TW201835167A - Curable resin composition, cured article and semiconductor device - Google Patents

Abstract

The present invention provides a curable resin composition having good solubility in silicone resin even the addition amount of rare earth compounds being increased, without precipitation, and capable of forming a cured article by being cured, which has good transparency and excellent thermal-resistance, especially with increase of hardness and brittle being inhibited even under a high temperature condition about 250 DEG C. The curable resin composition of the present invention comprises a polysiloxane (A) which is at least one selected from the group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in molecule and a polyorganosiloxysilalkylene (A2) having two or more alkenyl groups in molecule, a polysiloxane (B) which is at least one selected from the group consisting of a polyorganosiloxane (B1) having two or more hydrosilyl groups in molecule and a polyorganosiloxysilalkylene (B2) having two or more hydrosilyls group in molecule, and a rare earth compound (C), wherein the amount of rare earth metal atoms is 30~500 ppm base on the total amount of the curable resin composition. Further, the rare earth compound (C) represented by the formula (1) is the same as described in the specification.

Description

 Curable resin composition, cured product, and semiconductor device  

The present invention relates to a curable resin composition, a cured product of the curable resin composition, and a semiconductor device obtained by sealing a semiconductor element by using the curable resin composition as a sealant. Priority is claimed on Japanese Patent Application No. 2016-214739, filed on Jan.

As a sealant (curable resin composition) for protecting a semiconductor element in a semiconductor device, various resins are used. In particular, the sealant used in the optical semiconductor device is required to have heat resistance against heat generated in the semiconductor element during curing, and the hardness does not rise even under high temperature conditions, and the flexibility can be maintained.

As a sealant (curable resin composition) in an optical semiconductor device, in particular, in the use of illumination, as described in Patent Document 1, a methyl ketone-based resin having excellent heat resistance is mainly used. However, in the methyl fluorenone-based resin, methyl ketone is deteriorated under high temperature conditions of about 200 ° C, and the softness is lost, and the hardness is increased and the problem is embrittled.

In order to solve the above-mentioned problems, Patent Literatures 2 and 3 disclose that a carboxylate of a rare earth compound such as ruthenium is added to the composition of the hydrazinyl ketone rubber. Patent Literatures 2 and 3 report that the addition of a carboxylate such as a rare earth compound such as ruthenium can suppress the deterioration of methyl ketone, and it does not become hard under high temperature conditions of about 200 ° C, and can maintain flexibility, and transparency can be obtained. High hardened material.

 [Previous Technical Literature]  

[Patent Document 1] International Publication No. 2014/109349

[Patent Document 2] Japanese Patent No. 5422755

[Patent Document 3] International Publication No. 2015/186722

In recent years, heat generated by the increase in brightness of LEDs and the like has become large, and thus it is required to have higher heat resistance, and it is required to be hard and maintain flexibility even under high temperature conditions of about 250 ° C. material. Here, the inventors of the present invention have verified the compositions described in Patent Documents 2 and 3 in order to exhibit effects even under high temperature conditions of about 250 °C. In the composition described in Patent Documents 2 and 3, when the amount of the carboxylate added to the rare earth compound is increased, the carboxylate of the rare earth compound becomes insoluble in the fluorenone resin, and the carboxylic acid of the rare earth compound The acid salt precipitates (Comparative Example 1 of the present application). Further, it is known that in order to prevent precipitation of a carboxylate of a rare earth compound, when the amount of the carboxylate added to the rare earth compound is reduced, there is no effect on hardness improvement under high temperature conditions of about 250 ° C (the present application) Comparative Example 2).

Accordingly, an object of the present invention is to provide a curable resin composition which is excellent in solubility to an anthrone resin even if the amount of addition of a rare earth compound is increased, and a cured product can be formed by hardening, and the cured product has good transparency. It is excellent in heat resistance, and in particular, it is possible to suppress an increase in hardness or embrittlement even under high temperature conditions of about 250 °C. Further, another object of the present invention is to provide a cured product which is excellent in transparency and excellent in heat resistance, and in particular, hardness is not improved even under high temperature conditions of about 250 ° C, and flexibility can be maintained. Further, another object of the present invention is to provide a semiconductor device in which the curable resin composition is used as a sealant, and a sealed semiconductor device (particularly an optical semiconductor device) is a semiconductor device excellent in quality and durability ( Especially optical semiconductor devices).

The present inventors have found that a specific polyoxyalkylene having two or more alkenyl groups in a molecule, a specific polyoxyalkylene having two or more hydroquinone groups in a molecule, and a hardening of a specific rare earth compound are contained in a specific amount. The resin composition has a good solubility in the fluorenone resin of the rare earth compound, and by hardening, it is possible to form a cured product which does not increase in hardness even at a high temperature of about 250 ° C. .

That is, the present invention provides a curable resin composition comprising polyoxymethane (A), a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule, and two or more olefins in the molecule. At least one selected from the group consisting of polyorganomethoxy oxetane (A2); polyoxyalkylene (B) is a polyorganosiloxane having two or more hydroquinone groups in the molecule ( At least one selected from the group consisting of B1) and polyorganooxy oxetane (B2) having two or more hydroquinone groups in the molecule; and a rare earth compound represented by the following formula (1) (C) [M(L1)(L2)(L3)] (1) [In the formula (1), M is a rare earth metal atom, and L1, L2 and L3 are the same or different ligands, and are represented by the following formula ( Anion or enol anion of β-diketone or β-ketoester represented by 1a)

R ³¹ COCHR ³² COR ³³ (1a) (In the formula (1a), R ³¹ represents a linear or branched chain alkyl group having 1 to 30 carbon atoms which may also contain a halogen atom as a substituent, and R ³² represents a hydrogen atom. Or an alkyl group having 1 to 30 carbon atoms of a halogen atom as a substituent, and R ³³ represents a linear or branched chain alkyl group having 1 to 30 carbon atoms or an aromatic heterocyclic group which may have a halogen atom. Or -OR ^34. R ³⁴ represents a linear or divalent chain alkyl group having 1 to 30 carbon atoms which may have a halogen atom as a substituent. R ³¹ and R ³² may be bonded to each other to form a ring, R ³² and R ³³ may be bonded to each other to form a ring)], and the content of the rare earth metal atom is 30 to 500 ppm of the curable resin composition with respect to the total amount of the curable resin composition.

Further, in the curable resin composition of the present invention, it is preferred that the rare earth metal atom is at least one selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, and osmium.

Further, the curable resin composition of the present invention is preferably one which further contains a hydroquinone-based catalyst (E).

In addition, the curable resin composition of the present invention contains a polyorganosiloxane having the following average unit formula (a-1) and a polyorganic compound represented by the following average unit formula (a-2). At least one polydecane (D) selected from the group consisting of decyloxydecane is preferably the average unit (a-1) as the polyoxyalkylene (A): (R ¹ SiO _{3 / 2} ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5 [in the average unit formula (a-1), R ¹ represents the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. However, a part of R ¹ is an alkenyl group and is in the range of two or more in the molecule. X ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A1, a2, a3, a4, and a5 respectively indicate satisfaction: 1>a1≧0, 1>a2≧0, 1>a3>0, 1>a4≧0, 0.05≧a5≧0, a1+a4>0 And the value of a1+a2+a3+a4+a5=1]

Average unit formula (a-2): (R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 (SiO _4/2 ) _b4 (R ^A ) _b5 (X ² O _1/2 ) _b6 [In the average unit formula (a-2), R ² is the same or different, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a carbon number. 2 to 8 alkenyl groups. However, a part of R ² is an alkenyl group and is in the range of two or more in the molecule. R ^A is the same or different and represents an alkylene group having 1 to 14 carbon atoms. X ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. B1, b2, b3, b4, b5, and b6 respectively indicate satisfaction: 1>b1≧0, 1>b2>0, 1>b3≧0, 1>b4≧0, 0.7>b5>0, 0.05≧b6≧ 0, b3 + b4 > 0, and b1 + b2 + b3 + b4 + b5 + b6 = 1 value].

Moreover, the curable resin composition of the present invention contains a polyorganosiloxane having the following average unit formula (a-1)', and the following average unit formula (a-1)'' At least one selected from the group consisting of polyorganomethoxy oxetane as the polyoxyalkylene (D) preferred averaging unit formula (a-1)': (R ¹ SiO _3/2 ) _a1 ( R ¹ ₃ SiO _1/2 ) _a3 (X ¹ O _1/2 ) _a5 [In the average unit formula (a-1)', R ¹ is the same or different and is the same as described above. X ¹ is the same as described above. A1, a3, and a5 are respectively satisfied to satisfy: 1>a1>0, 1>a3>0, 0.05≧a5≧0, and a1+a3+a5=1]

The average unit formula (a-1)'': (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5 [in the average unit formula (a-1)'', R ¹ and X ^{1 are the} same as described above. A3, a4, and a5 are values indicating that 1>a3>0, 1>a4>0, 0.05≧a5≧0, and a3+a4+a5=1, respectively.

Further, in the curable resin composition of the present invention, the polyorganosiloxane having the average unit formula (a-1)' is preferably a sesquisesquioxane.

Further, in the curable resin composition of the present invention, the polysiloxane (D) is preferably contained in an amount of from 1 to 70% by weight based on the total amount of the polyoxyalkylene (A).

Further, the curable resin composition of the present invention is preferably a sealant.

Moreover, the curable resin composition of the present invention is preferably a resin composition for forming a lens.

Moreover, the present invention provides a cured product of the aforementioned curable resin composition.

Further, in the cured product of the present invention, when the thickness is 3 mm, the light transmittance at a wavelength of 450 nm is preferably 80% or more.

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

Moreover, the semiconductor device of the present invention includes a semiconductor element and a lens, and the lens is preferably a cured product of the curable resin composition described above.

Further, the semiconductor device of the present invention includes a semiconductor element and a sealing material and a lens for sealing the semiconductor element, wherein the sealing material is preferably a cured product of the curable resin composition, and the lens is preferably hardened as described above. A cured product of a resin composition.

Moreover, the semiconductor device of the present invention is preferably an optical semiconductor device.

In the curable resin composition of the present invention, even if the amount of the rare earth compound added is increased, the solubility in the fluorenone resin is good, and the curing property is excellent in transparency and heat resistance, particularly even in the case of increasing the amount of the rare earth compound. At a high temperature of about 250 ° C, it is also possible to suppress an increase in hardness or an embrittled cured product. The cured product of the present invention is excellent in transparency and excellent in heat resistance, and in particular, the hardness does not increase even under high temperature conditions of about 250 ° C, and the flexibility can be maintained. The semiconductor device of the present invention has excellent quality and durability.

100‧‧‧reflector

101‧‧‧Metal wiring (electrode)

102‧‧‧Optical semiconductor components

103‧‧‧Connecting 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 device is sealed with a cured product of a curable resin composition of the present invention. The left side view (a) is a perspective view, and the right side view (b) is a cross-sectional view.

<Curable resin composition>

The curable resin composition of the present invention contains a polyorganooxy oxane (A1) having two or more alkenyl groups in its molecule and a polyorganooxy oxetane having two or more alkenyl groups in the molecule (A2). At least one selected polyoxane (A) (in the case of simply referred to as "polyoxane (A)"); a polyorganic having two or more hydroquinone groups in the molecule At least one polysiloxane (B) selected from the group consisting of a siloxane (B1) and a polyorganomethoxy oxetane (B2) having two or more hydroquinone groups in the molecule (with a simple The case of the "polyoxane (B)") and the rare earth compound (C) represented by the formula (1) (which is simply referred to as "rare earth compound (C)") are essential components. In addition to the above-mentioned essential components, the curable resin composition of the present invention may contain, for example, a hydroquinone catalyst (E), a hardening retarder (F), a decane coupling agent (G), and the like which will be described later. .

[polyoxane (A)]

The polyoxyalkylene (A) is a polyoxyalkylene having two or more alkenyl groups in the molecule as described above. In other words, the polyoxyalkylene (A) is an alkenyl group-containing polyoxyalkylene, and is a component produced by a hydroquinone reaction of a component having a hydroquinone group (for example, a polyoxyalkylene (B) to be described later). .

The polyoxyalkylene (A) contains a polyorganosiloxane (A1) having two or more alkenyl groups in its molecule (a case of simply referred to as "polyorganosiloxane (A1)") and a molecule. At least 1 selected from the group consisting of polyorganooxy oxetane (A2) having two or more alkenyl groups (in the case of simply referred to as "polyorganooxy oxetane (A2)") Kind.

The above polyorganomethoxyantane (A2) means that -Si-R ^A -Si- (anthracene is contained in addition to -Si-O-Si- as a main chain) Base combination: R ^A represents an alkylene group of polyorganosiloxane. Further, the polyorganosiloxane (A1) is a polyorganosiloxane which does not contain the above-mentioned alkylene group as a main chain.

(polyorganooxane (A1))

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

Examples of the alkenyl group contained in the molecule of the polyorganosiloxane (A1) include 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, the alkenyl group is preferably a vinyl group. Further, the polyorganosiloxane (A1) may be one having only one type of alkenyl group, or may be one having two or more types of alkenyl groups. The alkenyl group possessed by the polyorganosiloxane (A1) is preferably one which is bonded to a ruthenium atom.

Examples of the group other than the alkenyl group which the polyorganosiloxane (A1) has may 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 or a hexyl group) or a cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group or a cyclopentyl group). Cyclohexyl, cyclododecyl, etc.), aryl (eg, phenyl, tolyl, xylyl, naphthyl, etc.), cycloalkyl-alkyl (eg, cyclohexylmethyl, methylcyclohexyl, etc.) An aralkyl group (for example, benzyl group, phenethyl group, etc.), a halogenated hydrocarbon group in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom (for example, chloromethyl group, 3-chloropropyl group, 3, 3) A monovalent substituted or unsubstituted hydrocarbon group or the like such as a halogenated alkyl group such as 3-trifluoropropyl or the like. Further, in the present specification, "the group bonded to a ruthenium atom" generally means a group which does not contain a ruthenium atom.

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

The polyorganosiloxane (A1) (polyoxane (A)) is preferably a polyorganosiloxane having the following average unit formula (a-1). The polyorganosiloxane which is represented by the above average unit formula (a-1) is one type of polyoxane (D) to be described later.

Average unit formula (a-1): (R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _{1 /2} ) _a5

In the above average unit formula (a-1), R ¹ is the same or different and represents an alkyl group having 1 to 10 carbon atoms (desirably an alkyl group having 1 to 6 carbon atoms) and an aryl group having 6 to 14 carbon atoms. (ideally a phenyl group), or an alkenyl group having 2 to 8 carbon atoms (ideally an alkenyl group having 2 to 6 carbon atoms). However, a part of R ¹ is an alkenyl group (preferably a vinyl group) and is in the range of two or more in the molecule. X ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (desirably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group).

In the above average unit formula (a-1), a1 is 0 or a positive number less than 1 (1>a1≧0), a2 is 0 or a positive number less than 1 (1>a2≧0), and a3 is less than 1 Positive number (1>a3>0), a4 is 0 or a positive number less than 1 (1>a4≧0), a5 is a positive number of 0 or less (0.05≧a5≧0), and the sum of a1 and a4 is a positive number (a1+a4>0), and the total of a1 to a5 is 1 (a1+a2+a3+a4+a5=1).

Further, the polyorganosiloxane (A1) is a polyorganosiloxane having the following average unit formula (a-1)', or a polyfluorene organooxane represented by an average unit formula (a-1)' It is better. The polyorganosiloxane having an average unit formula (a-1)' is preferably a heptadecane. The polyorganosiloxane having the average unit formula (a-1)' and the polyorganosiloxane having the average unit formula (a-1) are represented by an average unit formula (a-1)' The polyorganosiloxane is one of the polyorganosiloxanes represented by the above average unit formula (a-1) and the polysiloxane (D) described later.

Average unit formula (a-1)': (R ¹ SiO _3/2 ) _a1 (R ¹ ₃ SiO _1/2 ) _a3 (X ¹ O _1/2 ) _a5

In the above average unit formula (a-1)', R ¹ is the same or different and is the same as described above. X ¹ is the same as described above.

In the above average unit formula (a-1)', a1, a3, and a5 are the same as described above, and the total of a1, a3, and a5 is 1 (a1 + a3 + a5 = 1).

Average unit formula (a-1)'': (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5 averaging unit formula (a-1)'', R ¹ and X ^{1 are the} same as described above.

In the above average unit formula (a-1)', a3, a4, and a5 are the same as described above, and the total of a3, a4, and a5 is 1 (a3 + a4 + a5 = 1).

An example of the polyorganosiloxane (A1) is a linear polyorganosiloxane having two or more alkenyl groups in its 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 type of alkenyl group or two or more types of alkenyl groups. Further, the group other than the alkenyl group in the linear polyorganosiloxane may be a monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group (especially Methyl), aryl (especially phenyl).

In the above linear polyorganooxane, the ratio of the alkenyl group is preferably from 0.1 to 40 mol% with respect to the total amount (100 mol%) bonded to the base of the ruthenium atom. Further, the ratio of the alkyl group (particularly methyl group) is preferably from 1 to 20 mol% with respect to the total amount (100 mol%) of the group bonded to the ruthenium atom. Further, the ratio of the aryl group (especially phenyl group) is preferably from 30 to 90 mol% with respect to the total amount (100 mol%) bonded to the base of the ruthenium atom. In particular, by using a ratio of a total amount (100 mol%) of an aryl group (particularly a phenyl group) bonded to a group of a ruthenium atom to 40 mol% or more (for example, 45 to 80 mol%), As the linear polyorganosiloxane, the barrier property against the corrosive gas of the cured product tends to be improved. Further, by using a ratio of 90 mol% or more (for example, 95 to 99 mol%) relative to the total amount (100 mol%) of the alkyl group (particularly methyl group) bonded to the base of the ruthenium atom, hardening The thermal shock resistance of the article tends to be higher.

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

[In the above formula (I-1), 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. M1 is an integer from 5 to 2000]

As another example of the polyorganosiloxane (A1), there are two or more alkenyl groups in the molecule, and a branched chain polyorganofluorene having a fluorinated oxygen unit (T unit) represented by RSiO _3/2 . Oxytomane. Further, R is a monovalent substituted or unsubstituted hydrocarbon group. The alkenyl group which the divalent polyorganosiloxane has in the above may be a specific example of the above alkenyl group, and among them, a vinyl group is preferable. Further, it may be one having only one type of alkenyl group, or two or more types of alkenyl groups. Further, in the above-mentioned bifurcated chain polyorganosiloxane, as the base of the ruthenium atom other than the alkenyl group, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group may be mentioned, and among them, an alkyl group is preferable (especially Methyl), aryl (especially phenyl). Further, as R in the above T unit, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred.

In the above-mentioned bifurcated chain polyorganosiloxane, the ratio of the alkenyl group to the total amount (100 mol%) of the group bonded to the ruthenium atom is preferably from the viewpoint of the curability of the curable resin composition. It is 0.1 to 40 mol%. Further, the ratio of the alkyl group (particularly methyl group) is preferably from 10 to 40 mol% with respect to the total amount (100 mol%) of the group bonded to the ruthenium atom. Further, the ratio of the aryl group (especially phenyl group) is preferably from 5 to 70 mol% with respect to the total amount (100 mol%) bonded to the base of the ruthenium atom. In particular, in the case of the above-mentioned branched chain polyorganosiloxane, the ratio of the aryl group (especially phenyl group) is 40 moles relative to the total amount (100 mole%) bonded to the base of the ruthenium atom. Above % (ideally 45 to 60 mol%), the hardened material tends to have a higher barrier to corrosive gases. Further, the ratio of the alkyl group (particularly methyl group) to 50 mol% or more (preferably 60 to 99 mol%) is used with respect to the total amount (100 mol%) of the group bonded to the ruthenium atom. The thermal shock resistance of the cured product tends to be more improved.

The above-mentioned divergent chain polyorganosiloxane may be represented by the above average unit formula in which a1 is a positive number. In this case, it is preferable that a2/a1 is a number from 0 to 10, a3/a1 is a number from 0 to 0.5, a4/(a1+a2+a3+a4) is a number from 0 to 0.3, a5/(a1+a2 +a3+a4) is a number from 0 to 0.4. Further, the molecular weight of the branched chain polyorganosiloxane is converted into a weight average molecular weight of standard polystyrene by gel permeation chromatography (GPC), preferably 500 to 20,000, more preferably 700. To 6000.

As another example of the polyorganosiloxane (A1), for example, in the above average unit formula, a1 and a2 are 0, and X ¹ is a hydrogen atom having the following average unit formula: (R ^1a ₂ R ^1b SiO _1/2 ) _a6 (R ^1a ₃ SiO _1/2 ) _a7 (SiO _4/2 ) _a8 (HO _1/2 ) _a9 shows a polyorganosiloxane. In the above average unit formula, R ^1a is the same or different and represents a C _1-10 alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group. Among them, a methyl group is preferred. Further, R ^1b is the same or different and represents an alkenyl group, of which a vinyl group is preferred. Further, any one of a6, a7, a8, and a9 is satisfied: a6+a7+a8=1, a6/(a6+a7+a8)=0.01 to 0.35, a8/(a6+a7+a8)= A positive number of 0.40 to 0.65, a9/(a6+a7+a8)=0.005 to 0.03. However, a7 can also be 0. From the viewpoint of the curability of the curable resin composition, a6/(a6+a7+a8) is preferably from 0.2 to 0.3. Further, a8/(a6+a7+a8) is preferably from 0.55 to 0.60 from the viewpoint of hardness or mechanical strength of the cured product. Further, a9/(a6+a7+a8) is preferably from 0.01 to 0.025 from the viewpoint of adhesion of the cured product or mechanical strength. So as polyethylene oxide alkyl silicones, for example, to include SiO _4/2 units and _{(CH 3) 2 (CH 2} = CH) Si polyorganosiloxane SiO _1/2 siloxane units configured to SiO _4/2 a polyorganosiloxane such as a unit and a (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 unit and a (CH ₃ ) ₃ SiO _1/2 unit.

(polyorganomethoxy oxetane (A2))

The polyorganomethoxy oxetane (A2) has two or more alkenyl groups in the molecule as described above, and also contains an alkylene group-Si-R ^A -Si- (in addition to the oxane group). Alkylene-bonded: R ^A represents a polyalkylene oxide as a main chain. That is, the polyorganomethoxy oxetane (A2) does not contain the polyorganosiloxane which does not contain an alkylene group as the above-mentioned polyorganosiloxane (A1). The curable resin composition of the present invention can form a cured product which is more excellent in barrier properties against corrosive gas and thermal shock resistance by containing such a polyorganomethoxyantane (A2).

The polyorganomethoxy oxetane (A2) has an alkylene group (R ^A ) in the alkyl group bonded to the alkyl group, and examples thereof include a straight chain such as a methylene group, an ethyl group, and a propyl group. Or a divalent chain C _1-12 alkylene group or the like, and among them, a C _2-4 alkyl group (particularly, an ethyl group) is preferred. The polyorganomethoxyxanthene (A2) is difficult to produce a decyl alcohol by decomposition of heat or the like because it is difficult to produce a ring of a low molecular weight in the production step as compared with the polyorganooxane (A1). Since the polyorganomethoxy oxetane (A2) is used as the base (-SiOH), the surface of the cured product of the curable resin composition has a low adhesiveness and tends to be more difficult to yellow.

The polyorganomethoxyxanthene (A2) may be a linear, partially linear, divalent, or mesh-like molecular structure. Further, the polyorganomethoxy oxetane (A2) may be used singly or in combination of two or more. Specifically, two or more kinds of polyorganomethoxyxanthene (A2) having a different molecular structure may be used in combination, and, for example, a linear polyorganomethoxyantane (A2) and a branched chain may be used in combination. Polyorganomethoxy oxetane (A2).

The alkenyl group which the polyorganomethoxy oxoalkylene group (A2) 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, as the polyorganomethoxyxanthene (A2), only one type of alkenyl group may be used, or two or more types of alkenyl groups may be used. The polyorganooxy oxetane (A2) has an alkenyl group, preferably one which is bonded to a ruthenium atom.

The group other than the alkenyl group which the polyorgano methoxy oxane (A2) has is bonded to the fluorene atom, and examples thereof include a hydrogen atom and an organic group. The organic group may, for example, be the above-mentioned organic group (for example, a substituted or unsubstituted hydrocarbon such as an alkyl group, a cycloalkyl group, an aryl group, a cycloalkyl-alkyl group, an aralkyl group or a halogenated hydrocarbon group).

Further, in the polyorganomethoxyxanthene (A2), a hydroxyl group or an alkoxy group may be bonded to the group of the ruthenium atom.

The polyorganomethoxyxanthene (A2) is preferably a polyorganomethoxyxanthene represented by the following average unit formula (a-2). The polyorganomethoxyxanthene represented by the above average unit formula (a-2) is one type of polyfluorene oxide (D) to be described later.

Average unit formula (a-2): (R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 (SiO _4/2 ) _b4 (R ^A ) _b5 (X ² O _1/2 ) _b6

In the above average unit formula (a-2), R ² is the same or different, and represents an alkyl group having 1 to 10 carbon atoms (desirably an alkyl group having 1 to 6 carbon atoms) and an aryl group having 6 to 14 carbon atoms. (ideally a phenyl group), or an alkenyl group having 2 to 8 carbon atoms (ideally an alkenyl group having 2 to 6 carbon atoms). However, a part of R ² is an alkenyl group (preferably a vinyl group) and is in the range of two or more in the molecule. R ^A is the same or different and represents an alkylene group having 1 to 14 carbon atoms (ideally, an alkylene group having 1 to 8 carbon atoms). X ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (desirably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group).

In the above average unit formula (a-2), b1 represents 0 or a positive number that is less than 1 (1>b1≧0), b2 is a positive number that is less than 1 (1>b2>0), and b3 is a positive number that does not reach 1 (1>b3>0), b4 is a positive number of 0 or less than 1 (1>b4≧0), b5 is a positive number of 0.07 or less (0.7≧b5>0), and b6 is a positive number of 0 or less (0.05≧) B6≧0), the sum of b3 and b4 is a positive number (b3+b4>0), and the total of b1 to b6 is 1, that is, (b1+b2+b3+b4+b5+b6=1).

More specifically, for example, a polyorganomethoxy oxetane having a structure represented by the following formula (I-2) is exemplified as the polyorganooxy oxetane (A2).

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. R ¹² may, for example, be a specific example of the above monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, an aryl group, an aralkyl group, a halogenated hydrocarbon group or the like), and the above alkenyl group. However, at least two of R ¹² are alkenyl groups (especially vinyl groups). Further, R ¹² other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

In the above formula (I-2), R ^A is the same as the above, and represents an alkylene group, and among them, an alkylene group having 2 to 4 carbon atoms (particularly, an ethyl group) is preferable. Further, there are cases of a plurality of R ^A , and these may be the same or different.

In the above formula (I-2), r1 represents an integer of 1 or more (for example, 1 to 100). Further, r1 is an integer of 2 or more, and r1 is attached to the structure in parentheses, and each 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, r2 is an integer of 2 or more, and r2 is attached to the structure in parentheses, and each 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, r3 is an integer of 2 or more, and r3 is attached to the structure in parentheses, and each may be the same or different.

In the above formula (I-2), r4 represents an integer of 0 or more (e.g., 0 to 50). Further, r4 is an integer of 2 or more, and r4 is attached to the structure in parentheses, and each 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, when r5 is an integer of 2 or more, r5 is attached to the structure in parentheses, and each may be the same or different.

The addition form of each structural unit in the above formula (I-2) may be an irregular type or a block type. Moreover, the order of the sequence of each structural unit is also not particularly limited.

The terminal structure of the polyorganomethoxyxanthene having the structure represented by the formula (I-2), for example, a decyl group, an alkoxy fluorenyl group, or a trialkyl fluorenyl group (for example, a bracket attached to r5) Internal structure, trimethyl sulfhydryl, etc.). At the terminal of the polyorganomethoxy oxetane, various groups such as an alkenyl group or a hydroquinone group may be introduced.

The polyorganomethoxy oxetane (A2) can be produced by a conventional or conventional method, and the production method can be produced by, for example, the method described in JP-A-2012-140617. . Further, the product containing the polyorganooxy oxetane (A2) can be, for example, the trade names "ETERLED GD 1130", "ETERLED GD 1125", "ETERLED GS 5145", "ETERLED GS 5135", "ETERLED". GS 5120" (any one is made by Changxing Material Industry Co., Ltd.).

In addition, the polyoxyalkylene oxide (A) in the curable resin composition of the present invention may be used singly or in combination of two or more. The properties of the polyoxyalkylene (A) may be liquid or solid at 25 °C.

Further, the polyoxyalkylene (A) may have two or more alkenyl groups in the molecule, and may have a hydroquinone group. In this case, the polyoxyalkylene (A) may also be a polyoxyalkylene (B) to be described later.

In the curable resin composition of the present invention, the content (quantity) of the polyoxyalkylene (A) (total amount) is preferably from 50 to 99 with respect to the total amount (100% by weight) of the curable resin composition. The weight %, more preferably 60 to 97% by weight, still more preferably 70 to 95% by weight. When the content is 50% by weight or more, the toughness of the cured product tends to be improved. Further, the polyoxyalkylene (A) may contain a polyoxyalkylene (D) to be described later.

As the polyoxyalkylene oxide (A) in the curable resin composition of the present invention, only polyorganosiloxane (A1) may be used, or only polyorganomethoxyantane (A2) may be used. It is also possible to use a polyorganosiloxane (A1) together with a polyorganomethoxyxanthene (A2). When the polyorganosiloxane (A1) and the polyorganomethoxyantane (A2) are used in combination, the ratio of these is not particularly limited and can be appropriately set.

(polyoxane (D))

The polyoxyalkylene oxide (D) is a polyorganosiloxane selected from the above average unit formula (a-1), and a polyorganomethoxyantane derivative represented by the above average unit formula (a-2). Select at least one of the groups. Further, the polyoxyalkylene (D) is one type of the above polyoxyalkylene (A), and also has a polyoxyalkylene having a divergent chain structure. In the curable resin composition of the present invention, polyoxyalkylene oxide (D) is preferably used in combination with the above polyoxyalkylene oxide (A). As the polyoxyalkylene (D), a polyorganosiloxane having the above average unit formula (a-1)' and a polyorganosiloxane having the above average unit formula (a-1)'' are preferred. . Further, the polyoxyalkylene (D) may be used singly or in combination of two or more.

The total content of the polyoxyalkylene (D) is, for example, from 1 to 70% by weight, preferably from 3 to 50% by weight, more preferably from 5 to 40% by weight, based on the total amount of the polyoxyalkylene (A). It is particularly preferably from 8 to 30% by weight. Further, the total content of the polyoxyalkylene (D) is, for example, 1 to 60% by weight, preferably 2 to 50% by weight, more preferably 3 to 40% by weight, based on the total amount of the curable resin composition. When the polysiloxane (D) is contained in the above range, it is preferably 5 to 30% by weight, and a cured product having improved toughness and excellent strength can be obtained. Further, in the polyoxyalkylene (A), polysiloxane (D) is contained.

[polyoxane (B)]

As described above, the polyoxyalkylene (B) which is an essential component of the curable resin composition of the present invention is a polyorganosiloxane having two or more hydroquinone groups (Si-H) in the molecule. That is, the polyoxyalkylene (B) is a polyoxyalkylene having a hydroquinone group and is a component produced by a hydroquinone reaction of a component having an alkenyl group (for example, a polyoxyalkylene (A) or the like).

Polyoxyalkylene (B) is a polyorganosiloxane (B1) having two or more hydroquinone groups in the molecule (in the case of simply referred to as "polyorganosiloxane (B1)") and in the molecule. At least one selected from the group consisting of two or more hydroquinone-based polyorganooxy oxetane (B2) (in the case of simply referred to as "polyorganooxy oxetane (B2)") Polyorganosiloxane.

The above polyorganomethoxy oxetane (B2) means that, in addition to -Si-O-Si-(zepine oxide), it also contains -Si-R ^A -Si- (an alkyl group: R ^A represents a polyorganosiloxane which is an alkyl group as a main chain. Further, in the present specification, the polyorganosiloxane (B1) is a polyorganosiloxane which does not contain the above-mentioned alkylene group as a main chain. Further, in the above alkylene grouping, R ^A (alkylene group) is the same as above, and examples thereof include a linear or branched chain C _1-12 alkylene group, preferably a linear or branched chain. C _2-4 alkyl (especially, extended ethyl).

(polyorganooxane (B1))

The polyorganosiloxane (B1) may be a linear, partially branched, branched, or mesh-like molecular structure. Further, the polyorganosiloxane (B1) may be used singly or in combination of two or more. Specifically, two or more kinds of polyorganosiloxanes (B1) having different molecular structures may be used in combination. For example, a linear polyorganosiloxane (B1) and a branched polyorganosiloxane (B1) may be used in combination. ).

The polyorganosiloxane (B1) has a bond in the group of a ruthenium atom other than a hydrogen atom, and is, for example, a monovalently substituted or unsubstituted hydrocarbon group, and more specifically, an alkyl group or a square group. , an aralkyl group, a halogenated hydrocarbon group, and the like. Among them, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred. Further, the polyorganosiloxane (B1) may have an alkenyl group (for example, a vinyl group) as a group other than a hydrogen atom bonded to a ruthenium atom, or may be absent.

The property of the polyorganosiloxane (B1) may be liquid or solid. Among them, liquid is preferred, and the viscosity at 25 ° C is preferably from 0.1 to 1 billion mPa ‧ in liquid form.

The polyorganosiloxane (B1) is preferably a polyorganosiloxane having the following average unit formula (B-1).

Average unit formula (B-1): (R ³ SiO _3/2 ) _c1 (R ³ ₂ SiO _2/2 ) _c2 (R ³ ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (X ³ O _{1 /2} ) _c5

In the above average unit formula (B-1), R ³ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the hydrogen atom and the above monovalent substituted or unsubstituted hydrocarbon group may be mentioned. (e.g., an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, etc.), and the above alkenyl group. However, a part of R ³ is a hydrogen atom (a hydrogen atom constituting a hydroquinone group), and the ratio is such that the hydroquinone group is in the range of two or more in the molecule. For example, the ratio of hydrogen atoms is preferably from 0.1 to 40 mol% with respect to the total amount of R ³ (100 mol%). When the ratio of the hydrogen atoms is adjusted within the above range, the curability of the curable resin composition tends to be higher. Further, R ³ other than the hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

In the above average unit formula (B-1), X ³ 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 (B-1), 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 the total of c1 to c3 ( C1+c2+c3) is a positive number.

As an example of the polyorganosiloxane (B1), for example, a linear polyorganosiloxane having two or more hydroquinone groups in the molecule may be mentioned. In the above linear polyorganosiloxane, a group other than a hydrogen atom bonded to a ruthenium atom may, for example, be the above monovalent substituted or unsubstituted hydrocarbon group and the above alkenyl group, and among them, an alkyl group is preferred. In particular methyl), aryl (especially phenyl).

In the linear polyorganosiloxane described above, the ratio of hydrogen atoms (hydrogen atoms bonded to the ruthenium atom) is preferably 0.1 to 40 mol% with respect to the total amount (100 mol%) of the group bonded to the ruthenium atom. . Further, the ratio of the alkyl group (particularly methyl group) is preferably from 20 to 99 mol% with respect to the total amount (100 mol%) of the group bonded to the ruthenium atom. Further, the ratio of the aryl group (especially phenyl group) is preferably from 40 to 80 mol% with respect to the total amount (100 mol%) bonded to the base of the ruthenium atom. In particular, the ratio of the total amount (100 mol%) of aryl groups (particularly phenyl groups) bonded to the group of the ruthenium atom relative to the bond is 40 mol% or more (ideally 45 to 70 mol%) When the linear polyorganosiloxane is used, the barrier property of the cured product to the corrosive gas tends to be improved. Further, by using a ratio of a total amount (100 mol%) of an alkyl group (particularly a methyl group) bonded to a base of a ruthenium atom to 90 mol% or more (preferably 95 to 99 mol%) The heat shock resistance of the cured product tends to increase.

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

[In the above formula (II-1), R ²¹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ²¹ are hydrogen atoms. M2 is an integer from 5 to 1000]

Other examples of the polyoxyalkylene oxide (B1) include a branched chain polyorganosiloxane having two or more hydrofluorenyl groups in the molecule and a siloxane unit (T unit) represented by RSiO _3/2 . R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. In the above-mentioned divalent chain polyorganosiloxane, a group other than a hydrogen atom bonded to a halogen atom may, for example, be the above monovalent substituted or unsubstituted hydrocarbon group, and the above alkenyl group, of which an alkyl group is preferred. (especially methyl), aryl (especially phenyl). Further, R in the above T unit may, for example, be a hydrogen atom, the above monovalent substituted or unsubstituted hydrocarbon group, and the above alkenyl group, and among them, an alkyl group (particularly a methyl group) or an aryl group (particularly benzene) is preferred. base). The ratio of the total amount (100 mol%) of aryl groups (especially phenyl groups) in the above T unit is preferably 30 mol% from the viewpoint of the barrier property of the cured product to corrosive gases. the above.

In the above branched chain polyorganosiloxane, the ratio of the alkyl group (particularly methyl group) is preferably 70 to 95 mol% with respect to the total amount (100 mol%) of the group bonded to the ruthenium atom. Further, the ratio of the aryl group (especially phenyl group) is preferably from 10 to 70 mol% with respect to the total amount (100 mol%) bonded to the base of the ruthenium atom. In particular, by using a ratio of a total amount (100 mol%) of an aryl group (particularly a phenyl group) bonded to a group of a ruthenium atom to 10 mol% or more (for example, 10 to 70 mol%), When the branched chain polyorganosiloxane is used as described above, the barrier property against the corrosive gas tends to be improved. Further, by using a ratio of 50 mol% or more (for example, 50 to 90 mol%) relative to the total amount (100 mol%) of the alkyl group (particularly methyl group) bonded to the base of the ruthenium atom, Then, the thermal shock resistance of the cured product tends to be higher.

The above-mentioned bifurcated chain polyorganosiloxane can be expressed, for example, by the above average unit formula in which c1 is a positive number. In this case, preferably c2/c1 is a number from 0 to 10, c3/c1 is a number from 0 to 0.5, c4/(c1+c2+c3+c4) is a number from 0 to 0.3, c5/(c1+c2 +c3+c4) is a number from 0 to 0.4. Further, the molecular weight of the branched chain polyorganosiloxane is preferably from 300 to 10,000, more preferably from 500 to 10,000 by the gel permeation chromatography (GPC) conversion standard polystyrene. 3000.

(polyorganomethoxy oxetane (B2))

The polyorganomethoxy oxetane (B2) has two or more hydroquinone groups in the molecule as described above, and in addition to the oxoxane combination, it also contains a polyorganosiloxane having a hydrazine alkyl group as a main chain. alkyl. Further, an alkylene group bonded to the above alkylene group is, for example, preferably an alkylene group having a carbon number of 2 to 4 (particularly a vinyl group). The polyorganomethoxyxanthene (B2) is difficult to produce a low molecular weight ring in the production step as compared with the polyorganosiloxane (B1), and it is difficult to produce a stanol group by decomposition or the like by heating or the like. (-SiOH), when polyorganomethoxy oxetane (B2) is used, the surface adhesiveness of the cured product of the curable resin composition is lowered, and it tends to be more difficult to yellow.

The polyorganomethoxy oxetane (B2) may, for example, be a linear chain, a partially branched linear chain, a bifurcated chain, or a mesh-like molecular structure. In addition, the polyorganomethoxy oxetane (B2) may be used singly or in combination of two or more. Specifically, two or more kinds of polyorganomethoxyxanthene (B2) having a different molecular structure may be used in combination, and for example, a linear polyorganomethoxyantane (B2) may be used in combination with a divergence. A chain of polyorganomethoxy oxetane (B2).

The group other than the hydrogen atom of the polyorganomethoxy oxetane (B2) to be bonded to the ruthenium atom may, for example, be an organic group or the like. Examples of the organic group include the above monovalent substituted or unsubstituted hydrocarbon group and the above alkenyl group. Among them, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred. Further, the polyorganosiloxane (B2) may have an alkenyl group (for example, a vinyl group) as a group other than a hydrogen atom bonded to a ruthenium atom, or may be absent.

The polyorganomethoxyxanthene (B2) is preferably a polyorganomethoxyxanthene represented by the following average unit formula (B-2).

Average unit formula (B-2): (R ⁴ ₂ SiO _2/2 ) _d1 (R ⁴ ₃ SiO _1/2 ) _d2 (R ⁴ SiO _3/2 ) _d3 (SiO _4/2 ) _d4 (R ^A ) _d5 (X ⁴ O) _d6

In the above average unit formula (B-2), R ⁴ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and specific examples thereof include a hydrogen atom, the above monovalent substituted or unsubstituted hydrocarbon group. Examples (for example, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, etc.), and the above alkenyl group. However, a part of R ⁴ is a hydrogen atom, and the ratio thereof is a range of two or more in the regulatory molecule. For example, the ratio of hydrogen atoms is preferably from 0.1 to 50 mol%, more preferably from 5 to 35 mol%, relative to the total amount of R ⁴ (100 mol%). When the ratio of the hydrogen atom is adjusted to the above range, the curability of the curable resin composition tends to be higher. Further, R ⁴ other than the hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

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

In the above average unit formula (B-2), X ⁴ is the same as the above X ³ 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 (B-2), d1 is a positive number, d2 is a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is a positive number, and d6 is 0 or a positive number. Wherein d1 is preferably from 1 to 50, d2 is preferably from 1 to 50, d3 is preferably from 0 to 10, d4 is preferably from 0 to 5, and d5 is preferably from 1 to 30.

More specifically, for example, a polyorganomethoxyxanthene having a structure represented by the following formula (II-2) can be given.

In the above formula (II-2), R ²² is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. R ²² may, for example, be a specific example (for example, an alkyl group, an aryl group, an arylalkyl group or a halogenated hydrocarbon group) of a hydrogen atom or the above monovalent substituted or unsubstituted hydrocarbon group, and the above alkenyl group. However, at least two of R ²² are hydrogen atoms. Further, R ²² other than the hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

The above-mentioned formula (II-2) in the same as R ^A in formula (I-2) R ^A, represents alkylene, which preferably is a C _2-4 alkylene group (in particular ethyl stretch). Further, in the case where a plurality of R ^A are present, these may be the same or different.

In the above formula (II-2), q1 represents an integer of 1 or more (for example, 1 to 100). Further, in the case where q1 is an integer of 2 or more, the structures in the arc enclosed by q1 may be the same or different.

In the above formula (II-2), q2 represents an integer of 1 or more (for example, 1 to 400). Further, when q2 is an integer of 2 or more, the structure in parentheses enclosed by q2 may be the same or different.

In the above formula (II-2), q3 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, when q3 is an integer of 2 or more, the structure in parentheses enclosed by q3 may be the same or different.

In the above formula (II-2), q4 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, when q4 is an integer of 2 or more, the structure in parentheses enclosed by q4 may be the same or different.

In the above formula (II-2), q5 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, when q5 is an integer of 2 or more, the structure in parentheses enclosed by q5 may be the same or different.

Further, in the above formula (II-2), the addition form of each structural unit may be a random type or a block type.

The terminal structure of the polyorganomethoxyxanthene having the structure represented by the formula (II-2), for example, may be a decyl group, an alkoxy fluorenyl group or a trialkyl fluorenyl group (for example, q5 Attached to the structure in the arc, trimethyl sulfhydryl, etc.). Various groups such as a hydroquinone group may be introduced at the end of the polyorganomethoxy oxetane.

The polyorganooxy oxetane (B2) can be produced by a conventional or conventional method, and the production method can be produced, for example, by the method described in JP-A-2012-140617.

In the curable resin composition of the present invention, the polysiloxane (B) may be used singly or in combination of two or more. The properties of the polyoxyalkylene (B) may be, for example, liquid at 25 ° C or may be solid.

In the curable resin composition of the present invention, the content (mixing amount) of the polyoxyalkylene (B) is, for example, 1 to 100 parts by weight, based on 100 parts by weight of the total amount of the polyoxyalkylene (A). From 1.5 to 50 parts by weight, more preferably from 2 to 30 parts by weight, still more preferably from 2.5 to 15 parts by weight. By adjusting the content of the polyoxyalkylene (B) in the above range, the curability of the curable resin composition is further improved, and the cured product can be efficiently formed. When the content of the polyoxyalkylene (B) is within the above range, the properties such as heat resistance, thermal shock resistance, and reflow resistance of the cured product tend to be improved by sufficiently performing a curing reaction or the like.

The polyoxyalkylene oxide (B) in the curable resin composition of the present invention may be a polyoxyalkylene oxide (B1) alone or a polyorganomethoxy alkane (B2), or may be used in combination. A siloxane (B1) and a polyorganomethoxy oxetane (B2). When the polyorganosiloxane (B1) and the polyorganomethoxyantane (B2) are used in combination, the ratio of these is not particularly limited and can be appropriately set.

The total content (total content) of the polyoxyalkylene (A) and the polyoxyalkylene (B) is preferably from 60 to 99% by weight, more preferably from 70 to 96% by weight, based on the total amount of the curable resin composition. More preferably, it is 80 to 90% by weight. When the total content is adjusted to the above range, the toughness, heat resistance, and transparency of the cured product tend to be improved.

[ladder type sesquioxanes]

The curable resin composition of the present invention may contain a ladder-type sesquisesquioxane as an example of the above-mentioned sesquisesquioxane. The curable resin composition of the present invention contains a ladder-type sesquisilane component, and the flexibility and thermal shock resistance tend to be remarkably improved. As the ladder type sesquioxanes, one or more (preferably two or more) alkenyl groups and one or more (ideally 2 to 50) aryl groups in the molecule, and -Si having a trapezoidal structure can be used. -O-Si-backbone sesquioxanes.

The alkenyl group and the aryl group which are contained in the molecule of the ladder type sesquioxanes are the same as those of the above-mentioned examples of the alkenyl group and the aryl group which are contained in the molecule of the polyorganosiloxane (A1). The alkenyl group and the aryl group which the ladder type sesquioxanes have are preferably bonded to a base of a ruthenium atom.

The alkenyl group and the aryl group which are contained in the molecule of the ladder-type sesquisquioxane are bonded to a group of a ruthenium atom, and examples thereof include a hydrogen atom and an organic group. The organic group may, for example, be the above-mentioned monovalent substituted or unsubstituted hydrocarbon group or the like. Among them, an alkyl group (particularly a methyl group) is preferred. Further, the ladder-type sesquioxanes may have a hydroxyl group or an alkoxy group as a group bonded to a ruthenium atom.

The ratio of the alkenyl group in the entire ladder-type sesquioxanes (100% by weight) is not particularly limited as long as it is in the range of one or more alkenyl groups in the control component, and is, for example, 1.0 to 20.0. The weight % is preferably from 1.5 to 15.0% by weight. The ratio of the aryl group is, for example, 1.0 to 50.0% by weight, preferably 5.0 to 25.0% by weight. When the aryl group is contained in the above range, it is easy to obtain a cured product having various physical properties such as heat resistance, crack resistance, and gas barrier properties. The ratio of the alkyl group is, for example, 10.0 to 50.0% by weight, preferably 20.0 to 40.0% by weight. Further, the ratio of the alkenyl group, the aryl group and the alkyl group in the ladder-type sesquioxanes can be calculated, for example, by measurement by NMR spectrum (for example, ¹ H-NMR spectrum).

The sesquisesquioxane is a polysiloxane which uses a T unit (a unit formed by a trivalent group in which a ruthenium atom is bonded to three oxygen atoms) as a basic constituent unit, and its basic structural formula (experimental formula) is RSiO _{3/2 is} indicated. Examples of the structure of the Si-O-Si backbone of the sesquisesquioxane include a random structure, a cage structure, and a ladder structure.

The weight average molecular weight (Mw) of the ladder type sesquioxanes is preferably from 100 to 800,000, more preferably from 200 to 100,000, still more preferably from 300 to 10,000, particularly preferably from 500 to 8,000, most preferably from 1700. To 7000. When the Mw is less than 100, the heat resistance of the cured product is lowered. On the other hand, when the Mw exceeds 800,000, the compatibility with other components may be lowered. Further, the above Mw is a value converted to standard polystyrene by gel permeation chromatography (GPC).

The number average molecular weight (Mn) of the ladder type sesquioxanes is preferably from 80 to 800,000, more preferably from 150 to 100,000, still more preferably from 250 to 10,000, particularly preferably from 400 to 8,000, most preferably from 1,500. To 7000. When the Mn is less than 80, the heat resistance of the cured product may be lowered. On the other hand, when Mn exceeds 800,000, compatibility with other components may fall. Further, the above Mn is a value converted to standard polystyrene by gel permeation chromatography (GPC).

The molecular weight dispersion (Mw/Mn) of the standard polystyrene by gel permeation chromatography (GPC) is preferably 1.00 to 1.40, more preferably 1.35 or less (for example, 1.05 to 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 tends to decrease. On the other hand, when the molecular weight dispersion degree is set to 1.05 or more, it is easy to become liquid (liquid) at room temperature, and handling property may improve.

The number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight dispersion (Mw/Mn) can be measured by the following apparatus and conditions.

Alliance HPLC System 2695 (manufactured by Waters)

Refractive Index Detector 2414 (made by Waters)

Column: Tskgel GMH _HR -M‧2 (made by Toray Co., Ltd.)

Guard column: Tskgel guard column H _HR L (manufactured by Toray Industries Co., Ltd.)

Column thermostat: COLUMN HEATER U-620 (manufactured by Sugai Co., Ltd.)

Solvent: THF

Measuring temperature: 40 ° C

Molecular weight: conversion standard polystyrene

The ladder type sesquioxanes are preferably liquid at normal temperature (about 25 ° C). More specifically, at 23 ° C, the viscosity is preferably from 100 to 100,000 mPa ‧ s, more preferably from 500 to 10,000 mPa ‧ s, still more preferably from 1,000 to 8,000 mPa ‧ s When the viscosity is less than 100 mPa‧s, the heat resistance of the cured product is lowered. On the other hand, when the viscosity exceeds 100,000 mPa·s, the preparation or operation of the curable resin composition may become difficult. Further, the viscosity at 23 ° C was a rheometer (trade name "Physican 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, the number of revolutions : 8 rpm conditions can be measured.

Further, in the curable resin composition of the present invention, the ladder-type sesquioxanes may be used alone or in combination of two or more.

The curable resin composition of the present invention preferably contains ladder-type heptasilcosane from the viewpoint of strength (resin strength), flexibility, and thermal shock resistance of the cured product.

In the case where the curable resin composition of the present invention contains a ladder-type sesquisestamer, the content of the ladder sesquioxanes in the curable resin composition of the present invention (the amount of blending) is relative to the polyoxyalkylene oxide. The total amount of (A) and polyoxyalkylene (B) is 100 parts by weight, preferably 0.05 to 50 parts by weight, more preferably 0.1 to 45 parts by weight, still more preferably 0.2 to 40 parts by weight. Further, the content (adjusted amount) of the ladder type sesquisquioxane is preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight, even more preferably 0.05 to 15% by weight based on the curable resin composition (100% by weight). It is preferably from 0.1 to 10% by weight. By controlling the content of the ladder type heptasilane in the above range, the flexibility and thermal shock resistance of the cured product tend to be remarkably improved.

[Rare Earth Compound (C)]

The curable resin composition of the present invention contains the rare earth compound (C) (rare earth complex compound) represented by the following formula (1).

[M(L1)(L2)(L3)] (1) In the formula (1), M represents a rare earth metal atom, and L1, L2 and L3 represent the same or different ligands, and are represented by the following formula (1a) An anion or enol anion of the indicated beta-diketone or beta-ketoester.

R ³¹ COCHR ³² COR ³³ (1a)

In the formula (1a), R ³¹ represents a linear or branched chain alkyl group having 1 to 30 carbon atoms which may have a halogen atom as a substituent, and an alkyl group having 1 to 30 carbon atoms, preferably a carbon number of 1. The alkyl group to 20 is more preferably an alkyl group having 2 to 15 carbon atoms, still more preferably an alkyl group having 3 to 10 carbon atoms, particularly preferably an alkyl group having 3 to 10 carbon atoms having a branched chain. Examples of the alkyl group having a carbon number of 3 to 10 in a divergent chain include isopropyl, isobutyl, t-butyl, s-butyl, isopentyl, t-pentyl, isohexyl, t-hexyl, and iso- Heptyl, t-heptyl, isooctyl, t-octyl, 2-ethylhexyl, isodecyl, isodecyl and the like. These groups are preferably isopropyl, isobutyl, t-butyl, s-butyl, isopentyl or t-pentyl. The substituent may, for example, be a halogen atom, a hydroxyl group or a carboxyl group, and preferably has a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among them, a fluorine atom is preferred.

In the formula (1a), R ³² represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a halogen atom as a substituent, and the alkyl group having 1 to 30 carbon atoms is preferably a group as recited in the above R ³¹ . However, the most preferred group in R ³² is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. The above substituents are the same as those recited in the above R ³¹ .

In the formula (1a), R ³³ represents an alkyl group having 1 to 30 carbon atoms, an aromatic heterocyclic group or a -OR ³⁴ group which may contain a halogen atom as a substituent. R ³⁴ above represents an alkyl group having 1 to 30 carbon atoms which may contain a halogen atom as a substituent. These alkyl groups having 1 to 30 carbon atoms are preferably the same groups as those recited in the above R ³¹ . Examples of the aromatic heterocyclic group include a pyridyl group, a pyrimidinyl group, a pyrazolyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group, a furyl group, a thienyl group, a decyl group, an oxazolyl group, a thiazolyl group, and the like. Imidazolyl and the like. The above substituents are the same as those enumerated above in 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, in the anion or enol anion of the β-diketone or β-ketoester of the above formula (1a), the anion is a structure represented by the formula (1a'), and the enol anion is represented by the formula (1a''). Structure. In the formula (1a') and the formula (1a''), R ³¹ , R ³² and R ³³ are the same as described above.

The rare earth compound (C) is, for example, a compound represented by the following formula (1').

In the formula (1'), M is a rare earth metal atom, R ³⁵ represents an alkyl group having 1 to 30 carbon atoms which may contain a halogen atom as a substituent, and R ³⁶ represents a hydrogen atom or may contain a halogen as a substituent. The alkyl group having 1 to 30 carbon atoms of the atom, and R ³⁷ represents an alkyl group having 1 to 30 carbon atoms, an aromatic heterocyclic group or a -OR ³⁸ group which may contain a halogen atom as a substituent. R ³⁸ represents an alkyl group having 1 to 30 carbon atoms which may contain a halogen atom as a substituent. 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].

In the above-mentioned M, the rare earth metal atom is as described above, and the above-mentioned R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may contain a halogen atom having 1 to 30 carbon atoms as a substituent, preferably the above. The group recited in R ³¹ , wherein the aromatic heterocyclic group is the same as those recited in the above R ³³ , and the substituent is the same as those exemplified in the above R ³¹ .

Examples of the rare earth metal atom include ruthenium, osmium, iridium, osmium, iridium, osmium, and the like, but among them, ruthenium is preferred because it is easily available.

Among the rare earth compound (C), the compound represented by the following formula (1-1) is a compound represented by the following formula (1-1) from the viewpoint of excellent solubility in the fluorenone resin and excellent heat resistance. a compound represented by the formula (1-2) [Ce(DPM) ₃ : tris(trimethylethanemethylmethane)], a compound represented by the formula (1-3) [Ce(HFAA) ₃ : 铈3 (Fluorohexaacetone) is particularly good.

In the curable resin composition of the present invention, the rare earth compound (C) may be used alone or in combination of two or more. Further, a commercially available product can also be used as the rare earth compound (C).

The content of the rare earth metal atom (weight basis) is 30 to 500 ppm, preferably 35 to 400 ppm, more preferably 40 to 300 ppm, still more preferably 50 to 200 ppm, based on the total amount of the curable resin composition. 60 to 150 ppm. When the content of the rare earth metal atom is less than 30 ppm, the hardness of the cured product under high temperature conditions cannot be suppressed from increasing, and when it exceeds 500 ppm, the transparency of the cured product may be deteriorated.

The content (the amount of the rare earth compound (C)) is not particularly limited as long as the content of the rare earth metal atom is from 30 to 500 ppm, but is 100 parts by weight based on 100 parts by weight of the polyoxyalkylene (A). It is preferably 0.01 to 0.5 part by weight, more preferably 0.015 to 0.4 part by weight, still more preferably 0.02 to 0.3 part by weight, particularly preferably 0.02 to 0.2 part by weight. When the content of the rare earth metal atom is too small, the hardness of the cured product under high temperature conditions cannot be suppressed from increasing, and in many cases, the transparency of the cured product may be deteriorated. Further, in the polyoxyalkylene (A), the polyoxyalkylene (D) is contained.

In the curable resin composition of the present invention, even if the amount of the rare earth compound (C) added is increased, the solubility in the fluorenone resin (especially, polyoxyalkylene (A)) is good, and when it is formed into a cured product during the addition. The heat resistance is also improved, and in particular, at a high temperature of about 250 ° C, the hardness does not rise and the flexibility can be maintained.

[hydroquinone-based catalyst (E)]

The curable resin composition of the present invention may contain a hydroquinone-based catalyst (E). The curable resin composition of the present invention is composed of an aliphatic carbon-carbon double bond (particularly an alkenyl group) and a hydroquinone group in a curable resin composition upon heating by containing a hydroquinone catalyst. The hydroquinone reaction can be more efficiently carried out. In addition, the hydroquinone-based catalyst (E) may be used singly or in combination of two or more.

The hydroquinone-based catalyst (E) is exemplified by a catalyst for hydroquinonelation reaction such as a platinum-based catalyst, a ruthenium-based catalyst, or a palladium-based catalyst. Specific examples thereof include platinum fine powder and platinum black. Platinum supported ruthenium dioxide micropowder, platinum supported activated carbon, chloroplatinic acid, chloroplatinic acid and alcohol, aldehydes, ketones, etc., platinum olefins, platinum-carbonyl vinyl Platinum vinyl oxane sterilide such as platinum carbonyl conjugate, platinum-divinyltetramethyl dioxin oxime or platinum-cyclovinyl methyl oxime oxime, etc., platinum- A platinum-based catalyst such as a phosphine complex or a platinum-phosphoric acid complex, and a palladium-based catalyst or a ruthenium-based catalyst containing a platinum atom in the platinum-based catalyst substituted with a palladium atom or a hafnium atom. Among them, as a hydroquinone catalyst, a platinum-vinyl methyl oxane displacing body or a platinum-carbonyl vinyl methyl morph or a chloroplatinic acid, a complex of an alcohol or an aldehyde has a good reaction rate. Therefore, it is better.

In the case where the curable resin composition of the present invention contains a hydroquinone catalyst, the content (adjusted amount) of the hydroquinone catalyst is relative to the aliphatic carbon-carbon double bond contained in the curable resin composition. The total amount of binding (particularly alkenyl) is 1 mole, preferably 1 x 10 ^-8 to 1 x 10 ^-2 mole, more preferably 1.0 x 10 ^-6 to 1.0 x 10 ^-3 mole. By setting the content to 1 × 10 ^-8 mol or more, it is possible to form a cured product more efficiently. On the other hand, when the content is set to 1 × 10 ^-2 mol or less, a cured product having a more excellent color phase (less coloration) tends to be obtained.

The content (combination amount) of the hydrohaloalkylation catalyst (E), for example, the weight unit of platinum, palladium or rhodium in the hydroquinone catalyst, is 0.01 to 1000 ppm with respect to the total amount of the curable resin composition. The amount within the range is preferably in the range of from 0.1 to 500 ppm. When the content of the hydroquinone catalyst is in such a range, the cured product can be formed more efficiently, and a cured product having a more excellent hue can be obtained.

[hardening retarder (F)]

The curable resin composition of the present invention may contain a hardening retarder (F). The hardening retarder (F) is a catalyst activity for regulating a platinum group metal-based catalyst, and the curable resin composition of the present invention may be optionally added in order to prevent sticking or saponification before heat curing.

As the hardening retarder (F), a conventional or conventional compound which can delay hardening is used, and although it is not particularly limited, 1-ethynyl-1-cyclohexanol and 3-methyl-1-butyne are mentioned. 3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-3-trimethyldecyloxy- 1-butyne, 3-methyl-3-trimethyldecyloxy-1-pentyne, 3,5-dimethyl-3-trimethyldecyloxy-1-hexyne, 1-ethynyl Alkynyl compounds such as 1-trimethyldecyloxycyclohexane, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, crown ether compounds (for example, 12-crown-4, 15-crown-5) Polyether compound such as 18-crown-6, 24-crown-8, etc.; pyrrole compound, pyrazole compound, 3,5-dimethylpyrazole compound, imidazole compound, 1,2,3-triazole compound An azole compound such as a 1,2,4-triazole compound.

Further, the hardening retarder (F) may be used singly or in combination of two or more. Further, the hardening retarder (F) can be produced by a conventional or conventional method, or can be obtained from a commercially available product.

The content (mixing amount) of the hardening retarder (F) is not particularly limited as long as it does not impair the effect of the present invention, but is polymerized with respect to the polysiloxane (A) and the polyoxyalkylene (B). The total amount of the oxoxane (D) is 100 parts by weight, for example, 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight.

[decane coupling agent (G)]

The curable resin composition of the present invention may contain a decane coupling agent (G). In the case where the curable resin composition of the present invention contains the decane coupling agent (G), in particular, the cured product tends to have higher adhesion to the object.

As the decane coupling agent (G), a conventional or conventional decane coupling agent can be used, and examples thereof include 3-glycidoxypropyltrimethoxydecane and 2-(3,4-epoxy ring). An epoxy group-containing decane coupling agent such as hexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane; N-2-(Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2 -(Aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyanthracene -N-(1,3-dimethyl-butenyl)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-amino An amine group-containing decane coupling agent such as hydrochloride of ethyl-3-aminopropyltrimethoxydecane or N-(β-aminoethyl)-γ-aminopropylmethyldiethoxydecane ; tetramethoxy decane, tetraethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, methyl triethoxy decane, vinyl triethoxy Alkane, vinyl trimethoxy decane, vinyl ginseng (methoxy ethoxy decane), phenyl trimethoxy decane, diphenyl dimethoxy decane, vinyl triethoxy decane, γ- ( Methyl) propylene methoxy propyl triethoxy decane, γ-(meth) propylene methoxy propyl trimethoxy decane, γ-(methyl) propylene methoxy propyl methyl dimethoxy Decane, γ-(meth) propylene methoxy propyl methyl diethoxy decane, decyl propyl trimethoxy decane, decyl propyl triethoxy decane, alkoxy oligomer (for example, Product names "X-41-1053", "X-41-1059A", "KR-516", "X-41-1085", "X-41-1818", "X-41-1810", "X" -40-2651", "X-40-2665A", "KR-513", "KC-89S", "KR-500", "X-40-9225", "X-40-9246", "X -40-9250"; above, Shin-Etsu Chemical Industry Co., Ltd.). Among them, a cyclodecane coupling agent containing an epoxy group (particularly 3-glycidoxypropyltrimethoxydecane) can be preferably used.

In the curable resin composition of the present invention, the decane coupling agent (G) may be used singly or in combination of two or more. Further, as the decane coupling agent (G), a commercially available product may be used.

In the case where the curable resin composition of the present invention contains a decane coupling agent (G), the content (adjusted amount) of the decane coupling agent (G) in the curable resin composition of the present invention is relative to the curable resin composition ( 100% by weight), preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 5% by weight. When the content of the decane coupling agent (G) is 0.01% by weight or more, the cured product tends to have higher adhesion to the object. On the other hand, when the content of the decane coupling agent (G) is 15% by weight or less, a sufficient curing reaction proceeds, and the toughness and heat resistance of the cured product tend to be improved.

Further, the curable resin composition of the present invention may contain other components than the above components. As other components, for example, a polyoxyalkylene compound other than a polyoxyalkylene (A) or a polyoxyalkylene (B) (for example, a cyclic siloxane compound, a low molecular weight linear or a branched chain enthalpy) may be mentioned. An oxyalkyl compound or the like, an isocyanate compound, a hydroquinonelation reaction inhibitor, a solvent, various additives, and the like. As the additive, for example, precipitated cerium oxide, wet cerium oxide, gas phase cerium oxide, calcined cerium oxide, titanium oxide, aluminum oxide, glass, quartz, aluminum silicate, iron oxide, calcium carbonate, Inorganic fillers such as carbon black, tantalum carbide, tantalum nitride, boron nitride, etc., and inorganic fillers prepared by organic ruthenium compounds such as organohalodecane, organoalkoxydecane, and organic decazane ; an organic resin fine powder such as an anthrone resin, an epoxy resin or a fluorine-containing resin; a filler such as a conductive metal powder such as silver or copper; a solvent and a stabilizer (antioxidant, ultraviolet absorber, light stabilizer) , heat stabilizers, etc., flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, etc.), flame retardant additives, reinforcing materials (other fillers, etc.), nucleating agents, Coupling agent, slip agent, wax, plasticizer, release agent, impact modifier, hue modifier, fluidity improver, colorant (dye, pigment, etc.), dispersant, antifoaming agent, defoaming agent, Antibacterial agent, preservative, viscosity modifier, viscosity-increasing , Phosphor and so on. These other components may be used singly or in combination of two or more. Moreover, the content (mixing amount) of other components can be appropriately selected without impairing the effect range of the present invention.

The curable resin composition of the present invention preferably has an aliphatic carbon-carbon double bond (particularly, an alkenyl group) of 0.2 to 4 mols with respect to the hydroquinone group 1 mol present in the curable resin composition. The composition (mixing composition) is more preferably 0.5 to 3.0 m, and even more preferably 0.8 to 2.0 m. By controlling the ratio of hydroquinone group to aliphatic carbon-carbon double bond (particularly, alkenyl group) in the above range, heat resistance, transparency, thermal shock resistance and reflow resistance of the cured product, and corrosion resistance The barrier property of gas has a tendency to increase.

The curable resin composition of the present invention can be prepared by stirring and mixing the above components at room temperature. In addition, the curable resin composition of the present invention may be used as a composition in which one component is preliminarily mixed as a one-liquid system. For example, two or more components in separate storage may be used in the above-described ratio. The mixture is used as a composition of a multi-liquid system (for example, a two-liquid system). It is also necessary to adjust the temperature without hardening (for example, 30 to 100 ° C).

The curable resin composition of the present invention may be in any state of a solid or a liquid, but is usually a liquid at normal temperature (about 25 ° C).

The viscosity of the curable resin composition of the present invention at 23 ° C is preferably from 300 to 20,000 mPa ‧ s, more preferably from 500 to 10,000 mPa ‧ s, still more preferably from 1,000 to 8,000 mPa ‧ s By setting the viscosity to 300 mPa ‧ or more, the heat resistance of the cured product tends to be higher. On the other hand, by setting the viscosity to 20,000 mPa·s or less, the preparation of the curable resin composition is easy, the productivity and handleability are further improved, and the cured product is hard to remain bubbles, so the cured product ( In particular, the productivity or quality of the sealing material tends to increase.

[Sealants]

The curable resin composition of the present invention can be suitably used as a sealing composition for a semiconductor element (the case of "the sealing agent of the present invention"). Specifically, the sealing agent can be suitably used for sealing applications of an optical semiconductor element (LED element) of an optical semiconductor device (that is, as a sealing agent for an optical semiconductor). The cured product obtained by curing the above-mentioned sealant not only has high heat resistance and transparency peculiar to the polyoxyalkylene-based material, but also does not increase the hardness particularly at a high temperature of about 250 ° C, and can maintain flexibility. . For this reason, the sealant is particularly preferably used as a sealant for a high-brightness, short-wavelength optical semiconductor element.

The curable resin composition of the present invention is not limited to the above-mentioned use of the sealant, and is also suitable for use as a lens (optical lens, heat-resistant plastic lens, etc.), an optical member, a functional coating agent, a transparent machine, and the like. Reagents (heat-resistant transparent adhesives, etc.), electrical insulation materials (insulation films, etc.), laminates, coatings, inks, coatings, sealants, anti-resistants, composite materials, transparent substrates, transparent sheets, transparent films, optics Optical, or semiconductor-related applications such as components, optical shapes, electronic papers, touch panels, solar cell substrates, optical waveguides, light guide plates, and holographic memories, and from the viewpoint of excellent transparency when used as a cured product In other words, it can be suitably used as a lens for forming. That is, the curable resin composition of the present invention can be suitably used as a resin composition for forming a lens.

<hardened matter>

By hardening the curable resin composition of the present invention (particularly, it is cured by a hydroquinone reaction), a cured product (in the case of simply referred to as "the cured product of the present invention") can be obtained. In the case of hardening (especially, hardening by a hydroquinone reaction), conventionally known conditions can be appropriately selected, but from the viewpoint of the reaction rate, the temperature (hardening temperature) is preferably 25 to 180 ° C. More preferably, it is 60 to 150 ° C, and time (hardening time) is preferably 5 to 720 minutes. Further, the hardening may be carried out in one stage or in multiple stages. As the cured product of the present invention, for example, a sealing material, a lens, or the like can be given. The cured product of the present invention is not only highly heat-resistant and transparent, which is peculiar to a polyoxyalkylene-based material, and in particular, the hardness does not rise under high-temperature conditions of about 250 ° C, and the flexibility can be maintained.

The cured product of the present invention has high transparency. The cured product of the present invention has a light transmittance of 3 mm and a wavelength of 450 nm, preferably 80% or more, more preferably 85% or more, still more preferably 90% or more. The light transmittance can be measured using a light transmittance meter (UV-Vis spectrophotometer).

<semiconductor device>

By sealing the semiconductor element with the curable resin composition of the present invention (the sealing agent of the present invention), a semiconductor device (a case of simply referred to as "the semiconductor device of the present invention") can be obtained. In other words, the semiconductor device of the present invention is at least a semiconductor device having a semiconductor element and a sealing material for sealing the semiconductor device, and the sealing material is a semiconductor device of a cured product of the curable resin composition (sealant of the present invention) of the present invention. The production of the semiconductor device of the present invention can be carried out by a conventional or conventional method. For example, the sealing agent of the present invention can be applied by injecting it into a predetermined molding die and heating and hardening under predetermined conditions. The hardening temperature and the hardening time may be set in the same range as in the case of preparation of the cured product. The sealing agent for a semiconductor of the present invention has heat resistance and transparency, and is particularly suitable for use in an optical semiconductor device because the hardness does not rise under high temperature conditions of about 250 ° C and the flexibility can be maintained.

One example of the optical semiconductor device of the present invention is shown in Fig. 1. In the first drawing, 100 denotes a reflecting plate, 101 denotes a metal wiring (electrode), 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes a cured material (sealing material).

The semiconductor device of the present invention is a semiconductor device having a semiconductor element and a lens, and the lens is preferably a cured product having the curable resin composition of the present invention. Further, the semiconductor device of the present invention is a semiconductor device including a semiconductor element and a sealing material and a lens for sealing the semiconductor element, and the sealing material is preferably a cured product of the curable resin composition (sealant of the present invention) of the present invention. The lens is preferably a cured product of the curable resin composition of the present invention.

[Examples]

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

The ¹ H-NMR analysis of the product was carried out by JEOL ECA500 (500 MHz). Further, the weight average molecular weight of the product was measured by Alliance HPLC System 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), and column: Tskgel GMH _{HR -} M × 2 (manufactured by Toray Industries, Inc.) Guard column: Tskgel guard column H _HR L (manufactured by Toray Industries, Inc.), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C.

Manufacturing example 1

[Synthesis of Rare Earth Compound C-1]

In a four-necked flask, 4 g (21.7 mmol) of 2,7,7-trimethyl-3,5-octanedione and 36 g of 2-propanol were weighed and placed in a four-necked flask. The vessel was replaced with nitrogen, heated to 60 ° C, and 4.19 g of a 28 wt% sodium methoxide/methanol solution was added dropwise. After stirring for 1 hour, a solution of 2.70 g (7.24 mmol) of ruthenium chloride heptahydrate dissolved in 10 g of methanol was dropped. Thereafter, the mixture was stirred at 60 ° C, and after the salt was removed by a membrane filter, the solution was concentrated on a rotary evaporator to yield 4.18 g (yield: 83.8%) as a tan solid. The obtained rare earth compound C-1 is a compound represented by the above formula (1-1).

Manufacturing Example 2

[Synthesis of Rare Earth Compound C-2]

In a four-necked flask, 4 g (21.7 mmol) of 2,2,6,6-tetramethyl-3,5-heptanedione and 36 g of 2-propanol were weighed and placed in a four-necked flask. The vessel was replaced with nitrogen, heated to 60 ° C, and 4.19 g of a 28 wt% sodium methoxide/methanol solution was added dropwise. After stirring for 1 hour, a solution of 2.70 g (7.24 mmol) of ruthenium chloride heptahydrate dissolved in 10 g of methanol was dropped. Thereafter, the mixture was stirred at 60 ° C, and after removing the salt in the membrane filter, the solution was concentrated on a rotary evaporator to obtain 4.20 g (yield: 84.2%) of a purple solid. The obtained rare earth compound C-2 is a compound represented by the above formula (1-2).

Manufacturing Example 3

[Synthesis of Rare Earth Compound C-3]

In a four-necked flask, 4 g (19.2 mmol) of hexafluoroacetoxyacetone and 36 g of 2-propanol were weighed and placed in a four-necked flask. The vessel was replaced with nitrogen, heated to 60 ° C, and 3.71 g of a 28 wt% sodium methoxide/methanol solution was added dropwise. After stirring for 1 hour, a solution of 2.39 g (6.41 mmol) of ruthenium chloride heptahydrate dissolved in 2 g of methanol was dropped. Thereafter, the mixture was stirred at 60 ° C, and after the salt was removed by a membrane filter, the solution was concentrated on a rotary evaporator to obtain a pale yellow solid (4.05 g, yield: 83.2%). The obtained rare earth compound C-3 is a compound represented by the above formula (1-3).

Manufacturing Example 4

[Synthesis of polyorganosiloxane d-1]

In a four-necked flask, 40.10 g of methyltriethoxydecane, 3.38 g of phenyltriethoxydecane, and 17.69 g of methyl isobutyl ketone (MIBK) were placed, and the mixture was cooled to 10 °C so far. 4.33 g of water and 0.48 g of 5N hydrochloric acid were simultaneously dropped in the above mixture. After the dropping, the mixture was kept at 10 °C. Thereafter, 80.0 g of MIBK was added, and the reaction solution was diluted.

Next, the temperature of the reaction vessel was raised to 70 ° C, and 10.91 g of water was added at 70 ° C, and a polycondensation reaction was carried out under nitrogen at the same temperature. Further, 6.25 g of vinyltriethoxydecane was added, and the ripening reaction was carried out at the same temperature.

Next, 15.0 g of hexamethyldioxane was added to the obtained reaction solution, and the thiolation reaction was carried out at 70 °C. Thereafter, the reaction solution was cooled, and the lower layer was washed with water until neutral, and then the supernatant liquid was taken. Next, the solvent was distilled off from the supernatant liquid under the conditions of 1 mm Hg at 60 ° C to obtain a polyorganosilsesquioxane (polyorganoxane D-1) having a vinyl group and a trimethylsulfonium group at the terminal. A product of 19.0 g of a colorless transparent liquid was obtained.

Weight average molecular weight (Mw): 3000, phenyl content: 4 mol%, vinyl content: 6 mol%

¹ H-NMR (CDCl ₃ ) δ: -0.3-0.3 ppm (br), 5.7-6.2 ppm (br), 7.1-7.7 ppm (br)

Manufacturing Example 5

[Synthesis of polyorganosiloxane D-3]

In a four-necked flask, 42.61 g of methyltriethoxydecane, 6.76 g of phenyltriethoxydecane, and 17.69 g of methyl isobutyl ketone (MIBK) were placed, and the mixture was cooled to 10 ° C. until. 4.33 g of water and 0.48 g of SN hydrochloric acid were simultaneously dropped in the above mixture. After the dropping, the mixture was kept at 10 °C. Thereafter, 80.0 g of MIBK was added, and the reaction solution was diluted.

Next, the temperature of the reaction vessel was raised to 70 ° C, and 10.91 g of water was added at 70 ° C, and a polycondensation reaction was carried out under nitrogen at the same temperature. Further, 2.08 g of vinyltriethoxydecane was added, and the ripening reaction was carried out at the same temperature.

Next, 15.0 g of hexamethyldioxane was added to the obtained reaction solution, and the thiolation reaction was carried out at 70 °C. Thereafter, the reaction solution was cooled, and the lower layer was washed with water until it became neutral, and thereafter, the supernatant liquid was separated. Next, the solvent was distilled off from the supernatant liquid at 1 mm Hg at 60 ° C to obtain a polyorganosilsesquioxane (polyorganosiloxane) having a vinyl group and a trimethylsulfonium group at the end, and was prepared. Colorless transparent liquid product 19.0 g.

Weight average molecular weight (Mw): 2700, phenyl content: 4 mol%, vinyl content: 2 mol% ¹ H-NMR (CDCl ₃ ) δ: -0.3-0.3 ppm (br), 5.7-6.2 Ppm(br), 7.1-7.7ppm(br)

As the polyoxyalkylene (A), a terminal vinyl dimethyl fluorenone was used, and the trade name "DMS-V 35" (manufactured by Gelest Co., Ltd.) was used.

As the polyoxyalkylene (B), a terminal trimethylphosphonium-terminated methylhydroquinone-dimethyloxane was used to copolymerize an anthrone, and the trade name was "HMS-301" (manufactured by Gelest Co., Ltd.).

As the rare earth compound (C), the rare earth compounds C-1 to C-3 synthesized in the above Synthesis Examples 1 to 3 were used.

As the other rare earth compound (rare earth compound other than the rare earth compound (C)), the following rare earth compounds C-4 and C-5 are used.

Rare earth compound C-4: bismuth(III) 2-ethylhexanoate 49% 2-ethylhexanoic acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) (However, the value in Table 1 is 2-ethylhexyl) Effective amount of acid bismuth)

Rare earth compound C-5: cerium (IV) oxide (manufactured by Wako Pure Chemical Industries, Ltd.)

As the polyorganosiloxane (D), the polyorganosiloxanes D-1 and D-3 synthesized in the above Production Examples 4 and 5 and the polyorganosiloxane d-2 described below were used.

Polyorganooxane D-2: vinyl MQ resin, trade name "MQV-7" (manufactured by Nagase Industries Co., Ltd.)

As the hydroquinone catalyst (E), a PtVTS: 2% Pt-1,3-divinyltetramethyldioxanoxane xylene solution (manufactured by NE CHEMCAT Co., Ltd.) was used.

As the hardening retarder (F), 1-ethynylcyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

<Evaluation method of compatibility of rare earth compounds>

The polysiloxane (A), the polyoxyalkylene (B), the rare earth compound (C), other rare earth compounds, polyorganosiloxane (D), and hardening retarder (F) are described in Table 1. A predetermined ratio is mixed to prepare a formulation. The preparation liquid was stirred at 70 ° C for 4 hours, and then transferred to a transparent glass bottle, and the appearance after 168 hours at 23 ° C was visually confirmed according to the following evaluation criteria. The evaluation results are shown in Table 1.

(assessment basis)

○: no solid precipitates

×: There is solid precipitate

Example 1-8, Comparative Example 1

[Manufacture of Curable Resin Composition]

Using the method for evaluating the compatibility of the above-mentioned rare earth compound, the hydroquinone-based catalyst (E) was added in a predetermined amount as shown in Table 1 for each of the preparation liquids, and stirred for 10 minutes to obtain a curable resin composition. Further, the content of the rare earth metal atom in Table 1 and the content of the hydroquinone catalyst (E) are based on the weight reference value (ppm) of the total amount of the curable resin composition.

<initial hardness>

Each of the curable resin compositions of Examples 1 to 8 and Comparative Example 1 obtained above was poured into a rectangular mold having a thickness of 3 mm, a width of 10 mm, and a length of 50 mm, and heated at 100 ° C for 1 hour, followed by heating at 150 ° C for 5 hours. A cured product (thickness: 3 mm) of the above curable resin composition was produced. For the cured product, the initial hardness was measured in accordance with JIS K 6253-3 using a Durometer Hardness (model "GS-719G", manufactured by Teclock Co., Ltd.). The results of the evaluation are shown in Table 1.

<Light transmittance>

The cured product (thickness: 3 mm) produced by the initial hardness was measured for light transmittance at a wavelength of 450 nm using an ultraviolet-visible spectrophotometer (model "UV-2450", manufactured by Shimadzu Corporation). The results of the evaluation are shown in Table 1.

<hardness after heat aging test at 250 °C>

The cured product (thickness: 3 mm) produced by the above initial hardness was exposed to an environment of 250 ° C for 200 hours, and then the hardness was measured in the same manner as the initial hardness described above. The results of the evaluation are shown in Table 1.

From Examples 1 to 8 in which the rare earth compound (C) was used in the above Table 1, the compatibility with the fluorenone resin was good, and the transparency of the cured product was also good, and the increase in hardness was also suppressed under the high temperature condition of 250 °C. On the other hand, when the rare earth compound of Comparative Example 1 was used as the cerium 2-ethylhexanoate, it was precipitated without being dissolved in the fluorenone resin. In Comparative Example 2, since the content of bismuth 2-ethylhexanoate was small, it did not precipitate, but the hardness increased after the heat aging test at 250 °C. Further, in the case of using the cerium oxide as the rare earth compound of Comparative Example 3, it was precipitated without being dissolved in the fluorenone resin. Moreover, when the content of the rare earth compound (C) of Comparative Example 4 was too small, the hardness after the heat aging test of the cured product increased. Moreover, when the content of the rare earth compound (C) of Comparative Example 5 is too large, the transparency is deteriorated.

As a result of the above finishing, the constitution of the present invention and variations thereof are described as follows. Further, in the following description, the formula (chemical formula) is as described in the present specification.

[1] A curable resin composition comprising: polyoxyalkylene (A), which is a polyorganosiloxane (A1) having two or more alkenyl groups in its molecule, and a poly(alkene) having two or more alkenyl groups in the molecule. At least one selected from the group consisting of organic oxime oxane (A2); polyoxy siloxane (B) is a polyorganosiloxane (B1) having two or more hydroquinone groups in the molecule and At least one selected from the group consisting of polyorganomethoxy oxane (B2) having two or more hydroquinone groups in the molecule; and the rare earth compound (C) represented by the formula (1), The total amount of the curable resin composition is from 30 to 500 ppm of the rare earth metal atom.

[2] The curable resin composition according to [1], wherein, in the case of containing a polyorganosiloxane (A1), the alkenyl group of the polyorganosiloxane (A1) is a vinyl group, an allyl group, Butenyl, pentenyl, or hexenyl.

[3] The curable resin composition according to [1] or [2], which comprises a polyorganosiloxane having an average unit formula (a-1), and an average unit formula (a-2) At least one polydecane (D) selected from the group consisting of polyorganomethoxy oxetanes is shown as polyoxyalkylene (A).

[4] The curable resin composition according to [3], which comprises a polyorganosiloxane having an average unit formula (a-1)', and an average unit formula (a-1)' At least one selected from the group consisting of polyorganomethoxy oxetane is used as the polyoxyalkylene (D).

[5] The curable resin composition according to [4], wherein the polyorganosiloxane having an average unit formula (a-1)' is a sesquisesquioxane.

[6] The curable resin composition according to any one of [3] to [5] wherein the content of the polyoxyalkylene (D) is from 1 to 70 by weight based on the total amount of the polyoxyalkylene (A). %.

[7] The curable resin composition according to any one of [1] to [6] wherein, in the case of containing a polyorganosiloxane (A1), the polyorganosiloxane (A1) is intramolecular. A linear polyorganosiloxane having two or more alkenyl groups.

[8] The curable resin composition according to [7], wherein, in the linear polyorganosiloxane, the total amount (100 mol%) of the group bonded to the ruthenium atom, the alkenyl group The ratio is 0.1 to 40 mol%.

[9] The curable resin composition according to [7] or [8] wherein the linear polyorganosiloxane is a polyoxyalkylene represented by the formula (I-1).

[10] The curable resin composition according to any one of [1] to [6] wherein, in the case of the polyorganosiloxane (A1), the polyorganosiloxane (A1) is intramolecular. Two or more alkenyl groups having a divalent chain polyorganosiloxane having a siloxane unit (T unit) represented by RSiO _3/2 (R is a monovalent substituted or unsubstituted hydrocarbon group).

[11] The curable resin composition according to any one of [1] to [10] wherein, in the case of containing a polyorganomethoxyxanthene (A2), the alkyl group bonded to the alkyl group It is a linear or divalent chain C _1-12 alkylene group.

[12] The curable resin composition according to any one of [1] to [11] wherein, in the case of containing a polyorganomethoxy oxetane (A2), a polyorganomethoxy oxetane ( The alkenyl group of A2) is a substituted or unsubstituted alkenyl group (ideally a vinyl group).

[13] The curable resin composition according to any one of [1] to [12] wherein, in the case of containing a polyorganomethoxy oxetane (A2), a polyorganomethoxy oxetane ( A2) is a polyorganomethoxyxanthene represented by the average unit formula (a-2).

[14] The curable resin composition according to any one of [1] to [13] wherein, in the case of containing a polyorganomethoxy oxetane (A2), a polyorganomethoxy oxetane ( A2) is a polyorganomethoxyxanthene having a structure represented by the formula (I-2).

[15] The curable resin composition according to any one of [1] to [14], wherein the content (total amount) of the polyoxyalkylene (A) is 50 with respect to the total amount of the curable resin composition. Up to 99% by weight.

[16] The curable resin composition according to any one of [1] to [15] wherein, in the case of containing a polyorganosiloxane (B1), the polyorganosiloxane (B1) is an average unit type. Polyorganosiloxane which is represented by (B-1).

[17] The curable resin composition according to any one of [1] to [16] wherein, in the case of containing a polyorganosiloxane (B1), the polyorganosiloxane (B1) is intramolecular. A linear polyorganosiloxane having two or more hydroquinone groups.

[18] The curable resin composition according to [17], wherein the linear polyorganosiloxane is a total amount (100 mol%) of a group bonded to a ruthenium atom, and a hydrogen atom (in ruthenium) The ratio of the hydrogen atoms bonded in the atom is 0.1 to 40 mol%.

[19] The curable resin composition according to [17] or [18] wherein the linear polyorganosiloxane is a polyoxyalkylene represented by the formula (II-1).

[20] The curable resin composition according to any one of [1] to [16] wherein, in the case of containing a polyorganosiloxane (B1), the polyorganosiloxane (B1) is intramolecular. Two or more hydroquinone groups having a divalent chain polyorganosiloxane of a siloxane unit (T unit) represented by RSiO _3/2 (R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group).

[21] The curable resin composition according to any one of [1] to [20] wherein, in the case of containing a polyorganomethoxy oxetane (B2), a polyorganomethoxy oxetane ( The alkyl group bonded to the alkyl group of B2) is an alkylene group having 2 to 4 carbon atoms (desirably an ethyl group).

[22] The curable resin composition according to any one of [1] to [21] wherein, in the case of containing a polyorganomethoxy oxetane (B2), a polyorganomethoxy oxetane ( B2) is a polyorganomethoxyxanthene represented by the average unit formula (B-2).

[23] The curable resin composition according to any one of [1] to [22] wherein, in the case of containing a polyorganomethoxyantane (B2), a polyorganomethoxy oxetane ( B2) is a polyorganomethoxyxanthene having a structure represented by the formula (II-2).

[24] The curable resin composition according to any one of [1] to [23] wherein the content of the polyoxyalkylene (B) is 100 parts by weight based on the total amount of the polyoxyalkylene (A). 1 to 100 parts by weight.

[25] The curable resin composition according to any one of [1] to [24], wherein the polyoxyalkylene (A) and the polyoxyalkylene (B) are present in an amount relative to the total amount of the curable resin composition. The total content (total content) is 60 to 99% by weight.

[26] The curable resin composition according to any one of [1] to [25] which contains a ladder-type sesquisesquioxane.

[27] The curable resin composition according to any one of [1] to [26] wherein the rare earth compound (C) is a compound represented by the formula (1').

[28] The curable resin composition according to any one of [1], wherein the rare earth metal atom is selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, and osmium. At least one of them.

The hardening resin composition of any one of the above-mentioned [1], wherein the rare earth compound (C) is a compound represented by the formula (1-1) [铈 trimethyl octane] Diketone], a compound represented by the formula (1-2) [Ce(DPM) ₃ : tris(trimethylethanemethylmethane)], and a compound represented by the formula (1-3) [Ce(HFAA) ₃ : A compound of at least one of the group consisting of tris(hexafluoroacetamidoacetone).

[30] The curable resin composition according to any one of [1] to [29] wherein the content of the rare earth compound (C) is 0.01 to 0.5 with respect to 100 parts by weight of the polyoxyalkylene (A). Parts by weight.

[31] The curable resin composition according to any one of [1] to [30] further comprising a hydroquinone-based catalyst (E).

[32] The curable resin composition according to [31], wherein the hydroquinone catalyst (E) is a platinum-based catalyst, a ruthenium-based catalyst, or a palladium-based catalyst.

[33] The curable resin composition according to [32], wherein the total amount of the curable resin composition is hydrogen sulfhydryl group based on the weight unit of platinum, palladium or rhodium in the hydroquinone catalyst. The content of the catalytic agent (E) is from 0.01 to 1000 ppm.

[34] The curable resin composition according to any one of [1] to [33] further comprising a hardening retarder (F).

[35] The curable resin composition according to any one of [1] to [34] wherein, with respect to the polyoxyalkylene (A) and the polyoxyalkylene (B) and the polyoxyalkylene (D) The total amount of the hardening retarder (F) is 0.001 to 5 parts by weight based on 100 parts by weight.

[36] The curable resin composition according to any one of [1] to [35] further comprising a decane coupling agent (G).

[37] The curable resin composition according to any one of [1] to [36] which is a sealant.

[38] The curable resin composition according to any one of [1] to [37], which is a resin composition for forming a lens.

[39] A cured product of the curable resin composition according to any one of [1] to [38].

[40] The cured product according to [39], wherein the thickness is 3 mm, and the light transmittance is 80% or more at a wavelength of 450 nm.

[41] A semiconductor device comprising a semiconductor element and a cured semiconductor material, wherein the sealing material is a cured product of the curable resin composition according to [37].

[42] A semiconductor device comprising a semiconductor element and a lens, wherein the lens is a cured product of the curable resin composition according to [38].

[43] A semiconductor device comprising a semiconductor element, a sealing material for sealing the semiconductor element, and a lens, wherein the sealing material is a cured product of the curable resin composition according to [37], wherein the lens is as [38] A cured product of the curable resin composition described herein.

[44] The semiconductor device according to any one of [41] to [43], which is an optical semiconductor device.

[Industry use possibility]

The curable resin composition of the present invention can be used as a sealant for sealing a semiconductor element or a resin composition for forming a lens.

Claims (15)

A curable resin composition comprising: a polyorganosiloxane (A), a polyorganosiloxane (A1) having two or more alkenyl groups in its molecule, and a polyorganophosphonium having two or more alkenyl groups in its molecule. At least one selected from the group consisting of oxetane (A2); polyoxazane (B) consisting of polyorganosiloxane (B1) having two or more hydroquinone groups in the molecule and intramolecular At least one selected from the group consisting of polyorganomethoxy oxane (B2) having two or more hydroquinone groups; and a rare earth compound (C) represented by the following formula (1), [M ( L1) (L2) (L3)] (1) [In the formula (1), M is a rare earth metal atom, and L1, L2 and L3 are the same or different ligands, and are represented by the following formula (1a) Anion or enol anion of β-diketone or β-ketoester R ³¹ COCHR ³² COR ³³ (1a) In the formula (1a), R ³¹ represents a linear or branched chain which may contain a halogen atom as a substituent. An alkyl group having 1 to 30 carbon atoms, R ³² represents a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms which may have a halogen atom as a substituent, and R ³³ represents a linear or divalent chain carbon which may contain a halogen atom. alkyl group of 1 to 30, an aromatic heterocyclic group, or a group -OR ^34; R ³⁴ Herein may be an alkyl group as a chain of linear or difference halogen substituent group of carbon number 1 to 30; R ³¹ and R ³² may be bonded to each other to form a ring, R ³² and R ³³ may be bonded to each other to form a ring], relative The total amount of the hardenable resin composition is such that the content of the rare earth metal atom is 30 to 500 _p m .  The curable resin composition according to claim 1, wherein the rare earth metal atom is at least one selected from the group consisting of ruthenium, osmium, iridium, osmium, iridium, and osmium.    The curable resin composition according to claim 1 or 2 further contains a hydroquinone-based catalyst (E).   The curable resin composition according to any one of claims 1 to 3, wherein the polyorganosiloxane is represented by the following average unit formula (a-1), and the following average At least one polyoxane (D) selected from the group consisting of polyorganomethoxy oxane shown in the formula (a-2), as the polysiloxane (A), an average unit (a) -1): (R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5 [ In the average unit formula (a-1), R ¹ is the same or different and represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms; however, R A part of ¹ is an alkenyl group and is a range of two or more in the molecule; X ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a1, a2, a3, a4, and a5 respectively satisfy satisfaction: 1>a1 ≧0,1>a2≧0,1>a3>0,1>a4≧0, 0.05≧a5≧0, a1+a4>0, and a1+a2+a3+a4+a5=1 value]; Unit (a-2): (R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 (SiO _4/2 ) _b4 (R ^A ) _b5 ( X ² O _{1/2) b6} [average unit formula (a-2), R ² is identical or different, represent a carbon Alkyl having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or an alkenyl group having 2 to 8; however, a part of R ² is an alkenyl group, and the molecule becomes within the range of 2 or more; R ^A is The same or different, representing an alkylene group having 1 to 14 carbon atoms; X ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and b1, b2, b3, b4, b5, and b6 respectively satisfy: 1>b1 ≧0,1>b2>0,1>b3≧0,1>b4≧0,0.7>b5>0, 0.05≧b6≧0, b3+b4>0, and b1+b2+b3+b4+b5+ The value of b6=1]. The curable resin composition according to claim 4, wherein the polyorganosiloxane is represented by the following average unit formula (a-1), and the following average unit formula (a- 1) at least one selected from the group consisting of polyorganomethoxy oxetane shown as '', as the polysiloxane (D), the average unit formula (a-1)': (R ¹ SiO _3/2 ) _a1 (R ¹ ₃ SiO _1/2 ) _a3 (X ¹ O _1/2 ) _a5 [In the average unit formula (a-1)', R ¹ is the same or different and is the same as the above; X ¹ is the same as the above; a1, a3, and a5 represent values of 1>a1>0, 1>a3>0, 0.05≧a5≧0, and a1+a3+a5=1, respectively] averaging unit (a- 1) '': (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5 [in the average unit formula (a-1)'', R ¹ and X ¹ are The same as the above; a3, a4, and a5 indicate values satisfying: 1>a3>0, 1>a4>0, 0.05≧a5≧0, and a3+a4+a5=1, respectively.  The curable resin composition according to claim 5, wherein the polyorganosiloxane of the above average unit formula (a-1)' is a heptadecane.    The curable resin composition according to any one of claims 4 to 6, wherein the content of the polyoxyalkylene (D) is from 1 to 70 with respect to the total amount of the polyoxyalkylene (A). weight%.    The curable resin composition according to any one of claims 1 to 7, which is a sealant.    The curable resin composition according to any one of claims 1 to 7, which is a resin composition for forming a lens.    A cured product of a cured resin composition according to any one of claims 1 to 9 of the invention.    The cured product according to claim 10, wherein the light transmittance at a wavelength of 450 nm is 80% or more when the thickness is 3 mm.    A semiconductor device comprising a semiconductor element and a sealing material for sealing the semiconductor element, wherein the sealing material is a cured product of the curable resin composition according to claim 8 of the patent application.    A semiconductor device comprising a semiconductor element and a lens, wherein the lens is a cured product of the curable resin composition according to claim 9 of the patent application.    A semiconductor device comprising a semiconductor element, a sealing material for sealing the semiconductor element, and a lens, wherein the sealing material is a cured product of a curable resin composition according to claim 8 of the patent application, wherein the lens is as claimed The cured product of the curable resin composition according to item 9.    The semiconductor device according to any one of claims 12 to 14, which is an optical semiconductor device.