polyorganophosphonylalkylene alkylene may be a chain structure having either a linear chain or a branched chain as described above. As The above polyorganophosphonylalkylene alkylene, for example, a polyorganophosphonylalkylene alkylene having a branched chain and having an aryl group is preferred.

For example, GD-1130A (manufactured by Changxing Chemical Industry Co., Ltd.), GD-1130B (manufactured by Changxing Chemical Industry Co., Ltd.), and the like can be given as the polyorganophosphonylalkylene alkylene.

As the polyorganosiloxane (A), two or more (particularly two) of the above polyorganophosphonylalkylene alkylenes are preferably used. Among them, from the viewpoint of barrier property against a corrosive gas, a polyorganophosphonium alkylene alkylene having a group having an aliphatic carbon-carbon double bond and having an aryl group is used, and contains an aliphatic carbon-carbon double Two types of a bond group, a group having a Si-H bond, and a polyorganooxyalkylalkylalkylene group having an aryl group are preferred.

When the polyorganosiloxane (A) is used in two or more kinds, the total amount (100% by weight) of the polyorganooxyalkylene alkylene of the polyorganosiloxane (A) of the curable resin composition of the present invention is 100% by weight. The ratio is not particularly limited, but 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 particularly preferably 90% by weight or more. When the proportion of the polyorganooxyalkylalkylalkylene is less than 60% by weight, the cured product tends to be yellowish, and the surface tends to have a tendency to be lowered in adhesion.

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

The curable resin composition of the present invention may further comprise a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond (in the present specification, it may be simply referred to as "polyorganosiloxane (A1)"). As polyorganosiloxane (A). Any one of the partial structures and/or constituent components constituting the polyorganosiloxane (A1) may have the aforementioned aliphatic carbon-carbon double bond. Polyorgano-oxygen The substituent of the alkane (A1) (for example, a substituent possessed by a ruthenium atom) has the aforementioned aliphatic carbon-carbon double bond. Further, the aliphatic carbon-carbon double bond may be present in a main chain (straight chain and/or branched chain) composed of a decane bond (Si-O-Si) of a polyorganosiloxane (A1). End.

Examples of the group having an aliphatic carbon-carbon double bond include a vinyl group, an allyl group, a methallyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, and a 2-butene group. a C _2-20 alkenyl group (preferably C, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-hexenyl, etc.) _C2-10 alkenyl, more preferably C _2-4 alkenyl); cyclohexenyl, etc. the C _3-12 cycloalkenyl; bicyclic heptenyl group of crosslinking _{a 4-15} C cyclic unsaturated hydrocarbon group; a C _2-4 alkenyl group substituted with an aryl group or the like; a cinnamyl group or the like. Further, in the foregoing having aliphatic carbon - carbon double bonds, in the group represented by formula (4) it was also included three R 'is at least one of the aforementioned C _2-20 alkenyl group, a group of a C _3-12 cycloalkenyl group, a C _4-15 crosslinked cyclic unsaturated hydrocarbon group, a C _2-4 alkenyl substituted aryl group, a cinnamyl group or the like. Among them, an alkenyl group is preferred, and a C _2-20 alkenyl group is more preferred, and a vinyl group is particularly preferred.

The content of the aliphatic carbon-carbon double bond (vinyl equivalent) of the total amount (100% by weight) of the polyorganosiloxane (A) is not particularly limited, but is preferably 1.5 to 15.0% by weight, 2.0~. More preferably, it is 13.0% by weight, and particularly preferably 3.0 to 12.0% by weight. By having the aliphatic carbon-carbon double bond in the above range, it is easy to obtain a cured product having various physical properties such as heat resistance of the obtained cured product, crack resistance, and barrier property against a corrosive gas. Further, the content of the aliphatic carbon-carbon double bond can be measured, for example, by ¹ H-NMR or the like.

[Polyorganosiloxane (A2) having Si-H bond]

The curable resin composition of the present invention may further comprise a polyorganosiloxane (A2) having a Si-H bond (in the present specification, sometimes referred to as "polyorganosiloxane (A2)") as a polyorganic organic compound. Oxane (A). Any one of the partial structures and/or constituent components constituting the polyorganosiloxane (A2) may have the aforementioned Si-H bond. Further, a substituent of the polyorganosiloxane (A2) (for example, a substituent possessed by a ruthenium atom) may have the aforementioned Si-H bond. Further, the Si-H bond may be present at the end of a main chain (straight chain and/or branched chain) composed of a decane bond (Si-O-Si) of a polyorganosiloxane (A2).

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

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

The content of the polyorganosiloxane (A2) based on the total amount (total content, 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. good. By containing the polyorganosiloxane (A2) in the above range, it is easy to obtain a cured product having various physical properties such as heat resistance of the obtained cured product, crack resistance, and barrier property against a corrosive gas.

The ratio of the aliphatic carbon-carbon double bond of the polyorganosiloxane (A) (vinyl equivalent) a1 (mol/g) to the content of the Si-H bond (in terms of H) a2 (mol/g) a1/ A2 is preferably 0.80~1.10, 0.90~1.05 is better, and 0.95~1.00 is especially good. By making a1/a2 1.10 or less, the barrier property with respect to a corrosive gas can be improved especially. Further, by setting a1/a2 to 0.80 or more, the strength such as crack resistance can be particularly improved.

Furthermore, the polyorganosiloxane (A1) may be a polyorganosiloxane (A2) having a Si-H bond, or the polyorganosiloxane (A2) may also have an aliphatic carbon-carbon double Key polyorganooxane (A1).

Further, the polyorganosiloxane (A) may be constituted by only one of polyorganosiloxane (A1) or polyorganosiloxane (A2), or the polyorganosiloxane (A) may be mutually It is composed of two or more kinds of polyorganosiloxane (A1) and/or polyorganosiloxane (A2).

Further, when the polyorganosiloxane (A) is composed of two or more kinds of polyorganosiloxanes different from each other, at least one of the two or more polyorganosiloxanes is a polyorganosiloxane (A2). In the case of the polyorganosiloxane (A2), it is preferred to use the polyorganosiloxane (A1).

[Iso-cyanurate compound (B)]

The curable resin composition of the present invention contains the isomeric cyanurate compound (B). The curable resin composition of the present invention, by containing the isomeric cyanurate compound (B), particularly the cured product formed by hardening, has an improved barrier property against corrosive gas, and further, for the covering body The adhesion will increase. Among them, the isomeric isocyanate compound (B) preferably contains an isomeric cyanurate compound represented by the formula (1). In particular, isomeric cyanurate The compound (B) is preferably only an isomeric cyanurate compound represented by the formula (1).

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

In the formulae (2) and (3), R ¹ and R ² may be 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 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 second butyl group, and a pentyl group. , hexyl, heptyl, octyl, ethylhexyl and the like. Among the alkyl groups, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferable. It is particularly preferable that each of R ¹ and R ^{2 in the} formula (2) and the formula (3) is a hydrogen atom.

The heteropolycyanate compound (B) is not particularly limited, and examples thereof include monoallyldimethylisophthalocyanate and diallyl monomethylisocyanate. , triallyl isocyanurate, monoallyl propylene oxide isopropyl isocyanate, diallyl monoepoxy propyl isocyanurate, trisepoxypropyl Cyanurate, 1-allyl-3,5-bis(2-methylepoxypropyl)isocyanate, 1-(2-methylpropenyl)-3,5-di Epoxypropyl iso-isocyanate, 1-(2-methylpropenyl)-3,5-bis(2-methylepoxypropyl)isocyanate, 1,3-dienes Propyl-5-(2-methylepoxypropyl)isocyanate, 1,3-bis(2-methylpropenyl)-5-epoxypropyl isocyanate, 1 , 3-bis(2-methacryl)-5-(2-methylepoxypropyl)isocyanate, ginseng (2-methacryl)isomeric cyanurate, and the like. Monoallyl epoxypropyl isotrimer Cyanate esters are preferred. In addition, the above-mentioned isocyanurate compound (B) may be used alone or in combination of two or more.

From the viewpoint of improving the compatibility with other components, the isomeric cyanurate compound (B) may be previously mixed with a decane coupling agent and then blended with other components as will be described later.

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, based on the total amount (100% by weight) of the curable resin composition. 0.1 to 3 wt% is optimal. When the content of the isocyanurate compound (B) is less than 0.01% by weight, the barrier property of the cured product with respect to the corrosive gas and the adhesion to the coating body may be lowered. On the other hand, when the content of the isocyanurate compound (B) exceeds 10% by weight, solids may be precipitated in the curable resin composition, and the cured product may be cloudy. The ratio of the above heteropolycyanate compound (B) is not particularly limited, but from the viewpoint of the barrier property of the cured product with respect to the corrosive gas, for example, with respect to the polyorganosiloxane (A) and the sesquiterpene The total amount (100 parts by weight) of the oxyalkylene (D) is preferably 0.01 to 0.5 part by weight.

[decane coupling agent (C)]

The curable resin composition of the present invention may further contain a decane coupling agent (C). When the curable resin composition of the present invention contains the decane coupling agent (C), the barrier property of the cured product with respect to the corrosive gas is further improved, and in particular, the adhesion to the coating body is improved.

The compatibility of the decane coupling agent (C) with the polyorganosiloxane (A) and the isocyanurate compound (B) is good, and thus, for example, for the purpose of enhancing the relative isocyanate compound (B) Compatibility of other ingredients, It is premised that the composition of the isomeric cyanurate compound (B) and the decane coupling agent (C) is formed in advance, and when it is blended with other components, a uniform curable resin composition is easily obtained.

As the decane coupling agent (C), a known or even a conventional decane coupling agent can be used, and is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxydecane and 2-(3,4-ring). Epoxy-containing decane such as oxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, etc. Coupling agent; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2- (Amineethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-( 1,3-Dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-amineethyl-3-aminepropyltrimethyl An amine group-containing decane coupling agent such as oxydecane hydrochloride or N-(β-aminoethyl)-γ-aminopropylmethyldiethoxy decane; tetramethoxy decane, tetraethoxy矽, methyl triethoxy decane, dimethyl diethoxy decane, methyl triethoxy decane, vinyl triethoxy decane, vinyl three Oxydecane, vinyl ginseng (methoxyethoxy decane), phenyl trimethoxy decane, diphenyl dimethoxy decane, vinyl triethoxy decane, γ-(methyl) propylene oxime Oxypropyl triethoxy decane, γ-(meth) propylene oxypropyl trimethoxy decane, γ-(methyl) propylene methoxypropyl methyl dimethoxy decane, γ-(methyl) Propylene oxime propyl methyl diethoxy decane, decyl propyl trimethoxy decane, decyl propyl triethoxy decane, and the like. Among them, a decane coupling agent containing an epoxy group (particularly 3-glycidoxypropyltrimethoxydecane) can be suitably used. Furthermore, the foregoing The decane coupling agent (C) may be used alone or in combination of two or more.

The content of the decane coupling agent (C) is not particularly limited, but is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, and preferably 0.5 to 5 parts by weight based on the total amount (100% by weight) of the curable resin composition. % is particularly good. When the content of the decane coupling agent (C) is less than 0.01% by weight, the adhesion to the coating body is lowered, and in particular, it is not sufficiently obtained when it is used in combination with the isocyanurate compound (B). The effect (for example, the barrier property of a hardened substance with respect to a corrosive gas, etc.). On the other hand, when the content of the decane coupling agent exceeds 15% by weight, the curing is insufficient, and the toughness, heat resistance, and barrier property against the corrosive gas of the cured product are both lowered.

[sesquioxane (D)]

The curable resin composition of the present invention may further contain sesquiterpene oxide (D). The sesquioxane (D) is not particularly limited, and examples thereof include a sesquioxane having a random structure, a cage structure, and a ladder structure, and a sesquiterpene having a ladder structure is used. The sesquioxanes of the main component are preferred. The sesquiterpene oxide (D) preferably contains ladder type sesquiterpene oxide as a main component. Among them, the sesquioxane (D) is more preferably a ladder type sesquioxane.

The sesquioxane is one of polyoxyalkylenes. The polyoxyalkylene is generally a compound having a main chain composed of a siloxane chain (Si-O-Si), and as its basic constituent unit, an M unit (including a ruthenium atom bonded to one oxygen atom) a unit of a valence group, a unit D (a unit containing a divalent group in which a deuterium atom is bonded to two oxygen atoms), a T unit (a unit containing a trivalent group in which a deuterium atom is bonded to three oxygen atoms), and a Q unit. (contains a helium atom bonded to 4 oxygen atoms) The 4 valence unit).

The sesquiterpene oxide (D) is a polydecane which has the above T unit as a basic constituent unit, and its experimental formula (basic structural formula) is represented by RSiO _1.5 . Examples of the structure of the Si-O-Si skeleton of sesquioxane include a random structure, a cage structure, and a ladder structure, and a ladder type sesquiterpene oxide-based Si-O-Si skeleton having a ladder structure. The structure of sesquiterpene oxide.

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

When the curable resin composition of the present invention contains sesquiterpene oxide (D), particularly, the cured product formed by hardening is improved in barrier property against corrosive gas, and has high toughness (especially crack resistance). Propensity. The content (doping amount) of the sesquiterpene oxide (D) of the curable resin composition of the present invention is not particularly limited, but is 0.01 to 30 by weight based on the total amount (100% by weight) of the curable resin composition. % is more preferable, 0.1 to 20% by weight is more preferable, and 0.5 to 10% by weight is particularly preferable.

[Zinc compound (E)]

The curable resin composition of the present invention contains a zinc compound (E). The curable resin composition of the present invention tends to have a higher barrier property against H ₂ S gas by including the zinc compound (E).

The zinc compound (E) is not particularly limited, and examples thereof include a compound or a metal salt containing zinc. For example, Zinc diketone complex of zinc acetoacetate, bis(octane-2,4-dione)zinc or zinc naphthenate, zinc octoate, zinc acetate, zinc (meth)acrylate An inorganic zinc compound represented by a zinc carboxylate such as zinc neodecanoate or a zinc oxide represented by zinc oxide or zinc stannate, or a mixture thereof. Among them, zinc carboxylate is preferred, and zinc naphthenate and zinc octoate are particularly preferred. The zinc compound (E) preferably contains at least zinc carboxylate (particularly zinc naphthenate or zinc octoate). Among them, the zinc compound (E) is more preferably only a zinc carboxylate (particularly zinc naphthenate or zinc octoate).

The zinc compound (E) is not particularly limited, but is preferably 2 to 30% by weight, based on the total weight (100% by weight) of the zinc compound, from the viewpoint of the barrier property against the corrosive gas. Preferably, it is 5 to 20% by weight, and particularly preferably 6 to 17% by weight.

The content of the zinc compound (E) is not particularly limited, but is a total amount (100 parts by weight) based on the polyorganosiloxane (A) and the sesquioxane (D) (excluding sesquiterpene). In the case of the oxyalkylene (D), the polyorganosiloxane (A) is preferably 0.01 parts by weight or more and less than 0.1 parts by weight, 0.03 parts by weight or more and less than 0.1 parts by weight, more preferably 0.05 parts by weight or more and less than 0.1 parts by weight. 0.07 parts by weight or more and less than 0.1 parts by weight is particularly preferred. When 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, when the content of the zinc compound (E) is 0.1 part by weight or more, the barrier property against the SO _X gas may be lowered.

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

[hydrogenated catalyzed catalyst]

The curable resin composition of the present invention may further contain a hydroquinone catalyst. The curable resin composition of the present invention can efficiently carry out a hardening reaction (hydrogenation reaction) by including a hydroquinone catalyst. As the hydrohaloalkylation catalyst, a known catalyst for hydroquinonelation reaction such as a platinum-based catalyst, a rhodium-based catalyst, or a palladium-based catalyst can be listed. Specific examples thereof include platinum fine powder, platinum black, platinum-supporting cerium oxide micropowder, platinum-carrying activated carbon, chloroplatinic acid, chloroplatinic acid, and alcohol, aldehyde, ketone, and the like. Platinum carbonyl complex of platinum, olefin olefin complex, platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldioxane complex or platinum-cyclovinyl a platinum-based catalyst such as a platinum-vinyl oxane complex, a platinum-phosphine complex, a platinum-phosphite complex, or the like, and a platinum-based catalyst as described above. A palladium-based catalyst or a ruthenium-based catalyst containing a palladium atom or a ruthenium atom in place of a platinum atom. In addition, the hydrohalogenated catalyst may be used singly or in combination of two or more.

The content of the hydrohalogenation catalyst in the curable resin composition of the present invention is not particularly limited. For example, in the hydroquinone catalyst, platinum, palladium or rhodium is a weight unit and is in the range of 0.01 to 1,000 ppm. The amount is preferably in a range of from 0.1 to 500 ppm. When the content of the hydroquinone catalyst is within the above range, the crosslinking rate is not remarkably slowed, and the cured product is less likely to cause problems such as coloring, which is preferable.

[hydrogenation reaction inhibitor]

The curable resin composition of the present invention is used to adjust the hardening reaction ( The rate of the hydroquinonelation reaction may also include a hydroquinone reaction inhibitor. Examples of the hydrohaloalkylation reaction inhibitor include 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol. Alkenynyl; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene-1-yne and the like; alkyne, benzothiazole, benzotriene Oxazole and the like. The hydrohaloalkylation reaction inhibitor may be used singly or in combination of two or more. The content of the hydroquinonelation reaction inhibitor varies depending on the crosslinking conditions of the curable resin composition, but it is preferably in the range of 0.00001 to 5% by weight in the curable resin composition.

[Other alkoxylate compounds]

The curable resin composition of the present invention may further contain a cyclic oxirane having two or more aliphatic carbon-carbon double bonds in a molecule (in one molecule) as another oxoxane compound. Further, 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 one molecule (in one molecule) as another siloxane compound. The above-mentioned cyclic oxime may be used singly or in combination of two or more. The content (mixing amount) of the cyclic oxirane of the curable resin composition of the present invention is not particularly limited, but is preferably 0.01 to 30% by weight based on the total amount (100% by weight) of the curable resin composition. 0.1 to 20% by weight is more preferably 0.5 to 10% by weight.

[Other decane compounds]

The curable resin composition of the present invention may further contain another decane compound (for example, a compound having a hydrofluorenyl group). As the other decane compound, for example, a methyl group (dimethyl dimethyl decyloxy group) may be mentioned. 矽, 肆 (dimethyl decyloxy) decane, 1,1,3,3-tetramethyldioxane, 1,1,3,3,5,5-hexamethyltrioxane, 1 1,1,3,5,5,5-heptamethyltrioxane, 1,1,3,3,5,5,7,7-octamethyltetraoxane, 1,1,1 ,3,5,5,7,7,7-nonamethyltetraoxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentaoxane, 1 A linear or branched chain oxirane having a Si-H group such as 1,1,3,5,5,7,7,9,9,9-undecylpentaoxane or the like. In addition, the decane compound may be used alone or in combination of two or more. The content of the decane compound is not particularly limited, but is preferably 0 to 5% by weight or less, more preferably 0 to 1.5% by weight based on the total amount (100% by weight) of the curable resin composition.

[Solvent]

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

[additive]

The curable resin composition of the present invention may further comprise precipitated cerium oxide, wet cerium oxide, fumed silica, calcined cerium oxide, titanium oxide, aluminum oxide, glass, quartz, aluminosilicate. Inorganic fillers such as iron oxide, zinc oxide, calcium carbonate, carbon black, tantalum carbide, tantalum nitride, boron nitride, etc., and organic fillers, organohaloxanes, organic decazins An inorganic filler which is treated with an organic hydrazine compound; an organic resin fine powder such as an anthrone resin, an epoxy resin or a fluororesin; a filler such as a conductive metal powder such as silver or copper; Anti-setting agent (antioxidant, UV absorber, light stabilizer, thermal stabilizer, etc.), flame retardant (phosphorus flame retardant, halogen flame retardant, inorganic flame retardant, etc.), flame retardant Reinforcing materials (other fillers, etc.), crystal nucleating agents, coupling agents, slip agents, waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, fluidity improvers, colorants (dyes, A conventional additive such as a pigment, a dispersant, an antifoaming agent, a defoaming agent, an antibacterial agent, a preservative, a viscosity adjuster, and a tackifier is used as the other optional component. 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, and is a composition of 0.2 to 4 moles with respect to the hydroquinone 1 molar which is present in the curable resin composition, such as an aliphatic carbon-carbon double bond. The composition is preferably, more preferably 0.5 to 1.5 m, and most preferably 0.8 to 1.2 m. By controlling the ratio of the hydroquinone alkyl group to the 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. tendency.

The curable resin composition of the present invention is not particularly limited and can be stirred at room temperature. The above components were mixed and prepared. In addition, the curable resin composition of the present invention may be used as a one-component composition in which each component is directly mixed, and for example, two or more components to be separately stored may be used before use. A composition of a multi-liquid system (for example, a two-liquid system) used in a predetermined ratio is used.

The curable resin composition of the present invention is not particularly limited, but is preferably a liquid at normal temperature (about 25 ° C). More specifically, this issue The curable resin composition of Ming, as the viscosity at 23 ° C, 300 ~ 20000 mPa. s is better, more preferably 500~10000mPa. s, especially good for 1000~8000mPa. s. Viscosity is less than 300mPa. In the case of s, there is a case where the heat resistance of the cured product is lowered. On the other hand, the viscosity exceeds 20,000 mPa. In the case of s, the preparation or treatment of the curable resin composition becomes difficult, and it is easy to leave bubbles in the cured product. Further, as the viscosity of the curable resin composition, for example, a rheometer (trade name "PhysicaUDS-200", manufactured by Anton Paar Co., Ltd.) and a cone plate (cone diameter: 16 mm, cone angle = 0) can be used, and the temperature is: The measurement was carried out under the conditions of 23 ° C and the number of rotations: 20 rpm.

[hardened material]

The curable resin composition of the present invention is cured by a curing reaction (hydrogenation reaction) to obtain a cured product (hereinafter sometimes referred to as "the cured product of the present invention"). The conditions at the time of the hardening reaction are not particularly limited, and can be appropriately selected according to conventionally known conditions. For example, from the viewpoint of the reaction rate, the temperature (hardening temperature) is 25 to 180 ° C (more preferably 60 to 150 ° C). Preferably, the time (hardening 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 the reflow step and adhesion to the package, and It is also excellent in barrier properties against corrosive gases.

[Sealing 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 material) 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, reflow resistance and relative resistance are obtained. It has good barrier properties to corrosive gases. Therefore, the sealing material of the present invention can be used particularly as a sealing material for a semiconductor element of a semiconductor device, and particularly as a sealing material for an optical semiconductor element (particularly, a high-brightness, short-wavelength optical semiconductor element) of an optical semiconductor device. By sealing a semiconductor element (particularly an optical semiconductor element) by using the sealing material of the present invention, a semiconductor device (particularly an optical semiconductor device) excellent in durability and quality can be obtained.

[Examples]

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

The ¹ H-NMR analysis of the reaction product and the product was carried out using JEOL ECA500 (500 MHz). Further, the measurement of the number average molecular weight and the weight average molecular weight of the reaction product and the product was carried out in an Alliance HPLC system 2695 (manufactured by Waters), a Refractive Index Detector 2414 (manufactured by Waters), and a column: Tskgel GMH _{HR -} M × 2 (TOSOH). (manufacturing system), protective column: Tskgel guardcolumn H _HR L (manufactured by TOSOH), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 °C.

[polyorganooxane (A)]

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

GD-1130A: manufactured by Changxing Chemical Industry Co., Ltd., vinyl content 4.32% by weight, phenyl content 44.18% by weight, SiH group content (calculated by hydride) 0% by weight, number average molecular weight 1107, weight average molecular weight 6099

GD-1130B: Changxing Chemical Industry Co., Ltd., vinyl content 3.45 wt%, phenyl content 50.96 wt%, SiH group content (hydrogen conversion) 0.17 wt%, number average molecular weight 631, weight average molecular weight 1305

OE-6630A: manufactured by Dow Corning Toray, having a vinyl content of 2.17 wt%, a phenyl content of 51.94 wt%, a SiH group content (calculated by hydride) of 0 wt%, a number average molecular weight of 2532, a weight average molecular weight of 4490

OE-6630B: manufactured by Dow Corning Toray Co., Ltd., vinyl content 3.87 wt%, phenyl content 50.11 wt%, SiH group content (calculated by hydride) 0.17 wt%, number average molecular weight 783, weight average molecular weight 1330

[Iso-cyanurate compound (B)]

The following products were used as the isocyanurate compound (B).

Monoallyl epoxypropyl isomeric cyanurate: Shikoku Chemical Industry Co., Ltd.

[decane coupling agent (C)]

The following products were used as the decane coupling agent (C).

3-glycidoxypropyltrimethoxydecane: Dow Corning Toray

[Synthesis of sesquioxane (D)]

<Synthesis Example 1>

To the reaction vessel were added 15.86 g of phenyltriethoxydecane (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 foregoing mixture, 4.32 g of water and 0.16 g of hydrochloric acid of 5 N (hydrogen chloride of 2.4 mmol) were added dropwise over 1 hour. After the dropwise addition, the mixture was kept at 10 ° C for 1 hour. Thereafter, 26.78 g of MIBK was added, and the reaction solution was diluted.

Next, the temperature of the reaction vessel is raised to 70 ° C, at 70 ° C At the time point, 0.16 g of 5N hydrochloric acid (hydrogen chloride of 25 mmol) was added, and a polycondensation reaction was carried out under nitrogen for 4 hours.

Next, 11.18 g of divinyltetramethyldioxane and 3.25 g of hexamethyldioxane were added to the reaction solution, and the oximation reaction was carried out at 70 ° C for 4 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer became neutral, and then the supernatant liquid was taken. Then, the solvent was distilled off from the supernatant liquid at a temperature of 1 mmHg and 40 ° C to obtain a colorless transparent liquid reaction product (a ladder type sesquiterpene oxide having a vinyl group at the end, and 13.0 g). The above reaction had a number average molecular weight (Mn) of 840 and a molecular weight dispersion of 1.06.

[Zinc compound (E)]

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

Zinc naphthenate: manufactured by Nippon Chemical Industry Co., Ltd. under the trade name "NAPHTHEX Zinc" (Zn: 8%)

Zinc octoate: manufactured by Japan Chemical Industry Co., Ltd. under the trade name "NIKKA OCTHIX Zinc" (Zn: 15%)

<Examples and Comparative Examples>

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

According to Tables 1 and 2, the isocyanurate compound (B) and the decane coupling agent (C) are mixed at a predetermined weight ratio (units of the amounts of the components in Tables 1 and 2). Thereafter, the zinc compound (E) and the sesquiterpene oxide (D) were mixed and stirred at 60 ° C for 2 hours. Thereafter, after cooling to room temperature, the polyorganosiloxane (A) was mixed and stirred at room temperature for 30 minutes to obtain a curable resin composition.

Furthermore, in Tables 1 and 2, regarding zinc naphthenate and zinc octoate, Show the amount of mineral spirits removed from "NAPHTHEX Zinc" and "NIKKA OCTHIX Zinc".

[Measurement of photometric maintenance 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 × 2.8 mm) shown in Fig. 1 and heated at 60 ° C for 1 hour, followed by The mixture was heated at 80 ° C for 1 hour and at 150 ° C for 4 hours to prepare a sample. Furthermore, it can also be in LED package After the body was injected with a curable resin composition, it was heated at 150 ° C for 1 hour to prepare a sample.

For the above-mentioned samples, a full beam (manufactured by Optronic Laboratories Co., Ltd., multi-spectrophotometry system "OL771") was used, and a total beam (unit: 1 m) at a current of 20 mA was measured and used as a corrosive test. Full beam.

Next, the respective samples were subjected to the SO _X corrosivity test and the H ₂ S corrosivity test described later, and the total light beam was measured in the same manner as described above, and this was used as the total light beam after the corrosive test.

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

Photometric maintenance rate (%) = (full beam after corrosion test / full beam after corrosion test) × 100

[SO _X Corrosion Test]

Each of the above samples and 0.3 g of sulfur powder (KISHIDA Chemical Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was placed in a box made of aluminum. Next, the aluminum box was placed in an oven (manufactured by Yamato Scientific Co., Ltd., model number "DN-64"), and after the oven temperature was set to 80 ° C, it was taken out after 24 hours, and the total light beam was measured as described above.

[H ₂ S Corrosion Test]

The sample was placed in a gas corrosion tester (manufactured by Suga Tester Co., Ltd., model "GS-UV") 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 aforementioned full beam was measured.

[Evaluation of corrosion resistance]

The evaluation criteria for corrosion resistance are as follows.

A: The photometric maintenance rate of the SO _X corrosion test is 85% or more, and the luminosity maintenance rate of the H ₂ S corrosion test is 99% or more.

B: The photometric maintenance rate of the SO _X corrosion test is 85% or more, and the luminosity maintenance rate of the H ₂ S corrosivity test is less than 99%.

C: SO _X corrosion test luminosity maintenance rate is less than 85%

In Comparative Examples 1 to 3, the SO _X corrosion resistance was sufficient, but the H ₂ S corrosion resistance was insufficient.

On the other hand, in the comparative examples 4 to 6, when the zinc compound (E) described in the range of Patent Document 4 was added, although the H ₂ S corrosion resistance was improved, the SO _X corrosion resistance unexpectedly decreased.

Therefore, in the examples, when Comparative Examples 4 to 6 were adjusted to a small amount on the comparative examples 4 to 6, the H ₂ S corrosion resistance was maintained, and the SO _X corrosion resistance was confirmed to be improved.

Further, according to the comparison of Examples 2, 4, and 6, it was confirmed that the increase in the corrosion resistance of H ₂ S was not caused by the increase in the sesquioxane (B), and the SO _X corrosion resistance was improved.

Further, according to the comparison between Example 5 and Example 4, it was confirmed that the addition of Example 5 and Example 4 did not lower the corrosion resistance to H ₂ S and the SO _X corrosion resistance was improved.

According to the above, by adding the 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.

[Industrial availability]

The curable resin composition and cured product of the present invention require heat resistance, transparency, flexibility, and barrier against corrosive gases. The use of a sexual adhesive, a coating agent, a sealing material, etc. is useful. In particular, the curable resin composition and the cured product of the present invention can be suitably used as a sealing material for an optical semiconductor element (for example, an LED element, a semiconductor laser element, a photovoltaic power generation element, a CCD element, or the like).

Claims (14)

A curable resin composition comprising a polyorganosiloxane (A), an isocyanurate compound (B), and a zinc compound (E), which is characterized by a polyorganoquinone. The oxane (A) is a polyorganosiloxane having an aryl group, and may further comprise a sesquiterpene oxide (D) in an amount relative to the polyorganosiloxane (A) and The total amount (100 parts by weight) of the sesquioxane (D) is 0.01 parts by weight or more and less than 0.1 parts by weight. The curable resin composition of claim 1, wherein the polyorganosiloxane (A) has a number average molecular weight (Mn) of 500 to 4,000 in terms of standard polystyrene by gel permeation chromatography. The curable resin composition of claim 1 or 2, wherein the polyorganosiloxane (A) has a weight average molecular weight in terms of standard polystyrene by gel permeation chromatography as Mw and a number average molecular weight as Mn The molecular weight dispersion (Mw/Mn) is from 0.95 to 6.00. The curable resin composition according to any one of claims 1 to 3, wherein the polyorganosiloxane (A) is a polyorganosiloxane (A1) having an aliphatic carbon-carbon double bond. The curable resin composition according to any one of claims 1 to 4, wherein the polyorganosiloxane (A) is a polyorganosiloxane (A2) having a Si-H bond. The curable resin composition according to any one of claims 1 to 5, wherein the isomeric isocyanate compound (B) comprises an isomeric cyanurate compound represented by the formula (1); [In the formula (1), R ^x , R ^y , and R ^z may be the same or different, and represent a group represented by the formula (2) or a group represented by the formula (3); In the formulae (2) and (3), R ¹ and R ² may be the same or different and each represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms]]. The curable resin composition of claim 6, wherein one or more 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 any one of claims 1 to 7, wherein the zinc compound (E) contains zinc carboxylate. The curable resin composition according to any one of claims 1 to 8, wherein the polyorganosiloxane (A) is a polyorganosiloxane comprising a structure represented by the formula (6); [In the formula (6), R ²¹ to R ²⁶ may be the same or different and each represents a hydrogen atom, an aryl group, a monovalent hydrocarbon group or a monovalent heterocyclic group; however, one or more of R ²¹ to R ²⁶ are a monovalent group containing an aliphatic carbon-carbon unsaturated bond; further, one or more of R ²¹ to R ²⁶ is an aryl group; R ²⁷ represents a divalent hydrocarbon group; and r and s each represent an integer of 1 or more]. The curable resin composition according to any one of claims 1 to 9, which further comprises a decane coupling agent (C). The curable resin composition according to any one of claims 1 to 10, wherein the sesquiterpene oxide (D) contains ladder type sesquiterpene oxide. A cured product obtained by hardening the curable resin composition according to any one of claims 1 to 11. A sealing material obtained by using the curable resin composition according to any one of claims 1 to 11. A semiconductor device obtained by using the sealing material of claim 13.