TW201906933A - Curable silicone resin composition and cured product thereof - Google Patents

Abstract

The purpose of the present invention is to provide a curable silicone resin composition for forming a material (a sealing material, a lens, etc.) which has excellent sulfur barrier properties and maintains thermal shock resistance. The present invention provides a curable silicone resin composition containing components (A), (B), (C), and (D). (A): A polysiloxane having two or more alkenyl groups and one or more aryl groups in the molecule, (B): a polyorganosiloxane having one or more hydrosilyl groups and not having an aliphatic unsaturated group in the molecule, (C): an isocyanurate compound represented by formula (1), (D): a branched polyorganosiloxane having one or more alkenyl groups in the molecule [In each formula, symbols are as defined in the description].

Description

 Curable polyoxynene resin composition and cured product thereof  

The present invention relates to a curable polyoxyxene resin composition and a cured product thereof, a sealant using the above-described curable polyoxynoxy resin composition, and a sealing agent for sealing a semiconductor element (particularly an optical semiconductor element). The resulting semiconductor device (especially an optical semiconductor device). The present application claims priority from Japanese Patent Application No. 2017-120445 filed on June 20, 2017 in Japan, and its contents are hereby incorporated herein.

As the sealing material for protecting the semiconductor element in the semiconductor device such as the optical semiconductor device, a variety of resin materials are used. In recent years, the high current of the optical semiconductor device is progressing, and the sealing material of the optical semiconductor device is required to have high heat resistance and light resistance. Therefore, as the resin of the above sealing material, a polyoxymethylene resin having high heat resistance and light resistance is used.

However, the general polyoxynene resin has a high gas permeability, and in the case of being used in an optical semiconductor device, there is a case where the electrode is vulcanized by a sulfur compound such as SO _X or hydrogen sulfide to cause a decrease in luminosity. Therefore, in the case of the sealing material in the optical semiconductor device, a phenyl fluorene which can form a material (hardened material) which is excellent in barrier properties against such a sulfur compound (hereinafter sometimes referred to as "sulfur barrier property") is gradually used. Oxygen sealing material.

However, the phenylpolyfluorene-based sealing material has a high sulfur barrier property as compared with the conventional methylpolyoxygen-based sealing material used in the prior art, but its characteristics are still insufficient. In fact, even in the case where a phenylpolyfluorene-based sealing material is used, there is a problem that the corrosion of the electrode due to the corrosive gas is progressing over time in the optical semiconductor device, and the electrification characteristics are deteriorated.

Moreover, in order to improve sulfur barrier properties, there is a method of adding ladder type sesquiterpene oxide, but there is a case where thermal shock resistance is lowered.

In order to improve the barrier properties against the sulfur barrier properties of the sealing material, there is also a method of blending a specific component with a sealant (a hardening composition for forming a sealing material). For example, it has been reported (for example, Patent Document 1) that the addition of an isomeric isocyanate compound such as monoallyl isocyanuric acid diglycidyl ester or triglycidyl isocyanurate exhibits the above-mentioned sulfur. The effect of barrier improvement.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] International Publication No. 2014/125964

 [Summary of the Invention]  

However, monoallyl isocyanuric acid diglycidyl ester is solid at room temperature, and if it is mixed without heating, a uniform sealant cannot be obtained. Further, when the amount of the mixture is increased, the solid of monoallyl isocyanuric acid diglycidyl ester is precipitated in the sealing agent. On the other hand, the triglycidyl isocyanurate is also solid at room temperature, especially because it has low solubility in the sealant, and it is difficult to obtain a uniform sealant even by heating. Further, even when it is temporarily dissolved, there is a problem that a solid of triglycidyl isocyanate precipitates when the sealant is returned to room temperature. As described above, it has not been found that the problem of the barrier property of the sealing material against the corrosive gas can be efficiently increased without causing the problem of precipitation of the above-mentioned solid.

Therefore, an object of the present invention is to provide a curable polyoxyxene resin composition which is capable of forming one side to maintain heat resistance and thermal shock resistance without causing the problem of solid precipitation as described above, and especially for A material (hardened material) having a barrier property (sulfur barrier property) of a corrosive gas (for example, SO _X gas).

Further, another object of the present invention is to provide a material (cured material) which is excellent in heat resistance and thermal shock resistance and is particularly excellent in sulfur barrier properties.

Further, another object of the present invention is to provide a sealant using the curable resin composition and a quality and durability obtainable by sealing a semiconductor element (particularly an optical semiconductor element) by using the sealant. Excellent semiconductor device (especially optical semiconductor device).

Furthermore, another object of the present invention is to provide an optical semiconductor device excellent in quality and durability, which comprises a lens formed by the cured product.

The present inventors have found that the composition (the curable polyanthracene resin composition) containing the following essential components does not cause the problem of solid precipitation described above, and can be formed while being cured. The present invention has been completed by a material (cured product) having excellent heat resistance, thermal shock resistance, and sulfur barrier properties, and is an essential component selected from the group consisting of two or more alkenyl groups and one or more aryl groups contained in a molecule. a specific polyorganosiloxane, and a polyorgano siloxy silalkylene having a polyalkylene group having two or more alkenyl groups and one or more aryl groups in the molecule At least one polyoxoxane group of the group of organooxanes; a polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturation; having a specific structure An isomeric cyanurate compound; and a branched polyorganosiloxane having one or more alkenyl groups in the molecule.

That is, the present invention provides a curable polyoxyxene resin composition comprising the following components (A), (B), (C), and (D).

(A): a polyorganosiloxane (A1) selected from the group consisting of two or more alkenyl groups and one or more aryl groups in the molecule, and two or more alkenyl groups and one or more in the molecule. At least one polyfluorene oxide of the group of aryl polyorgano alkoxyoxyalkylene groups (A2); (B): having one or more hydroquinone groups in the molecule and having no aliphatic unsaturation Polyorganosiloxane; (C): an iso-cyanate compound represented by the following formula (1);

In the formula (1), R ^a , R ^b and R ^c are the same or different and each represents a group represented by the formula (1a), a group represented by the formula (1b), a hydrogen atom or an alkyl group. However, at least one of R ^a , R ^b and R ^c is a group represented by the formula (1a).

[In the formula (1a), R ^d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. s represents an integer from 2 to 10. 〕

In the formula (1b), R ^e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. t represents an integer from 1 to 10. 〕〕

(D): a branched polyorganosiloxane having one or more alkenyl groups in the molecule.

The curable polyoxyxene resin composition may further contain the following component (E).

(E): Hydrogenation catalyst containing platinum group metals

The curable polyoxyxene resin composition may further contain the following component (G).

(G): an iso-cyanate compound represented by the following formula (2)

In the formula (2), R ^f , R ^g and R ^h are the same or different and each represents a group represented by the formula (2a) or a group represented by the formula (2b). However, at least one of R ^f , R ^g and R ^h is a group represented by the formula (2b). 〕

[In the formula (2a), R ⁱ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. 〕

In the formula (2b), R ^j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. 〕

The curable polyoxyxene resin composition may further contain the following component (F).

(F): ladder type polyorganosilsesquioxane having one or more alkenyl groups in the molecule

The curable polyoxyxene resin composition may further contain the following (H) component.

(H): decane coupling agent

The curable polyoxyxene resin composition may further comprise a phosphor.

Further, the present invention provides a cured product of a curable polyoxyxene resin composition.

The curable polyanthracene resin composition may be a resin composition for optical semiconductor sealing.

The curable polyanthracene resin composition may be a resin composition for forming a lens for an optical semiconductor.

Moreover, the present invention provides an optical semiconductor device comprising: an optical semiconductor element; and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the resin composition for optical semiconductor sealing.

Furthermore, the present invention provides an optical semiconductor device comprising: an optical semiconductor element and a lens, wherein the lens is a cured product of a resin composition for forming the optical semiconductor lens.

The curable polyanthracene resin composition of the present invention has a composition as described above, and is solid-formed in a curable polyoxynoxy resin composition (for example, a curable polyoxyxylene resin composition which has been adjusted to room temperature). The problem will not happen. Therefore, the curable polyoxyxylene resin composition of the present invention is easy to prepare and easy to handle. Further, since the curable polyoxyxene resin composition of the present invention has the above-described configuration, it can be cured to maintain heat resistance (for example, moisture absorption reflow resistance) and thermal shock resistance, and particularly A hardened material excellent in barrier properties (sulfur barrier properties) of a corrosive gas (for example, SOx gas). Therefore, in the case where the cured product is used as a sealing material or a lens of a semiconductor element in a semiconductor device, corrosion of an electrode of the semiconductor device is highly suppressed, and durability of the semiconductor device is remarkably improved. Therefore, the curable polyoxyxene resin composition of the present invention can be preferably used as a material (sealant) or a lens for forming a sealing material for forming an optical semiconductor element (LED element) in an optical semiconductor device. Resin composition. The optical semiconductor device which can be obtained as a sealant or a resin composition for forming a lens using the curable polyoxyxylene resin composition of the present invention has excellent quality and durability.

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

101‧‧‧Metal wiring (electrode)

102‧‧‧Optical semiconductor components

103‧‧‧bonding line

104‧‧‧ hardened material (sealing material)

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

Fig. 2 is a chart showing the ¹ H-NMR spectrum of the product obtained in Synthesis Example 1 (polyorganosilsesquioxane having a vinyl group).

Fig. 3 is a graph showing the FT-IR spectrum of the product (polyorganosilsesquioxane having a vinyl group) obtained in Synthesis Example 1.

 [Formation for implementing the invention]    <Sclerosing Polyoxyl Resin Composition>  

The curable polyanthracene resin composition of the present invention is a curable composition containing the following components (A), (B), (C), and (D) as essential components. That is, the curable polyoxyxylene resin composition of the present invention is an addition-curable polyoxyxylene resin composition which can be cured by a hydroquinone reaction. In addition, the curable polyoxyxene resin composition of the present invention may contain, for example, any components other than these essential components, such as (E) component, (F) component, (G) component, and (H) component mentioned later.

(A): a polyorganosiloxane (A1) selected from the group consisting of two or more alkenyl groups and one or more aryl groups in the molecule, and two or more alkenyl groups and one or more in the molecule. At least one polyfluorene oxide of the group of aryl polyorgano alkoxyoxyalkylene groups (A2); (B): having one or more hydroquinone groups in the molecule and having no aliphatic unsaturation Polyorganosiloxane; (C): an iso-cyanate compound represented by the following formula (1);

In the formula (1), R ^a , R ^b and R ^c are the same or different and each represents a group represented by the formula (1a), a group represented by the formula (1b), a hydrogen atom or an alkyl group. However, at least one of R ^a , R ^b and R ^c is a group represented by the formula (1a).

[In the formula (1a), R ^d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. s represents an integer from 2 to 10. 〕

In the formula (1b), R ^e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. t represents an integer from 1 to 10. 〕〕

(D): a branched polyorganosiloxane having one or more alkenyl groups in the molecule.

 [(A) component]  

The component (A) which is an essential component of the curable polyanthracene resin composition of the present invention is a polyorganic compound selected from the group consisting of two or more alkenyl groups and one or more aryl groups contained in the molecule, as described above. a fluorinated alkane (A1) (hereinafter, a case where it is simply referred to as "polyorganosiloxane (A1)"), and a polyorganodecyloxy group having two or more alkenyl groups and one or more aryl groups in the molecule. At least one polyoxyalkylene group of the group of the alkyl group (A2) (hereinafter, referred to as "polyorganoquinoloxyalkylene group (A2)"). Therefore, in the curable polyoxyxylene resin composition of the present invention, the component (A) is a component which undergoes a hydroquinone reaction with a component having a hydroquinone group (for example, a component (B) or the like). However, the component (A) does not include a component (D) or a component (F) which will be described later.

The curable polyanthracene resin composition of the present invention can form a cured product excellent in sulfur barrier properties and thermal shock resistance by containing the component (A). Therefore, the quality of the optical semiconductor device as the sealing material is improved.

The polyorganoquinoloxyalkylene group (A2) in the present specification means that -Si-O-Si-(a decane bond) is contained as a main chain, and -Si-R ^A -Si- ( ^A polyorganosiloxane having an alkyl group bond: R ^A represents an alkylene group. On the other hand, the polyorganosiloxane (A1) in the present specification is a polyorganosiloxane which does not contain the above-mentioned alkylene bond as a main chain.

 (polyorganooxane (A1))  

The polyorganosiloxane (A1) has two or more alkenyl groups and one or more aryl groups in the molecule, and has a -Si-O-Si-(decane bond) as a main chain, and does not include A polyorganosiloxane having an alkyl group.

Examples of the polyorganosiloxane (A1) include a linear, partially branched, linear, branched, and mesh-like molecular structure. Further, the polyorganosiloxane (A1) may be used singly or in combination of two or more. Specifically, two or more polyorganosiloxanes (A1) having different molecular structures may be used in combination, and, for example, a linear polyorganosiloxane (A1) and a branched polyorganosiloxane may be used in combination. (A1).

The alkenyl group which the polyorganosiloxane (A1) has in the molecule may, for example, be a substituted or unsubstituted alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group and the like. Among them, in the case of an alkenyl group, a vinyl group is preferred. Further, the polyorganosiloxane (A1) may be one having only one type of alkenyl group or two or more types of alkenyl groups. The polyorganosiloxane (A1) has an alkenyl group, preferably one which has been bonded to a ruthenium atom.

Examples of the aryl group which the polyorganosiloxane (A1) has in the molecule include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an aralkyl group (for example, a benzyl group, a phenethyl group, etc.). Or a substituted C _6-14 aryl group or the like. The substituent in the substituted aryl group may, for example, be a substituted or unsubstituted C _1-8 alkyl group, a halogen atom, a hydroxyl group or a carboxyl group. Among them, in the case of the above aryl group, a phenyl group is preferred. Further, the polyorganosiloxane (A1) may be one having only one aryl group or two or more aryl groups. The aryl group which the polyorganosiloxane (A1) has is not particularly limited, but is preferably a group which has been bonded to a ruthenium atom. The polyorganosiloxane (A1) is a cured product excellent in sulfur barrier properties as compared with a polyorganosiloxane having no aryl group by having one or more aryl groups in the molecule.

The base other than the alkenyl group and the aryl group of the polyorganosiloxane (A1) may, for example, be a hydrogen atom or an organic group. The organic group may, for example, be an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the like) or a cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group, or a ring). a halogenated hydrocarbon group in which a cycloalkyl-alkyl group (e.g., a cyclohexylmethyl group, a methylcyclohexyl group, etc.), a hydrogen atom having 1 or more of the hydrocarbon groups, which has been substituted with a halogen atom, is a pentyl group, a cyclohexyl group, a cyclododecyl group or the like. (e.g., a substituted or unsubstituted hydrocarbon group such as a chloromethyl group, a 3-chloropropyl group, a halogenated alkyl group such as a 3,3,3-trifluoropropyl group or the like). Further, in the present specification, the "base which has been bonded to a ruthenium atom" is generally referred to as a group which does not contain a ruthenium atom. Among them, an alkyl group (especially a methyl group) is preferred.

Further, the polyorganosiloxane (A1) may have a hydroxyl group or an alkoxy group as a group which has been bonded to a ruthenium atom.

The property of the polyorganosiloxane (A1) is not particularly limited. For example, at 25 ° C, it may be liquid or solid.

In the case of polyorganosiloxane (A1), the following average unit formula is preferred: (R ^1a SiO _3/2 ) _a1 (R ^1a ₂ SiO _2/2 ) _a2 (R ^1a ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ^1a O _1/2 ) _a5

The polyorganosiloxane is shown. In the above average unit formula, R ^1a is the same or different, and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, a halogenated hydrocarbon group, etc.) may be mentioned. And the above alkenyl group, aryl group. However, a part of R ^1a is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to be in the range of two or more in the molecule. For example, the ratio of the alkenyl group to the total amount of R ^1a (100 mol%) is preferably 0.1 to 40 mol%. When the ratio of the alkenyl group is controlled to the above range, the curability of the curable polyoxynene resin composition tends to be improved. Further, a part of R ^1a is an aryl group (especially a phenyl group), and the ratio thereof is controlled to be one or more in the molecule. For example, the ratio of the aryl group to the total amount of R ^1a (100 mol%) is preferably from 30 to 70 mol%. By controlling the ratio of the aryl group to the above range, the sulfur barrier property of the cured product tends to be further improved. Further, in the case of R ^1a other than the alkenyl group and the aryl group, an alkyl group (particularly a methyl group) is preferred.

In the above average unit formula, X ¹ is a hydrogen atom or an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and particularly preferably a methyl group.

In the above average unit formula, a1 is 0 or a positive number, a2 is 0 or a positive number, a3 is 0 or a positive number, a4 is 0 or a positive number, a5 is 0 or a positive number, and (a1+a2+a3) is a positive number.

An example of the polyorganosiloxane (A1) is a linear polyorganosiloxane having two or more alkenyl groups and one or more aryl groups in the molecule. The alkenyl group which the linear polyorganosiloxane has is a specific example of the above-mentioned alkenyl group, and among them, a vinyl group is preferable. Further, it may be one having only one type of alkenyl group, or one having two or more types of alkenyl groups. Further, the aryl group which the linear polyorganosiloxane has is exemplified by the above-mentioned aryl group, and among them, a phenyl group is preferable. Further, it may be one having only one aryl group or one having two or more kinds of aryl groups. In addition, examples of the group bonded to the ruthenium atom other than the alkenyl group and the aryl group in the linear polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group, but Further preferred is an alkyl group (especially a methyl group).

In the above linear polyorganosiloxane, the ratio of the alkenyl group to the total amount (100 mol%) of the group bonded to the ruthenium atom is preferably from 0.1 to 40 mol%. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is preferably 40 to 60 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is preferably from 30 to 70 mol%. In particular, the use of an aryl group (especially a phenyl group) for a total amount (100 mol%) of a group bonded to a ruthenium atom is 40 mol% or more (for example, 45 to 70 mol%). The linear polyorganosiloxane of the above-mentioned type tends to have a higher sulfur barrier property of the cured product. Further, by using an alkyl group (especially a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 50 mol% or more (for example, 55 to 60 mol%). However, there is a tendency that the thermal shock resistance of the cured product is further improved.

The linear polyorganosiloxane is expressed, for example, by the following formula (I-1).

[In the above formula, R ¹¹ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ¹¹ are alkenyl groups, and at least one of them is an aryl group. M1 is an integer from 5 to 1000]

Other examples of the polyorganosiloxane (A1) include an alkenyl group having two or more alkenyl groups and one or more aryl groups in the molecule and having R ^a SiO _3/2 Branched polyorganosiloxane of unit (T unit). However, as described above, the branched polyorganosiloxane does not contain a component corresponding to the component (F) described later. Further, R ^a is a monovalent substituted or unsubstituted hydrocarbon group. The alkenyl group which the branched polyorganosiloxane has is a specific example of the above-mentioned alkenyl group, and among them, a vinyl group is preferable. Further, it may be one having only one type of alkenyl group, or one having two or more types of alkenyl groups. Further, the aryl group which the branched polyorganosiloxane has is exemplified by the above-mentioned aryl group, and among them, a phenyl group is preferable. Further, it may be one having only one aryl group or one having two or more kinds of aryl groups. In addition, examples of the group bonded to the ruthenium atom other than the alkenyl group and the aryl group in the branched polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group, but Further preferred is an alkyl group (especially a methyl group). Further, as for R ^a in the above T unit, among them, an aryl group (especially a phenyl group) is preferable.

In the branched polyorganosiloxane, the ratio of the alkenyl group to the total amount of the group bonded to the ruthenium atom (100 mol%) is based on the hardenability of the curable polyanthracene resin composition. Good is 0.1~40%. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is preferably 40 to 60 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is preferably from 30 to 70 mol%. In particular, the use of an aryl group (especially a phenyl group) for a total amount (100 mol%) of a group bonded to a ruthenium atom is 40 mol% or more (for example, 45 to 70 mol%). The branched polyorganosiloxane may have a tendency to increase the sulfur barrier properties of the cured product. Further, by using an alkyl group (especially a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 50 mol% or more (for example, 55 to 60 mol%). However, there is a tendency that the thermal shock resistance of the cured product is further improved.

The branched polyorganosiloxane may be represented by the above average unit formula in which a1 is a positive number. In this case, a2/a1 is preferably 0 to 10, a3/a1 is preferably 0 to 0.5, and a4/(a1+a2+a3+a4) is preferably 0 to 0.3, a5/( A1+a2+a3+a4) is preferably a number from 0 to 0.4. Further, the molecular weight of the branched polyorganosiloxane is preferably from 500 to 10,000, more preferably from 700 to 3,000, in terms of a standard polystyrene conversion by GPC.

The polyorganosiloxane (A1) can be produced by a conventionally known method, and as a product containing a polyorganosiloxane (A1), for example, the trade name "OE6630" (Dow Corning Toray Co.) can be obtained. , Ltd.) and so on.

In addition, the polyorganosiloxane (A1) may be used singly or in combination of two or more kinds in the curable polyanthracene resin composition of the present invention. For example, two or more kinds of polyorganosiloxanes (A1) having different molecular structures may be used in combination, and specifically, a linear polyorganosiloxane (A1) and a branched polyorganosiloxane may be used in combination. The aspect of the alkane (A1) and the like.

 (polyorganotinoalkyloxyalkylene (A2))  

The polyorganoquinoloxyalkylene group (A2) has two or more alkenyl groups and one or more aryl groups in the molecule, and contains -Si-O-Si-(a decane bond) as a main chain. In addition, a polyorganosiloxane (polyorganoquinoloxyalkylene group) of -Si-R ^A -Si- (an alkyl group: R ^A represents an alkylene group) is further included. That is, the polyorganoquinoloxyalkylene group (A2) does not contain a polyorganosiloxane such as a polyorganosiloxane (A1) which does not have an alkylene bond. The curable polyanthracene resin composition of the present invention contains a polyorganoquinoloxyalkylene group (A2), and can form a cured product excellent in sulfur barrier properties and thermal shock resistance. Further, since it is hardened to form a cured product having a high sulfur barrier property, is not easily yellowed, and has low viscosity or no viscosity, the quality of the optical semiconductor device as the sealing material is improved.

The alkylene group of the polyorganoquinolyloxyalkylene group (A2) in the alkylene group having an alkyl group in the molecule may, for example, be a methylene group, an ethyl group, a propyl group or the like. A chain or branched C _1-12 alkylene group or the like, wherein a C _2-4 alkyl group (especially an ethyl group) is further preferred. The polyorganoquinoloxyalkylene group (A2) is less prone to a low molecular weight ring in the production step because the main chain contains only a decane bond, compared with a polyorganosiloxane having no hydrazine alkyl bond. It is not easy to decompose to generate a sterol group (-SiOH) by heating or the like, and thus the surface adhesion of the cured product of the curable polyoxyxylene resin composition by using the polyorganoquinoloxyalkylene group (A2) (viscosity) will be reduced, and there will be a tendency to become less susceptible to yellowing.

The polyorganoquinoloxyalkylene group (A2) may, for example, be a molecular structure having a linear or branched chain (for example, a partially branched linear chain, a branched chain, a mesh, or the like). Wait. Further, in the case of the polyorganoquinoloxyalkylene group (A2), it is preferred to have a branched molecular structure from the viewpoint of mechanical strength of the cured product.

The alkenyl group having a polyorganoquinoloxyalkylene group (A2) in the molecule may be substituted or unsubstituted with a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group or the like. Alkenyl. Examples of the substituent in the substituted alkenyl group include a halogen atom, a hydroxyl group, a carboxyl group and the like. Among them, in view of the above alkenyl group, a vinyl group is preferred. Further, the polyorganoquinoloxyalkylene group (A2) may be one having only one type of alkenyl group or two or more types of alkenyl groups. The alkenyl group of the polyorganoquinoloxyalkylene group (A2) is not particularly limited, but is preferably a group which has been bonded to a ruthenium atom.

Examples of the aryl group of the polyorganoquinoloxyalkylene group (A2) in the molecule include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an aralkyl group (for example, a benzyl group, A substituted or unsubstituted C _6-14 aryl group or the like such as phenethyl or the like. The substituent in the substituted aryl group may, for example, be a substituted or unsubstituted C _1-8 alkyl group, a halogen atom, a hydroxyl group or a carboxyl group. Among them, in the case of the above aryl group, a phenyl group is preferred. Further, the polyorganoquinoloxyalkylene group (A2) may be one having only one aryl group or two or more kinds of aryl groups. The aryl group which the polyorganoquinoloxyalkylene group (A2) has is not particularly limited, but is preferably a group which has been bonded to a ruthenium atom. The polyorganoquinoloxyalkylene group (A2) is a cured product excellent in sulfur barrier properties as compared with a polyorganosiloxane having no aryl group by having one or more aryl groups in the molecule.

The polyorganoquinolyloxyalkylene group (A2) is not particularly limited as long as it is bonded to a ruthenium atom other than the alkenyl group and the aryl group in the molecule, but may, for example, be a hydrogen atom. , organic base, etc. The organic group may, for example, be an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the like) or a cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group or a ring). a pentyl group, a cyclohexyl group, a cyclododecyl group, etc., a cycloalkane-alkyl group (for example, a cyclohexylmethyl group, a methylcyclohexyl group, etc.), or a halogen atom in which one or more hydrogen atoms in a hydrocarbon group have been replaced by a halogen atom A monovalent substituted or unsubstituted hydrocarbon group such as a hydrocarbon group (for example, a halogenated alkyl group such as chloromethyl, 3-chloropropyl or 3,3,3-trifluoropropyl). Further, in the present specification, the "base which has been bonded to a ruthenium atom" is generally referred to as a group which does not contain a ruthenium atom. Among them, an alkyl group (especially a methyl group) is preferred.

Further, the polyorganoquinoloxyalkylene group (A2) may have a hydroxyl group or an alkoxy group as a group which has been bonded to a ruthenium atom.

The property of the polyorganoquinoloxyalkylene group (A2) is not particularly limited. For example, at 25 ° C, it may be in the form of a liquid or a solid.

In the case of the polyorganoquinoloxyalkylene group (A2), the following average unit formula is preferred: (R ^1b ₂ SiO _2/2 ) _b1 (R ^1b ₃ SiO _1/2 ) _b2 (R ^1b SiO _{3 /2} ) _b3 (SiO _4/2 ) _b4 (R ^A ) _b5 (X ^1b O) _b6

The polyorganoquinoloxy oxime alkyl group shown. In the above average unit formula, R ^1b is the same or different, and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, a halogenated alkyl group, etc.) may be mentioned. And the above alkenyl group, aryl group. However, a part of R ^1b is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to be in the range of two or more in the molecule. For example, the ratio of the alkenyl group to the total amount of R ^1b (100 mol%) is preferably 0.1 to 40 mol%. When the ratio of the alkenyl group is controlled to the above range, the curability of the curable polyoxynene resin composition tends to be improved. Further, a part of R ^1b is an aryl group (especially a phenyl group), and the ratio thereof is controlled to be in the range of one or more in the molecule. For example, the ratio of the aryl group to the total amount of R ^1b (100 mol%) is preferably 10 to 50 mol%. By controlling the ratio of the aryl group to the above range, the sulfur barrier property of the cured product tends to be further improved. In the case of R ^1b other than the alkenyl group and the aryl group, an alkyl group (particularly a methyl group) is preferred.

In the above average unit formula, R ^A is as described above and is an alkylene group. Very good for stretching ethyl.

In the above average unit formula, X ^1b is a hydrogen atom or an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and particularly preferably a methyl group.

In the above average unit formula, b1 is a positive number, b2 is a positive number, b3 is a zero or a positive number, b4 is a zero or a positive number, b5 is a positive number, and b6 is a zero or a positive number. Wherein b1 is preferably 1 to 200, b2 is preferably 1 to 200, b3 is preferably 0 to 10, b4 is preferably 0 to 5, and b5 is preferably 1 to 100. In particular, when (b3+b4) is a positive number, the polyorganoquinoloxyalkylene group (A2) has a branched chain (branched main chain) and tends to have a higher mechanical strength of the cured product.

The polyorganoquinoloxyalkylene group (A2) is more specifically, for example, a polyorganoquinoloxyalkylene group having a structure represented by the following formula (I-2).

In the above formula (I-2), R ¹² is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of R ¹² include specific examples of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group or a halogenated hydrocarbon group), and the above-mentioned alkenyl group and aryl group. However, at least two of R ¹² are alkenyl groups (especially vinyl groups), and at least one of R ¹² is an aryl group (especially a phenyl group). Further, in the case of R ¹² other than the alkenyl group and the aryl group, an alkyl group (particularly a methyl group) is preferred.

In the above formula (I-2), R ^A represents an alkylene group in the same manner as described above, and further preferably a C _2-4 alkylene group (especially an ethyl group). In addition, in the case where a plurality of R ^A are present, the same may or may not be the same.

In the above formula (I-2), r1 represents an integer of 1 or more (for example, 1 to 100). Further, in the case where r1 is an integer of 2 or more, the structures in the parentheses marked with r1 may be the same or different.

In the above formula (I-2), r2 represents an integer of 1 or more (for example, 1 to 400). Further, in the case where r2 is an integer of 2 or more, the structures in the parentheses marked with r2 may be the same or different.

In the above formula (I-2), r3 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, in the case where r3 is an integer of 2 or more, the structures in the parentheses marked with r3 may be the same or different.

In the above formula (I-2), r4 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, in the case where r4 is an integer of 2 or more, the structures in the parentheses marked with r4 may be the same or different.

In the above formula (I-2), r5 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, in the case where r5 is an integer of 2 or more, the structures in the parentheses marked with r5 may be the same or different.

Further, the addition form of each structural unit in the above formula (I-2) is not particularly limited, and may be a random type or a block type. Further, the order of arrangement of the respective structural units is also not particularly limited.

The terminal structure of the polyorganoquinoloxyalkylene group having a structure represented by the formula (I-2) is not particularly limited, and examples thereof include a decyl group, an alkoxy fluorenyl group, and a trialkyl fluorenyl group. (for example, a structure in the parentheses of r5, a trimethylsulfonyl group, etc.). At the terminal of the polyorganoquinoloxyalkylene group, various groups such as an alkenyl group or a hydroquinone group may be introduced.

The polyorganoquinoloxyalkylene group (A2) can be produced by a conventionally known method, and the production method thereof is not particularly limited, but the method described in, for example, JP-A-2012-140617 can be used. To manufacture. Further, as a product containing a polyorganoquinoloxyalkylene group (A2), for example, the trade names "ETERLED GS5155", "ETERLED GS5145", "ETERLED GS5135", and "ETERLED GS5120" (all of which are Changxing Materials Industry) are available. System) and so on.

In addition, the polyorganoquinoloxyalkylene group (A2) may be used singly or in combination of two or more kinds in the curable polyanthracene resin composition of the present invention. For example, two or more kinds of polyorganoquinoloxyalkylene groups (A2) having different molecular structures may be used in combination, and specific examples thereof include a linear polyorganodecyloxyalkylene group (A2) and A branched polyorganoquinoloxyalkylene group (A2) or the like.

The content (mixing amount) of the component (A) in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is preferably a composition (100% by weight) based on the curable polyoxyxylene resin composition. 0.1 to 60% by weight, more preferably 0.1 to 55% by weight, still more preferably 0.1 to 50% by weight. When the content of the component (A) is 0.1% by weight or more, the thermal shock resistance of the cured product tends to be further improved. Further, when the polyorganoquinoloxyalkylene group (A2) is used as the component (A), the viscosity of the cured product is lowered, so that the quality of the optical semiconductor device tends to be improved. On the other hand, when the content of the component (A) is 60% by weight or less, the yellowing resistance of the cured product tends to increase, and the factor (B) to (B) can be efficiently obtained. D) The effect of the increase in the component (for example, improvement in hardenability, improvement in sulfur barrier properties, improvement in adhesion, etc.).

In the (A) component of the curable polyoxyxylene resin composition of the present invention, only polyorganosiloxane (A1) or polyorganoalkyloxyalkylene (A2) may be used. Further, a polyorganosiloxane (A1) and a polyorganoquinoloxyalkylene group (A2) may also be used in combination. In the case of using a polyorganosiloxane (A1) and a polyorganoquinoloxyalkylene group (A2), the ratio is not particularly limited and can be appropriately set.

 [(B) component]  

The component (B) in the curable polyoxyxylene resin composition of the present invention is a polyorganosiloxane having one or more hydroquinone groups (Si-H) in the molecule and having no aliphatic unsaturation. Therefore, in the curable polyoxyxylene resin composition of the present invention, the component (B) is a component which undergoes a hydroquinone reaction with a component having an alkenyl group (for example, a component (A) or the like). The curable polyoxyxylene resin composition of the present invention contains the component (B), whereby the hardening reaction by the hydroquinone reaction can be efficiently carried out. Moreover, the cured product exhibits excellent sulfur barrier properties.

The number of the hydroquinone groups in the molecule (B) is not particularly limited as long as it is one or more, but it is preferably two or more from the viewpoint of the curability of the curable polyoxyn resin composition. (for example, 2~50).

The component (B) is not particularly limited, but preferably has one or more (preferably two or more) hydroquinone groups in the molecule, and does not have an aliphatic unsaturation and an alkylene oxide. A polyorganosiloxane having a base bond (there is only a case of "polyorganosiloxane (B1)").

Further, the component (B) has no aliphatic unsaturated group in the molecule as described above. The aliphatic hydrocarbon group having a non-aromatic carbon-carbon unsaturated bond as the aliphatic unsaturated group may, for example, be an ethylenically unsaturated group or an acetylene unsaturated group. The ethylenically unsaturated group may, for example, be an alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group or a 5-hexenyl group (for example, a C _2-20 alkenyl group (especially C) _2-10 alkenyl), etc.; alkadienyl groups such as 1,3-butadienyl (especially C _4-10 alkadienyl, etc.); acryloyloxy, methacryloxyloxy Or an alkenylcarbonyloxy group; an alkenylcarbonylamino group such as an acrylamide group or the like. The acetylene unsaturated group may, for example, be an alkynyl group such as an ethynyl group or a propargyl group (for example, a C _2-20 alkynyl group (especially a C _2-10 alkynyl group) or the like); an ethynylcarbonyloxy group; An alkynylcarbonyloxy group such as an alkynylcarbonyloxy group; an alkynylcarbonylamino group such as an ethynylcarbonylamino group.

The polyorganosiloxane (B1) may, for example, be a linear or branched (molecular structure having a partial branch, a linear chain, a branched chain, a mesh, or the like). Further, the polyorganosiloxane (B1) may be used singly or in combination of two or more. For example, two or more kinds of polyorganosiloxanes (B1) having different molecular structures may be used in combination, and specifically, a linear polyorganosiloxane (B1) and a branched polyorganosiloxane may be used in combination. The aspect of the alkane (B1) and the like.

Among the groups of the polyorganosiloxane (B1) which have been bonded to the ruthenium atom, the group other than the hydrogen atom is not particularly limited, and examples thereof include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (but And the above-mentioned aryl group, more specifically an alkyl group, an aryl group, a halogenated hydrocarbon group or the like. Among them, an alkyl group (especially a methyl group) and an aryl group (especially a phenyl group) are preferred.

Further, the component (B1) may have a hydroxyl group or an alkoxy group as a group which has been bonded to a ruthenium atom.

The property of the polyorganosiloxane (B1) is not particularly limited. For example, at 25 ° C, it may be liquid or solid. Further, it is preferably liquid, and more preferably has a viscosity of from 0.1 to 1 billion mPa·s at 25 ° C.

In the case of polyorganosiloxane (B1), the following average unit formula is preferred: (R ² SiO _3/2 ) _c1 (R ² ₂ SiO _2/2 ) _c2 (R ² ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (X ² O _1/2 ) _c5

The polyorganosiloxane is shown. In the above average unit formula, R ² is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (except for the aliphatic unsaturated group), and examples thereof include a hydrogen atom and one of the above. Specific examples of the substituted or unsubstituted hydrocarbon group (for example, an alkyl group, a halogenated alkyl group, etc.), and the above-mentioned aryl group. However, a part of R ² is a hydrogen atom (a hydrogen atom constituting a hydroquinone group), and the ratio thereof is controlled so that hydroquinone is one or more (preferably two or more) in the molecule. For example, the ratio of the hydrogen atom to the total amount of R ² (100 mol%) is preferably 0.1 to 40 mol%. When the ratio of the hydrogen atoms is controlled within the above range, the curability of the curable polyoxynene resin composition tends to be improved. Further, R ² other than the hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (especially a phenyl group).

In the above average unit formula, X ² is a hydrogen atom or an alkyl group similarly to X ¹ described above. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and particularly preferably a methyl group.

In the above average unit formula, c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1+c2+c3) is a positive number.

An example of the polyorganosiloxane (B1) is a linear polyorganosiloxane having one or more (preferably two or more) hydroquinone groups in the molecule. The group bonded to the ruthenium atom other than the hydrogen atom in the linear polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (however, an aliphatic unsaturated group) Except for the above) and the above-mentioned aryl group, among which, an alkyl group (especially a methyl group) and an aryl group (especially a phenyl group) are preferred.

In the above linear polyorganosiloxane, the ratio of the hydrogen atom (the hydrogen atom bonded to the ruthenium atom) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited. However, it is preferably 0.1 to 40% by mole. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably 20 to 99 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably 10 to 50 mol%. In particular, an aryl group (especially a phenyl group) is used as a ratio of a total amount (100 mol%) of a group bonded to a ruthenium atom to 10 mol% or more (for example, 20 to 50 mol%). The linear polyorganosiloxane of the above-mentioned type tends to have a higher sulfur barrier property of the cured product. Further, by using an alkyl group (especially a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 90 mol% or more (for example, 95 to 99 mol%). However, there is a tendency that the thermal shock resistance of the cured product is further improved.

The linear polyorganosiloxane is, for example, represented by the following formula (II-1).

[In the above formula, R ²¹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (except for the aliphatic unsaturated group). However, at least one (preferably at least two) of R ²¹ is a hydrogen atom. M2 is an integer from 5 to 1000. 〕

Further, in the linear polyorganosiloxane of the above formula (II-1), the above R ²¹ may be a hydroxyl group or an alkoxy group. Further, the monovalent substituent or the unsubstituted hydrocarbon group in the above R ²¹ (except for the aliphatic unsaturated group) may have a hydroxyl group or an alkoxy group.

In another example of the polyorganosiloxane (B1), one or more (preferably two or more) hydroquinone groups in the molecule may be mentioned, and the _rhodium represented by R ^b SiO _3/2 may be used. Branched polyorganosiloxane of oxyalkyl unit (T unit). The branched polyorganosiloxane also contains a polyorganosiloxane having a three-dimensional structure such as a mesh. Further, R ^b is a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group (except for the aliphatic unsaturated group). The group bonded to the ruthenium atom other than the hydrogen atom in the branched polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (however, an aliphatic unsaturated group) Except for the above) and the above-mentioned aryl group, among which, an alkyl group (especially a methyl group) and an aryl group (especially a phenyl group) are preferred. Further, examples of R ^b in the above T unit include a hydrogen atom, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (except for the aliphatic unsaturated group), and the above-mentioned aryl group, but among them, Preferred are alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups). The ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of R ^{b in} the above T unit is not particularly limited, but is preferably 30 mol from the viewpoint of sulfur barrier properties of the cured product. %the above.

In the above branched polyorganosiloxane, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably 70. ~95 moles %. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably from 10 to 70 mol%. In particular, an aryl group (especially a phenyl group) is used as a ratio of a total amount (100 mol%) of a group bonded to a ruthenium atom to 10 mol% or more (for example, 10 to 70 mol%). The branched polyorganosiloxane may have a tendency to increase the sulfur barrier properties of the cured product. Further, by using an alkyl group (especially a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 50 mol% or more (for example, 50 to 90 mol%). However, there is a tendency that the thermal shock resistance of the cured product is further improved.

The branched polyorganosiloxane may be represented, for example, by the above average unit formula in which c1 is a positive number. This case is not particularly limited, but c2/c1 is preferably 0 to 10, c3/c1 is preferably 0 to 0.5, and c4/(c1+c2+c3+c4) is preferably 0 to 0.3. The number c5/(c1+c2+c3+c4) is preferably 0 to 0.4. Further, the molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably from 300 to 10,000, more preferably from 500 to 3,000.

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

The content (mixing amount) of the component (B) in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is preferably a composition (100% by weight) based on the curable polyoxyxylene resin composition. 1 to 60% by weight, more preferably 5 to 55% by weight, still more preferably 10 to 50% by weight. When the content of the component (B) is 1% by weight or more, the curability of the curable polyoxynene resin composition is further improved, and the sulfur barrier property tends to be further improved. On the other hand, when the content of the component (B) is 60% by weight or less, the thermal shock resistance of the cured product tends to be further improved.

 [(C) component]  

The component (C) in the curable polyoxyxylene resin composition of the present invention is a compound represented by the above formula (1). The curable polyanthracene resin composition of the present invention can form a cured product excellent in sulfur barrier properties by containing the component (C) as an essential component. Further, the component (C) is considered to be because the solubility in the curable polyoxyxene resin composition of the present invention is good, and even in the case of an increase or a case where the curable polyoxynene resin composition is not heated. It does not precipitate as a solid. Therefore, the curable polyxanthine resin composition of the present invention does not cause a problem of solid precipitation to a high degree, and the sulfur barrier property to the cured product. In the past, a component having an effect of improving the sulfur barrier properties of the cured product has a problem in that solid precipitation occurs in order to increase the sulfur barrier property. Therefore, it is difficult to achieve both of the above characteristics.

In the formula (1), R ^a , R ^b and R ^c are the same or different and each represents a group represented by the formula (1a), a group represented by the formula (1b), a hydrogen atom or an alkyl group. However, at least one of R ^a , R ^b and R ^c is a group represented by the formula (1a).

In the formula (1a), R ^d represents a hydrogen atom or a linear or branched alkyl group (linear or branched C _1-8 alkyl group) having 1 to 8 carbon atoms. The linear or branched C _1-8 alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group or a pentyl group. Hexyl, heptyl, octyl, ethylhexyl and the like. Among the above alkyl groups, a linear or branched C _1-3 alkyl group such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. Among them, in terms of R ^d , it is particularly preferably a hydrogen atom.

In the formula (1a), s represents an integer of 2 to 10. Further, it is preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and further preferably an integer of 2 to 4. When s is in the above range, the precipitation of the solid in the curable polyoxynene resin composition tends to be suppressed, and the sulfur barrier property of the cured product tends to be balanced to a higher degree.

Further, in the case where two or three of R ^a , R ^b , and R ^c in the formula (1) are a group represented by the formula (1a), the groups represented by the formula (1a) may be the same. Can be different.

In the formula (1b), R ^e represents a hydrogen atom or a linear or branched alkyl group (linear or branched C _1-8 alkyl group) having 1 to 8 carbon atoms. The linear or branched C _1-8 alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group or a pentyl group. Hexyl, heptyl, octyl, ethylhexyl and the like. Among the above alkyl groups, a linear or branched C _1-3 alkyl group such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. Among them, in terms of R ^e , it is particularly preferably a hydrogen atom.

t in the formula (1b) represents an integer of 1 to 10. Among them, it is preferably an integer of 1 to 6.

Further, in the case where two of R ^a , R ^b , and R ^c in the formula (1) are a group represented by the formula (1b), the groups represented by the formula (1b) may be the same or different. Further, the isomeric cyanurate compound (C) may not have a group represented by the formula (1b).

The alkyl group of R ^a , R ^b , and R ^c may be any of a straight chain, a branched chain, and a cyclic group, and is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a propyl group. a linear or branched alkyl group such as isopropyl, butyl, isobutyl, secondary butyl, pentyl, hexyl, heptyl, octyl or ethylhexyl (for example, straight or branched) A C _1-8 alkyl group; a cyclic alkyl group (cycloalkyl group) such as a cyclohexyl group, a methylcyclohexyl group or a dimethylcyclohexyl group.

The curable polyoxyxene resin composition of the present invention contains the component (C), and the cured product exhibits sulfur barrier properties, and is presumed to be independent of the state of reaction with other components and the unreacted state, but because of hardening. The isocyanurate skeleton in the component (C) captures a corrosive gas such as SOx gas.

In the case of the component (C), for example, one of R ^a , R ^b and R ^c in the formula (1) is a compound represented by the formula (1a), and R in the formula (1) ^a, R ^b, and compound in th formula R ^c 2 (1a) the group shown by the formula (1) R ^a, R ^b and R ^c are all compounds of formula (1a) as shown in the group. In particular, in the point where the problem of solid precipitation is unlikely to occur, it is preferred that two or three of R ^a , R ^b and R ^c in the formula (1) are a compound represented by the formula (1a), and more preferably The compound of the formula (1) wherein all of R ^a , R ^b and R ^c are a group represented by the formula (1a).

The component (C) is presumed to have a group represented by the above formula (1a) in the molecule as a necessary base, and has and does not have the base (for example, triglycidyl isocyanurate, The effect of improving the sulfur barrier property of the same or higher than the monoallyl isocyanuric acid diglycidyl ester, and the curable polyoxyxylene resin composition of the present invention as compared with the case where the above-mentioned base is not provided The other components (especially the component (A) and the component (B)) have a very good compatibility, and as a result, the problem of solid precipitation in the curable polyoxynene resin composition does not occur, and also It is easily dissolved in other components during preparation. Therefore, the productivity of the curable polyoxynene resin composition is improved. In addition, even if the content of the component (C) is increased, the problem of the solid precipitation described above does not occur, and therefore the sulfur barrier property of the cured product due to the increase in the component (C) is remarkable. The ground lifting system is possible.

The component (C) can be used, for example, by reacting with a compound which reacts with an epoxy group such as an alcohol or an acid anhydride, and then modifying it.

When the component (C) is a group having the formula (1b), it may be used, for example, by reacting it with a compound having a hydroquinone group (hydroquinone reaction). For example, it is also possible to use a ladder type sesquiterpene oxide which is a component (F) which will be described later, and a hydroquinone catalyst which is a component (E), to be reacted as a curable polyfluorene oxygen of the present invention. A constituent component of the resin composition.

In the curable polyoxyxylene resin composition of the present invention, the component (C) may be used singly or in combination of two or more. In addition, as a component (C), a commercial item such as "TEPIC-VL" (manufactured by Nissan Chemical Industries Co., Ltd.) can be obtained.

The content (mixing amount) of the component (C) in the curable polyoxynoxy resin composition of the present invention is not particularly limited, but is preferably a composition (100% by weight) based on the curable polyoxyxylene resin composition. 0.01 to 10% by weight, more preferably 0.03 to 5% by weight, still more preferably 0.05 to 3% by weight, particularly preferably 0.1 to 2% by weight. When the content of the component (C) is 0.01% by weight or more, the sulfur barrier property of the cured product tends to be further improved. On the other hand, when the content of the component (C) is 10% by weight or less, a cured product having more excellent heat resistance, toughness, transparency, and the like tends to be obtained.

 [(D) component]  

The component (D) in the curable polyanthracene resin composition of the present invention is a branched polyorganosiloxane having one or more alkenyl groups in the molecule as described above (sometimes referred to as " (D) Ingredients"). In the curable polyoxyxylene resin composition of the present invention, the component (D) and the component (A) are components which undergo a hydroquinone reaction with a component having a hydroquinone group (for example, a component (B)). The curable polyanthracene resin composition of the present invention may further improve the heat resistance, thermal shock resistance, and sulfur barrier properties of the cured product by including the component (D).

The component (D) is a branched polyorgano group having one or more alkenyl groups in the molecule and having a -Si-O-Si-(decane bond) as a main chain and having no alkyl group bond. A siloxane (a polyorganosiloxane having a branched main chain). Further, the component (D) also contains a polyorganosiloxane having a three-dimensional structure such as a mesh shape. However, the component (D) described later does not include the component (F) described later.

The alkenyl group which the (D) component has in the molecule may, for example, be a substituted or unsubstituted alkenyl group described above, and among them, a vinyl group is preferred. Further, the component (D) may be one having only one type of alkenyl group, or one having two or more kinds of alkenyl groups. The alkenyl group which the (D) component has is not particularly limited, but is preferably bonded to a ruthenium atom.

The number of the alkenyl groups in the molecule (D) is not particularly limited as long as it is one or more, but it is preferably two or more from the viewpoint of the curability of the curable polyoxynene resin composition. For example, 2~50).

The group which is bonded to the ruthenium atom other than the alkenyl group which the component (D) has is not particularly limited, and examples thereof include a hydrogen atom and an organic group. The organic group may, for example, be an organic group (for example, a substituted or unsubstituted hydrocarbon such as an alkyl group, a cycloalkyl group, a cycloalkane group or a halogenated hydrocarbon group) and the above-mentioned aryl group.

Further, the component (D) may have a hydroxyl group or an alkoxy group as a group bonded to a ruthenium atom.

The property of the component (D) is not particularly limited. For example, at 25 ° C, it may be in the form of a liquid or a solid.

In the case of the component (D), the following average unit formula is preferred: (R ⁸ SiO _3/2 ) _d1 (R ⁸ ₂ SiO _2/2 ) _d2 (R ⁸ ₃ SiO _1/2 ) _d3 (SiO _{4/ 2} ) _d4 (X ³ O _1/2 ) _d5

The polyorganosiloxane is shown. In the above average unit formula, R ⁸ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, a halogenated hydrocarbon group, etc.) may be mentioned. And the above alkenyl group, and the above aryl group. However, a part of R ⁸ is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to be in the range of one or more (preferably two or more) in the molecule. For example, the ratio of the alkenyl group to the total amount of R ⁸ (100 mol%) is preferably from 0.1 to 40 mol%. When the ratio of the alkenyl group is controlled to the above range, the curability of the curable polyoxynene resin composition tends to be improved. Further, R ⁸ other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (especially a phenyl group).

In the above average unit formula, X ³ is the same as the above X ^1a and is a hydrogen atom or an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and particularly preferably a methyl group.

In the above average unit, d1 is 0 or a positive number, d2 is 0 or a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is 0 or a positive number, and (d1+d2+d3) and (d1+d4) They are positive numbers.

Specific examples of the component (D) include branched polyorganoindoles having two or more alkenyl groups in the molecule and having a fluorene oxide unit (T unit) represented by R ^c SiO _3/2 . Oxytomane. Further, R ^c is a monovalent substituted or unsubstituted hydrocarbon group. The alkenyl group which the branched polyorganosiloxane has is a specific example of the above-mentioned alkenyl group, and among them, a vinyl group is preferable. Further, it may be one having only one type of alkenyl group, or one having two or more types of alkenyl groups. Further, examples of the group bonded to the ruthenium atom other than the alkenyl group in the branched polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (including an aryl group). However, among them, an alkyl group (especially a methyl group) and an aryl group (especially a phenyl group) are preferred. Further, in the above T unit, R ^c is preferably an alkyl group (particularly a methyl group) or an aryl group (especially a phenyl group).

In the branched polyorganosiloxane, the ratio of the total number of alkenyl groups bonded to the ruthenium atom (100 mol%) is not particularly limited, but the composition of the curable polyxanthene resin is The viewpoint of hardenability is preferably from 0.1 to 40 mol%. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably 20 to 60 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably from 5 to 70 mol%. In particular, the use of an aryl group (especially a phenyl group) for a total amount (100 mol%) of a group bonded to a ruthenium atom is 40 mol% or more (for example, 45 to 60 mol%). The branched polyorganosiloxane may have a tendency to increase the sulfur barrier properties of the cured product. Further, by using an alkyl group (especially a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 30 mol% or more (for example, 35 to 60 mol%). However, there is a tendency that the thermal shock resistance of the cured product is further improved.

The branched polyorganosiloxane may be represented by the above average unit formula in which d1 is a positive number. This case is not particularly limited, but d2/d1 is preferably 0 to 10, d3/d1 is preferably 0 to 0.5, and d4/(d1+d2+d3+d4) is preferably 0 to 0.3. The number of d5/(d1+d2+d3+d4) is preferably 0 to 0.4. Further, the molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, more preferably 700 to 3,000.

Further, in the curable polyoxyxylene resin composition of the present invention, the component (D) may be used singly or in combination of two or more.

The content (mixing amount) of the component (D) in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is preferably 100 parts by weight based on 100 parts by total of the components (A) and (B). It is 50 to 200 parts by weight, more preferably 75 to 175 parts by weight, still more preferably 100 to 150 parts by weight. When the content of the component (D) is controlled within the above range, the thermal shock resistance, sulfur barrier properties, and heat resistance of the cured product may be further improved.

 [(E) component]  

The curable polyoxyxene resin composition of the present invention may also contain a hydroquinone catalyst containing a platinum group metal (sometimes referred to as "(E) component"). That is, the component (E) is a hydroquinone catalyst containing at least one metal (platinum group metal) selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum. The curable polyoxyxene resin composition of the present invention may contain the component (E), and the hydroquinone reaction between the alkenyl group and the hydroquinone group in the curable polyoxyxylene resin composition is efficiently carried out by heating. .

As the component (E), a conventional hydroquinone catalyst (for example, a platinum-based catalyst, a ruthenium-based catalyst, a palladium-based catalyst, or the like) can be used, and specific examples thereof include platinum fine powder. Platinum black, platinum supported vermiculite micropowder, platinum supported activated carbon, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum olefin complex, platinum-carbonyl vinyl a platinum-vinyl group such as a platinum complex such as a methyl complex or a platinum-divinyltetramethyldioxane complex or a platinum-cyclovinylmethyloxane complex a platinum-based catalyst such as a sulfoxane complex, a platinum-phosphine complex, a platinum-phosphite complex, or a palladium atom or a ruthenium atom substituted with a platinum atom in the platinum-based catalyst It is a catalyst or a catalyst. Among them, in the case of the component (E), a platinum-based catalyst (a platinum-containing hydroquinone catalyst), especially a platinum-vinyl methyl oxime complex or a platinum-carbonyl vinyl methyl methoxide is preferred. The complex or the complex of chloroplatinic acid with an alcohol or an aldehyde is preferred because of the good reaction rate.

Further, in the curable polyoxyxylene resin composition of the present invention, the component (E) may be used singly or in combination of two or more.

The content (mixing amount) of the component (E) in the curable polyoxynene resin composition of the present invention is not particularly limited, but is relative to the total amount of the alkenyl group contained in the curable polyoxynoxy resin composition. Mohr (per 1 m), preferably 1 x 10 ^-8 to 1 x 10 ^-2 mol, more preferably 1.0 x 10 ^-6 to 1.0 x 10 ^-3 mol. When the content of the component (E) is 1 × 10 ^-8 mol or more, the cured product tends to be formed more efficiently. On the other hand, when the content of the component (E) is 1 × 10 ^-2 mol or less, a cured product having a more excellent hue (less coloration) tends to be obtained.

Further, the content (doping amount) of the component (E) in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is preferably, for example, a platinum group metal in a hydroquinone catalyst in units of weight. The amount in the range of 0.01 to 1000 ppm is more preferably in the range of 0.1 to 500 ppm. When the content of the component (E) is in the above range, the cured product can be formed more efficiently, and a cured product having a more excellent hue can be obtained.

 [(F) component]  

The curable polyanthracene resin composition of the present invention may be a ladder type polyorganosilsesquioxane (may be referred to as "(F) component") having one or more alkenyl groups in the molecule. When the curable polyoxyxene resin composition of the present invention contains the component (F), the sulfur barrier property (especially SO _X barrier property) of the cured product tends to be remarkably improved. The (F) component can be used in a polyorgano-powdered powder of a poly-organic powder having one or more (preferably two or more) alkenyl groups in the molecule and having a ladder-like structure of -Si-O-Si- skeleton. The alkane is not particularly limited. As a particularly preferable aspect of the component (F), for example, the ladder-type polyorganosilsesquioxane (a) and the ladder-type polyorganosilsesquioxane (b) described below can be mentioned. However, the component (F) is not limited to the following ladder type polyorganosilsesquioxane.

‧ ladder type polyorganosilsesquioxane (a): having two or more alkenyl groups in the molecule, and having a number average molecular weight of 500 to 1,500 in terms of standard polystyrene by gel permeation chromatography, and molecular weight A ladder type polyorganopyroxane having a degree of dispersion (Mw/Mn) of 1.00 to 1.40.

‧ ladder type polyorganosilsesquioxane (b): part or all of the molecular chain end of the polyorganosilsesquioxane having a ladder structure, having a constituent unit represented by formula (III-3-1) (T unit) and a polyorganosil sesquioxane residue of a constituent unit (M unit) represented by formula (III-3-2) (sometimes referred to as "polyorganopsoid sulfonate residue (R)" a ladder type polyorganopyloxane.

Component (F) has a stair-like structure, and this can be confirmed by the following method: in the FT-IR spectrum in the vicinity of ^1050cm-1 (e.g., 1000 ~ ^-1 1100cm) 1150cm ^-1 vicinity of (e.g., more than 1100cm ^-1 1200cm ^-1 or less) has an intrinsic absorption peak (that is, at least two absorption peaks at 1000 to 1200 cm ^-1 ) [Reference: RHRaney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. Further, the FT-IR spectrum can be measured, for example, by the following apparatus and conditions.

Measuring device: product name "FT-720" (manufactured by Horiba Ltd.)

Measuring method: transmission method

Optical resolution: 4cm ^-1

Measuring the wave number field: 400~4000cm ^-1

Accrued count: 16 times

‧ ladder type polyorganopyloxane (a)

However, the ladder type polyorganosilsesquioxane (a) may be other sesquiterpene oxide structures further having a cage structure or a random structure in addition to the ladder structure.

The standard polystyrene-equivalent number average molecular weight (Mn) of the ladder type polyorganopyloxane (a) by gel permeation chromatography is 500 to 1,500, preferably 550 to 1,450, more preferably 600 to 600. 1400. When Mn is less than 500, for example, the physical properties (heat resistance, sulfur barrier properties, and the like) of the cured product tend to be lowered. On the other hand, when Mn exceeds 1,500, it tends to be solid at room temperature, and the workability tends to be lowered. Further, there is a case where the compatibility with other components is deteriorated.

The standard polystyrene-converted molecular weight dispersion (Mw/Mn) of the ladder type polyorganosilsesquioxane (a) by gel permeation chromatography is 1.00 to 1.40, preferably 1.35 or less (for example, 1.05~) 1.35), more preferably 1.30 or less (for example, 1.10 to 1.30). When the molecular weight dispersion degree exceeds 1.40, for example, the low molecular weight oxirane increases, and the adhesion of the cured product or the sulfur barrier property tends to decrease. On the other hand, for example, when the molecular weight dispersion degree is 1.05 or more, it is likely to be liquid (liquid) at room temperature, and the workability may be improved.

Further, the number average molecular weight and the molecular weight dispersion degree of the ladder type polyorganosilsesquioxane (a) were measured by the following apparatus and conditions.

Measuring device: product name "LC-20AD" (Shimadzu Corporation (stock) system)

Pipe column: Shodex KF-801×2, KF-802, and KF-803 (Showa Denko)

Measuring temperature: 40 ° C

Lysate: THF, sample concentration 0.1~0.2% by weight

Flow rate: 1mL/min

Detector: UV-VIS detector (product name "SPD-20A", Shimadzu Corporation)

Molecular weight: standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) in the nitrogen gas atmosphere of the ladder type polyorganosilsesquioxane (a) is not particularly limited, but is preferably 150 ° C or higher, more preferably 240 ° C or higher, and further Good is 260~500°C, especially good is above 262°C, and best is above 265°C. When the 5% weight loss temperature is 150° C. or higher (especially 240° C. or higher), the heat resistance required for various applications tends to be easily satisfied. Further, the 5% weight loss temperature is a temperature at a time point when the weight before heating is reduced by 5% at the time of heating at a fixed temperature increase rate, and is an index of heat resistance. The 5% weight reduction temperature was measured by TGA (thermogravimetric analysis) under the conditions of a nitrogen gas atmosphere at a temperature increase rate of 20 ° C /min.

The ladder type polyorganosilsesquioxane (a) is not particularly limited, but is preferably a liquid at room temperature (25 ° C). Specifically, the viscosity at 25 ° C is not particularly limited, but is preferably 30,000 Pa ‧ s or less (for example, 1 to 30,000 Pa ‧ s), more preferably 25,000 Pa ‧ s or less, and still more preferably 10,000 Pa ‧ s or less . The viscosity was measured using a viscometer (trade name "MCR301", manufactured by Anton Paar Co., Ltd.) at a vibration angle of 5%, a frequency of 0.1 to 100 (1/s), and a temperature of 25 °C.

The ladder type polyorganosquioxane (a) is, for example, represented by the following formula (III-2), and has two or more alkenyl groups in the molecule, and a gel permeation layer is used. The standard polystyrene-equivalent molecular weight (Mn) of the analytical polystyrene is 500 to 1500, and the molecular weight dispersion (Mw/Mn) is 1.00 to 1.40.

In the above formula (III-2), R ⁴² is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of R ⁴² include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group or an aryl group).

The ladder type polyorganosilsesquioxane (a) may have an alkenyl group as R ⁴² or may not. The ladder type polyorganosquioxane (a) is preferably R ⁴² other than the alkenyl group in the above formula (III-2), and has at least 1 selected from the group consisting of an alkyl group and an aryl group. More preferably, it has at least one selected from the group consisting of a phenyl group and a methyl group.

a ratio of a phenyl group, a vinyl group, and a methyl group (total content) in the total amount (100% by weight) of R ⁴² in the above formula (III-2) of the ladder type polyorganosiloxime (a) It is not particularly limited, but is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, still more preferably 80 to 100% by weight.

The ratio (content) of the phenyl group in the total amount (100% by weight) of R ⁴² in the above formula (III-2) of the ladder type polyorganosilsesquioxane (a) is not particularly limited, but is preferably It is 0 to 100% by weight, more preferably 1 to 100% by weight, still more preferably 5 to 100% by weight. The proportion (content) of the vinyl group in the total amount (100% by weight) of R ⁴² in the above formula (III-2) of the ladder type polyorganosiloxanes (a) is not particularly limited, but is preferably It is 0 to 100% by weight, more preferably 1 to 100% by weight, still more preferably 5 to 90% by weight, particularly preferably 10 to 80% by weight. The ratio (content) of the methyl group in the total amount (100% by weight) of R ⁴² in the above formula (III-2) of the ladder type polyorganosilsesquioxane (a) is not particularly limited, but is preferably It is 0 to 100% by weight, more preferably 1 to 100% by weight, still more preferably 5 to 100% by weight.

Further, the composition of R ⁴² in the above formula (III-2) of the ladder type polyorganosilsesquioxane (a) (for example, the ratio of a phenyl group, a vinyl group, a methyl group, etc.) is, for example, The NMR spectrum (for example, ¹ H-NMR spectrum) measurement or the like is calculated.

In the above formula (III-2), R ⁴³ is the same or different and represents a hydrogen atom, an alkyl group, a valence group represented by the following formula (III-2-1), and the following formula (III-2-2). A base of one of the valences shown, or a base of one of the formulas (III-2-3) below.

In the above formula (III-2-1), R ⁴⁴ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of R ⁴⁴ include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group and an aryl group), and among them, an alkyl group is also preferable. Further, in the above formula (III-2-1), R ⁴⁵ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of R ⁴⁵ include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group and an aryl group), and among them, an alkyl group is also preferable. In the above formula (III-2-1), n1 represents an integer of 0 or more. In the case of n1, it is preferably 0 to 5, more preferably 0 to 3, still more preferably 0.

In the above formula (III-2-2), R ⁴⁴ is the same as or different from R ⁴⁴ in the formula (III-2-1), and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. In the case of R ⁴⁴ , an alkyl group is further preferred. Further, in the above formula (III-2-2), R ⁴⁵ is the same or different as R ⁴⁵ in the formula (III-2-1), and is a monovalent substituted or unsubstituted hydrocarbon group. In the case of R ⁴⁵ , an alkyl group is further preferred. In the above formula (III-2-2), R ⁴⁶ is an alkenyl group, and among them, a vinyl group is further preferable. Further, in the above formula (III-2-2), n2 represents an integer of 0 or more. In the case of n2, it is preferably 0 to 5, more preferably 0 to 3, still more preferably 0.

In the above formula (III-2-3), R ⁴⁴ is the same as or different from R ⁴⁴ in the formula (III-2-1), and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. In the case of R ⁴⁴ , an alkyl group is further preferred. Further, in the above formula (III-2-3), R ⁴⁷ is the same or different, and is a monovalent saturated aliphatic hydrocarbon group, and examples thereof include an alkyl group, a cycloalkyl group and the like, but among them, an alkane is preferable. Base (especially methyl). In the above formula (III-2-3), n3 represents an integer of 0 or more. In the case of n3, it is preferably 0 to 5, more preferably 0 to 3, still more preferably 0.

In the above formula (III-2), n represents an integer of 0 or more. The above n is usually an even number of 0 or more (for example, an even number of 2 or more). The above n is not particularly limited as long as it is controlled to have a number average molecular weight of 500 to 1,500, and a molecular weight dispersion of 1.00 to 1.40, which is controlled by the ladder type polyorganosilsesquioxane (a). When the molecular weight dispersion degree of the ladder type polyorganosilsesquioxane (a) exceeds 1.00, the ladder type polyorganosilsesquioxane (a) is generally a polyorganic half of the formula represented by the formula (III-2). A mixture of two or more different types of decane and n. In particular, the ladder type polyorganosilsesquioxane (a) preferably contains a component having n of 1 or more (especially 2 or more) as an essential component.

The ladder type polyorganosquioxane (a) has two or more alkenyl groups in the molecule. The alkenyl group which the ladder type polyorganosquioxane (a) has is particularly preferably a vinyl group. In the case of the ladder type polyorganosquioxane (a) represented by the formula (III-2), for example, any one of R ^{42 in} the formula (III-2) is an alkenyl group having R Any one of ⁴⁴ and R ^{45 which} is a base of the formula (III-2-1) having an alkenyl group, a base having a valence of the formula (III-2-2), and having R ⁴⁴ Any one of the formulas represented by the formula (III-2-3) which is an alkenyl group, and the like.

The ladder-type polyorganosilsesquioxane (a) can be produced by a known method, and is not particularly limited, but can be, for example, Japanese Patent Laid-Open No. Hei 4-28722, No. 2010-518182 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is produced by the method disclosed in the literature of Japanese Laid-Open Patent Publication No. 2005-239829, and the like.

‧ ladder type polyorganopyloxane (b)

The polyorganosilsesquioxane having a ladder structure in the ladder type polyorganosilsesquioxane (b) is, for example, represented by the following formula (III-3).

In the above formula (III-3), p represents an integer of 1 or more (for example, 1 to 5000), preferably an integer of 1 to 2,000, and more preferably an integer of 1 to 1000. R ⁴⁸ in the formula (III-3) is the same or different and is a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group. T represents a terminal group.

a group (for example, R ⁴⁸ in the formula (III-3)) which has been directly bonded to a ruthenium atom in the above polyorganosilsesquioxane in the ladder type polyorganosilsesquioxane (b) is not It is particularly limited, but preferably a monovalent substitution or a ratio of the unsubstituted hydrocarbon group to the total amount of the above groups (100 mol%) is 50 mol% or more, more preferably 80 mol% or more, further Good for more than 90%. In particular, substituted or unsubstituted C _1-10 alkyl (especially C _1-4 alkyl of methyl, ethyl, etc.), substituted or unsubstituted C _6-10 aryl (especially phenyl), substituted The total amount of the above-mentioned groups (100 mol%) of the C _7-10 aralkyl group (especially benzyl group) which is unsubstituted is preferably 50 mol% or more, more preferably 80 mol%. The above is further preferably 90 mol% or more.

The ladder type polyorganosilsesquioxane (b) is a part or the whole of a molecular chain terminal of a polyorganosilsesquioxane having the above-described ladder-like structure, and has a polyorganosilsesquioxane residue (R). In the case of the above poly( sesquioxane) represented by the above formula (III-3), part or all of the T in the ladder polyorganosilsesquioxane (b) formula (III-3) has been Substituted by the above polyorganosquioxane residue (R).

The polyorgane sesquioxane residue (R) is at least a residue of a structural unit represented by the formula (III-3-1) and a structural unit represented by the formula (III-3-2) as described above.

R ⁴⁹ in the above formula (III-3-1) represents an alkenyl group. Specific examples of the above alkenyl group include a C _2-10 alkenyl group, more preferably a C _2-4 alkenyl group, and still more preferably a vinyl group.

The R ⁵⁰ in the above formula (III-3-2) is the same or different and represents a monovalent substituted or unsubstituted hydrocarbon group. The above-mentioned substituted or unsubstituted hydrocarbon group may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group or an aryl group). With respect to R ⁵⁰ , it is preferably an alkyl group, more preferably a C _1-20 alkyl group, still more preferably a C _1-10 alkyl group, particularly preferably a C _1-4 alkyl group, most preferably a methyl group. . Particularly preferred is that R ⁵⁰ in the formula (III-3-2) is a methyl group.

The polyorgane sesquioxane residue (R) may be, for example, a structural unit represented by the above formula (III-3-1) and a structural unit represented by the above formula (III-3-2). A constituent unit represented by the following formula (III-3-1').

R ⁴⁹ ' in the above formula (III-3-1') means a monovalent group other than an alkenyl group. Specifically, for example, a hydrogen atom, a halogen atom, a monovalent organic group other than an alkenyl group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur-containing group may be mentioned. The base of the atom, etc.

The amount of the ruthenium atom bonded to the three oxygen atoms represented by the formula (III-3-1) in the above-mentioned polyorganopyloxane residue (R) is not particularly limited, but is opposite to the constituent polyorganism. The total amount of ruthenium atoms (100 mol%) of the sesquioxane residue (R) is preferably from 20 to 80 mol%, more preferably from 25 to 60 mol%. When the content is less than 20 mol%, the amount of the alkenyl group which the ladder type polyorganosquioxane (b) has may be insufficient, and the hardness of the cured product may not be sufficiently obtained. On the other hand, if the content exceeds 80 mol%, many sterol groups or hydrolyzable silyl groups remain in the ladder type polyorganosilsesquioxane (b), so that it may not be liquid. The case of the ladder type polyorganosilsesquioxane (b) is obtained. Since the condensation reaction proceeds further between the ladder type polyorganosilsesquioxane (b) and the molecular weight is easily changed, the storage stability may be deteriorated.

The amount of the ruthenium atom bonded to one oxygen atom represented by the formula (III-3-2) in the above polyorganosquipene oxide residue (R) is not particularly limited, but is relative to the constituent polyorganism. The total amount of ruthenium atoms (100 mol%) of the sesquioxane residue (R) is preferably from 20 to 85 mol%, more preferably from 30 to 75 mol%. If the content is less than 20 mol%, the sterol group or the hydrolyzable sulfhydryl group in the ladder type polyorganosilsesquioxane (b) tends to remain, and the ladder type polyorganopose sesquioxide cannot be obtained in liquid form. The case of alkane (b). Since the condensation reaction proceeds further between the ladder type polyorganosilsesquioxane (b) and the molecular weight is easily changed, the storage stability may be deteriorated. On the other hand, when the content exceeds 85 mol%, the amount of the alkenyl group which the ladder type polyorganosilsesquioxane (b) has may be insufficient, and the hardness of the cured product may not be sufficiently obtained.

The Si—O—Si structure (skeleton) which the polyorganosquipene oxide residue (R) has is not particularly limited, and examples thereof include a ladder structure, a cage structure, a random structure, and the like. .

The ladder type polyorganosilsesquioxane (b) can be represented, for example, by the following formula (III-3'). The p and R ⁴⁸ in the formula (III-3') are the same as those in the above formula (III-3). A in the formula (III-3') represents a polyorganosilsesquioxane residue (R), or a hydroxyl group, a halogen atom, an alkoxy group or a decyloxy group, and part or all of A is a polyorganosene sesquiterpene. Oxylkane residue (R). The four A's can be the same or different. Further, in the case where the plural (2 to 4) of A in the formula (III-3') is a polyorganosilsesquioxane residue (R), each A may also have another formula (III-3). A of the molecule shown by ') is bonded by a Si or O-Si bond of 1 or more.

The number of the alkenyl groups in the molecule in the ladder-type polyorganosilsesquioxane (b) is not particularly limited as long as it is one or more, but preferably two or more (for example, 2 to 50) More preferably 2~30. By having an alkenyl group in the above range, it is possible to easily obtain various physical properties such as heat resistance, crack resistance, and a cured product excellent in barrier properties to sulfur compounds. Further, the number of alkenyl groups can be calculated, for example, by ¹ H-NMR spectrum measurement or the like.

The content of the alkenyl group in the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 0.7 to 5.5 mmol/g, more preferably 1.1 to 4.4 mmol/g. Further, the proportion (weight basis) of the alkenyl group contained in the ladder-type polyorganosiloxanes (b) is not particularly limited, but is preferably 2.0 to 15.0% by weight, more preferably 3.0, in terms of vinyl groups. ~12.0% by weight.

The weight average molecular weight (Mw) of the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably from 100 to 800,000, more preferably from 200 to 100,000, still more preferably from 300 to 10,000. The best is 500~8000, and the best is 1700~7000. When the Mw is 100 or more, the heat resistance of the cured product is not easily lowered. On the other hand, when Mw is 800,000 or less, compatibility with other components is hard to fall. Further, the above Mw is calculated from the molecular weight in terms of standard polystyrene by gel permeation chromatography.

The number average molecular weight (Mn) of the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably from 80 to 800,000, more preferably from 150 to 100,000, still more preferably from 250 to 10,000. The best is 400~8000, the best is 1500~7000. When Mn is 80 or more, the heat resistance of the cured product is not easily lowered. On the other hand, when Mn is 800,000 or less, the compatibility with other components is not easily lowered. Further, the above Mn is calculated from the molecular weight in terms of standard polystyrene by gel permeation chromatography.

The ladder type polyorganosilsesquioxane (b) is preferably a liquid at normal temperature (about 25 ° C). More specifically, the viscosity at 23 ° C is preferably from 100 to 100,000 mPa ‧ , more preferably from 500 to 10,000 mPa ‧ s, still more preferably from 1,000 to 8,000 mPa ‧ s. When the viscosity is 100 mPa·s or more, the heat resistance of the cured product is not easily lowered. On the other hand, when the viscosity is 100,000 mPa·s or less, preparation or treatment of the curable polyoxynene resin composition is easy. In addition, the viscosity at 23 ° C can be measured using a rheometer (trade name "Physica UDS-200", manufactured by Anton Paar Co., Ltd.) and a cone plate (cone diameter: 16 mm, cone angle = 0 °) at a temperature of 23 ° C. Number: 20 rpm conditions were measured.

The method for producing the ladder type polyorganosquioxane (b) is not particularly limited, and for example, it has a ladder structure and has a sterol group and/or a hydrolyzable thiol group at the end of the molecular chain. A method of forming the above sesquiterpene oxide residue (R) at the molecular chain end of the polyorganosilsesquioxane of either or both of an alcohol group and a hydrolyzable thiol group. Specifically, it can be produced by a method disclosed in the literature of International Publication No. 2013/176238 or the like.

Further, the ladder-type polyorganosilsesquioxanes (a) and (b) may have a hydroxyl group or an alkoxy group as a group bonded to a ruthenium atom.

Further, in the curable polyoxyxylene resin composition of the present invention, the component (F) may be used singly or in combination of two or more.

The curable polyanthracene resin composition of the present invention preferably contains a component (F) from the viewpoint of sulfur barrier properties and strength (resin strength) of the cured product, and more preferably contains a ladder type polyorganosilsesquioxane. (a) and/or ladder polyorganosilsesquioxane (b).

The content (mixing amount) of the component (F) in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is preferably 100 parts by weight based on 100 parts by total of the components (A) and (B). It is 0.01 to 50 parts by weight, more preferably 0.01 to 45 parts by weight, still more preferably 0.01 to 40 parts by weight. In addition, it is preferable that the content (mixing amount) of the component (F) is 0.1 to 20% by weight, more preferably 0.1 to 20% by weight, based on the curable polyoxynoxy resin composition (100% by weight). It is 0.1 to 15% by weight, and more preferably 0.2 to 10% by weight. When the content of the component (F) is controlled within the above range, the sulfur barrier property of the cured product tends to be remarkably improved.

 [(G) component]  

The curable polyanthracene resin composition of the present invention may contain an isomeric cyanurate compound represented by the following formula (2) (sometimes referred to as "(G) component"). In the case where the curable polyoxyxene resin composition of the present invention contains the component (G), the adhesion to the adherend of the cured product is further improved, and the sulfur barrier property tends to be changed more.

In the formula (2), R ^f , R ^g and R ^h are the same or different and each represents a group represented by the formula (2a) or a group represented by the formula (2b). However, at least one of R ^f , R ^g and R ^h is a group represented by the formula (2b).

In the formula (2a), R ⁱ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (linear or branched C _1-8 alkyl group). The linear or branched C _1-8 alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group or a pentyl group. , hexyl, heptyl, octyl, ethylhexyl and the like. Among the above alkyl groups, a linear or branched C _1-3 alkyl group such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. Among them, in the case of R ⁱ , it is particularly preferably a hydrogen atom.

Further, in the case where two of R ^f , R ^g , and R ^h in the formula (2) are a group represented by the formula (2a), the groups represented by the formula (2a) may be the same or different. Further, the isomeric cyanurate compound (D) may not have a group represented by the formula (2a).

In the formula (2b), R ^j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (linear or branched C _1-8 alkyl group). The linear or branched C _1-8 alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group or a pentyl group. , hexyl, heptyl, octyl, ethylhexyl and the like. Among the above alkyl groups, a linear or branched C _1-3 alkyl group such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. Among them, in terms of R ^j , it is particularly preferably a hydrogen atom.

Further, in the case where two or three of R ^f , R ^g , and R ^h in the formula (2) are a group represented by the formula (2b), the groups represented by the formula (2b) may be the same. Can be different.

In the case of the component (G), for example, one of R ^f , R ^g , and R ^h in the formula (2) is a compound represented by the formula (2b) (sometimes referred to as ""monoallyl isocyanuric acid diglycidyl ester compound"), and two of R ^f , R ^g , and R ^h in the formula (2) are compounds represented by the formula (2b) (sometimes called "Diallyl isocyanuric acid monoglycidyl ester compound"), and R ^f , R ^g and R ^h in the formula (2) are all compounds represented by the formula (2b) (sometimes referred to as "Triallyl isocyanurate").

The monoallyl isocyanuric acid diglycidyl ester compound may, for example, be monoallyl isocyanuric acid diglycidyl ester or 1-allyl-3. 5-bis(2-methylepoxypropyl)isomeric cyanurate, 1-(2-methylpropenyl)-3,5-isocyanuric acid diglycidyl ester, 1-(2 -Methacrylyl)-3,5-bis(2-methylepoxypropyl)isocyanate or the like.

The above-mentioned diallyl isocyanuric acid monoglycidyl ester compound, specifically, for example, diallyl isocyanuric acid monoglycidyl ester, 1,3-diallyl group -5-(2-methylepoxypropyl)isocyanate, 1,3-bis(2-methylpropenyl)-5-isocyanuric acid glycidyl ester, 1,3- Bis(2-methylpropenyl)-5-(2-methylepoxypropyl)isocyanate or the like.

Specific examples of the above triallyl isocyanurate include, for example, triallyl isocyanurate and stilbene (2-methacryl) isocyanurate. Wait.

In the curable polyoxyxylene resin composition of the present invention, the component (G) may be used singly or in combination of two or more. Further, the component (G) can be, for example, a commercially available product.

When the component (G) is a group represented by the formula (2a), it may be modified, for example, by reacting with a compound which reacts with an epoxy group such as an alcohol or an acid anhydride.

Since the component (G) has a group represented by the formula (2b), it can be used, for example, by reacting it with a compound having a hydroquinone group (hydroquinone reaction). For example, the above monoallyl isocyanuric acid diglycidyl ester compound may be reacted with a ladder type polyorganosilsesquioxane having the above (F) component in the presence of a hydroquinone catalyst. It is a constituent component of the curable polyoxynene resin composition of the present invention.

The component (G) may be blended with other components after mixing with the decane coupling agent of the component (H) as described later, from the viewpoint of improving the compatibility with other components.

The content (mixing amount) of the component (G) in the curable polyoxynoxy resin composition of the present invention is not particularly limited, but is preferably a composition (100% by weight) based on the curable polyoxynoxy resin composition. 0.01 to 6% by weight, more preferably 0.05 to 4% by weight, still more preferably 0.1 to 3% by weight. When the content of the component (G) is 0.01% by weight or more, the sulfur barrier property of the cured product and the adhesion to the adherend tend to be improved. On the other hand, when the content of the component (G) is 6% by weight or less, the problem of precipitation of solids in the curable polyoxynene resin composition tends to be suppressed.

In the case where the curable polyoxyxene resin composition of the present invention contains the component (G), the total (the total content) of the components (C) and (G) is not particularly limited, but is relative to the curable polyoxyl The resin composition is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 3% by weight, particularly preferably 0.4 to 2% by weight. When the total content is 0.01% by weight or more, the sulfur barrier property of the cured product tends to be remarkably improved. On the other hand, when the content of the total content is 15% by weight or less, the problem of precipitation of solids in the curable polyoxynoxy resin composition tends to be suppressed.

 [(H) component]  

The curable polyoxyxene resin composition of the present invention may also contain a decane coupling agent (sometimes referred to as "(H) component"). The curable polyoxyxene resin composition of the present invention contains the component (H), whereby the adhesion to the cured product of the adherend tends to be improved.

The component (H) has good compatibility with the component (A), the component (B), the component (C), the component (D), the component (F), and the component (G). Therefore, for example, G) The compatibility of the components with respect to other components is improved, and after the components of the (G) component and the (H) component are formed in advance, and blended with other components, a uniform hardenable polyoxyl resin composition can be easily obtained. Things.

The (H) component may be any conventionally used decane coupling agent, and is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxydecane and 2-(3, Epoxy containing 4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, etc. Base decane coupling agent; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Baseline, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 -triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2 - an amine group containing a hydrochloride of aminoethyl-3-aminopropyltrimethoxydecane, or N-(β-aminoethyl)-γ-aminopropylmethyldiethoxydecane Decane coupling agent; tetramethoxy decane, tetraethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, vinyl triethoxy decane, vinyl trimethoxy矽, vinyl methoxy (methoxy methoxy decane), phenyl trimethoxy decane, diphenyl dimethoxy decane, vinyl triethoxy decane, γ-(methyl) propylene decyloxy Propyltriethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(methyl And propylene methoxy propyl methyl diethoxy decane, decyl propyl trimethoxy decane, decyl propyl triethoxy decane, and the like. Among them, an epoxy group-containing decane coupling agent (particularly 3-glycidoxypropyltrimethoxydecane) is preferred. Further, the component (H) may be used alone or in combination of two or more.

The content (mixing amount) of the component (H) in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is preferably a composition (100% by weight) based on the curable polyoxynoxy resin composition. 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.4 to 5% by weight. When the content of the component (H) is 0.01% by weight or more, the adhesion to the adherend is improved, and particularly when the component (G) is used in combination, the curing is more sufficiently performed. On the other hand, when the content of the component (H) is 15% by weight or less, the hardening is not sufficiently insufficient, and the sulfur barrier property and the thermal shock resistance of the cured product are more easily improved.

 [(I) component]  

The curable polyoxyxylene resin composition of the present invention may further contain a zinc complex or a zinc salt selected from the group consisting of zinc carboxylate and the following formula (3) (however, zinc acetoacetate is excluded). At least one zinc compound in the group (the case where it is only referred to as "(I) component").

[Zn(L1)(L2)] (3)

Wherein L1 and L2 are the same or different and represent the following formula (3a) R ³¹ COCHR ³² COR ³³ (3a)

An anion of the β-diketone or β-ketoester or an enolate anion]

Further, the above zinc acetoacetate is also referred to as bis(2,4-pentanedione) zinc.

The curable resin composition of the present invention contains the above component (I), and in particular, the sulfur barrier property tends to be improved.

Further, the curable polyanthracene resin composition of the present invention is added by adding the zinc complex or the zinc salt represented by the above formula (3) as the component (I) (however, the zinc acetoacetate is excluded). The amount of the polyoxyxylene resin (especially the above (A) component, (B) component, (D) component, (F) component, etc.) is also good, and when the cured product is prepared by adding Sulfur barrier properties, especially not only for the barrier properties of hydrogen sulfide, but also for the barrier properties of SO _X .

The zinc carboxylate in the component (I) may, for example, be zinc naphthenate, zinc octoate, zinc acetylacetate, zinc (meth)acrylate or zinc neodecanoate, preferably naphthenic acid. Zinc, zinc octoate, more preferably zinc octoate.

In the formula (3a), R ³¹ represents a substituted or unsubstituted C _1-30 alkyl group, and in the case of a C _1-30 alkyl group, preferably a C _1-20 alkyl group, more preferably a C _2-15 alkyl group. Further, a group is further preferably a C _3-10 alkyl group, particularly preferably a branched C _3-10 alkyl group. Examples of the branched C _3-10 alkyl group include an isopropyl group, an isobutyl group, a tertiary butyl group, a secondary butyl group, an isopentyl group, a tertiary pentyl group, an isohexyl group, and a tertiary hexyl group. , isoheptyl, tertiary heptyl, isooctyl, trioctyl, 2-ethylhexyl, isodecyl, isodecyl, and the like. Among these, the most preferred are isopropyl, isobutyl, tert-butyl, secondary butyl, isopentyl, and tertiary pentyl. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group and the like.

In the formula (3a), R ³² represents a hydrogen atom or a substituted or unsubstituted C _1-30 alkyl group, and in the case of a C _1-30 alkyl group, a group as exemplified in the above R ³¹ is preferred, but in the case of R ^{In 32} , the most preferred group is a hydrogen atom. The above substituents are the same as those recited in the above R ³¹ .

In the formula (3a), R ³³ represents a substituted or unsubstituted C _1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an -OR ³⁴ group. The above R ³⁴ represents a substituted or unsubstituted C _1-30 alkyl group. The C _1-30 alkyl group is preferably the same group as those recited in the above R ³¹ . The aromatic heterocyclic group may, for example, be a pyridyl group, a pyrimidinyl group, a pyrazolyl group or a pyrene group. Base Base, three Base, furanyl, thienyl, fluorenyl, Azolyl, thiazolyl, imidazolyl and the like. The above substituents are the same as those recited in the above R ³¹ . R ³¹ and R ³² may be bonded to each other to form a ring, and R ³² and R ³³ may be bonded to each other to form a ring.

Further, the anion of the β-diketone or β-ketoester of the above formula (3a) or the anion of the enolate anion is a structure represented by the formula (3a'), and the enolate anion is of the formula (3a") The structure shown is that R ³¹ , R ³² , and R ³³ in the formula (3a') and the formula (3a") are the same as described above.

Further, in the component (I), a compound represented by the following formula (3') is preferred.

[In the formula (3'), R ³⁵ represents a substituted or unsubstituted C _1-30 alkyl group, R ³⁶ represents a hydrogen atom, or a substituted or unsubstituted C _1-30 alkyl group, and R ³⁷ represents a substitution or Unsubstituted C _1-30 alkyl, substituted or unsubstituted aromatic heterocyclic group, or -OR ³⁸ group. R ³⁸ represents a substituted or unsubstituted C _1-30 alkyl group. R ³⁵ and R ³⁶ may be bonded to each other to form a ring, and R ³⁶ and R ³⁷ may be bonded to each other to form a ring]

With respect to the above-mentioned substituted or unsubstituted C _1-30 alkyl C _1-30 alkyl group in R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ , the above-mentioned R ³¹ group is preferred, The aromatic heterocyclic group is the same as those recited in the above R ³³ , and the above substituent is the same as those exemplified in the above R ³¹ .

In the above (I) component, a compound represented by the following formula (3-1) [bis(2,2,7-trimethyl-3,5-octanedione acid) zinc] is particularly preferable. A compound represented by the formula (3-2) [Zn(DPM) ₂ : bis(trimethylethenyl)methane zinc].

In the curable polyoxyxylene resin composition of the present invention, the component (I) may be used singly or in combination of two or more. Further, as the component (I), a commercially available product can also be used.

The content (mixing amount) of the component (I) in the curable polyoxyxylene resin composition of the present invention is preferably 0.01 to 5 by weight based on the curable polyoxynoxy resin composition (100% by weight). More preferably, it is 0.05 to 3% by weight, further preferably 0.1 to 2% by weight, particularly preferably 0.1 to 1.5% by weight. When the content of the component (I) is 0.01% by weight or more, the sulfur barrier property of the cured product, in particular, not only the barrier property to hydrogen sulfide, but also the barrier property to SO _X is improved, and by making it When it is 5% by weight or less, the precipitation of the solid due to the component (I) tends to be suppressed in the curable polyoxyxene resin composition.

Further, the content (mixing amount) of the component (I) is preferably 0.02 to 10 parts by weight, more preferably 0.05 to 6 parts by weight, even more preferably 0.1% by weight based on 100 parts by weight of the component (A). ~4 parts by weight, particularly preferably 0.1 to 3 parts by weight. When the content of the component (I) is 0.02 parts by weight or more, the sulfur barrier property of the cured product, in particular, not only the barrier property to hydrogen sulfide, but also the barrier property to SO _X is improved, and When it is 10 parts by weight or less, the precipitation of the solid due to the component (I) tends to be easily suppressed.

 [other polyorganosiloxanes]  

The curable polyanthracene resin composition of the present invention may be other than the above-mentioned component (A), component (D), and component (F), and may contain other polyorganosiloxane having an alkenyl group in the molecule. (Sometimes referred to as "other polyorganosiloxanes"). By including other polyorganosiloxanes, there is a case where the viscosity of the curable polyoxynene resin composition or the balance of the physical properties (e.g., mechanical properties) of the cured product can be adjusted.

The other polyorganooxane may, for example, be a linear polyorganosiloxane having one or more alkenyl groups in the molecule (having one or more alkenyl groups in the molecule and having an anthracene) An alkane bond is used as a main chain, and a linear polyorganosiloxane having no alkyl group bond is added.

In the curable polyanthracene resin composition of the present invention, the above-mentioned linear polyorganosiloxane may be used singly or in combination of two or more.

The alkenyl group which the linear polyorganosiloxane has in the molecule may, for example, be a substituted or unsubstituted alkenyl group described above, and among them, a vinyl group is preferred. Further, the linear polyorganosiloxane may have only one type of alkenyl group, or may have two or more types of alkenyl groups. The alkenyl group which the linear polyorganosiloxane has is not particularly limited, but is preferably bonded to a ruthenium atom.

The number of the alkenyl group which the linear polyorganosiloxane has in the molecule is not particularly limited as long as it is one or more, but it is preferably from the viewpoint of the curability of the curable polyoxynene resin composition. It is 2 or more (for example, 2 to 50).

The group bonded to the ruthenium atom other than the alkenyl group of the linear polyorganosiloxane has not been particularly limited, and examples thereof include a hydrogen atom and an organic group. The organic group may, for example, be an organic group (for example, a substituted or unsubstituted hydrocarbon group such as an alkyl group, a cycloalkyl group, a cycloalkyl-alkyl group or a halogenated hydrocarbon group) and the above-mentioned aryl group.

Further, the linear polyorganosiloxane may have a hydroxyl group or an alkoxy group as a group bonded to a ruthenium atom.

The properties of the linear polyorganosiloxane are not particularly limited. For example, at 25 ° C, the liquid may be in the form of a liquid or a solid.

The above linear polyorganosiloxane includes the following average unit formula: (R ⁴ ₂ SiO _2/2 ) _e1 (R ⁴ ₃ SiO _1/2 ) _e2 (X ⁴ O _1/2 ) _E3

The polyorganosiloxane is shown. In the above average unit formula, R ⁴ is the same or different, and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, a halogenated hydrocarbon group, etc.) may be mentioned. And the above alkenyl group, and the above aryl group. However, a part of R ⁴ is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to be in the range of one or more (preferably two or more) in the molecule. For example, the ratio of the alkenyl group to the total amount of R ⁴ (100 mol%) is preferably from 0.1 to 40 mol%. When the ratio of the alkenyl group is controlled to the above range, the curability of the curable polyoxynene resin composition tends to be improved. Further, R ⁴ other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (especially a phenyl group).

In the above average unit formula, X ⁴ is the same as the above X ^1a and is a hydrogen atom or an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and particularly preferably a methyl group.

In the above average unit formula, e1 is a positive number, e2 is 0 or a positive number, and e3 is 0 or a positive number.

An example of the linear polyorganosiloxane described above is a linear polyorganosiloxane having two or more alkenyl groups in a molecule. The alkenyl group which the linear polyorganosiloxane has is a specific example of the above-mentioned alkenyl group, and among them, a vinyl group is preferable. Further, it may be one having only one type of alkenyl group, or one having two or more kinds of alkenyl groups. Further, the group bonded to the ruthenium atom other than the alkenyl group in the linear polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (including an aryl group). However, among them, an alkyl group (especially a methyl group) and an aryl group (especially a phenyl group) are preferred.

In the above linear polyorganosiloxane, the ratio of the total number of alkenyl groups to the base to which the ruthenium atom is bonded (100 mol%) is not particularly limited, but is preferably 0.1 to 40 mol%. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably from 1 to 20 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably from 30 to 90 mol%. In particular, an aryl group (especially a phenyl group) is used as a ratio of a total amount (100 mol%) of a group bonded to a ruthenium atom to 40 mol% or more (for example, 45 to 80 mol%). The linear polyorganosiloxane of the above-mentioned type tends to have a higher sulfur barrier property of the cured product. Further, by using an alkyl group (especially a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 90 mol% or more (for example, 95 to 99 mol%). However, there is a tendency that the thermal shock resistance of the cured product is further improved.

The linear polyorganosiloxane is, for example, represented by the following formula (IV-1).

[In the above formula, R ⁵¹ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least one (preferably at least two) of R ⁵¹ is an alkenyl group. M3 is an integer from 5 to 1000. 〕

The content (doping amount) of the other polyorganosiloxane in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is relative to the curable polyoxynene resin composition (100% by weight). It is preferably from 0.01 to 30% by weight, more preferably from 0.1 to 20% by weight. By controlling the content of the other polyorganosiloxane to be in the above range, it is possible to adjust the balance between the viscosity of the curable polyoxynene resin composition and the physical properties of the cured product.

 [hydroquinone reaction inhibitor]  

The curable polyanthracene resin composition of the present invention may further contain a hydroquinone reaction inhibitor in order to adjust the rate of the hardening reaction (hydroquinonelation reaction). In the above-described hydroquinone reaction inhibitor, a conventional hydroquinone reaction inhibitor can be used, and it is not particularly limited, but, for example, 3-methyl-1-butyn-3-ol, 3 , an alkynyl alcohol such as 5-dimethyl-1-hexyn-3-ol or phenylbutanol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexyl An alkyne compound such as alkene-1-alkyne; thiazole, benzothiazole, benzotriazole, and the like. The hydroquinone reaction inhibitor may be used singly or in combination of two or more. The content (mixing amount) of the hydroquinone reaction inhibitor differs depending on the crosslinking conditions of the curable polyoxynoxy resin composition, etc., but practically, it is a composition with respect to the curable polydecane resin (100 weight). The content of %) is preferably in the range of 0.00001 to 5% by weight.

 [cyclic alkane]  

The curable polyoxyxylene resin composition of the present invention may contain, for example, a cyclic oxirane having two or more aliphatic carbon-carbon double bonds (especially an alkenyl group) in the molecule as the above-mentioned polyorganism. A oxoxane compound other than a oxoxane (component (A), component (B), component (D), component (F), or other polyorganosiloxane). Further, the curable polyanthracene resin composition of the present invention may contain a cyclic siloxane having two or more hydroquinone groups in the molecule as the above-mentioned oxoxane compound. Each of the above cyclic oxiranes may be used singly or in combination of two or more. The content (doping amount) of the above cyclic oxirane in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is compared with the curable polyoxynene resin composition (100% by weight). It is preferably from 0.01 to 30% by weight, more preferably from 0.1 to 20% by weight, still more preferably from 0.5 to 10% by weight.

 [solvent]  

The curable polyoxyxene resin composition of the present invention may also contain a solvent. The solvent is not particularly limited as long as it is a conventionally used organic solvent or water, and examples thereof include toluene, hexane, isopropanol, methyl isobutyl ketone, and cyclopentanone. , propylene glycol monomethyl ether acetate, and the like. Further, the solvent may be used singly or in combination of two or more. Further, the content thereof is not particularly limited and may be appropriately selected.

 [fluorescent body]  

The curable polyoxyxene resin composition of the present invention may also contain a phosphor. As the phosphor, a conventional to conventional phosphor (for example, a phosphor or the like known in the field of optical semiconductor devices) can be used, and is not particularly limited, but for example, it is intended to impart blue light to the sealing material. In the case of a conversion function to white light, a general formula A ₃ B ₅ O ₁₂ : M (wherein A represents a group selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm) In the above element, B represents one or more elements selected from the group consisting of Al, Ga, and In, and M represents one or more selected from the group consisting of Ce, Pr, Eu, Cr, Nd, and Er. YAG-based phosphor microparticles (for example, Y ₃ Al ₅ O ₁₂ :Ce phosphor microparticles, (Y,Gd,Tb) ₃ (Al,Ga) ₅ O ₁₂ :Ce phosphor Microparticles, etc.; citrate-based phosphor fine particles (for example, (Sr, Ca, Ba) ₂ SiO ₄ : Eu, etc.). Further, the phosphor may be a surface treatment person which is known and used. Further, the phosphors may be used alone or in combination of two or more.

The content (mixing amount) of the phosphor in the curable polyoxynene resin composition of the present invention is not particularly limited, but is preferably 0.01 with respect to the curable polyoxynene resin composition (100% by weight). ~20% by weight, more preferably 0.5 to 10% by weight. By containing the phosphor in the above range, in the optical semiconductor device, the wavelength conversion function of the light due to the sealing material can be sufficiently exhibited, and the viscosity of the curable polyoxyn resin composition does not change. It is too high, and there is a tendency to improve workability in the production of hardened materials (especially in sealing work).

 [Other ingredients]  

The curable polyoxyxene resin composition of the present invention may contain components other than the above components (may be referred to as "other components"). The other components are not particularly limited, and examples thereof include vermiculite filler, titanium oxide, aluminum oxide, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, and carbonized ruthenium. An inorganic filler such as tantalum nitride or boron nitride; or an inorganic filler in which the filler is treated with an organic ruthenium compound such as an organic halogenated decane, an organoalkoxysilane or an organic decane; Organic resin fine powder such as polyoxyxylene resin, epoxy resin or fluororesin; filler or stabilizer for conductive metal powder such as silver or copper (antioxidant, ultraviolet absorber, light stabilizer, heat stabilization) Agents, etc., flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant auxiliaries, reinforcing materials (other fillers, etc.), nucleating agents, decane coupling agents Coupling agent, slip agent, wax, plasticizer, mold release agent, impact modifier, color improver, fluidity improver, colorant (dye, pigment, etc.), surface conditioner (for example, various polyethers) Modified oxirane, polyester modified oxirane, phenyl modified Known as a compound such as a sulfonium alkane or an alkyl modified oxime, a dispersant, an antifoaming agent, a deaerator, an antibacterial agent, a preservative, a viscosity modifier, a tackifier, and other functional additives. Conventional additives, etc. These other components may be used alone or in combination of two or more. Further, the content (mixing amount) of the other components is not particularly limited and can be appropriately selected.

The curable polyoxyxene resin composition of the present invention is not particularly limited, but is preferably an alkenyl group such as 0.2 to 4 mol with respect to the hydroquinone group 1 mol present in the curable polyoxynoxy resin composition. The composition of the ear (blending composition) is more preferably 0.5 to 1.5 moles, still more preferably 0.8 to 1.2 moles. When the ratio of the hydroquinone group to the alkenyl group is controlled to the above range, the thermal shock resistance of the cured product and the sulfur barrier property tend to be further improved.

The total amount (total content) of the component (A), the component (B), the component (D), the component (F), and other polyorganosiloxanes contained in the curable polyoxyxylene resin composition of the present invention It is not particularly limited, but is preferably 70% by weight or more (for example, 70% by weight or more and less than 100% by weight), and more preferably 80% by weight or more based on the curable polyoxyxylene resin composition (100% by weight). (for example, 80 to 99% by weight), further preferably 90% by weight or more (for example, 90 to 99% by weight). When the total amount is 70% by weight or more, the heat resistance and transparency of the cured product tend to be improved.

The total amount (total content) of the component (A), the component (D), the component (F), and other polyorganosiloxanes contained in the curable polyoxyxylene resin composition of the present invention is not particularly limited. However, it is preferably 40 to 90% by weight, more preferably 50 to 85% by weight, still more preferably 60 to 80% by weight based on the curable polyoxynene resin composition (100% by weight). When the total amount is 40% by weight or more, the durability and transparency of the cured product tend to be improved. On the other hand, when the total amount is 90% by weight or less, the hardenability tends to be improved.

The content (mixing amount) of the component (B) in the curable polyoxyxylene resin composition of the present invention is not particularly limited, but is relative to the component (A), the component (D), the component (F), and others. The total amount (total content) of the polyorganosiloxane is 100 parts by weight, preferably 1 to 200 parts by weight. When the content of the component (B) is controlled within the above range, the curability of the curable polyoxynene resin composition is further improved, and the cured product tends to be efficiently formed.

The total amount (total content; 100% by weight) of the component (A), the component (D), the component (F), and other polyorganosiloxanes contained in the curable polyoxynene resin composition of the present invention The ratio of the component (A) is not particularly limited, but is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 15% by weight or more (for example, 15 to 90% by weight), further It is preferably 20% by weight or more (for example, 20 to 80% by weight). When the ratio is 10% by weight or more, the thermal shock resistance of the cured product is further improved, and the viscosity tends to be lowered.

The total amount (total content; 100% by weight) of the component (A), the component (D), the component (F), and other polyorganosiloxanes contained in the curable polyoxynene resin composition of the present invention The ratio (total ratio) of the component (D) to the component (F) is not particularly limited, but is preferably more than 0% by weight and 90% by weight, more preferably 5 to 85% by weight, still more preferably 10 to 80% by weight. weight%. By setting the above ratio to 90% by weight or less, the component (A) can be relatively increased, so that the thermal shock resistance of the cured product is further improved, and the viscosity is also lowered. On the other hand, for example, when the ratio is 10% by weight or more, the balance between mechanical properties and optical properties of the cured product is further improved.

The total amount (total content) of the (A) component, the (B) component, the (D) component, the (F) component, and other polyorganosiloxanes contained in the curable polyoxyxene resin composition of the present invention 100% by weight), the ratio of the component (A) is not particularly limited, but is preferably 5% by weight or more (for example, 5 to 100% by weight), more preferably 10% by weight or more, still more preferably 15% by weight. 50% by weight. When the ratio is 5% by weight or more, the viscosity of the cured product is further reduced, and the thermal shock resistance tends to be good.

The curable polyoxyxene resin composition of the present invention is not particularly limited, and for example, it can be prepared by stirring and mixing the above components at room temperature (or while heating as needed). In addition, the curable polyanthracene resin composition of the present invention can be used as a composition of one liquid system in which all components are directly mixed, and for example, two or more components prepared separately can be used. A composition of a multi-liquid system (for example, a two-liquid system) used for mixing at a predetermined ratio before use is used.

The curable polyoxyxene resin composition of the present invention is not particularly limited, but is preferably a liquid at normal temperature (about 25 ° C). More specifically, the curable polyoxyxylene resin composition of the present invention preferably has a viscosity at 25 ° C of 300 to 20,000 mPa ‧ s, more preferably 500 to 10,000 mPa ‧ s, still more preferably 1000~8000mPa‧s. When the viscosity is 300 mPa ‧ s or more, the heat resistance of the cured product tends to increase. On the other hand, when the viscosity is 20,000 mPa·s or less, the preparation of the curable polyoxynene resin composition is easy, and the productivity or workability thereof is further improved, and the bubbles are less likely to remain. In the case of hardened materials, there is a tendency for the productivity or quality of the cured product (especially the sealing material) to be improved. Further, the viscosity of the curable polyanthracene resin composition was measured by the same method as the above-described viscosity of the ladder type polyorganosilsesquioxane (a).

 <hardened matter>  

A cured product (sometimes referred to as "the cured product of the present invention") can be obtained by curing the curable polyoxyxene resin composition of the present invention (especially by hardening by a hydroquinone reaction). The conditions at the time of hardening are not particularly limited, and may be appropriately selected from conventionally known conditions. For example, the temperature (hardening temperature) is preferably from 25 to 180 ° C (more preferably from 60 to 2). 150 ° C), time (hardening time) is preferably 5 to 720 minutes. The cured product of the present invention has high heat resistance and transparency unique to the polyoxyalkylene-based material, thermal shock resistance, adhesion to an adherend, and sulfur barrier properties, particularly not only hydrogen sulfide. The barrier property is also excellent in barrier properties of SO _X. Further, in the case of containing the component (G), a cured product having particularly excellent thermal shock resistance can be obtained.

 <Sealant, optical semiconductor device>  

The curable polyoxyxylene resin composition of the present invention is particularly preferably used as a sealing resin composition (photoresin composition for optical semiconductor sealing) of an optical semiconductor element (LED element) in an optical semiconductor device (sometimes) It is called "the sealant of the present invention"). The sealing material (cured material) obtainable by curing the sealant of the present invention is heat-resistant impact resistance and adhesion to the adherend in addition to the high heat resistance and transparency peculiar to the polyoxyalkylene-based material. The adhesion and sulfur barrier properties are particularly excellent not only for barrier properties of hydrogen sulfide but also for SO _X barrier properties. Therefore, the sealant of the present invention is particularly preferably used as a sealant for a high-brightness, short-wavelength optical semiconductor element. The optical semiconductor device can be sealed by using the sealing agent of the present invention to obtain an optical semiconductor device (sometimes referred to as "the optical semiconductor device of the present invention"). In other words, the optical semiconductor device of the present invention includes at least an optical semiconductor element and a sealing material for sealing the optical semiconductor element, and the sealing material is a hardenable polyoxymethylene resin composition of the present invention (the sealing agent of the present invention). An optical semiconductor device of a cured product (hardened product of the present invention). Further, the sealing of the optical semiconductor element can be carried out by a conventionally known method, and is not particularly limited. For example, it can be carried out under predetermined conditions by injecting the sealing agent of the present invention into a predetermined molding die. It is carried out by heat hardening. The hardening temperature and the hardening time are not particularly limited, and can be appropriately set in the same range as in the case of curing the cured product. An example of an optical semiconductor device of the present invention is shown in FIG. In Fig. 1, 100 denotes a reflector (resin composition for light reflection), 101 denotes a metal wiring (electrode), 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes a cured product (sealing material).

 <Composition for forming a lens for optical semiconductors, optical semiconductor device>  

Moreover, the composition of the curable polyoxyxylene resin of the present invention can be preferably used as a composition for forming a lens (a lens for an optical semiconductor) provided in an optical semiconductor device (a composition for forming a lens for an optical semiconductor) (something) (sometimes referred to as "the composition for forming a lens of the present invention"). A lens obtainable by curing the lens forming composition of the present invention has high heat resistance and transparency, and is excellent in adhesion to an adherend and sulfur barrier properties, particularly not only for hydrogen sulfide. The barrier property is also excellent in barrier properties of SO _X . An optical semiconductor device (this may also be referred to as "the optical semiconductor device of the present invention") may be obtained by using the lens forming composition of the present invention. In other words, the optical semiconductor device of the present invention includes at least an optical semiconductor element and a lens, and the lens is a cured product of the curable polyoxyxene resin composition of the present invention (the lens forming composition of the present invention) (the present invention) Optical semiconductor device of cured material). In addition, the production of the optical semiconductor lens using the lens forming composition of the present invention can be carried out by a conventionally known method, and is not particularly limited, but, for example, the lens of the present invention can be formed. A method of injecting a composition into a predetermined molding die and performing heat curing under predetermined conditions, or a method of applying heat by a predetermined condition by a dispenser or the like, or the like is carried out. The hardening temperature and the hardening time are not particularly limited, and can be appropriately set in the same range as in the case of curing the cured product. The optical semiconductor device of the present invention is not particularly limited as long as it has the above-described lens. For example, in the case where the optical semiconductor device of the present invention has a sealing material, part or all of the optical semiconductor device may be disposed on the surface of the sealing material. The aspect of the optical semiconductor device of the optical semiconductor device is sealed (that is, the cured product of the present invention serves as a sealing material and a lens). More specifically, the aspects disclosed in, for example, International Publication No. 2012/147342, JP-A-2012-188627, JP-A-2011-233605, and the like can be cited.

The optical semiconductor device of the present invention may be an optical semiconductor device including an optical semiconductor element, a sealing material and a lens for sealing the optical semiconductor element, and the sealing material is a curable polyoxyxene resin composition of the present invention. The cured product of the present invention is a cured product of the present invention, which is a cured product of the curable polyoxyxylene resin composition of the present invention (the lens forming composition of the present invention) (hardening of the present invention) ()).

The curable polyoxyxene resin composition of the present invention is not limited to the above-mentioned sealant application (sealing agent use for optical semiconductor element) and lens formation use (lens formation use in optical semiconductor device), and can be preferably used. For example, a use of a bonding agent (for example, a use of a bonding agent for an optical semiconductor), a sealing agent for a semiconductor element in a semiconductor device other than an optical semiconductor device, a functional coating agent, a heat-resistant plastic lens, a transparent machine, an adhesive (heat resistance) Transparent adhesive, etc.), electrical insulating material (insulating film, etc.), laminated board, coating film, ink, paint, sealant, photoresist, composite material, transparent substrate, transparent sheet, transparent film, optical element Optical, optical, optical, electronic, touch panels, solar cell substrates, optical waveguides, light guides, holographic memory, etc., optical or semiconductor-related applications.

In particular, the curable polyoxyxene resin composition of the present invention can be preferably used for a sealing material which is coated with an optical semiconductor element in a high-brightness ‧ short-wavelength optical semiconductor device which is difficult to cope with with a conventional resin material A sealing material for covering a semiconductor element in a semiconductor device (power semiconductor or the like) having high heat resistance and high withstand voltage.

 [Examples]  

The present invention will be described in more detail below based on the examples, but the invention is not limited by the examples. Further, the unit of the blending ratio of each component presented in Table 1 is part by weight.

The ¹ H-NMR analysis of the product and product produced in the synthesis example was carried out by JEOL ECA500 (500 MHz). Further, the number average molecular weight and the weight average molecular weight of the product and the product were measured by Alliance HPLC System 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), and column: Tskgel GMH _{HR -} M × 2 ( TOSOH (manufactured by TOSOH), protective column: Tskgel guard column H _HR L (manufactured by TOSOH), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C, borrowed It is carried out by standard polystyrene conversion.

 Synthesis Example 1    [Manufacture of polyorganosilsesquioxane having vinyl group]  

9.64 g (65 mmol) of vinyltrimethoxydecane, 38.67 g (195 mmol) of phenyltrimethoxydecane, and 8.31 g of methyl isobutyl ketone (MIBK) were fed under a nitrogen stream, and a thermometer, a stirring device, and the like were placed. A 100 ml flask (reaction vessel) of a reflux condenser and a nitrogen introduction tube was cooled, and the mixture was cooled to 10 ° C or lower. 6.48 g (360 mmol) of water and 0.24 g of 5N hydrochloric acid (1.2 mmol of hydrogen chloride) were added dropwise to the above mixture. Then, 40 g of MIBK was added, and the reaction solution was diluted.

Next, the temperature of the reaction vessel was raised to 70 °C. 9.36 g (520 mmol) of water was added thereto, and a polycondensation reaction was carried out under a nitrogen stream. Next, 21.11 g (130 mmol) of hexamethyldioxane was added to the reaction solution after the polycondensation reaction, and the mixture was stirred at 70 ° C to carry out a silylation reaction. Then, the mixture was cooled and washed with water until the lower layer became neutral. After the upper layer liquid was separated and taken out, the solvent was distilled off from the supernatant liquid under the conditions of 1 mmHg and 40 ° C to obtain a colorless transparent liquid product (38.6 g; A polyorganosilsesquioxane having a vinyl group).

The product (the product after the deuteration reaction) had a number average molecular weight of 1,280 and a molecular weight dispersion of 1.13. Further, Fig. 2 is a graph showing the ¹ H-NMR spectrum of the above product (solvent: deuterated chloroform). Furthermore, the FT-IR spectrum of the above product was measured under the above conditions, and it was confirmed that there were two absorption peaks at 1000 to 1200 cm ^-1 . Fig. 3 is a graph showing the FT-IR spectrum of the above product.

The product (product after the deuteration reaction) corresponds to the above-mentioned component (F) (more specifically, the ladder polyorganosilsesquioxane (a)).

The description of each component described in Table 1 is presented below.

 (agent A)  

Polyorgano alkoxyalkylene alkyl (GS5145A): trade name "ETERLED GS5145A" [polyoxyalkylene oxide containing polyorganoquinoloxyalkylene alkyl (A2)], manufactured by Changxing Material Industry, aryl (phenyl The ratio is about 24 mol%, and contains a hydroquinone catalyst [(E) component].

Polyorganosiloxane (OE-6630A): trade name "OE-6630A" [Phenyl polyoxyl resin containing polyorganosiloxane (A1)], manufactured by Dow Corning Toray Co., Ltd., containing hydroquinone Catalyst [(E) component].

Isocyanurate compound (C) (TEPIC-VL): a product of the following formula, manufactured by Nissan Chemical Industries Co., Ltd., under the trade name "TEPIC-VL" (component (C)).

Ladder type polyorganosquioxane (F) (Synthesis Example 1): Compound [(F) component] obtained in Synthesis Example 1.

The isocyanurate compound (MA-DGIC): the product name "MA-DGIC" (component (G)), a compound of the following formula, manufactured by Shikoku Kasei Kogyo Co., Ltd.

Heteropolycyanate compound (TEPIC): a product of the following formula, manufactured by Nissan Chemical Industries Co., Ltd. under the trade name "TEPIC" (component (G)).

Nikka Octix Zinc: trade name "Nikka Octix Zinc" [zinc 2-ethylhexanoate], manufactured by Nippon Chemical Industry Co., Ltd.

A decane coupling agent (OFS-6040): trade name "XIAMETER OFS-6040" [3-glycidoxypropyltrimethoxydecane, (H) component], manufactured by Dow Corning.

 (B agent)  

Polyorganosiloxane (GS5145B): trade name "ETERLED GS5145B" (polyoxyl resin, containing (B) component and (D) component), manufactured by Changxing Materials Industry Co., Ltd.

Polyorganosiloxane (OE-6630B): trade name "OE-6630B" (polyoxyl resin, comprising (B) component and (D) component), manufactured by Dow Corning Toray Co., Ltd.

 Example 1    [Manufacture of Curable Polyoxynene Resin Composition]  

First, as shown in Table 1, 20 parts by weight of the product name "ETERLED GS5145A" and the trade name "TEPIC-VL" (0.1 part by weight) were mixed, and the mixture was stirred at 40 ° C for 2 hours to prepare a dose A.

Then, 80 parts by weight of the product name "ETERLED GS5145B" as a B agent was mixed with 20.1 parts by weight of the A agent obtained above, and a public-rotary stirring device (trade name "THINKY MIXER", manufactured by THINKY CORPORATION, model number: ARE-310) was stirred for 5 minutes, and subjected to degassing for 2 minutes to carry out kneading, thereby producing a uniform liquid curable polyoxynene resin composition.

 [Manufacture of Optical Semiconductor Devices]  

The curable polyanthracene resin composition obtained above was injected into an LED package (InGaN element, 3.0 mm × 3.0 mm) as shown in Fig. 1, and heated at 60 ° C for 1 hour, followed by heating at 80 ° C. In the hour, the film was further heated at 150 ° C for 4 hours to produce an optical semiconductor device in which the optical semiconductor element was sealed by the cured product of the curable polyoxynoxy resin composition.

 Examples 2 to 10, Comparative Examples 1 to 5  

In the same manner as in Example 1, except that the composition of the curable polyoxyxene resin composition was changed as shown in Table 1, a curable polyoxynoxy resin composition and an optical semiconductor device were produced.

 (Evaluation)  

The following evaluations were carried out on the curable polyanthracene resin composition and the optical semiconductor device obtained above. The evaluation results are shown in Table 1. Further, in Comparative Example 3, since the trade name "TEPIC" was not dissolved in the curable polyoxynoxy resin composition, it was not evaluated.

 [sulfur corrosion test]  

The optical semiconductor device manufactured above was used as a sample.

First, the total amount of light flux (unit: lm) when a current of 20 mA was applied was measured using a total luminous flux measuring machine (manufactured by Optronic Laboratories, Inc., multispectral radiation measuring system "OL771"), and this was regarded as "SO _X corrosiveness". The total luminous flux before the test."

Next, the above sample and 0.3 g of sulfur powder (KISHIDA CHEMICAL Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was further placed in an aluminum case. Next, the above-mentioned aluminum box was placed in an oven (manufactured by Yamato Scientific Co., Ltd., model: DN-64) at 80 ° C, and taken out one day later. With respect to the sample after heating, the total luminous flux was measured in the same manner as described above, and this was regarded as "the total luminous flux after the SO _X corrosivity test". The total luminous flux maintenance ratio (%) before and after the SO _X corrosivity test was calculated [= 100 × (total luminous flux (lm) after SO _X corrosive test) / (total luminous flux (lm) before SO _X corrosive test) )].

The higher the luminosity maintenance ratio, the more the cured product (sealing material) exhibits excellent barrier properties against the SO _X corrosive gas. Further, for each of the curable polyoxyxylene resin compositions (for each of the examples and the comparative examples), 10 optical semiconductor devices were measured. The photometric maintenance ratio was calculated, and the photometric maintenance ratios are shown in Table 1. Average value (N=10). The results are presented in Table 1.

 [thermal shock test]  

The optical semiconductor device manufactured above was used as a sample. The sample was used for each of the curable polyoxynoxy resin compositions. In addition, the sample was used after it was confirmed that it was turned on when the current was 20 mA before the test.

For the above sample, a thermal shock tester (ESPEC (manufactured by ESPEC), model: TSB-21) was used, and exposed to a temperature of -40 ° C for 5 minutes, followed by exposure at a temperature of 100 ° C for 5 minutes as a thermal shock of 1 cycle. 1000 cycles were implemented. Then, with respect to the sample after the thermal shock imparted to 1000 cycles, a current of 20 mA was applied, and the number of unlit samples was calculated. On the other hand, the case where the number of the unlit samples was 0 was evaluated as ○ (the thermal shock resistance was good), and the case where the number of the unlit samples was one or more was evaluated as × (the thermal shock resistance was poor). The results are presented in Table 1.

 [Moisture absorption reflow test]  

The optical semiconductor device manufactured above was used as a sample. For the sample, 10 each of the curable polyoxynene resin compositions was used. In addition, the sample was used after it was confirmed that it was turned on when the current was 20 mA before the test.

The sample was placed in a constant temperature and humidity chamber (ESPEC, model "SH-641") adjusted to 30 ° C and 60% RH, and taken out after 192 hours. Then, each of the above-mentioned samples was subjected to heat treatment at 260 ° C for 10 seconds twice using a reflow furnace (manufactured by ANTOM Co., model "UNI-5016F"). Then, the sample after the secondary heat treatment using the reflow furnace was energized to a current of 20 mA, and the number of unlit samples was calculated. On the other hand, the case where the number of unlit samples was 0 was evaluated as ○ (the moisture absorption reflow property was good), and the case where the number of unlit samples was one or more was evaluated as × (the moisture reflowability was poor) ). The results are presented in Table 1.

 [Comprehensive judgment]  

The curable polyanthracene resin composition obtained in the examples and the comparative examples was evaluated based on the following criteria based on the evaluation results of the three items of the SO _X corrosion test, the thermal shock test, and the moisture absorption reflow test. Comprehensive judgment.

○ (good): The evaluation result of the SO _X corrosion test was 80% or more, the evaluation result of the thermal shock test was ○, and the evaluation result of the moisture absorption reflow test was ○.

× (defect): The evaluation result of the SO _X corrosion test was 80% or more, the evaluation result of the thermal shock test was ○, and the evaluation result of the moisture absorption reflow test was ○.

The variations of the invention described above are noted below.

[1] A curable polyoxyxylene resin composition comprising the following components (A), (B), (C), and (D).

(A): a polyorganosiloxane (A1) selected from the group consisting of two or more alkenyl groups (preferably vinyl groups) and one or more aryl groups (preferably phenyl groups) contained in the molecule, and At least one group of polyorganoquinoloxyalkylene groups (A2) having two or more alkenyl groups (preferably vinyl groups) and one or more aryl groups (preferably phenyl groups) in the molecule Polysiloxane; (B): polyorganooxynonane having one or more (preferably two or more, more preferably 2 to 50) hydroquinone groups in the molecule and having no aliphatic unsaturation (C): an isomeric cyanurate compound represented by the following formula (1);

In the formula (1), R ^a , R ^b and R ^c are the same or different and each represents a group represented by the formula (1a), a group represented by the formula (1b), a hydrogen atom or an alkyl group. However, at least one of R ^a , R ^b and R ^c (preferably 2 or 3, more preferably 3) is a group represented by the formula (1a).

[In the formula (1a), R ^d represents a hydrogen atom or a linear or branched alkyl group (preferably a hydrogen atom) having 1 to 8 carbon atoms. s represents an integer of 2 to 10 (preferably 2 to 8, more preferably 2 to 6, further preferably 2 to 4). 〕

In the formula (1b), R ^e represents a hydrogen atom or a linear or branched alkyl group (preferably a hydrogen atom) having 1 to 8 carbon atoms. t represents an integer of 1 to 10 (preferably 1 to 6). 〕〕

(D): a branched polyorganosiloxane having one or more (preferably two or more, more preferably 2 to 50) alkenyl groups (preferably vinyl groups) in the molecule.

[2] The curable polyanthracene resin composition according to the above [1], wherein the polyorganosiloxane (A1) has an alkyl group (preferably a methyl group) other than the alkenyl group and the aryl group.

[3] The curable polyanthracene resin composition according to the above [1] or [2] wherein the polyorganosiloxane (A1) is an average unit formula: (R ^1a SiO _3/2 ) _a1 (R ^1a ₂ SiO _2/2 ) _a2 (R ^1a ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ^1a O _1/2 ) _a5

[In the average unit formula, R ^1a is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R ^1a is an alkenyl group (preferably a vinyl group), and the ratio thereof is two or more in the molecule. A part of R ^1a is an aryl group (preferably a phenyl group), and the ratio thereof is one or more in the molecule. X ¹ is a hydrogen atom or an alkyl group (preferably a methyl group). A1 is 0 or a positive number, a2 is 0 or a positive number, a3 is 0 or a positive number, a4 is 0 or a positive number, a5 is 0 or a positive number, and (a1+a2+a3) is a positive number. 〕

The polyorganosiloxane is shown.

[4] The curable polyanthracene resin composition according to the above [3], wherein the ratio of the alkenyl group (preferably a vinyl group) to the total amount of R ^1a (100 mol%) is 0.1 to 40 mol. ear%.

[5] The curable polyanthracene resin composition according to the above [3] or [4], wherein the ratio of the aryl group (preferably a phenyl group) to the total amount of R ^1a (100 mol%) is 30~70% by mole.

[6] The curable polyanthracene resin composition according to any one of the above [3], wherein R ^1a other than the alkenyl group and the aryl group is an alkyl group (preferably a methyl group).

[7] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganosiloxane (A1) has two or more alkenyl groups in the molecule ( A linear polyorganosiloxane having one or more aryl groups (preferably a phenyl group) is preferred.

[8] The curable polyanthracene resin composition according to [7], wherein the polyorganosiloxane (A1) further has an alkyl group (preferably a methyl group).

[9] The curable polyanthracene resin composition according to the above [7] or [8], which is an alkenyl group (preferably a vinyl group) having a total amount of a group bonded to a ruthenium atom (100 mol) The ratio of the ear %) is 0.1 to 40 mol%.

[10] The curable polyanthracene resin composition according to the above [8] or [9], which is a total amount of an alkyl group (preferably a methyl group) bonded to a ruthenium atom (100 mol) The ratio of the ear %) is 40 to 60 mol% (preferably 50 mol% or more, more preferably 55 to 60 mol%).

[11] The curable polyanthracene resin composition according to any one of the above [7] to [10] wherein the aryl group (preferably a phenyl group) is a group bonded to a ruthenium atom. The ratio of the amount (100 mol%) is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%).

[12] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganosiloxane (A1) is represented by the following formula (I-1).

[In the above formula, R ¹¹ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ¹¹ are alkenyl groups (preferably vinyl groups), and at least one is an aryl group (preferably a phenyl group). M1 is an integer from 5 to 1000]

[13] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganosiloxane (A1) has two or more alkenyl groups in the molecule ( It is preferably a vinyl group and one or more aryl groups (preferably a phenyl group) and has R ^a SiO _3/2 [R ^a is a monovalent substituted or unsubstituted hydrocarbon group. a branched polyorganosiloxane having a oxoxane unit (T unit) as shown.

[14] The curable polyanthracene resin composition according to the above [13], wherein the polyorganosiloxane (A1) further has an alkyl group (preferably a methyl group).

[15] The curable polyanthracene resin composition according to the above [13] or [14], which is an alkenyl group (preferably a vinyl group) to a total amount of a group bonded to a ruthenium atom (100 mol) The ratio of the ear %) is 0.1 to 40 mol%.

[16] The curable polyanthracene resin composition according to the above [14] or [15], which is a total amount of an alkyl group (preferably a methyl group) bonded to a ruthenium atom (100 mol) The ratio of the ear %) is 40 to 60 mol% (preferably 50 mol% or more, more preferably 55 to 60 mol%).

[17] The curable polyanthracene resin composition according to any one of the above [13] to [16] wherein the aryl group (preferably a phenyl group) is a group bonded to a ruthenium atom. The ratio of the amount (100 mol%) is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%).

[18] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganoquinoloxyalkylene group (A2) has an alkylene group in the molecule. The alkyl group in the base bond is a linear or branched C _1-12 alkyl group (preferably a C _2-4 alkyl group, more preferably an ethyl group).

[19] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganoquinoloxyalkylene group (A2) further has an alkyl group (preferably methyl).

[20] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganoquinoloxyalkylene group (A2) is an average unit formula: ( R ^1b ₂ SiO _2/2 ) _b1 (R ^1b ₃ SiO _1/2 ) _b2 (R ^1b SiO _3/2 ) _b3 (SiO _4/2 ) _b4 (R ^A ) _b5 (X ^1b O) _b6

[In the average unit formula, R ^1b is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R ^1b is an alkenyl group (preferably a vinyl group), and the ratio thereof is two or more in the molecule. A part of R ^1b is an aryl group (preferably a phenyl group), and the ratio thereof is one or more in the molecule. R ^A is an alkylene group (preferably an extended ethyl group). X ^1b is a hydrogen atom or an alkyl group (preferably a methyl group). B1 is a positive number (preferably 1 to 200), b2 is a positive number (preferably 1 to 200), b3 is 0 or a positive number (preferably 0 to 10), and b4 is 0 or a positive number (preferably 0 to 5) ), b5 is a positive number (preferably 1 to 100), and b6 is 0 or a positive number. 〕

The polyorganoquinoloxy oxime alkyl group shown.

[21] The curable polyanthracene resin composition according to the above [20], wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount of R ^1b (100 mol%) is 0.1 to 40 mol. ear%.

[22] The curable polyanthracene resin composition according to the above [20] or [21], wherein the ratio of the aryl group (preferably phenyl group) to the total amount of R ^1b (100 mol%) is 10~50% by mole.

[23] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganoquinoloxyalkylene group (A2) has the following formula (I- 2) A polyorganoquinoloxyalkylene group of the structure shown.

[In the formula (I-2), R ¹² is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ¹² are alkenyl groups (preferably vinyl groups), and at least one of R ¹² is an aryl group (preferably a phenyl group). R ^A is an alkylene group (preferably a C _2-4 alkylene group, more preferably an extended ethyl group). R1 represents an integer of 1 or more (preferably 1 to 100). R2 represents an integer of 1 or more (preferably 1 to 400). R3 represents an integer of 0 or more (preferably 0 to 50). R4 represents an integer of 0 or more (preferably 0 to 50). R5 represents an integer of 0 or more (preferably 0 to 50). 〕

[24] The curable polyanthracene resin composition according to the above [23], wherein R ¹² other than the alkenyl group and the aryl group is an alkyl group (preferably a methyl group).

[25] The curable polyanthracene resin composition according to any one of the above [1], wherein the content (mixing amount) of the component (A) is different from that of the curable polydecane resin. The content (100% by weight) is 0.1 to 60% by weight (preferably 0.1 to 55% by weight, more preferably 0.1 to 50% by weight).

[26] The curable polyanthracene resin composition according to any one of [1] to [25] wherein the polyorganosiloxane (B1) is an average unit formula: (R ² SiO _{3 ) /2} ) _c1 (R ² ₂ SiO _2/2 ) _c2 (R ² ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (X ² O _1/2 ) _c5

[In the above average unit formula, R ² is the same or different and is a hydrogen atom, or a monovalent substitution or an unsubstituted hydrocarbon group (except for the aliphatic unsaturated group). However, a part of R ² is a hydrogen atom (a hydrogen atom constituting a hydroquinone group), and the ratio of hydroquinone is one or more (preferably two or more) in the molecule. X ² is a hydrogen atom or an alkyl group (preferably a methyl group). C1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1+c2+c3) is a positive number. 〕

The polyorganosiloxane is shown.

[27] The curable polyanthracene resin composition according to the above [26], wherein the ratio of the hydrogen atom to the total amount of R ² (100 mol%) is 0.1 to 40 mol%.

[28] The curable polyanthracene resin composition according to the above [26] or [27] wherein R ² other than a hydrogen atom is selected from the group consisting of an alkyl group (preferably a methyl group) and an aryl group ( At least one of the group of phenyl groups is preferred.

[29] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganosiloxane (B1) has one or more molecules (preferably Two or more) hydroquinone-based linear polyorganosiloxanes.

[30] The curable polyanthracene resin composition according to the above [29], wherein the group bonded to the ruthenium atom other than the hydrogen atom is selected from the group consisting of an alkyl group (preferably a methyl group) and an aromatic group. At least one of the group of groups (preferably phenyl groups).

[31] The curable polyanthracene resin composition according to the above [29] or [30], which is a total of a hydrogen atom (a hydrogen atom bonded to a ruthenium atom) to a group bonded to a ruthenium atom. The ratio of the amount (100 mol%) is 0.1 to 40 mol%.

[32] The curable polyanthracene resin composition according to the above [30] or [31], which is a total amount of an alkyl group (preferably a methyl group) bonded to a ruthenium atom (100 mol) The ratio of the ear %) is 20 to 99 mol% (preferably 90 mol% or more, more preferably 95 to 99 mol%).

[33] The curable polyanthracene resin composition according to any one of [30] to [32] wherein the aryl group (preferably a phenyl group) is bonded to a ruthenium atom. The ratio of the amount (100 mol%) is 10 to 50 mol% (preferably 20 to 50 mol%).

[34] The curable polyanthracene resin composition according to any one of [1] to [33] wherein the polyorganosiloxane (B1) is represented by the following formula (II-1).

[In the above formula, R ²¹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (except for the aliphatic unsaturated group). However, at least one (preferably at least two) of R ²¹ is a hydrogen atom. M2 is an integer from 5 to 1000. 〕

[35] The curable polyanthracene resin composition according to any one of the above [1], wherein the polyorganosiloxane (B1) has one or more molecules (preferably Two or more) hydroquinone groups and having R ^b SiO _3/2 [R ^b is a hydrogen atom, or a monovalent substitution or an unsubstituted hydrocarbon group (except for aliphatic unsaturated groups)] A branched polyorganosiloxane of an alkane unit (T unit).

[36] The curable polyanthracene resin composition according to the above [35], wherein the group bonded to the ruthenium atom other than the hydrogen atom is selected from the group consisting of an alkyl group (preferably a methyl group) and a aryl group. At least one of the group of groups (preferably phenyl groups).

[37] The curable polyanthracene resin composition according to the above [36], which is a total amount (100 mol%) of an alkyl group (preferably a methyl group) bonded to a ruthenium atom. The ratio is 70 to 95 mol% (preferably 50 mol% or more, more preferably 50 to 90 mol%).

[38] The curable polyanthracene resin composition according to the above [36] or [37], which is a total amount of an aryl group (preferably a phenyl group) bonded to a ruthenium atom (100 mol) The ratio of the ear %) is 10 to 70 mol%.

[39] The curable polyanthracene resin composition according to any one of the above [1], wherein the content (mixing amount) of the component (B) is relative to the curable polyoxyl resin composition. The substance (100% by weight) is 1 to 60% by weight (preferably 5 to 55% by weight, more preferably 10 to 50% by weight).

[40] The curable polyanthracene resin composition according to any one of the above [1], wherein the content (mixing amount) of the component (C) is relative to the curable polyoxyl resin composition. The content (100% by weight) is 0.01 to 10% by weight (preferably 0.03 to 5% by weight, more preferably 0.05 to 3% by weight, still more preferably 0.1 to 2% by weight).

[41] The curable polyanthracene resin composition according to any one of the above [1], wherein the component (D) is an average unit formula: (R ⁸ SiO _3/2 ) _d1 (R ⁸ ₂ SiO _2/2 ) _d2 (R ⁸ ₃ SiO _1/2 ) _d3 (SiO _4/2 ) _d4 (X ³ O _1/2 ) _d5

[In the above average unit formula, R ⁸ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, a part of R ⁸ is an alkenyl group (preferably a vinyl group), and the ratio thereof is one or more (preferably two or more) in the molecule. X ³ is a hydrogen atom or an alkyl group (preferably a methyl group). D1 is 0 or a positive number, d2 is 0 or a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is 0 or a positive number, and (d1+d2+d3) and (d1+d4) are positive numbers, respectively. 〕

The polyorganosiloxane is shown.

[42] The curable polyanthracene resin composition according to any one of the above [1], wherein a group other than the alkenyl group in the component (D) which is bonded to a ruthenium atom is selected. At least one selected from the group consisting of an alkyl group (preferably a methyl group) and an aryl group (preferably a phenyl group).

[43] The curable polyanthracene resin composition according to any one of the above [1], wherein the alkenyl group (preferably a vinyl group) in the component (D) has been bonded to a ruthenium atom. The ratio of the total amount of the bond base (100 mol%) is 0.1 to 40 mol%.

[44] The curable polyanthracene resin composition according to the above [42] or [43], which is an alkyl group (preferably a methyl group) to a total amount of a group bonded to a ruthenium atom (100 mol) The ratio of the ear %) is 20 to 60 mol% (preferably 30 mol% or more, more preferably 35 to 60 mol%).

[45] The curable polyanthracene resin composition according to any one of the above [42] to [44] wherein the aryl group (preferably a phenyl group) is a group bonded to a ruthenium atom. The ratio of the amount (100 mol%) is 5 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 60 mol%).

[46] The curable polyanthracene resin composition according to any one of the above [1], wherein the content (mixing amount) of the component (D) is relative to the component (A) and the aforementioned The total amount of the component (B) is 50 to 200 parts by weight (preferably 75 to 175 parts by weight, more preferably 100 to 150 parts by weight).

[46] The curable polyanthracene resin composition according to any one of the above [1] to [45], which comprises the following component (E).

(E): Hydrogenation catalyst containing platinum group metals

[47] The curable polyanthracene resin composition according to the above [46], wherein the content (the blending amount) of the component (E) is relative to the total amount of the alkenyl group contained in the curable polydecane resin composition. The amount of 1 mol (per 1 mol) is 1 x 10 ^-8 ~ 1 x 10 ^-2 mol (preferably 1.0 x 10 ^-6 ~ 1.0 x 10 ^-3 mol).

[48] The curable polyanthracene resin composition according to the above [46] or [47] wherein the content (mixing amount) of the component (E) is a platinum group metal in a hydroquinone catalyst in units of weight It is an amount in the range of 0.01 to 1000 ppm (preferably in the range of 0.1 to 500 ppm).

[49] The curable polyanthracene resin composition according to any one of the above [1] to [48], which comprises the following (G) component.

(G): an iso-cyanate compound represented by the following formula (2)

In the formula (2), R ^f , R ^g and R ^h are the same or different and each represents a group represented by the formula (2a) or a group represented by the formula (2b). However, at least one of R ^f , R ^g and R ^h is a group represented by the formula (2b). 〕

[In the formula (2a), R ⁱ represents a hydrogen atom or a linear or branched alkyl group (preferably a hydrogen atom) having 1 to 8 carbon atoms. 〕

In the formula (2b), R ^j represents a hydrogen atom or a linear or branched alkyl group (preferably a hydrogen atom) having 1 to 8 carbon atoms. 〕

[50] The curable polyanthracene resin composition according to the above [49], wherein the content (mixing amount) of the component (G) is 0.01 with respect to the curable polyoxynoxy resin composition (100% by weight). ~6 wt% (preferably 0.05 to 4 wt%, more preferably 0.1 to 3 wt%).

[51] The curable polyanthracene resin composition according to the above [49] or [50], wherein the total content (total content) of the component (C) and the component (G) is relative to the curable polypeptone The oxygen resin composition is 0.01 to 15% by weight (preferably 0.1 to 10% by weight, more preferably 0.2 to 3% by weight, still more preferably 0.4 to 2% by weight).

[52] The curable polyanthracene resin composition according to any one of the above [1] to [51], which comprises the following (F) component.

(F): a ladder type polyorganosilsesquioxane having one or more (preferably two or more) alkenyl groups (preferably vinyl groups) in the molecule

[53] The curable polyanthracene resin composition according to the above [52], wherein the component (F) has two or more alkenyl groups (preferably a vinyl group) in the molecule and is infiltrated by a gel. Chromatography standard polystyrene-equivalent molecular weight molecular weight of 500-1500, and molecular weight dispersion (Mw / Mn) of 1.00 ~ 1.40 ladder polyorganopyloxane (sometimes called "ladder poly Organic sesquiterpene oxide (a)").

[54] The curable polyanthracene resin composition according to the above [53], wherein the amount of the ladder polyorganosilazoxane (a) converted by a standard polystyrene by gel permeation chromatography The average molecular weight (Mn) is 550 to 1450 (preferably 600 to 1400).

[55] The curable polyoxyxene resin composition according to the above [53] or [54], wherein the ladder polyorganosilazoxane (a) is a standard polyphenylene by gel permeation chromatography The molecular weight dispersion (Mw/Mn) in terms of ethylene is 1.05 to 1.35 (preferably 1.10 to 1.30).

[56] The curable polyanthracene resin composition according to any one of the above [53], wherein the ladder type polyorganosilsesquioxane (a) is represented by the following formula (III-2) As shown in the figure, it has two or more alkenyl groups in the molecule, and the number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography is 500 to 1,500, and the molecular weight dispersion degree (Mw/Mn) ) is a ladder type polyorganopyroxane of 1.00 to 1.40.

[In the above formula (III-2), R ⁴² is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. R ⁴³ is the same or different and represents a hydrogen atom, an alkyl group, a valence group represented by the following formula (III-2-1), and a valence group represented by the following formula (III-2-2). Or a base of one of the formulas (III-2-3) below. n represents an integer of 0 or more (preferably an even number of 2 or more).

[In the above formula (III-2-1), R ⁴⁴ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R ⁴⁵ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). N1 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, still more preferably 0). 〕

[In the above formula (III-2-2), R ⁴⁴ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R ⁴⁵ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R ⁴⁶ is an alkenyl group (preferably a vinyl group). N2 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, still more preferably 0). 〕

[In the above formula (III-2-3), R ⁴⁴ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R ⁴⁷ is the same or different and is a monovalent saturated aliphatic hydrocarbon group (preferably an alkyl group, more preferably a methyl group). N3 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, still more preferably 0). 〕〕

[57] The curable polyanthracene resin composition according to any one of [52], wherein the content (mixing amount) of the component (F) is relative to the component (A) and the aforementioned The total amount of the component (B) is 0.01 to 50 parts by weight (preferably 0.01 to 45 parts by weight, more preferably 0.01 to 40 parts by weight).

[58] The curable polyanthracene resin composition according to any one of the above [1] to [57], which comprises the following (H) component.

(H): decane coupling agent

[59] The curable polyanthracene resin composition according to the above [58], wherein the (H) component is an epoxy group-containing decane coupling agent (preferably 3-glycidoxypropyltrimethoxy) Base decane).

[60] The curable polyanthracene resin composition according to the above [58] or [59], wherein the content (mixing amount) of the component (H) is relative to the curable polyoxynoxy resin composition (100 weight) %) is 0.01 to 15% by weight (preferably 0.1 to 10% by weight, more preferably 0.4 to 5% by weight).

[61] The curable polyanthracene resin composition according to any one of the above [1] to [60], which comprises the following component (I).

(I): at least one zinc compound selected from the group consisting of zinc carboxylate and zinc complex or zinc salt represented by the following formula (3) (but excluding zinc acetoacetate) [Zn ( L1)(L2)] (3)

Wherein L1 and L2 are the same or different and represent the following formula (3a) R ³¹ COCHR ³² COR ³³ (3a)

[In the formula (3a), R ³¹ represents a substituted or unsubstituted C _1-30 alkyl group (preferably a branched C _3-10 alkyl group). R ³² represents a hydrogen atom, or a substituted or unsubstituted C _1-30 alkyl group (preferably a hydrogen atom). R ³³ represents a substituted or unsubstituted C _1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an -OR ³⁴ group. R ³⁴ represents a substituted or unsubstituted C _1-30 alkyl group. R ³¹ and R ³² may be bonded to each other to form a ring, and R ³² and R ³³ may be bonded to each other to form a ring. 〕

The anion of the β-diketone or β-ketoester or the enolate anion is shown. 〕

[62] The curable polyanthracene resin composition according to the above [61], wherein the zinc carboxylate is selected from the group consisting of zinc naphthenate, zinc octoate, zinc acetate, zinc (meth) acrylate, and new At least one of the group of zinc phthalate (preferably at least one selected from the group consisting of zinc naphthenate and zinc octoate, more preferably zinc octoate).

[63] The curable polyanthracene resin composition according to the above [61] or [62] wherein the component (I) is a compound represented by the formula (3').

[In the formula (3'), R ³⁵ represents a substituted or unsubstituted C _1-30 alkyl group (preferably a branched C _3-10 alkyl group), and R ³⁶ represents a hydrogen atom, or a substitution or a no Substituted C _1-30 alkyl group (preferably a hydrogen atom), R ³⁷ represents a substituted or unsubstituted C _1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an -OR ³⁸ group. R ³⁸ represents a substituted or unsubstituted C _1-30 alkyl group. R ³⁵ and R ³⁶ may be bonded to each other to form a ring, and R ³⁶ and R ³⁷ may be bonded to each other to form a ring]

[64] The curable polyanthracene resin composition according to any one of [61] to [63] wherein the component (I) is selected from the group consisting of bis(2,2,7-trimethyl-) At least one of the group consisting of zinc 3,5-octanedione acid and zinc bis(trimethylethenyl)methane.

[65] The curable polyanthracene resin composition according to any one of [61] to [64] wherein the content (mixing amount) of the component (I) is relative to the curable polydecane resin composition. The content (100% by weight) is 0.01 to 5% by weight (preferably 0.05 to 3% by weight, more preferably 0.1 to 2% by weight, still more preferably 0.1 to 1.5% by weight).

[66] The curable polyanthracene resin composition according to any one of the above [61], wherein the content (mixing amount) of the component (I) is 100% by weight based on the component (A). The serving is 0.02 to 10 parts by weight (preferably 0.05 to 6 parts by weight, more preferably 0.1 to 4 parts by weight, still more preferably 0.1 to 3 parts by weight).

[67] The curable polyanthracene resin composition according to any one of [1] to [66] further comprising a phosphor.

[68] The curable polyanthracene resin composition according to the above [67], wherein the content (mixing amount) of the phosphor is 0.01% with respect to the curable polyoxynoxy resin composition (100% by weight). 20% by weight (preferably 0.5 to 10% by weight).

[69] A cured product of the curable polyanthracene resin composition according to any one of the above [1] to [68].

[70] The curable polyanthracene resin composition according to any one of the above [1] to [68], which is a resin composition for semiconductor encapsulation.

[71] The use of the curable polyanthracene resin composition according to any one of the above [1] to [68] as a resin composition for semiconductor encapsulation.

[72] The curable polyanthracene resin composition according to any one of the above [1] to [68], which is a resin composition for forming a lens for an optical semiconductor.

[73] The use of the curable polyanthracene resin composition according to any one of the above [1] to [68] as a resin composition for forming a lens for an optical semiconductor.

[74] An optical semiconductor device comprising: an optical semiconductor element; and a sealing material for sealing the optical semiconductor element, wherein the sealing material is hardened by the curable polyoxyxene resin composition as described in [70] above. Things.

[75] An optical semiconductor device comprising: an optical semiconductor element and a lens, wherein the lens is a cured product of the curable polyoxyxene resin composition according to [72].

 [Industrial availability]  

The curable polyoxyxylene resin composition of the present invention can be preferably used as a sealing material or an optical lens for forming an optical semiconductor element (LED element) in an optical semiconductor device (sealant, lens formation) Resin composition).

Claims (11)

A curable polyoxyxylene resin composition comprising the following components (A), (B), (C), and (D), (A): selected from the group consisting of 2 a polyorganooxyalkylene oxide (A1) having one or more alkenyl groups and one or more aryl groups, and a polyorganodecyloxyalkylene group having two or more alkenyl groups and one or more aryl groups in the molecule (polyorgano siloxy silalkylene) (A2) at least one polyoxyalkylene; (B): polyorgano having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturation a halogenated alkane; (C): an isomeric cyanurate compound represented by the following formula (1); In the formula (1), R ^a , R ^b and R ^c are the same or different and each represents a group represented by the formula (1a), a group represented by the formula (1b), a hydrogen atom or an alkyl group, but R At least one of ^a , R ^b , and R ^c is a group represented by formula (1a) [In the formula (1a), R ^d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms; s represents an integer of 2 to 10] [In the formula (1b), R ^e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms; t represents an integer of 1 to 10] (D): one or more molecules are contained in the molecule. Branched polyorganosiloxane of the alkenyl group.  The sclerosing polyoxymethylene resin composition of claim 1, which comprises the following component (E), (E): a hydroquinone catalyst containing a platinum group metal.   The curable polyoxyxene resin composition according to claim 1 or 2, which comprises the following (G) component, (G): an isomeric cyanurate compound represented by the following formula (2) [In the formula (2), R ^f , R ^g and R ^h are the same or different and represent a group represented by the formula (2a) or a group represented by the formula (2b), but R ^f , R ^g , and At least one of R ^h is a group represented by the formula (2b)], [In the formula (2a), R ⁱ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms], [In the formula (2b), R ^j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms].  The sclerosing polyanthracene resin composition according to any one of claims 1 to 3, which comprises the following (F) component, (F): a ladder type polyorganic compound having one or more alkenyl groups in the molecule Semi-oxane.    The sclerosing polyoxymethylene resin composition according to any one of claims 1 to 4, which comprises the following (H) component, (H): a decane coupling agent.    The sclerosing polyoxymethylene resin composition according to any one of claims 1 to 5, further comprising a phosphor.    A hardened material which is a cured product of the curable polyoxynoxy resin composition according to any one of claims 1 to 6.    The curable polyanthracene resin composition according to any one of claims 1 to 6, which is a resin composition for sealing a photo-semiconductor.    The curable polyanthracene resin composition according to any one of claims 1 to 6, which is a resin composition for forming a lens for an optical semiconductor.    An optical semiconductor device comprising an optical semiconductor element and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the hardenable polyoxymethylene resin composition of claim 8.    An optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the hardenable polyoxymethylene resin composition of claim 9.