TW201546189A - Curable resin composition, cured product thereof, glycoluril derivative, and method for producing same - Google Patents

Abstract

The present invention pertains to a curable resin composition characterized in containing a polysiloxane (A) having two or more alkenyl groups per molecule that is at least one selected from the group consisting of polyorganosiloxanes (A1) and polyorganosiloxysilalkylenes (A2), a polysiloxane (B) having two or more hydrosilyl groups per molecule that is at least one selected from the group consisting of polyorganosiloxanes (B1) and polyorganosiloxysilalkylenes (B2), and a compound (C) represented by formula (1). The present invention provides a curable resin composition that makes it possible to form a cured product (sealing material) that is exceptional in terms of all of the following characteristics: thermal shock resistance, reflow resistance, and barrier properties with respect to corrosive gases (e.g., SOx gas). (In formula (1), at least one among Ra-Rd is a group selected from the group consisting of groups represented by formula (1b) and groups represented by formula (1c)).

Description

Curable resin composition and cured product thereof, acetylene urea derivative and preparation method thereof

The present invention relates to a curable resin composition and a cured product thereof, a sealant using the curable resin composition, and a semiconductor device obtained by sealing a semiconductor element (particularly an optical semiconductor element) using the above-described sealant (particularly Optical semiconductor device). Moreover, the present invention relates to an acetylene urea derivative which is particularly useful as a constituent component of the above-mentioned curable resin composition, and a method for producing the same. The priority of Japanese Patent Application No. 2014-089554, filed on Apr. 23, 2014, in Japan, is hereby incorporated by reference.

As the sealing material for covering the semiconductor element and protecting the semiconductor element, various resin materials are used. In particular, the sealing material in the optical semiconductor device is required to satisfy the barrier property against the corrosive gas such as the SOx gas and the heat-resistant squeezing property at a high level (it is difficult to generate the crack of the sealing material when the heat is applied by a hot and cold cycle or the like). Or peeling, characteristics of defects such as non-lighting of the optical semiconductor device, and reflow resistance (it is difficult to cause cracks or peeling of the sealing material, non-lighting of the optical semiconductor device, etc. when the heat of extremely high temperature is applied in the reflowing step) All of the characteristics of the defect).

However, the current situation is that it is difficult to satisfy all of these characteristics at the same time. The reason for this is that in general, it is desirable to improve the barrier properties mentioned above. In the case where the hardness of the sealing material is lowered, the heat-resistant punching property and the reflow resistance are impaired, and on the other hand, when the heat-resistant punching property and the reflow resistance are improved, the above-mentioned The tendency of the barrier property to decrease, and the characteristics of these have a relationship of substitution.

At present, as a sealing material for an optical semiconductor device, a phenyl fluorenone (phenyl fluorenone-based sealing material) having a good balance of barrier properties against a corrosive gas, heat-resistant squeezing property, and reflow resistance is widely used (for example, Refer to Patent Document 1).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent No. 4409160

However, the phenyl fluorenone-based sealing material has a higher barrier property against a corrosive gas than the conventional methyl ketone-based sealing material, but its characteristics are not sufficient. When a phenyl fluorenone-based sealing material is actually used, corrosion of the electrode due to a corrosive gas in the optical semiconductor device also progresses with time, and there is a problem that the electric conduction characteristics are deteriorated.

Therefore, an object of the present invention is to provide a hardened material (sealing material) which is excellent in all of the properties of the heat-resistant squeezing property, the reflow resistance, and the barrier property against a corrosive gas (for example, SOx gas). Resin composition.

Further, another object of the present invention is to provide a material (cured product) which is excellent in all of the properties of heat-resistant, reflow-resistant, and barrier properties against corrosive gases.

Further, another object of the present invention is to provide a sealant using the above-described curable resin composition and an excellent quality and durability obtained by sealing a semiconductor element (particularly an optical semiconductor element) by using the sealant. A semiconductor device (particularly an optical semiconductor device).

The inventors of the present invention have found that hardening is carried out by using a specific component containing two or more alkenyl groups in a molecule, a specific component having two or more hydrofluorenyl groups in a molecule, and an acetylene urea derivative having a specific structure as essential components. In the case of the resin composition, it is possible to form a cured product which is excellent in thermal shock resistance, reflow resistance, and barrier properties against a corrosive gas (for example, SOx gas), and further completes the present invention.

That is, the present invention provides a curable resin composition comprising polyoxyalkylene (A), polyoxyalkylene (B), and acetylene urea derivative (C), which is a polyoxane (A) system. a group selected from the group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganomethoxyalkylene group (A2) having two or more alkenyl groups in the molecule At least one of the polyoxyalkylene oxides (B) is selected from the group consisting of polyorganosiloxanes (B1) having two or more hydroalkylene groups in the molecule and two or more hydroquinones in the molecule. At least one of the group of the polyorganomethoxyalkylene groups (B2) of the group, the acetylene urea derivative (C) is represented by the following formula (1).

In the formula (1), R ^a to R ^d are the same or different ones, a group represented by the following formula (1a), a group represented by the following formula (1b), or a formula represented by the following formula (1c); base. However, at least one of R ^a to R ^d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c). R ^e and R ^f represent the same or different hydrogen atom or alkyl group.

In the formulae (1a) to (1c), s is the same as or different from 0 or 1 or more. In the formula (1b), R ^g represents the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. In the formula (1c), R ^h and R ⁱ represent the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents an integer of 0 or more. ]]

Further, the present invention provides the aforementioned curable resin composition, wherein the polyorganosiloxane (A1) has the following average unit formula: (R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (XO _1/2 ) _a5 represents a polyorganosiloxane.

[In the above average unit formula, R ¹ is a monovalent substituted or unsubstituted hydrocarbon group which is the same or different, but a part of R ¹ is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled to be two or more in the molecule. The range, X is a hydrogen atom or an alkyl group, a1 is 0 or a positive number, a2 is 0 or a positive number, a3 is 0 or a positive number, a4 is 0 or a positive number, a5 is 0 or a positive number, and (a1+a2+a3) is A positive number. ]

Furthermore, the present invention provides the above-mentioned curable resin composition, wherein the polyorganosiloxane (A1) is a linear polyorganosiloxane represented by the following formula (I-1).

[wherein, R ¹¹ is the same or different one-valent substituted or unsubstituted hydrocarbon group. However, at least two of R ¹¹ are alkenyl groups. M1 is an integer from 5 to 1000. ]

Moreover, the present invention provides the above-mentioned curable resin composition, wherein the polyorganosiloxane (A1) is a ladder-like polyorganosilsesquioxane (a) or (b).

. Straight-type polyorganosquioxane (a): having two or more alkenyl groups in the molecule, and having a number average molecular weight of 500 to 1,500 in terms of standard polystyrene by colloidal permeation chromatography, molecular weight dispersion (Mw /Mn) is a ladder-shaped polyorganopyroxane of 1.00 to 1.40.

. Ladder-type polyorganopyloxane (b): one or all of the ends of the molecular chain of the polyorganosilsesquioxane having a ladder structure a polyorganosilazoxane residue containing a structural unit (T unit) represented by formula (I-3-1) and a structural unit (M unit) represented by formula (I-3-2) (sometimes called It is a ladder-type polyorganopyloxane which is a "polyorganopylopropane residue (a)").

In the above formula (I-3-1), R ¹⁹ represents an alkenyl group, and in the above formula (I-3-2), R ²⁰ is the same or different, and represents a monovalent substituted or unsubstituted hydrocarbon group. ]

Furthermore, the present invention provides the above-mentioned curable resin composition, wherein the ladder-like polyorganosiloxime (a) is represented by the following formula (I-2) and has two or more alkenyl groups in the molecule. A ladder-type polyorganopyloxane having a number average molecular weight (Mn) of 500 to 1,500 and a molecular weight dispersion (Mw/Mn) of 1.00 to 1.40, which is converted by standard polystyrene, by colloidal permeation chromatography.

[In the above formula (I-2), R ¹² is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ¹³ is the same or different and represents a hydrogen atom, an alkyl group, and the following formula (I) -2-1) one of the valence groups shown, one of the valence groups represented by the following formula (I-2-2), or one of the valence groups represented by the following formula (I-2-3), and n represents 0. The above integer.

In the above formula (I-2-1), R ¹⁴ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ¹⁵ is a monovalent substituted or unsubstituted hydrocarbon group which is the same or different, N1 represents an integer of 0 or more.

In the above formula (I-2-2), R ¹⁴ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ¹⁵ is a monovalent substituted or unsubstituted hydrocarbon group which is the same or different. N2 represents an integer of 0 or more.

In the above formula (I-2-3), R ¹⁴ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ¹⁷ is a monovalent saturated aliphatic hydrocarbon group which is the same or different, and n3 represents An integer greater than 0. ]

Furthermore, the present invention provides the above-mentioned curable resin composition, wherein the polyorganosiloxanes having a ladder structure of the ladder-type polyorganosiloxanes (b) are represented by the following formula (I-3) .

In the above formula (I-3), p represents an integer of 1 or more, and R ¹⁸ represents the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and T represents a terminal group. ]

Furthermore, the present invention provides the above-mentioned curable resin composition, wherein the ladder-like polyorganosilsesquioxane (b) is a ladder-like polyorganosilazoxane represented by the following formula (I-3'). .

[In the above formula (I-3'), p represents an integer of 1 or more, and R ¹⁸ represents the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and A represents a polyorganosilsesquioxane residue. (a), or a hydroxyl group, a halogen atom, an alkoxy group, or a decyloxy group, but a part or all of A is a polyorganosquioxane residue (a). ]

Further, the present invention provides the aforementioned curable resin composition, wherein the polyorganosiloxane (A1) has 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 represents a polyorganosiloxane.

[In the above average unit formula, R ^1a represents the same or different alkyl group having 1 to 10 carbon atoms, and R ^1b is the same or differently different from the alkenyl group, and a6, a7, a8 and a9 all satisfy a6+a7+a8. =1, a6/(a6+a7)=0.15~0.35, a8/(a6+a7+a8)=0.53~0.62, a9/(a6+a7+a8)=0.005~0.03. ]

Further, the present invention provides the aforementioned curable resin composition, wherein the polyorganomethoxy fluorenyl group (A2) has the following average unit formula: (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 represents a polyorganooxyalkylene alkyl group.

[In the above average unit formula, R ² is a monovalent substituted or unsubstituted hydrocarbon group which is the same or different, but a part of R ² is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled to be 2 in the molecule. In the above range, R ^A is an alkylene group, b1 is a positive number, b2 is a positive number, b3 is a 0 or a positive number, b4 is a 0 or a positive number, and b5 is a positive number. ]

Furthermore, the present invention provides the above-mentioned curable resin composition, wherein the polyorganomethoxyalkylene group (A2) is a polyorganomethoxy fluorenyl group having a structure represented by the following formula (II-1).

[In the above formula (II-1), R ²¹ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, but at least two of R ²¹ are alkenyl groups, and R ^A represents an alkylene group, R1 represents an integer of 1 or more, and when r1 is an integer of 2 or more, the structures in the parentheses of the mark r1 may be the same or different, and r2 represents an integer of 1 or more, and when r2 is an integer of 2 or more, the bracket of the mark r2 is used. The internal structures may be the same or different, r3 represents an integer of 0 or more, and when r3 is an integer of 2 or more, the structures in the parentheses of the mark r3 may be the same or different, and r4 represents 0 or 1. When the above integer is r2 or an integer of 2 or more, the structures in the parentheses of the mark r4 may be the same or different, and r5 represents an integer of 0 or 1 or more, and when r5 is an integer of 2 or more, the parentheses of the mark r5 are included. The structures may be the same or different. ]

Moreover, the present invention provides the curable resin composition described above, wherein the content (mixing amount) (total amount) of the polyoxyalkylene (A) is 50% by weight based on the total amount (100% by weight) of the curable resin composition. % or more is less than 100% by weight.

Moreover, the present invention provides the curable resin composition described above, wherein the ratio of the total amount (100% by weight) of the polyorganosiloxane (A1) to the polysiloxane (A) contained in the curable resin composition is 50~100% by weight.

Moreover, the present invention provides the above-mentioned curable resin composition, which is a polyorganomethoxy hydrazine alkyl group (A2) with respect to the total amount (100% by weight) of the polyoxyalkylene (A) contained in the curable resin composition. The ratio is 0 to 60% by weight.

Further, the present invention provides the aforementioned curable resin composition, wherein the polyorganosiloxane (B1) has the following average unit formula: (R ³ SiO _3/2 ) _c1 (R ³ ₂ SiO _2/2 ) _c2 (R ³ ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (XO _1/2 ) _c5 represents a polyorganosiloxane.

[In the above average unit formula, R ³ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, but a part of R ³ is a hydrogen atom (a hydrogen atom constituting a hydrofluorenyl group), and the ratio control thereof To be in the range of 2 or more in the molecule, X is a hydrogen atom or an alkyl group, c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, and c5 is 0 or a positive number, and (c1+c2+c3) is a positive number. ]

Furthermore, the present invention provides the above-mentioned curable resin composition, wherein the polyorganosiloxane (B1) is a linear polyorganosiloxane represented by the following formula (III-1).

[In the above formula, R ³¹ is the same or different, and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ³¹ are hydrogen atoms. M2 is an integer from 5 to 1000. ]

Further, the present invention provides the aforementioned curable resin composition, wherein the polyorganomethoxy fluorenyl group (B2) has the following average unit formula: (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 represents a polyorganomethoxy group.

[In the above average unit formula, R ⁴ is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, which is the same or different, but a part of R ⁴ is a hydrogen atom, and the ratio thereof is controlled to be two or more in the molecule. Range, R ^A is an alkyl group, d1 is a positive number, d2 is a positive number, d3 is a zero or a positive number, d4 is a zero or a positive number, and d5 is a positive number. ]

Furthermore, the present invention provides the above-mentioned curable resin composition, wherein the polyorganomethoxyalkylene group (B2) is a polyorganomethoxy fluorenyl group having a structure represented by the following formula (IV-1).

[In the above formula (IV-1), R ⁴¹ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, but at least two of R ⁴¹ are a hydrogen atom, and R ^A represents an alkylene group, Q1 represents an integer of 1 or more, and when q1 is an integer of 2 or more, the structures in parentheses of the mark q1 may be the same or different, q2 represents an integer of 1 or more, and when q2 is an integer of 2 or more, the bracket of the mark q2 is used. The internal structures may be the same or different, q3 represents an integer of 0 or more, and when q3 is an integer of 2 or more, the structures in the parentheses of the mark q3 may be the same or different, and q4 represents 0 or 1. When the above integer is an integer of 2 or more, the structures in the parentheses of the mark q4 may be the same or different, q5 represents an integer of 0 or 1 or more, and when q5 is an integer of 2 or more, the parentheses of the mark q5 are included. The structures may be the same or different. ]

Moreover, the present invention provides the curable resin composition described above, wherein the content (doping amount) of the polyoxyalkylene (B) is from 1 to 200 parts by weight based on 100 parts by weight of the total amount of the polyoxyalkylene (A).

Moreover, the present invention provides the curable resin composition described above, wherein the total content (total content) of the polysiloxane (A) and the polyoxyalkylene (B) in the curable resin composition (100% by weight) is 70% by weight or more.

Further, the present invention provides the above-mentioned curable resin composition, which is a polyorganomethoxy hydrazine alkyl group (100% by weight) based on the total content (100% by weight) of polyoxyalkylene (A) and polyoxyalkylene (B) The ratio (total ratio) of A2) to polyorganomethoxy fluorenylalkylene group (B2) is 3% by weight or more.

Moreover, the present invention provides the curable resin composition described above, wherein the content (mixing amount) of the compound (C) of the curable resin composition is relative to polyoxyalkylene (A) and polyoxyalkylene (B). The total amount is more than 0 parts by weight and 20 parts by weight or less in terms of 100 parts by weight.

Further, the above-mentioned curable resin composition is provided, which comprises a hydrogenated decylation catalyst.

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

Further, the above-mentioned curable resin composition is provided as a sealant.

Moreover, the present invention provides a semiconductor device obtained by sealing a semiconductor element using the above-described curable resin composition.

Furthermore, the aforementioned semiconductor device is provided as an optical semiconductor device.

Further, the present invention provides an acetylene urea derivative which is represented by the following formula (1).

In the formula (1), R ^a to R ^d are the same or different ones, a group represented by the following formula (1a), a group represented by the following formula (1b), or a formula represented by the following formula (1c); base. However, at least one of R ^a to R ^d is a group selected from the group consisting of a group represented by the formula (113) and a group represented by the formula (1c). R ^e and R ^f represent the same or different hydrogen atom or alkyl group.

In the formulae (1a) to (1c), s is the same as or different from 0 or 1 or more. In the formula (1b), R ^g represents the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. In the formula (1c), R ^h and R ⁱ represent the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents an integer of 0 or more. ]]

Moreover, the present invention provides a method for producing an acetylene urea derivative, which is a method for producing an acetylene urea derivative represented by the following formula (1). It is characterized by comprising at least one selected from the group consisting of a compound represented by the following formula (i), a compound represented by the following formula (ii), and a compound represented by the following formula (iii). The compound is subjected to a hydrogenation oximation reaction step.

In the formula (1), R ^a to R ^d are the same or different ones, a group represented by the following formula (1a), a group represented by the following formula (1b), or a formula represented by the following formula (1c); base. However, at least one of R ^a to R ^d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c). R ^e and R ^f represent the same or different hydrogen atom or alkyl group.

In the formulae (1a) to (1c), s is the same as or different from 0 or 1 or more. In the formula (1b), R ^g represents the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. In the formula (1c), R ^h and R ⁱ represent the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents an integer of 0 or more. ]]

[In the formula (i), s, R ^e , and R ^{f are the} same as described above. ]

HSi(OR ^g ) ₃ (ii)

[In the formula (ii), R ^g is the same as described above. ]

[In the formula (iii), R ^h , R ⁱ , and t are the same as described above. ]

Since the curable resin composition of the present invention has the above-described configuration, it can be cured to form heat-resistant repellency, reflow-resistant property, and barrier property against a corrosive gas (for example, SOx gas). A cured product excellent in properties. In detail, when the cured product is used as a sealing material for an optical semiconductor device, when a high-temperature heat is applied to a thermal semiconductor device such as a thermal cycle or a reheating step, the sealing material is hard to be cracked. Or peeling off, and it is difficult to produce a defect that the optical semiconductor device does not light. Further, since the cured product has a good barrier property against a corrosive gas (particularly, SOx gas), when used as a sealing material for an optical semiconductor device, corrosion of the electrode of the device can be highly suppressed, and light can be remarkably improved. Durability of semiconductor devices. Therefore, the curable resin composition of the present invention is particularly useful as The optical semiconductor device obtained by sealing the optical semiconductor element by the curable resin composition (sealant) of the present invention has excellent quality and durability.

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

101‧‧‧Metal wiring (electrode)

102‧‧‧Optical semiconductor components

103‧‧‧bonding wire

104‧‧‧ hardened material (sealing material)

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

[Formation of the Invention]

<Curable resin composition>

The curable resin composition of the present invention is a composition comprising polyoxyalkylene (A), polyoxyalkylene (B), and acetylene urea derivative (C) as essential components, and the polyoxyalkylene (A) It is selected from the group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganooxyalkylene group (A2) having two or more alkenyl groups in the molecule. At least one of the group, the polyoxyalkylene (B) is selected from the group consisting of a polyorganosiloxane (B1) having two or more hydroalkylalkyl groups in the molecule and two or more hydrogens in the molecule. At least one of the group of a polyalkyloxyalkylene group (B2) of a decyl group, the acetylene urea derivative (C) (sometimes abbreviated as "acetylene urea derivative (C)" or "ingredient ( C)") is represented by the following formula (1). The curable resin composition of the present invention may contain, for example, other components such as a hydrogenated decylation catalyst described later, in addition to the above-mentioned essential components.

[polyoxane (A)]

The polyoxyalkylene (A) which is an essential component of the curable resin composition of the present invention is selected from the group consisting of polyorganosiloxane (A1) having two or more alkenyl groups in the molecule as described above ( It is sometimes abbreviated as "polyorganosiloxane (A1)") and a polyorganomethoxyalkylene group (A2) having two or more alkenyl groups in the molecule (sometimes abbreviated as "polyorganomethoxy group" At least one of the group of alkyl (A2)"). In other words, the polyoxyalkylene (A) is a polyoxyalkylene having an alkenyl group and is a component which produces a hydrogenation oximation reaction with a component having a hydroquinone group (for example, a polyoxyalkylene (B) or the like described later). .

The polyorganomethoxy fluorenylalkyl group (A2) of the present specification has two or more alkenyl groups in the molecule, and contains -Si in addition to -Si-O-Si-(nonaneline bond). -R ^A -Si- (an alkylene bond: R ^A represents an alkylene group) as a main chain polyorganosiloxane. Then, the polyorganosiloxane (A1) of the present specification is a polyorganosiloxane having two or more alkenyl groups in the molecule and not including the above-described decane bond as a main chain.

1. Polyorganosiloxane (A1)

Examples of the polyorganosiloxane (A1) include those having a linear, branched, or branched molecular structure having a linear shape. In addition, the polyorganosiloxane (A1) may be used alone or in combination of two or more. For example, polyorganoindoles having different molecular structures can be used in combination Two or more kinds of oxyalkylenes (A1) may be used in combination, for example, a linear polyorganosiloxane (A1) and a branched polyorganosiloxane (A1).

The alkenyl group which the polyorganosiloxane (A1) has in the molecule may, for example, be a substituted or unsubstituted alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group. Examples of the substituent include a halogen atom, a hydroxyl group, and a carboxyl group. Among them, a vinyl group is preferred. Further, the polyorganosiloxane (A1) may be one having only one type of alkenyl group or two or more types of alkenyl groups. The alkenyl group which the polyorganosiloxane (A1) has is not particularly limited, but is preferably bonded to a ruthenium atom.

The group other than the alkenyl group of the polyorganosiloxane (A1) which is bonded to the ruthenium atom is not particularly limited, and examples thereof include a hydrogen atom and an organic group. Examples of the organic group include an alkyl group [e.g., a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.], a cycloalkyl group (e.g., a cyclopropyl group, a cyclobutyl group, a cyclopentyl group). , cyclohexyl, cyclododeyl, etc.], aryl [e.g., phenyl, tolyl, xylyl, naphthyl, etc.], cycloalkyl-alkyl [e.g., cyclohexylmethyl, methylcyclohexyl, etc. a halogenated hydrocarbon group in which one or more hydrogen atoms of a hydrocarbon group are substituted with a halogen atom [for example, chloromethyl, 3-chloropropyl, 3, 3,] A monovalent substituted or unsubstituted hydrocarbon group such as a halogenated alkyl group such as 3-trifluoropropyl or the like. Further, in the present specification, "a group bonded to a germanium atom" generally means a group which does not contain a germanium atom.

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

The property of the polyorganosiloxane (A1) is not particularly limited, and may be liquid or solid.

As the polyorganosiloxane (A1), the following average unit formula: (R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 The polyorganooxy alkane represented by _a4 (XO _1/2 ) _a5 is preferred. In the above average unit formula, R ¹ is the same or different monovalent substituted or unsubstituted hydrocarbon group, and specific examples thereof (for example, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, a halogenated hydrocarbon group, etc.) may be mentioned. . However, ^one part of R ¹ is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to be in the range of two or more in the molecule. For example, 0.1 to 40 mol% is preferable with respect to the ^ratio of the total amount (100 mol%) of alkenyl groups of R ¹ . When the ratio of the alkenyl group is controlled to the above range, the curability of the curable resin composition tends to be further improved. Further, R ¹ other than the alkenyl group, an alkyl group (particularly a methyl group), and an aryl group (particularly a phenyl group) are preferred.

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

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

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

The ratio of the linear polyorganosiloxane to the total amount (100 mol%) of the alkenyl group bonded to the ruthenium atom is not particularly limited, but is preferably 0.1 to 40 mol%. Further, the ratio of the alkyl group (particularly methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but preferably 1 to 20 mol%. Further, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) bonded to the base of the ruthenium atom is not particularly limited, but 30 to 90 mol% is preferable. In particular, as the above-mentioned linear polyorganosiloxane, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) relative to the group bonded to the ruthenium atom is 40 mol% or more. (For example, 45 to 80 mol%), there is a tendency that the barrier property of the cured product with respect to the corrosive gas is further improved. Further, by using a ratio of a total amount (100 mol%) of an alkyl group (particularly a methyl group) bonded to a group bonded to a ruthenium atom to 90 mol% or more (for example, 95 to 99 mol%) There is a tendency for the heat-resistant squeezing property of the hardened material to be further improved.

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

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

Other examples of the polyorganosiloxane (A1) include a branched polycondensation having two or more alkenyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO _3/2 . Organic oxirane. Further, R is a monovalent substituted or unsubstituted hydrocarbon group. The above specific examples of the alkenyl group of the branched polyorganosiloxane include a vinyl group. Further, it may be one having only one type of alkenyl group, or one having two or more types of alkenyl groups. Further, examples of the group bonded to the ruthenium atom other than the alkenyl group of the branched polyorganosiloxane may, for example, be the above-mentioned monovalent substituted or unsubstituted hydrocarbon group in which an alkyl group (especially a methyl group) is used. An aryl group (especially a phenyl group) is preferred. 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.

The ratio of the branched chain polyorganosiloxane to the total amount (100 mol%) of the alkenyl group bonded to the ruthenium atom is not particularly limited, but from the viewpoint of the curability of the curable resin composition 0.1 to 40 mol% is preferred. Further, the ratio of the alkyl group (particularly methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but 10 to 40 mol% is preferable. Further, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) bonded to the base of the ruthenium atom is not particularly limited, but 5 to 70 mol% is preferable. In particular, as the branched chain polyorganosiloxane, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) relative to the group bonded to the ruthenium atom is 40 mol% or more. (For example, 45 to 60 mol%), there is a tendency that the barrier property of the cured product with respect to the corrosive gas is further improved. Further, by using a ratio of the total amount (100 mol%) of the alkyl group (especially methyl group) bonded to the ruthenium atom to 50 mol% or more (for example, 60 to 99 mol%) There is a tendency for the heat-resistant squeezing property of the hardened material to be further improved.

The branched polyorganosiloxane may be represented by the above average unit formula in which a1 is a positive number. In this case, it is not particularly limited, but a2/a1 is a number from 0 to 10, a3/a1 is a number from 0 to 0.5, and a4/(a1+a2+a3+a4) is a number from 0 to 0.3, a5/ The number of (a1+a2+a3+a4) of 0 to 0.4 is preferable. Further, the molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably from 500 to 10,000, more preferably from 700 to 3,000.

As the branched chain polyorganosiloxane, particularly from the viewpoint of remarkably enhancing the barrier property of the cured product to a corrosive gas, the following ladder-type polyorganopyloxane (a) or (b) is used. Preferably.

. Straight-type polyorganosquioxane (a): having two or more alkenyl groups in the molecule, and having a number average molecular weight of 500 to 1,500 in terms of standard polystyrene by colloidal permeation chromatography, molecular weight dispersion (Mw /Mn) is a ladder-shaped polyorganopyroxane of 1.00 to 1.40.

. a ladder-type polyorganosquioxane (b): a part or all of a molecular chain end of a polyorganosilsesquioxane having a ladder structure, having a composition represented by the formula (I-3-1) a polyorgane sesquioxane residue of a unit (T unit) and a constituent unit (M unit) represented by the formula (I-3-2) (sometimes referred to as "polyorganopylopropane oxide residue (a) ))) ladder-type polyorganopyloxane.

. Ladder-type polyorganopyloxane (a)

Polyorgano silsesquioxane ladder type silicon siloxane (a) having a ladder-like structure, but this is in accordance with the FT-IR spectrum in the vicinity of 1050cm ^-1 (e.g., 1000 ~ 1100cm ^-1) in the vicinity of 1150cm ^-1 (e.g., More than 1100 cm ^-1 1200 cm ^-1 or less) each has an intrinsic absorption peak (that is, at least 2 absorption peaks at 1000 to 1200 cm ^-1 ) and is confirmed [Reference: RHRaney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. Further, the FT-IR spectrum can be measured, for example, by the following apparatus and conditions.

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

Measuring method: transmission method

Decomposition energy: 4cm ^-1

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

Cumulative number: 16 times

However, the ladder-type polyorganosilsesquioxane (a) may have a ladder-like structure or other sesquiterpene oxide structure having a cage structure or a random structure.

The standard polystyrene-equivalent number average molecular weight (Mn) of the colloidal permeation chromatography of the ladder-type polyorganopyloxane (a) is from 500 to 1,500, preferably from 550 to 1,450, more preferably from 600 to 1,400. . When Mn is less than 500, for example, the physical properties (heat resistance, gas barrier properties, and the like) of the cured product tend to decrease. On the other hand, when Mn is greater than 1500, there is room temperature. It tends to become a solid and the handling property tends to decrease. Further, there is a case where the compatibility with other components is deteriorated.

The standard polystyrene-converted molecular weight dispersion (Mw/Mn) of colloidal permeation chromatography of ladder-type polyorganopyloxane (a) is 1.00 to 1.40, 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 is more than 1.40, for example, a low molecular weight oxirane increases, and the adhesion of the cured product or the gas barrier property tends to decrease. On the other hand, for example, when the molecular weight dispersion degree is 1.05 or more, it is likely to become a liquid (liquid) at room temperature, and the handleability may be improved.

Further, the number average molecular weight and the molecular weight dispersion degree of the ladder-type polyorganosiloxanes (a) can be measured by the following apparatus and conditions.

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

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

Measuring temperature: 40 ° C

Dissolved solution: THF, sample concentration 0.1~0.2% by weight

Flow rate: 1mL/min

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

Molecular weight: standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) in the nitrogen atmosphere of the ladder-type polyorganopyloxane (a) is not particularly limited, but is preferably 150 ° C or higher, more preferably 240 ° C or higher, and more preferably 260~500°C, especially better than 262°C, and most preferably 265°C or above. When the 5% weight loss temperature is less than 150 ° C (especially less than 240 ° C), there is a case where the required heat resistance cannot be satisfied depending on the application. Further, the 5% weight loss temperature is a temperature at a time point when the weight before heating is reduced by 5% at the time of heating at a constant temperature increase rate, and is an index of heat resistance. The 5% weight loss temperature was measured by a TGA (thermogravimetric analysis) under a nitrogen atmosphere at a temperature increase rate of 20 ° C /min.

The ladder-type polyorganosilsesquioxane (a) is not particularly limited, but is preferably a liquid at room temperature (25 ° C). Specifically, the viscosity at 25 ° C is not particularly limited, but is 30000 Pa. Preferably, s (for example, 1 to 30000 Pa.s) is more preferably 25,000 Pa. Below s, the best is 10000Pa. s below. The viscosity can be measured using a viscometer (trade name "MCR301", manufactured by ANTON PAAR Co., Ltd.) at a vibration angle of 5%, a frequency of 0.1 to 100 (1/s), and a temperature of 25 °C.

The ladder-type polyorganosquioxane (a), for example, is represented by the following formula (I-2), and has two or more alkenyl groups in the molecule, and is subjected to standard polymerization by colloidal permeation chromatography. A ladder-type polyorganopyroxane having a number average molecular weight (Mn) in terms of styrene of 500 to 1,500 and a molecular weight dispersion (Mw/Mn) of 1.00 to 1.40.

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. Specific examples of R ¹² include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group).

The ladder-type polyorganosquioxane (a) may have an alkenyl group as R ¹² or may not. The ladder-type polyorganosquioxane (a), which is R ¹² other than the alkenyl group in the above formula (I-2), has at least one selected from the group consisting of an alkyl group and an aryl group. The group is preferably a group having at least one selected from the group consisting of a phenyl group and a methyl group.

a ratio (total content) of a phenyl group, a vinyl group, and a methyl group in the total amount (100% by weight) of R ¹² of the above formula (I-2) of the ladder-type polyorganosilsesquioxane (a), and It is not particularly limited, but is preferably from 50 to 100% by weight, more preferably from 70 to 100% by weight, still more preferably from 80 to 100% by weight.

The proportion (content) of the phenyl group in the total amount (100% by weight) of R ¹² of the above formula (I-2) of the ladder-type polyorganosiloxanes (a) is not particularly limited, but is 0 to 100. The weight % is preferably from 1 to 100% by weight, more preferably from 5 to 100% by weight. The ratio (content) of the vinyl group in the total amount (100% by weight) of R ¹² of the above formula (I-2) of the ladder-type polyorganosiloxanes (a) is not particularly limited, but is 0 to 100. The weight % is preferably from 1 to 100% by weight, more preferably from 5 to 90% by weight, particularly preferably from 10 to 80% by weight. The proportion (content) of the methyl group in the total amount (100% by weight) of R ¹² of the above formula (I-2) of the ladder-type polyorganosiloxanes (a) is not particularly limited, but is 0 to 100. The weight % is preferably from 1 to 100% by weight, more preferably from 5 to 100% by weight.

Further, the composition of R ¹² of the above formula (I-2) of the ladder-type polyorganopyloxane (a) (for example, a ratio of a phenyl group, a vinyl group, a methyl group, etc.), for example, NMR can be used. The spectrum (for example, ¹ H-NMR spectrum) measurement or the like is calculated.

In the above formula (I-2), R ¹³ is the same or different, and represents a hydrogen atom, an alkyl group, a valent group represented by the following formula (I-2-1), and the following formula (I-2-2). One of the valence groups shown, or one of the valent groups represented by the following formula (I-2-3).

In the above formula (I-2-1), R ¹⁴ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of R ¹⁴ include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group), and an alkyl group is preferred. Further, in the above formula (I-2-1), R ¹⁵ is a monovalent substituted or unsubstituted hydrocarbon group which is the same or different. Specific examples of R ¹⁵ include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group), and an alkyl group is preferred. In the above formula (I-2-1), n1 represents an integer of 0 or more. As n1, it is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0.

In the above formula (I-2-2), R R 14 in the formula (I-2-1) of the same ^14, based same or different, is a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group of. As R ¹⁴ , an alkyl group is preferred. Further, in the above formula (I-2-2), R R 15 in the formula (I-2-1) of the same ^15, the same or different, is based price of a substituted or unsubstituted hydrocarbon group. As R ¹⁵ , an alkyl group is preferred. In the above formula (I-2-2), R ¹⁶ is an alkenyl group, and among them, a vinyl group is preferred. Further, in the above formula (I-2-2), n2 represents an integer of 0 or more. As n2, it is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0.

In the above formula (I-2-3), R R 14 in the formula (I-2-1) of the same ^14, based same or different, is a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group of. As R ¹⁴ , an alkyl group is preferred. Further, in the above formula (I-2-3), R ¹⁷ is a monovalent saturated aliphatic hydrocarbon group which is the same or different, and examples thereof include an alkyl group, a cycloalkyl group and the like, but among them, an alkyl group (especially Methyl) is preferred. In the above formula (I-2-3), n3 represents an integer of 0 or more. As n3, it is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0.

In the above formula (I-2), n represents an integer of 0 or more. The above n is usually an even number of 0 or more (for example, an even number of 2 or more). The above n is not particularly limited as long as the number average molecular weight of the ladder-type polyorganosilsesquioxane (a) is controlled to 500 to 1,500 and the molecular weight dispersion degree is controlled to 1.00 to 1.40. When the molecular weight dispersion degree of the ladder-type polyorganosquioxane (a) is more than 1.00, the ladder-type polyorganosiloxanes (a) are generally represented by the formula (I-2). The organic sesquioxane is a mixture of two or more kinds of n. In particular, the ladder-type polyorganopyloxane (a) preferably contains a component having n of 1 or more (particularly 2 or more) as an essential component.

The ladder-shaped polyorganosquioxane (a) has two or more alkenyl groups in the molecule. The alkenyl group which the ladder type polyorganosquioxane (a) has, especially a vinyl group is preferable. When the ladder-type polyorganosquioxane (a) is represented by the formula (I-2), for example, any one of R ¹² of the formula (I-2) is an alkenyl group and has R ^{14 .} And one of R ¹⁵ is a monovalent group represented by the formula (I-2-1) of the alkenyl group, and has a monovalent group represented by the formula (I-2-2), and has a group of R ¹⁴ Any one of them is a monovalent group represented by the formula (I-2-3) of an alkenyl group.

The ladder-type polyorganosilsesquioxane (a) can be produced by a conventionally known method, and is not particularly limited. For example, JP-A-4-28722, JP-A-2010-518182, and JP-A-2010-518182 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The method disclosed in the documents disclosed in Japanese Laid-Open Patent Publication No. 2005-239829, and the International Publication No. 2013/176238.

. Ladder-type polyorganopyloxane (b)

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

In the above formula (I-3), p represents an integer of 1 or more (for example, 1 to 5000), preferably an integer of 1 to 2,000, and more preferably an integer of 1 to 1000. R ¹⁸ in the formula (I-3) is the same or different in the hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. T represents a terminal group.

The ladder-type polyorganosiloxanes (b) are directly bonded to the base of the ruthenium atom in the above polyorganosquioxane (for example, R ^{18 of the} formula (I-3)), and are not particularly limited. However, the proportion of the monovalent substituted or unsubstituted hydrocarbon group relative to the total amount (100 mol%) of the above base is preferably 50 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol%. More than 8% of the ear. In particular, a substituted or unsubstituted C _1-10 alkyl group (particularly, a C _1-4 alkyl group such as a methyl group, an ethyl group, etc.), substituted or unsubstituted, relative to the total amount (100 mol%) of the above group. The total amount of C _6-10 aryl (especially phenyl), substituted or unsubstituted C _7-10 aralkyl (particularly benzyl) is preferably 50 mol% or more, more preferably 80 mol. More than %, and then more than 90% by mole.

The ladder-type polyorganosilopentane (b) has a polyorganosilsesquioxane residue (a) partially or wholly at one end of the molecular chain of the polyorganosilsesquioxane having the above-described ladder structure. When the polyorganosilsesquioxane is represented by the above formula (I-3), the ladder-type polyorganosilsesquioxane (b) is a part or all of T in the formula (I-3) A sesquioxane residue (a) is substituted.

The polyorgane sesquioxane residue (a), as described above, is a residue comprising at least a constituent unit represented by the formula (I-3-1) and a constituent unit represented by the formula (I-3-2). base.

R ¹⁹ of the above formula (I-3-1) represents an alkenyl group. The above specific examples include the above-mentioned specific examples, and a C _2-10 alkenyl group is preferred, a C _2-4 alkenyl group is more preferred, and a vinyl group is more preferred.

R ²⁰ in the above formula (I-3-2) represents the monovalent substituted or unsubstituted hydrocarbon group identically or differently. The above-mentioned substituted or unsubstituted hydrocarbon group may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group). R ^{20 is} preferably an alkyl group, more preferably a C _1-20 alkyl group, still more preferably a C _1-10 alkyl group, particularly preferably a C _1-4 alkyl group, most preferably a methyl group. In particular, R ²⁰ in the formula (I-3-2) is preferably a methyl group.

The polyorgane sesquiterpene oxide residue (a) may be, for example, a constituent unit represented by the above formula (I-3-1) and a constituent unit represented by the above formula (I-3-2). It has a structural unit represented by the following formula (I-3-1').

R ¹⁹ ' in the above formula (I-3-1') represents a monovalent group excluding an alkenyl group. Specifically, for example, a hydrogen atom, a halogen atom, a monovalent organic group excluding an alkenyl group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom-containing group may be mentioned. Base and so on.

The amount of the ruthenium atom bonded by the three oxygen atoms represented by the formula (I-3-1) of the polyorganosilcosidine residue (a) is not particularly limited, and the polyorgano sesquiterpene is formed. The total amount (100 mol%) of the ruthenium atom of the oxyalkylene residue (a) is preferably from 20 to 80 mol%, more preferably from 25 to 60 mol%. When the content is less than 20 mol%, the amount of the alkenyl group which the ladder type polyorganosquioxane (b) has is not sufficient, and the hardness of the hardened material is not obtained. On the other hand, when the content is more than 80 mol%, a large amount of sterol groups or hydrolyzable decyl groups remain in the ladder-type polyorganosiloxanes (b), and thus it is sometimes impossible to obtain a ladder-like polyorganic compound. The semi-oxane (b) is in the form of a liquid. Further, since the condensation reaction proceeds in the product to change the molecular weight, the storage stability may be deteriorated.

The amount of the argon atom bonded by one oxygen atom represented by the formula (I-3-2) of the polyorganosilazoline residue (a) is not particularly limited, but is relatively small. The total amount (100 mol%) of the ruthenium atom of the oxirane residue (a) is preferably from 20 to 85 mol%, more preferably from 30 to 75 mol%. When the content is less than 20 mol%, a sterol group or a hydrolyzable decyl group is liable to remain in the ladder-type polyorganosilsesquioxane (b), and a ladder-like polyorganopyroxane is sometimes not obtained ( b) is liquid. Further, since the condensation reaction proceeds in the product to change the molecular weight, the storage stability may be deteriorated. On the other hand, when the content is more than 85 mol%, the amount of the alkenyl group which the ladder-type polyorganosilsesquioxane (b) has is not sufficient, and the hardness of the hardened material is not obtained.

The Si—O—Si structure (skeleton) which is contained in the polyorganosil sesquioxane residue (a) is not particularly limited, and examples thereof include a ladder structure, a cage structure, and a random structure.

The ladder-type polyorganosquioxane (b) can be represented, for example, by the following formula (I-3'). P and R ¹⁸ in the formula (I-3') are the same as those in the above formula (I-3). The A group in the formula (I-3') represents a polyorganosquioxane residue (a), or a hydroxyl group, a halogen atom, an alkoxy group, or a decyloxy group, and a part or all of A is a polyorganic compound. Semiaoxane residue (a). The four A's can be the same or different. Further, when a plurality (2 to 4) of A in the formula (I-3') is a polyorganosilane residue (a), the respective A may be separated from each other by one or more Si. The -O-Si bond is bonded.

The number of the alkenyl groups in the molecule of the ladder-type polyorganosiloxanes (b) is not particularly limited, but is preferably 2 to 50, more preferably 2 to 30. By having an alkenyl group in the above range, it is easy to obtain a cured product which is excellent in various physical properties such as heat resistance, crack resistance, and barrier property against a corrosive gas. Further, the number of alkenyl groups can be calculated, for example, by ¹ H-NMR spectrum measurement or the like.

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

The weight average molecular weight (Mw) of the ladder-type polyorganosiloxanes (b) is not particularly limited, but is preferably from 100 to 800,000, more preferably from 200 to 100,000, and even more preferably from 300 to 10,000. The best is 500~8000, and the best is 1700~7000. When the Mw is less than 100, the heat resistance of the cured product may be lowered. On the other hand, when Mw is more than 800,000, compatibility with other components may fall. Further, the above Mw can be calculated, for example, from the molecular weight in terms of standard polystyrene by colloidal permeation chromatography.

The number average molecular weight (Mn) of the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably from 80 to 800,000, more preferably 150~100,000, and then good is 250~10,000, especially good 400~8000, the best is 1500~7000. When Mn is less than 80, the heat resistance of the cured product may be lowered. On the other hand, when Mn is more than 800,000, the compatibility with other components may fall. Further, the Mn can be calculated, for example, from a molecular weight in terms of standard polystyrene by colloidal permeation chromatography.

The ladder-type polyorganosquioxane (b) is preferably a liquid at normal temperature (about 25 ° C). More specifically, its viscosity at 23 ° C is 100 ~ 100000 mPa. s is better, more preferably 500~10000mPa. s, better than 1000~8000mPa. s. Viscosity is less than 100mPa. In the case of s, there is a case where the heat resistance of the cured product is lowered. On the other hand, the viscosity is greater than 100,000 mPa. In the case of s, the preparation or handling of the curable resin composition becomes difficult. Further, for the viscosity at 23 ° C, for example, a rheometer (trade name "Physica UDS-200", manufactured by Anton Paar Co., Ltd.) and a cone plate (cone diameter: 16 mm, cone angle = 0°) can be used, at a temperature: The measurement was carried out under the conditions of 23 ° C and the number of rotations: 20 rpm.

The method for producing the ladder-type polyorganosquioxane (b) is not particularly limited, and examples thereof include a sterol group and/or a hydrolyzable decyl group at the end of the molecular chain with respect to a ladder-like structure. A method of forming the above sesquiterpene oxide residue (a) at the terminal of the molecular chain of the polyorganosilsesquioxane (either or both of a sterol group and a hydrolyzable decyl group). Specifically, it can be produced by the method disclosed in the literature of International Publication No. 2013/176238 or the like.

As another example of the polyorganosiloxane (A1), for example, a1 and a2 are 0, and X is a hydrogen atom in the above 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 represents a polyorganosiloxane. In the above average unit formula, R ^1a represents the alkyl group having 1 to 10 carbon atoms, which may be the same or different, 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 ring. Hexyl, wherein a methyl group is preferred. Further, R ^1b is the same or differently different from the alkenyl group, and a vinyl group is preferred. Furthermore, a6, a7, a8 and a9 all satisfy a6+a7+a8=1, a6/(a6+a7)=0.15~0.35, a8/(a6+a7+a8)=0.53~0.62, a9/( A6+a7+a8) = 0.005~0.03. Furthermore, a7 can also be zero. From the viewpoint of the curability of the curable resin composition, a6/(a6+a7) is preferably 0.2 to 0.3. Further, from the viewpoint of the hardness or mechanical strength of the cured product, a8/(a6+a7+a8) is preferably 0.55 to 0.60. Further, from the viewpoint of the adhesion or mechanical strength of the cured product, a9/(a6+a7+a8) is preferably 0.01 to 0.025. Examples of the polyorganosiloxane which are as described above include polyorganosiloxanes of SiO _4/2 units and (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 units, and 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.

Further, the polyorganosiloxane (A1) may have two or more alkenyl groups in the molecule, and may even have a hydroquinone group. In this case, the polyorganosiloxane (A1) may also be a polyorganosiloxane (B1) to be described later.

2. Polyorganooxyalkylene alkyl (A2)

The polyorganomethoxy fluorenylalkyl group (A2), as described above, is a polyorganoquinone having two or more alkenyl groups in the molecule and containing an anthracene bond as a main chain in addition to a siloxane chain. Oxytomane. Further, as the alkylene group of the above-mentioned oxime bond, a C2-4 alkyl group (especially an ethyl group) is preferred. on The polyorganomethoxy fluorenylalkylene group (A2) is less likely to produce a low molecular weight ring in the production step than the polyorganosiloxane (A1), and it is difficult to decompose by heating or the like to produce a sterol group ( -SiOH), when the polyorganomethoxy group is used (A2), the surface adhesiveness (viscosity) of the cured product of the curable resin composition tends to be low, and it tends to be more difficult to yellow.

Examples of the polyorganomethoxyoxyalkylene group (A2) include a linear, branched, or lattice molecular structure having a linear chain and a part of branches. In addition, the polyorganomethoxy fluorenylalkyl group (A2) may be used alone or in combination of two or more. For example, two or more kinds of polyorganomethoxy fluorenylalkyl groups (A2) having different molecular structures may be used in combination, and for example, a linear polyorganomethoxy fluorenyl group (A2) and a branched chain may be used in combination. Polyorganooxy oxime alkyl (A2).

The specific example of the alkenyl group which the polyorganomethoxy fluorenylalkyl group (A2) has in the molecule is preferably the vinyl group. Further, the polyorganooxyalkylene group (A2) may be one having only one type of alkenyl group or two or more types of alkenyl groups. The alkenyl group which the polyorganooxy oxoalkylene group (A2) has is not particularly limited, but is preferably bonded to a ruthenium atom.

The group other than the alkenyl group of the polyorganooxy oxoalkylene group (A2) which is bonded to the fluorene atom is not particularly limited, and examples thereof include a hydrogen atom and an organic group. The organic group may, for example, be a monovalent substituted or unsubstituted hydrocarbon group or the like. Among them, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferred.

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

The property of the polyorganooxyalkylene group (A2) is not particularly limited, and may be liquid or solid.

As the polyorganomethoxy fluorenylalkyl group (A2), the following average unit formula: (R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 ( The polyorganomethoxy fluorenylalkyl group represented by SiO _4/2 ) _b4 (R ^A ) _{b5 is} preferred. In the above average unit formula, R ² is the same or different monovalent substituted or unsubstituted hydrocarbon group, and the above specific examples (for example, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, a halogenated alkyl group, etc.) may be mentioned. ). However, one part of R ² is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to be in the range of two or more in the molecule. For example, the ratio of the total amount (100 mol%) of alkenyl groups relative to R ² is preferably from 0.1 to 40 mol%. When the ratio of the alkenyl group is controlled to the above range, the curability of the curable resin composition tends to be further improved. Further, R ² 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 average unit formula, R ^{A is} as defined above as an alkylene group, particularly preferably an ethylidene group.

In the above average unit formula, b1 is a positive number, b2 is a positive number, b3 is 0 or a positive number, b4 is 0 or a positive number, and b5 is a positive number. Preferably, b1 is 1 to 200, b2 is 1 to 200, b3 is 0 to 10, b4 is 0 to 5, and b5 is preferably 1 to 100. In particular, when (b3+b4) is a positive number, the mechanical strength of the cured product tends to be further improved.

The polyorganomethoxy fluorenylalkyl group (A2), and more specifically, a polyorganomethoxy fluorenylalkyl group having a structure represented by the following formula (II-1) is exemplified.

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. Examples of R ²¹ include the above specific examples (for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a halogenated hydrocarbon group, etc.). However, at least two of R ²¹ are alkenyl groups (especially vinyl groups). Further, R ²¹ 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 (II-1), R ^A is the same as defined above, and represents an alkylene group in which a C _2-4 alkyl group (particularly an ethyl group) is preferred. Furthermore, when there are a plurality of R ^A , the same may be the same or different.

In the above formula (II-1), r1 represents an integer of 1 or more (for example, 1 to 100). Further, when r1 is an integer of 2 or more, the structures in the brackets of the mark r1 may be the same or different.

In the above formula (II-1), r2 represents an integer of 1 or more (for example, 1 to 400). Further, when r2 is an integer of 2 or more, the structures in the parentheses of the mark r2 may be the same or different.

In the above formula (II-1), r3 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, when r3 is an integer of 2 or more, the structures in the brackets of the mark r3 may be the same or different.

In the above formula (II-1), r4 represents an integer of 0 or 1 or more (for example, 0 to 50). Further, when r4 is an integer of 2 or more, the structures in the brackets of the mark r4 may be the same or different.

In the above formula (II-1), 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, the structures in the brackets of the mark r5 may be the same or different.

Further, the addition form of each structural unit of the above formula (II-1) is not particularly limited, and may be a random type or a block type.

The terminal structure of the polyorganomethoxy fluorenyl group having a structure represented by the formula (II-1) is not particularly limited, and examples thereof include a decyl alcohol group, an alkoxyalkyl group, and a trialkyl decyl group ( For example, the structure of the label r5, trimethyldecyl group, etc.). In the terminal of the polyorganomethoxyalkylene group, various groups such as an alkenyl group or a hydrofluorenyl group may be introduced.

The polyorganomethoxy oxoalkylene group (A2) can be produced by a known method or a conventional method, and the production method thereof is not particularly limited. For example, it can be produced by the method described in JP-A-2012-140617. In addition, as a product containing a polyorganooxyalkylene group (A2), for example, the product names "ETERLED GD1130" and "ETERLED GD1125" (both manufactured by Changxing Chemical Industry Co., Ltd.) can be obtained.

The curable resin composition of the present invention preferably contains at least the branched chain polyorganosiloxane as the polyorganosiloxane (A1), more preferably from the viewpoint of barrier properties and strength (resin strength) of the cured product. The ladder-type polyorganopyloxane (a) or (b) is contained, and it is particularly preferable to contain a polyorganooxyalkylene group (A2) in addition to the above.

The content (mixing amount) (total amount) of the polyoxyalkylene (A) of the curable resin composition of the present invention is not particularly limited, but is 50% by weight based on the total amount (100% by weight) of the curable resin composition. More preferably, the weight % or more is less than 100% by weight, more preferably 60 to 99% by weight, and even more preferably 70 to 95% by weight. the amount%. When the content is 50% by weight or more, the durability and transparency of the cured product tend to be further improved.

The ratio of the total amount (100% by weight) of the polyorganosiloxane (A1) of the polyoxyalkylene (A) contained in the curable resin composition of the present invention is not particularly limited, but is 50 to 100% by weight. Preferably, it is more preferably 60 to 87% by weight, and still more preferably 50 to 85% by weight. When the ratio is less than 50% by weight, the resin strength and the barrier property against the SOx gas may be lowered.

The ratio of the total amount (100% by weight) of the polyorganooxyalkylene group (A2) of the polyoxyalkylene (A) contained in the curable resin composition of the present invention is not particularly limited, but is 0. It is preferably from 60% by weight, more preferably from 10 to 40% by weight, still more preferably from 15 to 30% by weight. When the ratio is more than 60% by weight, the barrier property of the cured product with respect to the SOx gas may be lowered.

[polyoxane (B)]

As described above, the polyoxyalkylene (B) which is an essential component of the curable resin composition of the present invention is selected from the group consisting of polyorganoquinones having two or more hydroalkylene groups (Si-H) contained in the molecule. Oxane (B1) (sometimes abbreviated as "polyorganosiloxane (B1)") and polyorganooxyalkylene (B2) having two or more hydroalkylalkyl groups in the molecule (sometimes referred to as abbreviations) It is at least one of the group of "polyorganomethoxy oxoalkylene (B2)"). That is, the polyoxyalkylene (B) is a polyoxyalkylene having a hydroquinone group, and is a component which produces a hydrogenation sulfonation reaction with a component having an alkenyl group (for example, a polyoxyalkylene (A) or the like).

The polyorganomethoxy fluorenylalkyl group (B2) of the present specification has two or more hydrofluorenyl groups in the molecule, and includes - in addition to -Si-O-Si-(a decane bond) Si-R ^A -Si- (an alkylene bond: R ^A represents an alkylene group) as a main chain polyorganosiloxane. Then, the polyorganosiloxane (B1) of the present specification is a polyorganosiloxane having two or more hydrofluorenyl groups in the molecule and not containing the above-described decane bond as a main chain. Further, R ^A (alkylene group) is the same as above, and examples thereof include a linear or branched C _1-12 alkylene group, preferably a linear or branched C _2-4. An alkyl group (especially an ethyl group).

1. Polyorganosiloxane (B1)

Examples of the polyorganosiloxane (B1) include a linear, branched, or lattice molecular structure having a linear chain and a part of branches. In addition, the polyorganosiloxane (B1) may be used alone or in combination of two or more. For example, two or more kinds of polyorganosiloxanes (B1) having different molecular structures may be used in combination. For example, a linear polyorganosiloxane (B1) and a branched polyorganosiloxane (B1) may be used in combination. ).

In the group bonded to the ruthenium atom of the polyorganosiloxane (B1), the group other than the hydrogen atom is not particularly limited, and examples thereof include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and more specifically, An alkyl group, an aryl group, an aralkyl group, a halogenated hydrocarbon group, etc. are mentioned. Among them, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferred. Further, the polyorganosiloxane (B1) may have an alkenyl group (for example, a vinyl group) as a group bonded to a halogen atom other than a hydrogen atom.

The property of the polyorganosiloxane (B1) is not particularly limited, and may be liquid or solid. Among them, the liquid is preferred, and the viscosity at 25 ° C is 0.1 to 1000000000 mPa. s liquid is better.

As the polyorganosiloxane (B1), the following average unit formula: (R ³ SiO _3/2 ) _c1 (R ³ ₂ SiO _2/2 ) _c2 (R ³ ₃ SiO _1/2 ) _c3 (SiO _4/2 The polyorganooxy alkane represented by _c4 (XO _1/2 ) _c5 is preferred. In the above average unit formula, R ³ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and examples thereof include a hydrogen atom and the above specific examples (for example, an alkyl group, an alkenyl group, an aryl group, and an aromatic group). Alkyl, halogenated alkyl, etc.). However, a part of R ³ is a hydrogen atom (a hydrogen atom constituting a hydrofluorenyl group), and the ratio thereof is controlled to be in the range of two or more in the molecule. For example, the ratio of the total amount (100 mol%) of hydrogen atoms to R ³ is preferably 0.1 to 40 mol%. When the ratio of the hydrogen atom is controlled to the above range, the curability of the curable resin composition tends to be further improved. Further, R ³ other than a 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, X is the same as the above, 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, c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1+c2+c3) is a positive number.

An example of the polyorganosiloxane (B1) is a linear polyorganosiloxane having two or more hydroalkylene groups in the molecule. The group bonded to the ruthenium atom other than the hydrogen atom of the linear polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group in which an alkyl group (especially a methyl group) or an aromatic group is used. The base (especially phenyl) is preferred.

The ratio of the above-mentioned linear polyorganosiloxane to the total amount (100 mol%) of hydrogen atoms (hydrogen atoms bonded to the ruthenium atom) bonded to the ruthenium atom is not particularly limited, but 0.1 ~40 mole% is preferred. Further, the ratio of the alkyl group (particularly methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but 20 to 99 mol% is preferable. Further, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) bonded to the base of the ruthenium atom is not particularly limited, but 40 to 80 mol% is preferable. In particular, as the above-mentioned linear polyorganosiloxane, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) relative to the group bonded to the ruthenium atom is 40 mol% or more. (For example, 45 to 70 mol%), there is a tendency that the barrier property of the cured product with respect to the corrosive gas is further improved. Further, by using a ratio of a total amount (100 mol%) of an alkyl group (particularly a methyl group) bonded to a group bonded to a ruthenium atom to 90 mol% or more (for example, 95 to 99 mol%) There is a tendency for the heat-resistant squeezing property of the hardened material to be further improved.

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

[In the above formula, R ³¹ is the same or different, and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ³¹ are hydrogen atoms. M2 is an integer from 5 to 1000. ]

Other examples of the polyorganosiloxane (B1) include a branched chain having two or more hydrofluorenyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO _3/2 . Polyorganosiloxane. Further, R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of the group bonded to the halogen atom other than the hydrogen atom of the branched chain polyorganosiloxane may, for example, be a monovalent substituted or unsubstituted hydrocarbon group in which an alkyl group (especially a methyl group) or an aromatic group is used. The base (especially phenyl) is preferred. Further, examples of R in the above T unit include a hydrogen atom and the above monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred. The ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of R in the above T unit is not particularly limited, but from the viewpoint of the barrier property of the cured product with respect to the corrosive gas, 30 Mo More than or equal to the ear.

The ratio of the above branched polyorganosiloxane to the total amount (100 mol%) of the alkyl group (especially methyl group) bonded to the ruthenium atom is not particularly limited, but is 70 to 95 mol. % is better. Further, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) bonded to the base of the ruthenium atom is not particularly limited, but 10 to 70 mol% is preferable. In particular, as the branched chain polyorganosiloxane, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) relative to the group bonded to the ruthenium atom is 10 mol% or more. (For example, 10 to 70 mol%), there is a tendency that the barrier property of the cured product with respect to the corrosive gas is further improved. Further, by using a ratio of the total amount (100 mol%) of the alkyl group (especially methyl group) bonded to the ruthenium atom to 50 mol% or more (for example, 50 to 90 mol%) There is a tendency for the heat-resistant squeezing property of the hardened material to be further improved.

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

2. Polyorganooxyalkylene alkyl (B2)

The polyorganomethoxy fluorenylalkyl group (B2), as described above, has two or more hydrofluorenyl groups in the molecule, and contains a decane bond in addition to a siloxane chain as a main chain. Organic oxirane. Further, as the alkylene group of the above-mentioned oxime bond, for example, a C _2-4 alkyl group (especially an ethyl group) is preferred. The polyorganomethoxy fluorenylalkylene group (B2) is less likely to generate a low molecular weight ring in the production step than the polyorganosiloxane (B1), and it is difficult to decompose by heating or the like to produce a sterol group ( -SiOH), when the polyorganomethoxy fluorene alkyl group (B2) is used, the surface adhesiveness (viscosity) of the cured product of the curable resin composition tends to be low, and it tends to be more difficult to yellow.

Examples of the polyorganomethoxyoxyalkylene group (B2) include a linear, branched, or mesh-like molecular structure having a linear chain and a part of branches. In addition, the polyorganomethoxy oxoalkylene group (B2) may be used alone or in combination of two or more. For example, two or more kinds of polyorganomethoxy fluorenylalkyl groups (B2) having different molecular structures may be used in combination, and, for example, a linear polyorganomethoxy oxime alkyl group (B2) and a branched chain may be used in combination. Polyorganooxy oxime alkyl (B2).

The group other than the hydrogen atom of the polyorganooxy oxoalkylene group (B2) bonded to the ruthenium atom is not particularly limited, and examples thereof include an organic group. The organic group may, for example, be a monovalent substituted or unsubstituted hydrocarbon group or the like. Among them, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferred.

The property of the polyorganooxyalkylene group (B2) is not particularly limited, and may be liquid or solid.

As the polyorganomethoxy fluorenylalkyl group (B2), the following average unit formula: (R ⁴ ₂ SiO _2/2 ) _d1 (R ⁴ ₃ SiO _1/2 ) _d2 (R ⁴ SiO _3/2 ) _d3 ( The polyorganomethoxy fluorenylalkyl group represented by SiO _4/2 ) _d4 (R ^A ) _{d5 is} preferred. In the above average unit formula, R ⁴ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and examples thereof include a hydrogen atom and the above specific examples (for example, an alkyl group, an alkenyl group, an aryl group, and an aromatic group). Alkyl, halogenated alkyl, etc.). However, one part of R ⁴ is a hydrogen atom, and the ratio thereof is controlled to be in the range of two or more in the molecule. For example, the ratio of the total amount (100 mol%) of hydrogen atoms to R ⁴ is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%. When the ratio of the hydrogen atom is controlled to the above range, the curability of the curable resin composition tends to be further improved. Further, R ⁴ other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group). In particular, the ratio of the aryl group (especially phenyl group) relative to the total amount (100 mol%) of R ⁴ is preferably 5 mol% or more (for example, 5 to 80 mol%), more preferably 10 mol%. %the above.

In the above average unit formula, R ^{A is} as described above as an alkylene group. In particular, it is preferred to extend the ethyl group.

In the above average unit formula, d1 is a positive number, d2 is a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, and d5 is a positive number. Preferably, d1 is 1~50, d2 is 1~50, d3 is 0~10, d4 is 0~5, and d5 is 1~30.

More specifically, for example, a polyorganomethoxy fluorenylalkyl group having a structure represented by the following formula (IV-1) can be given.

In the above formula (IV-1), R ⁴¹ is the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of R ⁴¹ include the above specific examples (for example, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, or a halogenated hydrocarbon group). However, at least two of R ⁴¹ are a hydrogen atom. Further, R ⁴¹ other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

The above formula (IV-1), the same as R ^A in the formula (II-1) to R ^A, and said alkylene, wherein the C _2-4 alkylene group (in particular, extend ethyl) preferred. Furthermore, when there are a plurality of R ^A , the same may be the same or different.

In the above formula (IV-1), q1 represents an integer of 1 or more (for example, 1 to 100). Further, when q1 is an integer of 2 or more, the structures in the brackets of the mark q1 may be the same or different.

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

In the above formula (IV-1), 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 structures in the parentheses of the mark q3 may be the same or different.

In the above formula (IV-1), 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 structures in the brackets of the mark q4 may be the same or different.

In the above formula (IV-1), 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 structures in the parentheses of the mark q5 may be the same or different.

Further, the addition form of each structural unit of the above formula (IV-1) is not particularly limited, and may be a random type or a block type.

The terminal structure of the polyorganomethoxy fluorenyl group having a structure represented by the formula (IV-1) is not particularly limited, and examples thereof include a decyl group, an alkoxyalkyl group, and a trialkyl decyl group ( For example, the structure of the mark q5, a trimethyldecyl group, etc.), etc. In the terminal of the polyorganomethoxyalkylene group, various groups such as an alkenyl group or a hydrofluorenyl group may be introduced.

The polyorganomethoxy fluorenylalkylene group (B2) can be produced by a known method or a conventional method, and the production method thereof is not particularly limited. For example, it can be produced by the method described in JP-A-2012-140617.

The content (mixing amount) (total amount) of the polyoxyalkylene (B) of the curable resin composition of the present invention is not particularly limited, but is relative to the total amount (100% by weight) of the polyoxyalkylene (A). It is preferably from 1 to 200 parts by weight. By controlling the content of the polyoxyalkylene (B) to the above range, the curability of the curable resin composition is further improved, and the cured product can be efficiently formed. tendency. When the content of the polyoxyalkylene (B) is out of the above range, the properties such as heat resistance, heat-resistant repellency, and reflow resistance of the cured product tend to decrease depending on the reason that the curing reaction is not sufficiently performed.

As the polyoxyalkylene oxide (B) which is a curable resin composition of the present invention, only polyorganosiloxane (B1) may be used, or only polyorganooxyalkylene (B2) may be used. It is also possible to use a polyorganosiloxane (B1) together with a polyorganooxime alkyl (B2). When the polyorganosiloxane (B1) and the polyorganooxyalkylene group (B2) are used in combination, the ratio is not particularly limited and may be appropriately set.

The total content (total content) of the content of the polyoxyalkylene (A) and the polyoxyalkylene (B) in the curable resin composition (100% by weight) of the present invention is not particularly limited, but is 70% by weight or more ( For example, 70% by weight or more and less than 100% by weight) is more preferable, more preferably 80% by weight or more, still more preferably 90% by weight or more. When the total content is 70% by weight or more, the heat resistance and transparency of the cured product tend to be further improved.

The polyorganomethoxy fluorenylalkyl group (A2) and the total content (100% by weight) of the polyoxyalkylene (A) and the polyoxyalkylene (B) contained in the curable resin composition of the present invention are The ratio (total ratio) of the polyorganooxyalkylene group (B2) is not particularly limited, but preferably 3% by weight or more (for example, 60 to 100% by weight), more preferably 10% by weight or more, and further Good is 15~50% by weight. When the ratio is 3% by weight or more, the surface adhesiveness of the cured product tends to be lower, and the heat-resistant punching performance tends to be good.

[acetylene urea derivative (C)]

The acetylene urea derivative (C) which is an essential component of the curable resin composition of the present invention is a compound represented by the above formula (1) (acetylene urea derivative). In the formula (1), Ra to Rd are the same or different, and represent a group represented by the following formula (1a), a group represented by the following formula (1b), or a group represented by the following formula (1c).

In the above formulae (1a) to (1c) (formula (1a), formula (1b), and formula (1c)), s is the same as or different from 0 or 1 or more. s is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3, from the viewpoint of the barrier property of the cured product to the corrosive gas. Further, the total of four s present in the above formula (1) may be the same or different.

The group represented by the above formula (1a) may, for example, be a vinyl group, an allyl group or the like. Further, when two or more groups represented by the formula (1a) are present in the formula (1), these may be the same or different.

In the above formula (1b), R ^g represents the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. The monovalent substituted or unsubstituted hydrocarbon group may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group), and specific examples thereof include a monovalent aliphatic hydrocarbon group (for example, an alkyl group). , alkenyl group, etc.; monovalent alicyclic hydrocarbon group (for example, cycloalkyl group, etc.); monovalent aromatic hydrocarbon group (for example, aryl group, etc.); monovalent heterocyclic group; aliphatic hydrocarbon group, alicyclic ring a monovalent group formed by bonding two or more kinds of a hydrocarbon group and an aromatic hydrocarbon group (for example, an alkyl group and/or an alkenyl group substituted with a cycloalkyl group, a cycloalkyl-alkyl group, an alkyl group and/or an alkenyl group substituted aromatic group) a group, an aryl-alkyl group; a group in which one or more hydrogen atoms of the groups are substituted by a substituent (for example, a halogen atom). Among them, as R ^g , a monovalent aliphatic hydrocarbon group is preferred, and an alkyl group (particularly a C _1-4 alkyl group) is more preferred. Furthermore, the three R ^g in the formula (1b) may be the same or different. Further, when two or more groups represented by the formula (1b) are present in the formula (1), these may be the same or different.

In the above formula (1c), R ^h and R ⁱ represent the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. The monovalent substituted or unsubstituted hydrocarbon group may, for example, be a monovalent substituted or unsubstituted hydrocarbon group (including an alkenyl group), and specific examples thereof include a monovalent aliphatic hydrocarbon group (for example, an alkyl group, Alkenyl group, etc.; monovalent alicyclic hydrocarbon group (for example, cycloalkyl group, etc.); monovalent aromatic hydrocarbon group (for example, aryl group, etc.); monovalent heterocyclic group; aliphatic hydrocarbon group, alicyclic a monovalent group formed by bonding two or more kinds of a hydrocarbon group and an aromatic hydrocarbon group (for example, an alkyl group and/or an alkenyl group substituted with a cycloalkyl group, a cycloalkyl-alkyl group, an alkyl group and/or an alkenyl group substituted aryl group An aryl-alkyl group; a group in which one or more hydrogen atoms of the groups are substituted by a substituent (for example, a halogen atom). Wherein, as R ^h and R ⁱ , a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group is preferred, and more preferably an alkyl group (particularly a methyl group), an alkenyl group (particularly a vinyl group) or an aryl group ( Especially phenyl). Further, the plurality of R ^h and the plurality of R ⁱ in the formula (1c) may be the same or different.

Further, in the above formula (1c), t represents an integer of 0 or more. As t, from the viewpoint of the barrier property of the cured product with respect to the corrosive gas, an integer of 1 to 100 is preferable, and an integer of 1 to 50 is more preferable, and preferably 1 to 30. The integer. Further, when two or more groups represented by the formula (1c) are present in the formula (1), these may be the same or different.

In the formula (1), at least one of R ^a to R ^d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c). That is, the acetylene urea derivative (C) has a Si-OR ^g group (particularly an alkoxyalkyl group) present in the group represented by the formula (1b) in the molecule and is present in the formula (1c) Any one or both of the hydroquinone groups in the group, and therefore, when the curable resin composition is hardened, it may be a component having an alkoxyalkylene group or a decyl group in the composition (for example, polyoxyalkylene oxide) (A), (B), etc., or a component having an alkenyl group (for example, polyoxyalkylene (A)), and can significantly improve the barrier property of the cured product with respect to a corrosive gas. Further, when the group represented by the formula (1a) is R ^a to R ^d , for example, it may be reacted with a component having a hydroquinone group (for example, polyoxyalkylene (B)) in the curable resin composition. Therefore, the barrier property of the hardened material with respect to the corrosive gas can be remarkably improved.

The ratio of the groups represented by the formulae (1a) to (1c) of the acetylene urea derivative (C) is not particularly limited. For example, R ^a ~ R ^d include all of the formula (1b) compound represented by the group; R ^a ~ all compounds of formula (1c) represented by the group of R ^d; R ^a ~ R ^d 1 ~3 are a group represented by the formula (1b), and the remainder is a compound of the formula represented by the formula (1a); 1 to 3 of R ^a to R ^d are a group represented by the formula (1b), and the remainder is a formula ( a compound of the formula shown in 1c); 1 to 3 of R ^a to R ^d are a group represented by the formula (1c), and the remainder is a compound of the formula represented by the formula (1a); having the formula (1a) The group represented by the formula (1b) and the group represented by the formula (1c) are all compounds such as R ^a to R ^d .

In the formula (1), R ^e and R ^f represent the same or different hydrogen atom or alkyl group. The alkyl group may, for example, be a C _1-20 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group or a dodecyl group. Among them, as R ^e and R ^f , a hydrogen atom or a C _1-4 alkyl group is preferred, and a hydrogen atom or a methyl group is more preferred.

In addition, the curable resin composition of the present invention contains the acetylene urea derivative (C), and exhibits excellent barrier properties against the corrosive gas of the cured product of the curable resin composition, and is presumed to be hardened. The acetylene urea skeleton of the acetylene urea derivative (C) can trap corrosive gases such as SOx gas.

The acetylene urea derivative (C) can be produced, for example, by a known or customary method using acetylene urea or a derivative thereof as a starting material, and the production method thereof is not particularly limited, and, for example, it is used as an acetylene urea derivative (C). An efficient production method includes a group selected from a compound selected from the group consisting of a compound represented by the following formula (i), a compound represented by the following formula (ii), and a compound represented by the following formula (iii); The step of performing a hydrogenation sulfanation reaction of at least one of the compounds in the process as a necessary step.

[In the formula (i), s, R ^e , and R ^{f are the} same as described above. ]

HSi(OR ^g ) ₃ (ii)

[In the formula (ii), R ^g is the same as described above. ]

[In the formula (iii), R ^h , R ⁱ , and t are the same as described above. ]

The hydrogenation sulfonation reaction can be carried out by a known method or a conventional method, conditions, and the like, and is not particularly limited. Further, the hydrogenation sulfonation reaction can be carried out in the presence of a hydrogenated decylation catalyst. For example, a hydrogenated decylation catalyst described later can be used. Further, when two or more kinds of compounds (the compound represented by the formula (ii) and the compound represented by the formula (iii)) are reacted with the compound represented by the formula (i), the hydrogenation sulfonation reaction can be carried out simultaneously. It can also be carried out one by one. Further, in the case of reacting the compound represented by the formula (i) with the compound represented by the formula (i), in order to prevent gelation by the crosslinking reaction, it is preferred to use the compound represented by the formula (i). The carbon-carbon double bond is reacted in such a manner that the hydrofluorenyl group of the compound represented by the formula (iii) is in an excess amount. In addition, the acetylene urea derivative (C) obtained by the above hydrogenation sulfonation reaction can be used as it is without purification (for example, it can be used as a constituent component of the curable resin composition of the present invention), and can be used in a known or customary manner. The purification means is used after purification.

In the curable resin composition of the present invention, the acetylene urea derivative (C) may be used singly or in combination of two or more.

The content (mixing amount) of the acetylene urea derivative (C) of the curable resin composition of the present invention is not particularly limited, but is relative to the total amount of polyoxyalkylene (A) and polyoxyalkylene (B). 100 parts by weight is preferably more than 0 parts by weight and 20 parts by weight or less, more preferably 0.01 to 18 parts by weight, still more preferably 0.1 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight. especially When the content is 0.01 parts by weight or more, the barrier properties and durability (heat-resistant repellency, reflow resistance, and the like) of the cured product with respect to the corrosive gas tend to be remarkably improved. On the other hand, when the content is 20 parts by weight or less, the transparency and durability (heat-resistant repellency, reflow resistance, and the like) of the cured product tend to be further improved.

[hydrogenated decane catalyst]

The curable resin composition of the present invention may further contain a hydrogenated decylation catalyst. The curable resin composition of the present invention tends to more efficiently carry out a hydrogenation oximation reaction between an alkenyl group and a hydrofluorenyl group in the curable resin composition by heating, including a hydrogenated decylation catalyst.

The above-mentioned hydrogenated decylation catalyst is exemplified by a known catalyst for a hydrogenation sulfonation 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, aldehyde, ketone, etc., platinum olefin complex, platinum-carbonyl vinyl methyl complex a platinum-methyl oxime complex such as a platinum carbonyl complex, a platinum-divinyltetramethyldioxane complex or a platinum-cyclovinyl methyl oxime complex, A platinum-based catalyst such as a platinum-phosphine complex or a platinum-phosphite complex, and a palladium-based catalyst or a ruthenium-based catalyst containing a palladium atom or a ruthenium atom instead of a platinum atom in the platinum-based catalyst. Among them, as the hydrogenated decylation catalyst, since the reaction speed of the platinum-vinyl methyl oxane complex or the platinum-carbonyl ethylene methyl complex or the chloroplatinic acid and the alcohol and the aldehyde complex is good, good.

In the curable resin composition of the present invention, the hydrogenated decylation catalyst may be used singly or in combination of two or more.

Silicon hydride curable resin composition of the present invention is the alkylation catalyst content (blending amount) is not particularly limited, with respect to the total amount of alkenyl groups contained in the curable resin composition of 1 mole of 1 × 10 ^{- 8} to 1 × 10 ^-2 moles are preferred, and more preferably 1.0 × 10 ^-6 to 1.0 × 10 ^-3 moles. When the content is 1 × 10 ^-8 mol or more, the cured product tends to be formed more efficiently. On the other hand, when the content is 1 × 10 ^-2 mol or less, a cured product having a more excellent hue (less coloration) tends to be obtained.

Further, the content (doping amount) of the hydrogenated decylation catalyst of the curable resin composition of the present invention is not particularly limited. For example, platinum, palladium or rhodium in the hydrogenated decylation catalyst is 0.01 by weight. The amount in the range of 1000 ppm is preferably in the range of 0.1 to 500 ppm. When the content of the hydrogenated decylation catalyst is in the above range, the cured product can be formed more efficiently, and a cured product having a more excellent hue can be obtained.

In addition, the curable resin composition of the present invention may contain components other than the above components (may be referred to as "other components"). The other component is not particularly limited, and examples thereof include a decyl alkane compound other than polysiloxane (A) and (B) (for example, a cyclic siloxane compound, a low molecular weight linear or branched chain). A decane compound, etc.), a decane coupling agent, a hydrogenation sulfonation reaction inhibitor, a solvent, various additives, and the like. Examples of the additive include precipitated cerium oxide, wet cerium oxide, smoked cerium oxide, calcined cerium oxide, titanium oxide, and aluminum oxide. Inorganic fillers such as glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, tantalum carbide, tantalum nitride, boron nitride, etc., and the use of organic halogenated decane, organic alkoxylate for these fillers An inorganic filler treated with an organic ruthenium compound such as decane or an organic decane, or an organic resin fine powder such as an oxime ketone resin, an epoxy resin or a fluororesin; or a filler such as a conductive metal powder such as silver or copper; , solvents, stabilizers (antioxidants, UV absorbers, light stabilizers, thermal stabilizers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), resistance Combustion aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents, slip agents, waxes, plasticizers, release agents, impact modifiers, hue modifiers, flow improvers, colorants ( Dyes, pigments, etc.), dispersants, defoamers, defoamers, antibacterial agents, preservatives, viscosity modifiers, tackifiers, phosphors, etc. These other components may be used alone or in combination of two or more. In addition, the content (mixing amount) of other components can be suitably selected in the range which does not impair the effect of this invention.

The curable resin composition of the present invention is not particularly limited, but is preferably a composition (mixed composition) of 0.2 to 4 moles per mole of the hydroquinone alkyl group present in the curable resin composition. More preferably, it is 0.5 to 1.5 m, and preferably 0.8 to 1.2 m. By controlling the ratio of the hydroquinone group to the alkenyl group to the above range, there is heat resistance, transparency, heat-resistant repellency and reflow resistance of the cured product, and barrier to corrosive gas (for example, SOx gas, etc.). The tendency to further improve.

The curable resin composition of the present invention is not particularly limited, and the above components may be stirred at room temperature. Prepared by mixing. Furthermore, the curable resin composition of the present invention can also be used as a direct use The composition of the one-liquid system in which the components are mixed first may be used as a composition of a multi-liquid system (for example, a two-liquid system) which is used in a predetermined ratio before being used in two or more components separately stored. Use.

The curable resin composition of the present invention is not particularly limited, but is preferably a liquid at normal temperature (about 25 ° C). More specifically, the curable resin composition of the present invention has a viscosity of 23 ° C, 300 to 20000 mPa. s is better, more preferably 500~10000mPa. s, better than 1000~8000mPa. s. By making the above viscosity 300mPa. Above s, there is a tendency that the heat resistance of the cured product is further improved. On the other hand, by making the above viscosity 20,000 mPa. In the following, the preparation of the curable resin composition is easy, the productivity or handleability is further improved, and the bubbles become difficult to remain in the cured product, so that the productivity or quality of the cured product (especially the sealing material) is further improved. Propensity. Further, the viscosity of the curable resin composition can be measured, for example, by the same method as the viscosity of the ladder-shaped polyorganosilazoxane (a).

<hardened matter>

By curing the curable resin composition of the present invention (particularly, it is cured by a hydrogenation reaction), a cured product (sometimes referred to as "the cured product of the present invention") can be obtained. The conditions for the hardening (especially the hardening by the hydrogenation reaction) are not particularly limited, and can be appropriately selected according to conventionally known conditions. For example, from the viewpoint of the reaction rate, the temperature (hardening temperature) is 25 to 180 ° C ( More preferably, it is preferably 60 to 150 ° C., and the time (hardening time) is preferably 5 to 720 minutes. The cured product of the present invention has not only high heat resistance and transparency peculiar to the polyoxyalkylene-based material, but also excellent heat-resistant and reflow-resistant properties, particularly with respect to corrosive gases (for example, SOx gas, etc.). Good barrier properties.

<Sealant, optical semiconductor device>

The curable resin composition of the present invention can be suitably used as a resin composition (sealant) for sealing a semiconductor element of a semiconductor device (may be referred to as "the sealant of the present invention"). Specifically, the sealing agent of the present invention is particularly suitably used for a resin composition (sealant) for sealing an optical semiconductor element (LED element) of an optical semiconductor device. The sealing material (cured material) obtained by curing the sealing agent of the present invention not only has high heat resistance and transparency peculiar to the polyoxyalkylene-based material, but also excellent in heat-resistant and reflow-resistant properties, particularly It has good barrier properties against corrosive gases (for example, SOx gas, etc.). Therefore, the sealant of the present invention can be suitably used as a sealant for a high-brightness, short-wavelength optical semiconductor element. An optical semiconductor device can be obtained by sealing the optical semiconductor element with the sealant of the present invention. The sealing of the optical semiconductor element can be carried out by a known method or a conventional method, and is not particularly limited. For example, the sealing agent of the present invention can be injected into a predetermined molding die and heat-hardened under predetermined conditions. The hardening temperature and the hardening time are not particularly limited, and can be set in the same range as in the preparation of the cured product. An example of the optical semiconductor device of the present invention is shown in Fig. 1. In the first drawing, 100 denotes a reflector (resin composition for light reflection), 101 denotes a metal wiring (electrode), 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes a cured product (sealing material).

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

The curable resin composition of the present invention is not limited to the above-mentioned use of the sealant (particularly, the use of the sealant of the optical semiconductor element), and can be suitably used, for example, as a functional coating agent, a heat-resistant plastic lens, a transparent machine, or an adhesive ( Heat-resistant transparent adhesive, etc.), electrical insulating material (insulating film, etc.), laminated board, coating, ink, paint, sealant, photoresist, composite material, transparent substrate, transparent sheet, transparent film, optical element, optical lens, Optical components, optical shapes, electronic paper, touch panels, solar cell substrates, optical waveguides, light guides, holographic memory, etc., optical or semiconductor related applications.

[Examples]

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

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

Manufacturing example 1

[Manufacture of ladder-shaped polyorganopyroxane]

A 100 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen introduction tube was charged with vinyltrimethoxysilane 65 mM (9.64 g) and phenyltrimethoxy hydride 195 under a nitrogen stream. Millol (38.67 g), and methyl isobutyl ketone (MIBK) 8.31 g, and the mixture was cooled to 10 °C. While the above mixture was taken for 1 hour, 360 mmol (6.48 g) of water and 0.24 g of hydrochloric acid of 5 N (1.2 mmol of hydrogen chloride) were added dropwise. After the dropwise addition, the mixture (reaction solution) was kept at 10 ° C for 1 hour to carry out a hydrolysis condensation reaction. Thereafter, MIBK 40g was added, and the reaction solution was diluted.

Next, the temperature of the reaction vessel was adjusted with a water bath, and the temperature of the reaction solution was raised to 70 ° C over 30 minutes. At a time point of 70 ° C, 520 mmol (9.36 g) of water was added, and a polycondensation reaction was carried out for 6 hours under the same temperature and a nitrogen stream. Next, hexamethyldioxane 130 mmol (21.11 g) was added to the reaction solution after the polycondensation reaction, and the decaneization reaction was carried out at 70 ° C for 3 hours. Thereafter, the mixture was cooled, washed with water until the lower layer was made neutral, and the supernatant was separated, and the solvent was distilled off from the supernatant liquid under conditions of 1 mmHg and 40 ° C to obtain a colorless transparent liquid product (38.6 g; Ladder-like polyorganosilsesquioxane having a vinyl group). In addition, the ladder-type polyorganosilsesquioxane obtained in Production Example 1 corresponds to the above-mentioned ladder-type polyorganosilogenes (a).

The product (the product after the alkylation reaction) had a number average molecular weight of 1,280 and a molecular weight dispersion of 1.13.

Manufacturing Example 2

[Synthesis of ladder-like polyorganosilsesquioxanes having a vinyl group and a trimethyldecyl group (TMS group) at the terminal]

In a 200 ml four-necked flask, 40.10 g of methyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.), 3.38 g of phenyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.), and methyl isobutyl ketone (MIBK) were added. ) 17.69g, the mix of these The material was cooled until 10 °C. While the above mixture was taken for 1 hour, 240 mmol (4.33 g) of water and 0.48 g of 5N hydrochloric acid (2.4 mmol of hydrogen chloride) were added dropwise. After the dropwise addition, the mixture was kept at 10 ° C for 1 hour. Thereafter, MIBK 80.0 g was added, and the reaction solution was diluted.

Next, the temperature of the reaction vessel was raised to 70 °C. At a time point of 70 ° C, 606 mmol (10.91 g) of water was added, and a polycondensation reaction was carried out for 9 hours under nitrogen. Further, 6.25 g of vinyltriethoxyoxane was added, and the reaction was carried out for 3 hours (cooking).

Next, 15.0 g of hexamethyldioxane was added to the above reaction solution, and the decaneization reaction was carried out at 70 ° C for 3 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer became neutral, and then the supernatant liquid was taken. Then, the solvent was distilled off from the supernatant liquid under the conditions of 1 mmHg and 60 ° C to obtain 19.0 g of a liquid product having a vinyl group and a TMS group having a vinyl group and a TMS group as a colorless and transparent liquid.

The weight average molecular weight (Mw) of the ladder-type polyorganosilsesquioxane having a vinyl group and a TMS group at the terminal is 3,000, and the vinyl group content (average content) per molecule is 4.00% by weight, phenyl/ The methyl/vinyl (mole ratio) is 5/80/15. In addition, the ladder-shaped polyorganosilsesquioxane obtained in Production Example 2 corresponds to the above-mentioned ladder-type polyorganosilogenephthale (b).

(1H-NMR spectrum of a ladder-type polyorganosiloid having a vinyl group and a TMS group at the terminal)

¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )): δ-0.3-0.3 ppm (br), 5.7-6.2 ppm (br), 7.1-7.7 ppm (br)

As the polyoxyalkylene oxides (A) and (B), in addition to the ladder-type polyorganosiloxanes obtained in Production Example 1 and Production Example 2, the following products can also be used.

ETERLED GD1130A: manufactured by Changxing Chemical Industry, having a vinyl content of 4.32% by weight, a phenyl content of 44.18% by weight, a number average molecular weight of 1107, a weight average molecular weight of 6099, and a hydrogenated decylation catalyst.

ETERLED GD1130B: manufactured by Changxing Chemical Industry, having a vinyl content of 3.45 wt%, a phenyl content of 50.96% by weight, a hydrofluorenyl (Si-H) content (in terms of hydride) of 0.17 wt%, a number average molecular weight of 631, and a weight average molecular weight of 1,305.

OE6630A: manufactured by Dow Corning Toray, having a vinyl content of 2.17 wt%, a phenyl content of 51.94 wt%, a hydroquinone content (calculated as hydride) of 0 wt%, a number average molecular weight of 2532, a weight average molecular weight of 4,490, and a hydrogenated decane. Catalyst.

OE6630B: manufactured by Dow Corning Toray, having a vinyl content of 3.87 wt%, a phenyl content of 50.11 wt%, a hydroquinone content (hydrogenated conversion) of 0.17 wt%, a number average molecular weight of 783, a weight average molecular weight of 1330

KER-2500A: manufactured by Shin-Etsu Chemical Co., Ltd., having a vinyl content of 1.53% by weight, a phenyl content of 0% by weight, a hydroquinone content (calculated as hydride) of 0.03% by weight, a number average molecular weight of 4453, a weight average molecular weight of 19,355, including Hydrogenated decane catalyst.

KER-2500B: Shin-Etsu Chemical Co., Ltd., vinyl content 1.08 wt%, phenyl content 0 wt%, hydroquinone content (hydrogenated conversion) 0.13 wt%, number average molecular weight 4636, weight average molecular weight 18814

ETERLED GD1012A: manufactured by Changxing Chemical Industry, with a vinyl content of 1.33 wt%, a phenyl content of 0 wt%, a hydroquinone content (calculated as hydride) of 0 wt%, a number average molecular weight of 5108, a weight average molecular weight of 23,385, and a hydrogenated decane Media.

ETERLED GD1012B: manufactured by Changxing Chemical Industry, having a vinyl content of 1.65 wt%, a phenyl content of 0 wt%, a hydroquinone content (calculated as hydride) of 0.19% by weight, a number average molecular weight of 4,563, and a weight average molecular weight of 21,873.

Further, as the acetylene urea derivative (C), the compounds obtained in the following Synthesis Examples 1 to 3 were used.

Synthesis Example 1

[Synthesis of an acetylene urea compound (acetylene urea derivative) having an average of 2 allyl groups and 2 trimethoxydecyl groups in one molecule]

In a 200 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen introduction tube, a tetraallyl acetylene urea compound TA-G (40.00 g, Shikoku Chemical Industry Co., Ltd.) was added under a nitrogen stream. A compound represented by the formula (i) in which s is 1, R ^e and R ^f are a hydrogen atom, methyl isobutyl ketone (40.00 g, manufactured by Kanto Chemical Co., Ltd.), and platinum-1,4-di a solution of vinyl-1,1,4,4-tetramethyldioxane complex in 1,3-divinyl-1,1,3,3-tetramethyldioxane (0.244 mg, Sigma, Inc., platinum content 3.0 wt%), and heated to 80 ° C. Then, a solution in which trimethoxysilane (32.33 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 g of methyl isobutyl ketone was added dropwise to the dropping funnel over 4 hours. And the mixture was aged for 4 hours to complete the reaction. After the reaction mixture was cooled, the solvent was distilled off under the conditions of 1 mmHg and 60 °C, and an excess amount of trimethoxysilane was added to obtain a colorless transparent liquid product (57.80 g; an average of 2 allyl groups in 2 molecules) a trimethoxy decyl acetylene urea compound).

FAB-MASS: 545 (H+)

Synthesis Example 2

[Synthesis of an acetylene urea compound (acetylene urea derivative) having an average of 2 hydroquinone groups and 2 trimethoxyalkyl groups in one molecule]

In a 100 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen introduction tube, 1,1,3,3-tetramethyldioxane (14.70 g, Tokyo Chemical Co., Ltd.) was added under a nitrogen stream. Industrial (stock), toluene (20.00g, manufactured by Kanto Chemical Co., Ltd.), and platinum-1,4-divinyl-1,1,4,4-tetramethyldioxane complex A solution of 1,3-divinyl-1,1,3,3-tetramethyldioxane (0.074 mg, manufactured by Sigma-Rich Company, platinum content 3.0 wt%), and heated until 80 °C. Then, the product (20.00 g) obtained in Synthesis Example 1 was dissolved in a solution of 20.00 g of toluene by dropwise addition of a funnel over 4 hours. And the mixture was aged for 4 hours to complete the reaction. After the reaction liquid was cooled, the solvent was distilled off under the conditions of 1 mmHg and 60 ° C, and an excess amount of 1,1,3,3-tetramethyldioxane was added to obtain a colorless transparent liquid product (26.84 g; An acetylene urea compound having 2 hydrofluorenyl groups and 2 trimethoxy decyl groups in one molecule.

FAB-MASS: 814 (H+)

Synthesis Example 3

[Synthesis of an acetylene urea compound (acetylene urea derivative) having 4 hydroquinone groups in one molecule]

In a 100 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen introduction tube, it was added under a nitrogen stream. 1,1,3,3-tetramethyldioxane (22.21g, manufactured by Tokyo Chemical Industry Co., Ltd.), toluene (20.00g, manufactured by Kanto Chemical Co., Ltd.), and platinum-1,4-divinyl A solution of 1,3-divinyl-1,1,3,3-tetramethyldioxane in the base-1,1,4,4-tetramethyldioxane complex (0.12 mg, Sigma) Made by Oric, with a platinum content of 0.3% by weight) and heated up to 70 °C. Then, a solution of the tetraallyl acetylene urea compound TA-G (10.00 g, manufactured by Shikoku Chemicals Co., Ltd.) dissolved in 10.00 g of toluene was added dropwise to the dropping funnel over 4 hours. And the mixture was aged for 4 hours to complete the reaction. And the mixture was aged for 4 hours to complete the reaction. After the reaction liquid was cooled, the solvent was distilled off under the conditions of 1 mmHg and 60 ° C, and an excess amount of 1,1,3,3-tetramethyldioxane was added to obtain a colorless transparent liquid product (23.20 g; 4 hydroquinone alkyl acetylene urea oxirane compounds).

FAB-MASS: 838 (H+)

Example 1

[Manufacture of curable resin composition]

First, as shown in Table 1, ETERLED GD1130A (20 parts by weight) and the compound (0.2 parts by weight) obtained in Synthesis Example 1 were mixed and stirred at room temperature for 1 hour to prepare a solvent A.

Next, ETERLED GD1130B (80 parts by weight) as a B agent was mixed with the A agent (20.2 parts by weight) obtained above, and when the mixture was stirred at room temperature for 1 hour, the compatibility of each component was good, and it was transparent and uniform. A liquid curable resin composition.

[Manufacture of optical semiconductor devices]

In the LED package (InGaN element, 3.5 mm × 2.8 mm) as shown in Fig. 1, the curable resin composition obtained above was injected. After heating at 60 ° C for 1 hour, followed by heating at 80 ° C for 1 hour, and heating at 150 ° C for 4 hours, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable resin composition was produced.

Examples 2 to 12 and Comparative Examples 1 to 5

The curable resin composition was produced in the same manner as in Example 1 except that the blending composition of the curable resin composition was changed as shown in Tables 1 and 2.

Moreover, the optical semiconductor device was produced in the same manner as in Example 1 using the curable resin composition obtained above.

(Evaluation)

The following evaluation was performed about the optical semiconductor device obtained above. The evaluation results are shown in Tables 1 and 2.

[Sulfur corrosion test]

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

First, the total beam (unit: lm) at the time of circulating a current of 20 mA was measured using a full beam measuring machine (manufactured by OPTRONIC LABORATORIES, multi-spectrophotometry system "OL771"), and this was used as a test. The front full beam".

Next, the above sample and 0.3 g of sulfur powder (KISHIDA CHEMICAL Co., Ltd.) were placed in a 450 ml glass bottle, and the above glass bottle was placed in a box made of aluminum. Next, the aluminum box was placed in an oven at 80 ° C (manufactured by Yamato Scientific Co., Ltd., model "DN-64"), and after 4 hours (Examples 10 to 12, Comparative Examples 4 and 5; The fluorenone system was taken out 24 hours later (Examples 1 to 9, Comparative Examples 1 to 3; phenyl fluorenone). With respect to the sample obtained as described above, the total light beam was measured in the same manner as described above, and this was referred to as "the full beam after the test".

Based on the value of the total light beam measured as described above, the photometric maintenance rate was calculated according to the following formula.

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

The higher the luminosity maintenance ratio, the better the barrier property of the cured product (sealing material) with respect to the corrosive gas.

Furthermore, in each of the curable resin compositions (each of the examples and comparative examples), for 10 optical semiconductor devices, the measurement was performed. The luminosity maintenance ratio was calculated, and the average value (N=10) of the luminosity maintenance ratios is shown in Tables 1 and 2.

[Hot rush test]

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

The sample was subjected to a hot stamping tester (ESPEC, model "TSB-21"), and was exposed to -40 ° C for 5 minutes, followed by exposure at 100 ° C for 5 minutes as a heat cycle of 1 cycle. In Examples 1 to 9 and Comparative Examples 1 to 3 (phenyl fluorenone), 1000 cycles of Examples 10 to 12 and Comparative Examples 4 and 5 (methylfluorenone) were carried out for 3000 cycles. Thereafter, a current of 20 mA was applied to the sample which was subjected to heat treatment for 1000 cycles or 3000 cycles, and the number of unlit samples was measured. Then, the durability against the hot stamping (heat resistance) was evaluated on the basis of the following criteria.

○ (good durability): the number of samples that are not lit is 0

× (poor durability): the number of samples that are not lit is one or more

[Moisture reflow test]

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

The sample was placed in a constant temperature and humidity chamber (ESPEC, model "SH-641") adjusted to 30 ° C and 60% RH, and taken out after 192 hours. Next, the above-mentioned sample was subjected to heat treatment at 260 ° C for two times for 10 seconds using a reflow furnace (manufactured by ANTOM Co., model "UNI-5016F"). Thereafter, the sample after the heat treatment using the reflow furnace was subjected to a current of 20 mA, and the number of unlit samples was measured. Then, the durability against moisture reflow (the reflow resistance after moisture absorption treatment) was evaluated on the basis of the following criteria.

○ (good durability): the number of samples that are not lit is 0

× (poor durability): the number of samples that are not lit is one or more

[Comprehensive judgment]

The comprehensive judgment was performed on the basis of the following criteria.

The luminosity maintenance rate measured in the sulphur corrosion test is 80% or more, and the case where the result of the thermal irrigating test and the moisture absorbing reflow test is ○ is judged as a comprehensive judgment ○ (excellent), and other cases are judged as comprehensive Determine × (poor).

[Industrial use]

The curable resin composition of the present invention is useful for applications such as an adhesive, a coating agent, a sealant, and the like which require heat resistance, transparency, heat-resistant repellency, reflow resistance, and barrier properties against corrosive gases. In particular, the curable resin composition of the present invention can be suitably used as a sealing agent for an optical semiconductor element (LED element).

Claims (8)

A curable resin composition comprising polyoxyalkylene (A), polyoxyalkylene (B), and an acetylene urea derivative (C) selected from the group consisting of molecules At least one of a group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups and a polyorganomethoxyalkylene group (A2) having two or more alkenyl groups in the molecule, The polyoxyalkylene (B) is selected from the group consisting of polyorganosiloxanes (B1) having two or more hydrofluorenyl groups in the molecule, and polyorganosiloxane having two or more hydroquinone groups in the molecule. At least one of the group of the alkylene group (B2), the acetylene urea derivative (C) is represented by the following formula (1). In the formula (1), R ^a to R ^d are the same or different ones, a group represented by the following formula (1a), a group represented by the following formula (1b), or a formula represented by the following formula (1c); a group; however, at least one of R ^a to R ^d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c); and R ^e and R ^f are the same or Differently representing a hydrogen atom or an alkyl group; In the formulae (1a) to (1c), s is the same or different, and represents an integer of 0 or more; in the formula (1b), R ^g is the same or different, and represents a hydrogen atom, or a monovalent substitution or no substitution. In the formula (1c), R ^h and R ⁱ represent the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents an integer of 0 or more]]. The curable resin composition of claim 1, which further comprises a hydrogenated decylation catalyst. A cured product obtained by hardening a curable resin composition of claim 1 or 2. The curable resin composition of claim 1 or 2 which is a sealant. A semiconductor device obtained by sealing a semiconductor element using the curable resin composition of claim 4. A semiconductor device according to claim 5, which is an optical semiconductor device. An acetylene urea derivative represented by the following formula (1), In the formula (1), R ^a to R ^d are the same or different ones, a group represented by the following formula (1a), a group represented by the following formula (1b), or a formula represented by the following formula (1c); a group; however, at least one of R ^a to R ^d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c); and R ^e and R ^f are the same or Differently representing a hydrogen atom or an alkyl group; In the formulae (1a) to (1c), s is the same or different, and represents an integer of 0 or more; in the formula (1b), R ^g is the same or different, and represents a hydrogen atom, or a monovalent substitution or no substitution. In the formula (1c), R ^h and R ⁱ represent the same or different hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents an integer of 0 or more]]. A method for producing an acetylene urea derivative, which is a method for producing an acetylene urea derivative represented by the following formula (1), which comprises a compound selected from the group consisting of the following formula (i), and the following a step of hydrogenating a hydrazine reaction of at least one compound of the compound represented by the formula (ii) and the compound represented by the following formula (iii), In the formula (1), R ^a to R ^d are the same or different ones, a group represented by the following formula (1a), a group represented by the following formula (1b), or a formula represented by the following formula (1c); a group; however, at least one of R ^a to R ^d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c); and R ^e and R ^f are the same or Differently representing a hydrogen atom or an alkyl group; In the formulae (1a) to (1c), s is the same or different, and represents an integer of 0 or more; in the formula (1b), R ^g is the same or different, and represents a hydrogen atom, or a monovalent substitution or no substitution. a hydrocarbon group; in the formula (1c), R ^h and R ⁱ are the same or different and represent a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group, and t represents an integer of 0 or more]]; [In the formula (i), s, R ^e , and R ^{f are the} same as defined above]; HSi(OR ^g ) ₃ (ii) [in the formula (ii), R ^g is the same as defined above]; [In the formula (iii), R ^h , R ⁱ , and t are the same as described above].