JP2016124958A - Curable resin composition and cured article thereof, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition enabling a material excellent in particularly barrier property to a corrosive gas to be formed by being cured.SOLUTION: There is provided the curable resin composition containing: polysiloxane (A) being at least one kind selected from a group consisting of polyorganosiloxane (A1) having two or more alkenyl groups in a molecule and polyorganosiloxy silalkylene (A2) having two or more alkenyl groups in a molecule; polysiloxane (B) being at least one kind selected from a group consisting of polyorganosiloxane (B1) having two hydroxyl groups in a molecule and polyorganosiloxy silalkylene (B2) having two or more hydrosilyl groups in a molecule; and a heterocyclic compound (C), the (C) heterocyclic compound being a heterocyclic compound (C) excluding an isocyanurate compound and having a heterocycle having at least one nitrogen atom, no sulfur atom and no nitrogen atom directly binding to hydrogen atom.SELECTED DRAWING: None

Description

  The present invention is obtained by sealing a curable resin composition and a cured product thereof, a sealing agent using the curable resin composition, and a semiconductor element (particularly an optical semiconductor element) using the sealing agent. The present invention relates to a semiconductor device (especially an optical semiconductor device).

Various resin materials are used as a sealing material for covering and protecting a semiconductor element in a semiconductor device. In particular, a sealing material in an optical semiconductor device is required to have excellent barrier properties against corrosive gases typified by sulfur compounds such as SO _x and H ₂ S.

As a sealing material in an optical semiconductor device, methylsilicone (methylsilicone-based sealing material) having excellent heat resistance is mainly used for lighting applications. For example, it is known that sulfur resistance against SO _X is improved by using as a sealant a resin composition in which a ladder type silsesquioxane, an isocyanurate compound, and a silane coupling agent are blended with methyl silicone. (For example, refer to Patent Document 1).

International Publication No. 2014/109349

  However, although the resin composition described in Patent Document 1 has a higher barrier property against corrosive gas than a conventionally used methylsilicone-based sealing material, its characteristics are still insufficient.

Accordingly, an object of the present invention is to provide a curable resin composition that can form a material (cured product) excellent in barrier properties against a corrosive gas (for example, SOx gas) by curing.
Another object of the present invention is to provide a material (cured product) having an excellent barrier property against a corrosive gas.
Furthermore, another object of the present invention is a quality obtained by sealing a sealing element using the curable resin composition, and sealing a semiconductor element (particularly an optical semiconductor element) using the sealing agent. Another object of the present invention is to provide a semiconductor device (particularly an optical semiconductor device) having excellent durability.

  The present inventor uses, as essential components, a specific polysiloxane having two or more alkenyl groups in the molecule, a specific polysiloxane having two or more hydrosilyl groups in the molecule, and a specific heterocyclic compound. According to the curable resin composition to be included, it was found that a cured product having an excellent barrier property against corrosive gas can be formed by curing, and the present invention has been completed.

  That is, the present invention is selected from the group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganosiloxysilalkylene (A2) having two or more alkenyl groups in the molecule. From at least one polysiloxane (A), a polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule, and a polyorganosiloxysilalkylene (B2) having two or more hydrosilyl groups in the molecule At least one selected from the group consisting of a polysiloxane (B) and a heterocyclic compound (C), the heterocyclic compound (C) having at least one nitrogen atom, and sulfur Heterocyclic compound (C) having a heterocycle having no atoms and having no nitrogen atom directly bonded to a hydrogen atom (provided that Providing a curable resin composition characterized in that it is except for rate compound).

  Furthermore, as the heterocyclic compound (C), pyridine, oxazole, pyrazine, triazine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, benzo [c] cinnoline, pyrimidine, derivatives thereof, pyrrolidine derivatives, pyrrole derivatives, At least one selected from the group consisting of piperidine derivatives, imidazole derivatives, pyrazole derivatives, imidazoline derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, benzimidazole derivatives, purine derivatives, carbazole derivatives, triazole derivatives, and benzotriazole derivatives The curable resin composition comprising the compound is provided.

［式（１ａ）中、Ｒ³¹は、水素原子、又は式（１ａ−Ｉ）で表される基を示す。Ｒ³²は、式（１ａ−Ｉ）で表される基、又は式（１ａ−II）で表される基を示す。

［式（１ａ−Ｉ）中、Ｒ³³は、同一又は異なって、置換基を有していてもよい炭化水素基を示す。］

［式（１ａ−II）中、Ｒ³⁴は、置換基を有していてもよい炭化水素基を示す。ｐは、１〜２０の整数を示す。］］
で表される化合物、下記式（１ｂ）

［式（１ｂ）中、Ｒ³⁵は、置換基を有していてもよい炭化水素基を示す。Ｒ³⁶及びＲ³⁷は、同一又は異なって、置換基を有していてもよいアリール基を示す。］
で表される化合物、下記式（１ｃ）

［式（１ｃ）中、Ｒ³⁸は、連結基を含んでいてもよい炭化水素基を示す。Ｒ³⁹は、二価の有機基を示す。Ｒ⁴⁰は、置換基を有していてもよい有機基を示す。］
で表される化合物、下記式（１ｄ）

［式（１ｄ）中、Ｒ⁴¹は、連結基を含んでいてもよい炭化水素基を示す。Ｒ⁴²及びＲ⁴³は、同一又は異なって、置換基を有していてもよい炭化水素基を示す。］
で表される化合物、下記式（１ｅ）

［式（１ｅ）中、Ｒ⁴⁴、Ｒ⁴⁵、及びＲ⁴⁶は、同一又は異なって、連結基を含んでいてもよい炭化水素基を示す。］
で表される化合物、及び下記式（１ｆ）

［式（１ｆ）中、Ｒ⁴⁷及びＲ⁴⁸は、同一又は異なって、連結基を含んでいてもよい炭化水素基を示す。］
で表される化合物からなる群より選択される１種以上の化合物である前記の硬化性樹脂組成物を提供する。 Furthermore, the heterocyclic compound (C) is represented by the following formula (1a)

[In the formula (1a), R ³¹ represents a hydrogen atom or a group represented by the formula (1a-I). R ³² represents a group represented by the formula (1a-I) or a group represented by the formula (1a-II).

[In the formula (1a-I), R ³³ are the same or different and each represents a hydrocarbon group which may have a substituent. ]

[In the formula (1a-II), R ³⁴ represents a hydrocarbon group which may have a substituent. p shows the integer of 1-20. ]]
A compound represented by formula (1b):

[In the formula (1b), R ³⁵ represents a hydrocarbon group which may have a substituent. R ³⁶ and R ³⁷ are the same or different and each represents an aryl group which may have a substituent. ]
A compound represented by formula (1c):

[In the formula (1c), R ³⁸ represents a hydrocarbon group which may contain a linking group. R ³⁹ represents a divalent organic group. R ⁴⁰ represents an organic group which may have a substituent. ]
A compound represented by formula (1d):

[In the formula (1d), R ⁴¹ represents a hydrocarbon group which may contain a linking group. R ⁴² and R ⁴³ are the same or different and each represents a hydrocarbon group which may have a substituent. ]
A compound represented by formula (1e):

[In the formula (1e), R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the same or different and each represents a hydrocarbon group which may contain a linking group. ]
And a compound represented by the following formula (1f)

[In formula (1f), R ⁴⁷ and R ⁴⁸ are the same or different and each represents a hydrocarbon group which may contain a linking group. ]
The curable resin composition is one or more compounds selected from the group consisting of compounds represented by:

  Furthermore, the said curable resin composition containing a hydrosilylation catalyst is provided.

［式（２）中、Ｒ^f、Ｒ^g、及びＲ^hは、同一又は異なって、式（２ａ）で表される基、又は式（２ｂ）で表される基を示す。但し、Ｒ^f、Ｒ^g、及びＲ^hのうち少なくとも１個は、式（２ｂ）で表される基である。

［式（２ａ）中、Ｒⁱは、水素原子又は炭素数１〜８の直鎖若しくは分岐鎖状のアルキル基を示す。］

［式（２ｂ）中、Ｒ^jは、水素原子又は炭素数１〜８の直鎖若しくは分岐鎖状のアルキル基を示す。］］
で表されるイソシアヌレート化合物（Ｄ）からなる群より選択される少なくとも１種を含む前記の硬化性樹脂組成物を提供する。 Furthermore, ladder-type polyorganosilsesquioxane and the following formula (2)

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

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

[In the formula (2b), R ^j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
The said curable resin composition containing at least 1 sort (s) selected from the group which consists of isocyanurate compound (D) represented by these is provided.

［式（３）中、Ｒ^a、Ｒ^b、及びＲ^cは、同一又は異なって、式（３ａ）で表される基、式（３ｂ）で表される基、水素原子、又はアルキル基を示す。但し、Ｒ^a、Ｒ^b、及びＲ^cのうち少なくとも１個は、式（３ａ）で表される基である。

［式（３ａ）中、Ｒ^dは、水素原子又は炭素数１〜８の直鎖若しくは分岐鎖状のアルキル基を示す。ｓは２〜１０の整数を示す。］

［式（３ｂ）中、Ｒ^eは、水素原子又は炭素数１〜８の直鎖若しくは分岐鎖状のアルキル基を示す。ｔは１〜１０の整数を示す。］］
で表されるイソシアヌレート化合物（Ｅ）を含む前記の硬化性樹脂組成物を提供する。 Further, the following formula (3)

[In the formula (3), R ^a , R ^b and R ^c are the same or different and represent a group represented by the formula (3a), a group represented by the formula (3b), a hydrogen atom or an alkyl group. Show. However, at least one of R ^a , R ^b and R ^c is a group represented by the formula (3a).

[In the formula (3a), R ^d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. s shows the integer of 2-10. ]

[In formula (3b), R ^e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. t shows the integer of 1-10. ]]
The said curable resin composition containing the isocyanurate compound (E) represented by these is provided.

［式（Ｖ）中、Ｒ⁶は、脂肪族炭素−炭素二重結合を有する基を示す。］
で表される単位構造及び下記式（VI）

［式（VI）中、Ｒ⁷は、同一又は異なって、炭化水素基を示す。］
で表される単位構造を含むポリオルガノシルセスキオキサン残基を有するラダー型シルセスキオキサン（Ｇ）を含む前記の硬化性樹脂組成物を提供する。 Furthermore, as the ladder-type polyorganosilsesquioxane, a part or all of the molecular chain terminals of the polyorganosilsesquioxane having a ladder structure may be represented by the following formula (V):

[In the formula (V), R ⁶ represents a group having an aliphatic carbon-carbon double bond. ]
The unit structure represented by the following formula (VI)

[In Formula (VI), R ⁷ is the same or different and represents a hydrocarbon group. ]
The curable resin composition comprising a ladder-type silsesquioxane (G) having a polyorganosilsesquioxane residue containing a unit structure represented by the formula:

［式（VII）中、Ｘは単結合、二価の炭化水素基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、又は、これらが複数個連結した基を示す。Ｒ⁸及びＲ⁹は、同一又は異なって、水素原子、ハロゲン原子、置換若しくは無置換の炭化水素基、アルコキシ基、アルケニルオキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシ基、アルキルチオ基、アルケニルチオ基、アリールチオ基、アラルキルチオ基、カルボキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アラルキルオキシカルボニル基、エポキシ基、シアノ基、イソシアナート基、カルバモイル基、イソチオシアナート基、ヒドロキシ基、ヒドロパーオキシ基、スルホ基、アミノ基若しくは置換アミノ基、メルカプト基、スルホ基、又は下記式（ｓ）

［式（ｓ）中、Ｒ⁵¹は、同一又は異なって、水素原子、ハロゲン原子、置換若しくは無置換の炭化水素基、アルコキシ基、アルケニルオキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシ基、アルキルチオ基、アルケニルチオ基、アリールチオ基、アラルキルチオ基、カルボキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アラルキルオキシカルボニル基、エポキシ基、シアノ基、イソシアナート基、カルバモイル基、イソチオシアナート基、ヒドロキシ基、ヒドロパーオキシ基、スルホ基、アミノ基若しくは置換アミノ基、メルカプト基、又はスルホ基を示す。］
で表される基を示す。ｎは１〜１００の整数を示す。］
で表される単位構造及び下記式（VIII）

［式（VIII）中、Ｒ¹⁰は、同一又は異なって、炭化水素基を示す。］
で表される単位構造を含むポリオルガノシルセスキオキサン残基を有するラダー型シルセスキオキサン（Ｈ）を含む前記の硬化性樹脂組成物を提供する。 Furthermore, as the ladder-type polyorganosilsesquioxane, a part or all of the molecular chain terminals of the polyorganosilsesquioxane having a ladder structure may be represented by the following formula (VII):

[In Formula (VII), X represents a single bond, a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, or a group in which a plurality of these are linked. R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an alkylthio group, an alkenylthio group. Group, arylthio group, aralkylthio group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxy group, hydroperoxy Group, sulfo group, amino group or substituted amino group, mercapto group, sulfo group, or the following formula (s)

[In formula (s), R ⁵¹ is the same or different and is a hydrogen atom, halogen atom, substituted or unsubstituted hydrocarbon group, alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, acyloxy group, alkylthio group. Group, alkenylthio group, arylthio group, aralkylthio group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxy group , A hydroperoxy group, a sulfo group, an amino group or a substituted amino group, a mercapto group, or a sulfo group. ]
The group represented by these is shown. n shows the integer of 1-100. ]
A unit structure represented by the following formula (VIII)

[In formula (VIII), R ¹⁰ is the same or different and represents a hydrocarbon group. ]
The curable resin composition comprising a ladder-type silsesquioxane (H) having a polyorganosilsesquioxane residue containing a unit structure represented by the formula:

  Furthermore, the curable resin composition is provided wherein the ladder-type polyorganosilsesquioxane is a ladder-type polyorganosilsesquioxane having a substituted or unsubstituted aryl group in part or all of the side chains.

  Furthermore, the said curable resin composition containing a silane coupling agent (F) is provided.

  Moreover, this invention provides the hardened | cured material obtained by hardening the said curable resin composition.

  Furthermore, the said curable resin composition which is a sealing agent is provided.

  Further, the present invention is a semiconductor device having a semiconductor element and a sealing material for sealing the semiconductor element, wherein the sealing material is a cured product of the curable resin composition. A semiconductor device is provided.

  Furthermore, the semiconductor device which is an optical semiconductor device is provided.

  Since the curable resin composition of the present invention has the above-described configuration, it is possible to form a cured product having excellent barrier properties against a corrosive gas (for example, SOx gas) by curing. For this reason, when the said hardened | cured material is used as a sealing material of the semiconductor element in a semiconductor device, corrosion of the electrode of the said semiconductor device is suppressed highly, and durability of the said semiconductor device improves remarkably. Therefore, the curable resin composition of the present invention can be preferably used as a material (sealing agent) for forming a sealing material for an optical semiconductor element (LED element) in an optical semiconductor device. The optical semiconductor device obtained by using the curable resin composition of the present invention as a sealant has excellent quality and durability.

It is the schematic which shows one Embodiment of the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the curable resin composition of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view.

<Curable resin composition>
The curable resin composition of the present invention comprises a group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganosiloxysilalkylene (A2) having two or more alkenyl groups in the molecule. A polysiloxane (A) that is at least one selected from the above (sometimes referred to simply as “polysiloxane (A)”), a polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule, and a molecule Polysiloxane (B) which is at least one selected from the group consisting of polyorganosiloxysilalkylene (B2) having two or more hydrosilyl groups therein (may be simply referred to as “polysiloxane (B)”) And a heterocyclic compound (C) as essential components. The heterocyclic compound (C) is a heterocyclic compound having a heterocyclic ring having at least one nitrogen atom, no sulfur atom, and no nitrogen atom directly bonded to a hydrogen atom ( C) (excluding isocyanurate compounds). In the present specification, the above-mentioned “heterocyclic compound (C) having a heterocyclic ring having at least one nitrogen atom, no sulfur atom, and no nitrogen atom directly bonded to a hydrogen atom (provided that "Except for isocyanurate compounds)" may be simply referred to as "heterocyclic compound (C)". The curable resin composition of the present invention may further contain other components such as a hydrosilylation catalyst described later, in addition to the above-described essential components.

[Polysiloxane (A)]
The polysiloxane (A), which is an essential component of the curable resin composition of the present invention, is a polysiloxane having two or more alkenyl groups in the molecule as described above. That is, the polysiloxane (A) is a polysiloxane having an alkenyl group, and a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, polysiloxane (B) described later). However, the polysiloxane (A) does not include those corresponding to “ladder type polyorganosilsesquioxane” described later.

  The polysiloxane (A) includes a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule (sometimes simply referred to as “polyorganosiloxane (A1)”) and two or more alkenyl groups in the molecule. A polysiloxane which is at least one selected from the group consisting of polyorganosiloxysilalkylene (A2) having the formula (sometimes referred to simply as “polyorganosiloxysilalkylene (A2)”).

In this specification, the polyorganosiloxysilalkylene (A2) means -Si-O-Si- (siloxane bond) as a main chain, -Si- ^RA -Si- (silalkylene bond: ^RA is alkylene) A polyorganosiloxane containing a group). And polyorganosiloxane (A1) in this specification is polyorganosiloxane which does not contain the said silalkylene bond as a principal chain.

(Polyorganosiloxane (A1))
Examples of the polyorganosiloxane (A1) include those having a linear, partially branched linear, branched, or network molecular structure. In addition, polyorganosiloxane (A1) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Specifically, two or more polyorganosiloxanes (A1) having different molecular structures can be used in combination, for example, a linear polyorganosiloxane (A1) and a branched polyorganosiloxane (A1) Can also be used together.

  Examples of the alkenyl group in the molecule of the polyorganosiloxane (A1) include substituted or unsubstituted alkenyl groups such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples of the substituent include a halogen atom, a hydroxy group, and a carboxy group. Among these, a vinyl group is preferable. The polyorganosiloxane (A1) may have only one alkenyl group or may have two or more alkenyl groups. Although the alkenyl group which polyorganosiloxane (A1) has is not specifically limited, It is preferable that it is a thing couple | bonded with the silicon atom.

  Although groups other than the alkenyl group which polyorganosiloxane (A1) has are not specifically limited, For example, a hydrogen atom, an organic group, etc. are mentioned. Examples of the organic group include alkyl groups [eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.], cycloalkyl groups [eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. , Cyclododecyl group, etc.], aryl group [eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.], cycloalkyl-alkyl group [eg, cyclohexylmethyl group, methylcyclohexyl group, etc.], aralkyl group [eg, A benzyl group, a phenethyl group, etc.], a halogenated hydrocarbon group in which one or more hydrogen atoms in the hydrocarbon group are substituted with a halogen atom [for example, chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoro Monovalent substituted or unsubstituted hydrocarbon groups such as halogenated alkyl groups such as propyl groups] And the like. In the present specification, the “group bonded to a silicon atom” usually means a group not containing a silicon atom.

  The polyorganosiloxane (A1) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.

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

As 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) a4 (X 1 O 1/2) a5
The polyorganosiloxane represented by these is preferable. In the above average unit formula, R ¹ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the above monovalent substituted or unsubstituted hydrocarbon group (for example, alkyl group, aryl Group, aralkyl group, halogenated hydrocarbon group and the like) and the above-mentioned alkenyl group. However, a part of R ¹ is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 or more in the molecule. For example, the ratio of the alkenyl group to the total amount of R ¹ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of the alkenyl group to the above range, the curability of the curable resin composition tends to be further improved. As R ¹ other than the alkenyl group, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.

In the above average unit formula, X ¹ is a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

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

  An example of the polyorganosiloxane (A1) is a linear polyorganosiloxane having two or more alkenyl groups in the molecule. Specific examples of the alkenyl group described above can be given as examples of the alkenyl group of the linear polyorganosiloxane, and among them, a vinyl group is preferable. In addition, you may have only 1 type of alkenyl group, and you may have 2 or more types of alkenyl groups. In addition, examples of the group bonded to the silicon atom other than the alkenyl group in the linear polyorganosiloxane include the monovalent substituted or unsubstituted hydrocarbon group described above, among which an alkyl group (particularly a methyl group). ) Or an aryl group (particularly a phenyl group).

  Although the ratio of the alkenyl group with respect to the total amount (100 mol%) of the groups bonded to the silicon atom in the linear polyorganosiloxane is not particularly limited, it is preferably 0.1 to 40 mol%. Moreover, the ratio of the alkyl group (especially methyl group) with respect to the total amount (100 mol%) of the group bonded to the silicon atom is not particularly limited, but is preferably 1 to 20 mol%. Furthermore, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 30 to 90 mol%. In particular, as the linear polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 80 mol%). By using a thing, there exists a tendency for the barrier property with respect to the corrosive gas of hardened | cured material to improve more. Moreover, a cured product is obtained by using a material in which the ratio of alkyl groups (particularly methyl groups) is 90 mol% or more (for example, 95 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. There is a tendency that the thermal shock resistance of is improved.

［上記式中、Ｒ¹¹は、同一又は異なって、一価の置換又は無置換炭化水素基である。但し、Ｒ¹¹の少なくとも２個はアルケニル基である。ｍ１は、５〜１０００の整数である。］ The linear polyorganosiloxane is represented by the following formula (I-1), for example.

[In the above formula, R ¹¹ are the same or different and each represents a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ¹¹ are alkenyl groups. m1 is an integer of 5 to 1000. ]

Another example of the polyorganosiloxane (A1) is a branched polyorganosiloxane having a siloxane unit (T unit) having two or more alkenyl groups in the molecule and represented by RSiO _3/2. It is done. However, as described above, the branched polyorganosiloxane does not include what is described later as “ladder type polyorganosilsesquioxane”. R is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the alkenyl group described above can be given as examples of the alkenyl group of the branched polyorganosiloxane. Among them, a vinyl group is preferable. In addition, you may have only 1 type of alkenyl group, and you may have 2 or more types of alkenyl groups. Examples of the group bonded to the silicon atom other than the alkenyl group in the branched polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group (particularly a methyl group). ) Or an aryl group (particularly a phenyl group). Furthermore, as R in the T unit, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.

  In the branched polyorganosiloxane, the ratio of alkenyl groups to the total amount of groups bonded to silicon atoms (100 mol%) is not particularly limited, but is 0.1 to 0.1 from the viewpoint of curability of the curable resin composition. 40 mol% is preferred. Moreover, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 10 to 40 mol%. Furthermore, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 5 to 70 mol%. In particular, as the branched polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 60 mol%). By using a thing, there exists a tendency for the barrier property with respect to the corrosive gas of hardened | cured material to improve more. Moreover, a cured product can be obtained by using a compound in which the ratio of alkyl groups (particularly methyl groups) is 50 mol% or more (for example, 60 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. There is a tendency that the thermal shock resistance of is improved.

  The branched polyorganosiloxane can be represented by the above average unit formula in which a1 is a positive number. In this case, although not particularly limited, a2 / a1 is a number from 0 to 10, a3 / a1 is a number from 0 to 0.5, a4 / (a1 + a2 + a3 + a4) is a number from 0 to 0.3, and a5 / (a1 + a2 + a3 + a4) is The number is preferably 0 to 0.4. The molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, more preferably 700 to 3000.

As yet another example of a polyorganosiloxane (A1), for example, in the above average unit formula, a1 and a2 are 0, the following average unit formula X ¹ is a hydrogen atom:
(R ^1a ₂ R ^1b SiO _1/2 ) _a6 (R ^1a ₃ SiO _1/2 ) _a7 (SiO _4/2 ) _a8 (HO _1/2 ) _a9
The polyorganosiloxane represented by these is mentioned. In the above average unit formula, R ^1a is the same or different and represents an alkyl group having 1 to 10 carbon atoms (C _1-10 alkyl group), for example, methyl group, ethyl group, propyl group, butyl group, pentyl group , A hexyl group, a cyclopentyl group, and a cyclohexyl group. Among them, a methyl group is preferable. R ^1b is the same or different and represents an alkenyl group, and among them, a vinyl group is preferable. Further, a6, a7, a8 and a9 are all a6 + a7 + a8 = 1, a6 / (a6 + a7) = 0.15 to 0.35, a8 / (a6 + a7 + a8) = 0.53 to 0.62, a9 / (a6 + a7 + a8) = A positive number satisfying 0.005 to 0.03. However, a7 may be 0. From the viewpoint of curability of the curable resin composition, a6 / (a6 + a7) is preferably 0.2 to 0.3. Moreover, it is preferable that a8 / (a6 + a7 + a8) is 0.55-0.60 from the viewpoint of the hardness and mechanical strength of the cured product. Furthermore, it is preferable that a9 / (a6 + a7 + a8) is 0.01-0.025 from the viewpoint of the adhesiveness and mechanical strength of the cured product. Examples of such polyorganosiloxanes include polyorganosiloxanes composed of SiO _4/2 units and (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 units, SiO _4/2 units and (CH ₃ ) Polyorganosiloxane composed of ₂ (CH ₂ ═CH) SiO _1/2 units and (CH ₃ ) ₃ SiO _1/2 units.

(Polyorganosiloxysilalkylene (A2))
As described above, the polyorganosiloxysilalkylene (A2) has two or more alkenyl groups in the molecule, and in addition to the siloxane bond as the main chain, the silalkylene bond-Si-R ^A -Si- (sil It is a polyorganosiloxane containing an alkylene bond: R ^A represents an alkylene group. That is, the polyorganosiloxysilalkylene (A2) does not include a polyorganosiloxane having no silalkylene bond such as the above-mentioned polyorganosiloxane (A1). When the curable resin composition of the present invention contains such a polyorganosiloxysilalkylene (A2), a cured product excellent in barrier properties against thermal corrosive gas and thermal shock resistance can be formed.

Examples of the alkylene group (R ^A ) in the silalkylene bond of the polyorganosiloxysilalkylene (A2) in the molecule include linear or branched C _1-12 alkylene such as methylene group, ethylene group and propylene group. A C _2-4 alkylene group (particularly an ethylene group) is preferable. The polyorganosiloxysilalkylene (A2) is less likely to produce a low molecular weight ring in the production process than the polyorganosiloxane (A1), and is not easily decomposed by heating or the like to produce a silanol group (—SiOH). When polyorganosiloxysilalkylene (A2) is used, the surface tackiness of the cured product of the curable resin composition is reduced, and it tends to be more difficult to yellow.

  Examples of the polyorganosiloxysylalkylene (A2) include those having a linear, partially branched linear, branched, or network molecular structure. In addition, polyorganosiloxysil alkylene (A2) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Specifically, two or more kinds of polyorganosiloxysilalkylene (A2) having different molecular structures can be used in combination, for example, linear polyorganosiloxysilalkylene (A2) and branched polyorganosiloxy. Silalkylene (A2) can also be used in combination.

  Examples of the alkenyl group that the polyorganosiloxysilalkylene (A2) has in the molecule include the above-mentioned substituted or unsubstituted alkenyl groups, and among them, a vinyl group is preferable. The polyorganosiloxysilalkylene (A2) may have only one alkenyl group or may have two or more alkenyl groups. The alkenyl group of the polyorganosiloxysilalkylene (A2) is not particularly limited, but is preferably bonded to a silicon atom.

  Although the group couple | bonded with silicon atoms other than the alkenyl group which polyorganosiloxysil alkylene (A2) has is not specifically limited, For example, a hydrogen atom, an organic group, etc. are mentioned. Examples of the organic group include the above-described organic groups (for example, substituted or unsubstituted hydrocarbons such as an alkyl group, a cycloalkyl group, an aryl group, a cycloalkyl-alkyl group, an aralkyl group, and a halogenated hydrocarbon group). It is done.

  The polyorganosiloxysilalkylene (A2) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.

  The property of the polyorganosiloxysilalkylene (A2) is not particularly limited, and may be liquid or solid at 25 ° C., for example.

As polyorganosiloxysilalkylene (A2), the following average unit formula:
(R ² ₂ SiO _2/2 ) _{b 1} (R ² ₃ SiO _1/2 ) _{b 2} (R ² SiO _3/2 ) _{b 3} (SiO _4/2 ) _{b 4} (R ^A ) _{b 5} (X ² O _1/2 ) _{b 6}
A polyorganosiloxysilalkylene represented by the formula is preferred. In the above average unit formula, R ² is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the above monovalent substituted or unsubstituted hydrocarbon group (for example, alkyl group, aryl Group, aralkyl group, halogenated hydrocarbon group and the like) and the above-mentioned alkenyl group. However, a part of R ² is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 or more in the molecule. For example, the ratio of the alkenyl group to the total amount of R ² (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of the alkenyl group to the above range, the curability of the curable resin composition tends to be further improved. 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 average unit formula, R ^A is an alkylene group as described above. An ethylene group is particularly preferable.

In the average unit formula, X ² is a hydrogen atom or an alkyl group as in X ¹ above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

  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, b5 is a positive number, b6 is 0 or a positive number. Among them, b1 is preferably 1 / (b1 + b2 + b3 + b4 + b5) to 200 / (b1 + b2 + b3 + b4 + b5), b2 is preferably 1 / (b1 + b2 + b3 + b4 + b5) to 200 / (b1 + b2 + b3 + b4 + b5), and b3 is preferably 0 / (5 + 4 + b3 + b4 + b3). b4 is preferably 0 / (b1 + b2 + b3 + b4 + b5) to 5 / (b1 + b2 + b3 + b4 + b5), and b5 is preferably 1 / (b1 + b2 + b3 + b4 + b5) to 100 / (b1 + b2 + b3 + b4 + b5). In particular, when (b3 + b4) is a positive number, the polyorganosiloxysilalkylene (A2) has a branched chain (branched main chain), and the mechanical strength of the cured product tends to be further improved.

More specifically, examples of the polyorganosiloxysilalkylene (A2) include polyorganosiloxysilalkylene having a structure represented by the following formula (I-2).

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

In the formula (I-2), R ^A represents an alkylene group as described above, and among them, a C _2-4 alkylene group (particularly an ethylene group) is preferable. In addition, when several ^RA exists, these may be the same and may differ.

  In said formula (I-2), r1 shows an integer greater than or equal to 1 (for example, 1-100). In addition, when r1 is an integer greater than or equal to 2, the structure in the parenthesis attached | subjected to r1 may be the same respectively, and may differ.

  In said formula (I-2), r2 shows an integer greater than or equal to 1 (for example, 1-400). In addition, when r2 is an integer greater than or equal to 2, the structure in the bracket | parenthesis which attached | subjected r2 may be respectively the same, and may differ.

  In said formula (I-2), r3 shows 0 or an integer greater than or equal to 1 (for example, 0-50). When r3 is an integer of 2 or more, the structures in parentheses to which r3 is attached may be the same or different.

  In said formula (I-2), r4 shows 0 or an integer greater than or equal to 1 (for example, 0-50). When r4 is an integer of 2 or more, the structures in parentheses to which r4 is attached may be the same or different.

  In said formula (I-2), r5 shows 0 or an integer greater than or equal to 1 (for example, 0-50). When r5 is an integer of 2 or more, the structures in parentheses to which r5 is attached may be the same or different.

  Moreover, the addition form of each structural unit in the said Formula (I-2) is not specifically limited, A random type may be sufficient and a block type may be sufficient. Further, the order of arrangement of each structural unit is not particularly limited.

  The terminal structure of the polyorganosiloxysilalkylene having the structure represented by the formula (I-2) is not particularly limited. For example, a silanol group, an alkoxysilyl group, a trialkylsilyl group (for example, parenthesis with r5 attached) Internal structure, trimethylsilyl group, etc.). Various groups such as an alkenyl group and a hydrosilyl group may be introduced at the terminal of the polyorganosiloxysilalkylene.

  The polyorganosiloxysylalkylene (A2) can be produced by a known or conventional method, and the production method is not particularly limited. For example, it can be produced by the method described in JP2012-140617A. Moreover, as a product containing polyorganosiloxysilalkylene (A2), for example, trade names “ETERLED GD1130”, “ETERLED GD1125”, “ETERLED GS5145”, “ETERLED GS5135”, “ETERLED GS5120” (all manufactured by Changko Material Industries) ) Etc. are available.

  In addition, in the curable resin composition of this invention, polysiloxane (A) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  In addition, polysiloxane (A) should just have two or more alkenyl groups in a molecule | numerator, and also may have a hydrosilyl group. In this case, the polysiloxane (A) may be a polysiloxane (B) described later.

  The content (blending amount) (total amount) of the polysiloxane (A) in the curable resin composition of the present invention is not particularly limited, but is 50 to 99 with respect to the total amount (100% by weight) of the curable resin composition. % By weight is preferable, more preferably 60 to 97% by weight, and still more preferably 70 to 95% by weight. By setting the content to 50% by weight or more, the toughness and transparency of the cured product tend to be further improved.

  As polysiloxane (A) in the curable resin composition of the present invention, only polyorganosiloxane (A1) can be used, or only polyorganosiloxysilalkylene (A2) can be used. Polyorganosiloxane (A1) and polyorganosiloxysilalkylene (A2) can also be used in combination. When the polyorganosiloxane (A1) and the polyorganosiloxysilalkylene (A2) are used in combination, these ratios are not particularly limited and can be appropriately set.

[Polysiloxane (B)]
The polysiloxane (B), which is an essential component of the curable resin composition of the present invention, is a polyorganosiloxane having two or more hydrosilyl groups (Si—H) in the molecule as described above. That is, the polysiloxane (B) is a polysiloxane having a hydrosilyl group, and is a component that causes a hydrosilylation reaction with a component having an alkenyl group (for example, polysiloxane (A)). However, the polysiloxane (B) does not include those described later as “ladder type polyorganosilsesquioxane”.

  The polysiloxane (B) is composed of a polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule (sometimes simply referred to as “polyorganosiloxane (B1)”) and two or more hydrosilyl groups in the molecule. A polyorganosiloxane having at least one selected from the group consisting of polyorganosiloxysilalkylene (B2) (sometimes simply referred to as “polyorganosiloxysilalkylene (B2)”).

In this specification, the polyorganosiloxysilalkylene (B2) means -Si-O-Si- (siloxane bond) as a main chain, -Si- ^RA -Si- (silalkylene bond: ^RA is alkylene) A polyorganosiloxane containing a group). And polyorganosiloxane (B1) in this specification is polyorganosiloxane which does not contain the said silalkylene bond as a principal chain. In addition, examples of R ^A (alkylene group) in the silalkylene bond include a linear or branched C _1-12 alkylene group as described above, and preferably a linear or branched C _{2. -4} alkylene group (especially ethylene group).

(Polyorganosiloxane (B1))
Examples of the polyorganosiloxane (B1) include those having a linear, partially branched linear, branched, and network molecular structure. In addition, polyorganosiloxane (B1) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Specifically, two or more polyorganosiloxanes (B1) having different molecular structures can be used in combination, for example, a linear polyorganosiloxane (B1) and a branched polyorganosiloxane (B1). Can also be used together.

  Among the groups bonded to the silicon atom of the polyorganosiloxane (B1), a group other than a hydrogen atom is not particularly limited. For example, the monovalent substituted or unsubstituted hydrocarbon group described above, more specifically, an alkyl group, An aryl group, an aralkyl group, a halogenated hydrocarbon group, etc. are mentioned. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable. The polyorganosiloxane (B1) may or may not have an alkenyl group (for example, a vinyl group) as a group bonded to a silicon atom other than a hydrogen atom.

  The property of the polyorganosiloxane (B1) is not particularly limited, and may be liquid or solid. Among these, a liquid is preferable, and a viscosity at 25 ° C. of 0.1 to 1 billion mPa · s is more preferable.

As polyorganosiloxane (B1), the following average unit formula:
(R ³ SiO _3/2 ) _{c 1} (R ³ ₂ SiO _2/2 ) _{c 2} (R ³ ₃ SiO _1/2 ) _{c 3} (SiO _4/2 ) _{c 4} (X ³ O _1/2 ) _{c 5}
The polyorganosiloxane represented by these is preferable. In the above average unit formula, R ³ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the hydrogen atom and the monovalent substituted or unsubstituted hydrocarbon group described above Examples (for example, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, etc.) and the above-mentioned alkenyl group are mentioned. However, a part of R ³ is a hydrogen atom (hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in a range where two or more hydrosilyl groups are present in the molecule. For example, the ratio of hydrogen atoms to the total amount of R ³ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable resin composition tends to be further improved. 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 average unit formula, X ³ is a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

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

  An example of the polyorganosiloxane (B1) is a linear polyorganosiloxane having two or more hydrosilyl groups in the molecule. Examples of the group bonded to a silicon atom other than a hydrogen atom in the linear polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group and the above-mentioned alkenyl group. Among them, an alkyl group ( In particular, a methyl group) and an aryl group (particularly a phenyl group) are preferable.

  The ratio of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount of groups bonded to silicon atoms (100 mol%) in the linear polyorganosiloxane is not particularly limited, but is 0.1 to 40 mol%. Is preferred. Moreover, the ratio of the alkyl group (especially methyl group) with respect to the total amount (100 mol%) of the group bonded to the silicon atom is not particularly limited, but is preferably 20 to 99 mol%. Furthermore, the ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 40 to 80 mol%. In particular, as the linear polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 70 mol%). By using a thing, there exists a tendency for the barrier property with respect to the corrosive gas of hardened | cured material to improve more. Moreover, a cured product is obtained by using a material in which the ratio of alkyl groups (particularly methyl groups) is 90 mol% or more (for example, 95 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. There is a tendency that the thermal shock resistance of is improved.

［上記式中、Ｒ²¹は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基である。但し、Ｒ²¹の少なくとも２個は水素原子である。ｍ２は、５〜１０００の整数である。］ The linear polyorganosiloxane is represented by, for example, the following formula (II-1).

[In the above formula, R ^{21 s} are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ²¹ are hydrogen atoms. m2 is an integer of 5 to 1000. ]

Another example of the polyorganosiloxane (B1) is a branched polyorganosiloxane having two or more hydrosilyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO _3/2. It is done. However, as described above, the branched polyorganosiloxane does not include what is described later as “ladder type polyorganosilsesquioxane”. R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of the group bonded to a silicon atom other than a hydrogen atom in the branched polyorganosiloxane include the monovalent substituted or unsubstituted hydrocarbon group described above and the alkenyl group described above. (Especially methyl group) and aryl group (particularly phenyl group) are preferable. Furthermore, examples of R in the T unit include a hydrogen atom, the above-described monovalent substituted or unsubstituted hydrocarbon group, and the above-described alkenyl group. Among them, an alkyl group (particularly a methyl group), an aryl group ( Particularly preferred is a phenyl group. The ratio of the aryl group (particularly phenyl group) to the total amount of R in the T unit (100 mol%) is not particularly limited, but is preferably 30 mol% or more from the viewpoint of the barrier property against the corrosive gas of the cured product.

  The ratio of alkyl groups (particularly methyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms in the branched polyorganosiloxane is not particularly limited, but is preferably 70 to 95 mol%. Furthermore, the ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 10 to 70 mol%. In particular, as the branched polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 10 mol% or more (for example, 10 to 70 mol%). By using a thing, there exists a tendency for the barrier property with respect to the corrosive gas of hardened | cured material to improve more. Moreover, a cured product is obtained by using a compound in which the ratio of the alkyl group (particularly methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is 50 mol% or more (for example, 50 to 90 mol%). There is a tendency that the thermal shock resistance of is improved.

  The branched polyorganosiloxane can be represented by, for example, the average unit formula in which c1 is a positive number. In this case, although not particularly limited, c2 / c1 is a number from 0 to 10, c3 / c1 is a number from 0 to 0.5, c4 / (c1 + c2 + c3 + c4) is a number from 0 to 0.3, and c5 / (c1 + c2 + c3 + c4) is The number is preferably 0 to 0.4. The molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 300 to 10,000, more preferably 500 to 3000.

(Polyorganosiloxysilalkylene (B2))
As described above, the polyorganosiloxysilalkylene (B2) is a polyorganosiloxane having two or more hydrosilyl groups in the molecule and containing a silalkylene bond as a main chain in addition to a siloxane bond. In addition, as an alkylene group in the said silalkylene bond, a _C2-4 alkylene group (especially ethylene group) is preferable, for example. The polyorganosiloxysilalkylene (B2) is less likely to produce a low molecular weight ring in the production process than the polyorganosiloxane (B1), and is not easily decomposed by heating or the like to produce a silanol group (—SiOH). When polyorganosiloxysilalkylene (B2) is used, the surface tackiness of the cured product of the curable resin composition is reduced, and it tends to be more difficult to yellow.

  Examples of the polyorganosiloxysilalkylene (B2) include those having a linear, partially branched, linear, branched or network molecular structure. In addition, polyorgano siloxysil alkylene (B2) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Specifically, two or more kinds of polyorganosiloxysilalkylene (B2) having different molecular structures can be used in combination, for example, linear polyorganosiloxysilalkylene (B2) and branched polyorganosiloxy. Silalkylene (B2) can also be used in combination.

  Although the group couple | bonded with silicon atoms other than the hydrogen atom which polyorganosiloxysil alkylene (B2) has is not specifically limited, For example, an organic group etc. are mentioned. As an organic group, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, the above-mentioned alkenyl group, etc. are mentioned, for example. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable. The polyorganosiloxane (B2) may or may not have an alkenyl group (for example, a vinyl group) as a group bonded to a silicon atom other than a hydrogen atom.

  The property of the polyorganosiloxysilalkylene (B2) is not particularly limited, and may be liquid or solid at 25 ° C., for example.

As polyorganosiloxysilalkylene (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 (SiO 4/2) d4 (R A) d5 (X 4 O) d6
A polyorganosiloxysilalkylene represented by the formula is preferred. In the above average unit formula, R ^{4 s} are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the hydrogen atom and the above monovalent substituted or unsubstituted hydrocarbon group (For example, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, etc.) and the above-mentioned alkenyl group. However, a part of R ⁴ is a hydrogen atom, and the ratio thereof is controlled within a range of 2 or more in the molecule. For example, the proportion of hydrogen atoms with respect to the total amount of R ⁴ (100 mol%) is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable resin composition tends to be further improved. 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 the average unit formula, R ^A is an alkylene group as described above. An ethylene group is particularly preferable.

In the average unit formula, X ⁴ is a hydrogen atom or an alkyl group as in X ³ above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

  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, d5 is a positive number, d6 is 0 or a positive number. Among them, d1 is preferably 1 / (d1 + d2 + d3 + d4 + d5) to 50 / (d1 + d2 + d3 + d4 + d5), d2 is preferably 1 / (d1 + d2 + d3 + d4 + d5) to 50 / (d1 + d2 + d3 + d4 + d5), and d3 is preferably 0 / (d3 + d + d + d4 + d4 + d3). d4 is preferably 0 / (d1 + d2 + d3 + d4 + d5) to 5 / (d1 + d2 + d3 + d4 + d5), and d5 is preferably 1 / (d1 + d2 + d3 + d4 + d5) to 30 / (d1 + d2 + d3 + d4 + d5).

More specifically, examples of the polyorganosiloxysilalkylene (B2) include polyorganosiloxysilalkylene having a structure represented by the following formula (II-2).

In said formula (II-2), R <^22> is the same or different, and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of R ²² include a hydrogen atom, specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.), and the above alkenyl group. It is done. However, at least two of R ²² are hydrogen atoms. R ²² other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

In the formula (II-2), R ^A, like R ^A in formula (I-2), an alkylene group, among them, C _2-4 alkylene group (in particular, an ethylene group) is preferable. In addition, when several ^RA exists, these may be the same and may differ.

  In said formula (II-2), q1 shows an integer greater than or equal to 1 (for example, 1-100). In addition, when q1 is an integer greater than or equal to 2, the structure in the bracket | parenthesis which attached | subjected q1 may each be the same, and may differ.

  In the above formula (II-2), q2 represents an integer of 1 or more (for example, 1 to 400). In addition, when q2 is an integer greater than or equal to 2, the structure in the bracket | parenthesis which attached | subjected q2 may each be the same, and may differ.

  In said formula (II-2), q3 shows 0 or an integer greater than or equal to 1 (for example, 0-50). In addition, when q3 is an integer greater than or equal to 2, the structure in the bracket | parenthesis which attached | subjected q3 may be respectively the same, and may differ.

  In said formula (II-2), q4 shows 0 or an integer greater than or equal to 1 (for example, 0-50). In addition, when q4 is an integer greater than or equal to 2, the structure in the parenthesis which attached | subjected q4 may be the same respectively, and may differ.

  In said formula (II-2), q5 shows 0 or an integer greater than or equal to 1 (for example, 0-50). In addition, when q5 is an integer greater than or equal to 2, the structure in the bracket | parenthesis which attached | subjected q5 may each be the same, and may differ.

  Moreover, the addition form of each structural unit in the formula (II-2) is not particularly limited, and may be a random type or a block type. .

  The terminal structure of the polyorganosiloxysilalkylene having the structure represented by the formula (II-2) is not particularly limited. For example, a silanol group, an alkoxysilyl group, a trialkylsilyl group (for example, a bracket with q5 attached) Internal structure, trimethylsilyl group, etc.). Various groups such as a hydrosilyl group may be introduced at the terminal of the polyorganosiloxysilalkylene.

  The polyorganosiloxysilalkylene (B2) can be produced by a known or conventional method, and the production method is not particularly limited. For example, it can be produced by the method described in JP2012-140617A.

  In addition, in the curable resin composition of this invention, polysiloxane (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Although content (blending amount) of the polysiloxane (B) in the curable resin composition of the present invention is not particularly limited, it is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of the polysiloxane (A). By controlling the content of polysiloxane (B) within the above range, the curability of the curable resin composition tends to be further improved and a cured product can be efficiently formed. When the content of the polysiloxane (B) is within the above range, the curing reaction proceeds sufficiently, and thus the properties of the cured product, such as heat resistance, thermal shock resistance, and reflow resistance, tend to be further improved. .

  As polysiloxane (B) in the curable resin composition of the present invention, only polyorganosiloxane (B1) can be used, or only polyorganosiloxysilalkylene (B2) can be used. Polyorganosiloxane (B1) and polyorganosiloxysilalkylene (B2) can also be used in combination. In the case where the polyorganosiloxane (B1) and the polyorganosiloxysilalkylene (B2) are used in combination, these ratios are not particularly limited and can be appropriately set.

  The total content (total content) of the polysiloxane (A) and the polysiloxane (B) in the curable resin composition (100% by weight) of the present invention is not particularly limited, but is preferably 60 to 99% by weight, More preferably, it is 70 to 96 weight%, More preferably, it is 80 to 90 weight%. By controlling the total content within the above range, the toughness, heat resistance and transparency of the cured product tend to be further improved.

[Heterocyclic Compound (C)]
The heterocyclic compound (C), which is an essential component of the curable resin composition of the present invention, has at least one nitrogen atom, does not have a sulfur atom, and has a nitrogen atom directly bonded to a hydrogen atom. It is a compound having a heterocyclic ring that does not. In the present specification, “heterocycle” refers to a heterocycle itself and does not include a substituent or the like bonded to the heterocycle. In the present specification, the above-mentioned “heterocycle having at least one nitrogen atom, no sulfur atom, and no nitrogen atom directly bonded to a hydrogen atom” is referred to as “nitrogen atom-containing heterocycle ( c) ". Therefore, the nitrogen atom-containing heterocycle (c) does not include a heterocycle having a nitrogen atom and a sulfur atom such as thiazole, or a heterocycle having a nitrogen atom directly bonded to a hydrogen atom such as pyrrolidine. The heterocyclic compound (C) does not include a compound having an isocyanurate ring (sometimes referred to as “isocyanurate compound”). The curable resin composition of the present invention uses the heterocyclic compound (C) having a nitrogen atom-containing heterocyclic ring (c) as the heterocyclic compound by including the heterocyclic compound (C) as an essential component. By this, it is presumed that it is caused by making it difficult to inhibit the curing when the curable resin composition is cured, but a cured product having an excellent barrier property against corrosive gas can be formed.

  Examples of the nitrogen atom-containing heterocyclic ring (c) include pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, imidazoline ring, pyrazine ring, triazine ring, morpholine ring, indole ring, Indole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, pteridine ring, acridine ring, carbazole ring, benzo [c] cinnoline ring, pyrimidine ring, triazole ring and the like can be mentioned. Among these, a pyrimidine ring, a triazine ring, a pyrazole ring, a benzimidazole ring, a purine ring, a piperidine ring, and a benzotriazole ring are preferable. In addition, only 1 type may be sufficient as the nitrogen atom containing heterocyclic ring (c) in a heterocyclic compound (C), and 2 or more types may be sufficient as it. Further, the number of nitrogen atom-containing heterocycles (c) in the heterocyclic compound (C) may be one, or may be two or more identical or different.

  Examples of the heterocyclic compound (C) include pyridine, oxazole, pyrazine, triazine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, benzo [c] cinnoline, pyrimidine, derivatives thereof, pyrrolidine derivatives, pyrrole derivatives, Examples include piperidine derivatives, imidazole derivatives, pyrazole derivatives, imidazoline derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, benzimidazole derivatives, purine derivatives, carbazole derivatives, triazole derivatives, and benzotriazole derivatives. Of these, pyrimidine, pyrimidine derivatives, triazine, triazine derivatives, pyrazole derivatives, benzimidazole derivatives, purine derivatives, piperidine derivatives, and benzotriazole derivatives are preferable. In this case, the compatibility with the polysiloxane (A) and the polysiloxane (B) and the solubility in the resin composition tend to be improved.

The heterocyclic compound (C) is preferably at least one compound selected from the group consisting of compounds represented by the following formulas (1a) to (1f). In this case, the compatibility with the polysiloxane (A) and the polysiloxane (B) and the solubility in the resin composition tend to be further improved.

In the above formula (1a), R ³¹ represents a hydrogen atom or a group represented by the following formula (1a-I).

In the above formula (1a-I), R ³³ (three R ³³ ) are the same or different and represent a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group optionally having a substituent for R ³³ include an alkyl group [eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.], cycloalkyl group [eg, cyclohexane Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclododecyl group, etc.], alkenyl group [eg, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, etc.], aryl group [eg, phenyl group, tolyl group] , Xylyl group, naphthyl group, etc.], cycloalkyl-alkyl group [eg, cyclohexylmethyl group, methylcyclohexyl group, etc.], aralkyl group [eg, benzyl group, phenethyl group, etc.], one or more hydrogen atoms in a hydrocarbon group A halogenated hydrocarbon group substituted with a halogen atom [for example, a chloromethyl group, - chloropropyl group, such monovalent substituted or unsubstituted hydrocarbon group of a halogenated alkyl group or the like] such as 3,3,3-trifluoropropyl groups. Examples of the substituent in the hydrocarbon group which may have a substituent include a halogen atom, a hydroxy group, and a carboxy group. In addition, as the substituent, two or more of the monovalent substituted or unsubstituted hydrocarbon groups are an ether bond (—O—), a thioether bond (—S—), an ester bond (—CO—O—), A group bonded through a linking group such as an amide bond (—CO—NH—) or a carbonyl group (—CO—) is also included. Examples of the hydrocarbon group which may have the above-described substituent include a linear or branched alkyl group having 1 to 10 carbon atoms (a linear or branched C _1-10 alkyl group), carbon, among others. An aryl group of several 6 to 10 is preferable. Examples of the linear or branched C _1-10 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl. Group, heptyl group, octyl group, ethylhexyl group and the like. Among the above alkyl groups, linear or branched C _1-3 alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. That is, as R ³³ , a linear or branched C _1-10 alkyl group (particularly, a linear or branched C _1-3 alkyl group) and an aryl group having 6 to 10 carbon atoms are among others. preferable.

Among them, the group represented by the formula (1a-I) is preferably a t-butyl group or a (1-methyl-1-phenyl) ethyl group. That is, R ³¹ is preferably a hydrogen atom, a t-butyl group, or a (1-methyl-1-phenyl) ethyl group.

In the above formula (1a), R ³² represents a group represented by the above formula (1a-I) or a group represented by the following formula (1a-II).

In the above formula (1a-II), R ³⁴ represents a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent in R ³⁴ include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, , Halogenated hydrocarbon groups and the like. Examples of the substituent in the hydrocarbon group which may have a substituent include specific examples of the substituent in the hydrocarbon group which may have a substituent as R ³³ described above. Examples of the hydrocarbon group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, and a hexyl group. Group, heptyl group, octyl group, ethylhexyl group, decyl group, dodecyl group and the like, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (linear or branched C _1-20 alkyl group). More preferably, it is a linear or branched C _1-10 alkyl group. In formula (1a-II), p represents an integer of 1 to 20 (preferably an integer of 1 to 8, more preferably an integer of 1 to 6).

R ³³ in the group represented by the formula (1a-I) as R ³² is the same or different and represents a hydrocarbon group which may have a substituent. As the hydrocarbon group which may have the above substituent, the hydrocarbon group which may have a substituent in R ³³ in the group represented by the formula (1a-I) as R ³¹ described above Specific examples are given. Examples of the hydrocarbon group which may have the above-described substituent include a linear or branched alkyl group having 1 to 10 carbon atoms (a linear or branched C _1-10 alkyl group), carbon, among others. An aryl group of several 6 to 10 is preferable. Of the linear or branched C _1-10 alkyl groups, linear or branched C _1-3 alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. That is, as R ³³ , a linear or branched C _1-10 alkyl group (particularly, a linear or branched C _1-3 alkyl group) and an aryl group having 6 to 10 carbon atoms are among others. preferable.

Among the compounds represented by the above formula (1a), R ³¹ is a hydrogen atom, or R ³³ is a linear or branched C _1-10 alkyl group (particularly, a linear or branched C 1 _1-3 is an alkyl group) or a group represented by formula (1a-I) is an aryl group having a carbon number of 6 to 10, R ³² is, R ³³ is a linear or branched C _1-10 alkyl A group represented by the formula (1a-I) which is a group (particularly a linear or branched C _1-3 alkyl group) or an aryl group having 6 to 10 carbon atoms, or R ³⁴ is a linear or branched chain The compound which is a group represented by the formula (1a-II), which is a C _1-20 alkyl group in the form of an integer of 1 to 8 (preferably 1 to 6), is particularly preferable.

Specific examples of the compound represented by the above formula (1a) include compounds represented by the following formulas (1a-III) to (1a-VII). In the following formulas (1a-V) and (1a-VI), Ph represents a phenyl group. Other specific examples of the compound represented by the formula (1a) include a 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) skeleton. Reaction product of carboxylic acid and polyethylene glycol [for example, reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 Etc.].

In the above formula (1b), R ³⁵ represents a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent in R ³⁵ include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, , Halogenated hydrocarbon groups and the like. Among them, an alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an ethylhexyl group, A linear or branched alkyl group having 1 to 10 carbon atoms such as a decyl group (a linear or branched C _1-10 alkyl group) is more preferable, and a linear or branched C _1-8 alkyl group is more preferable. More preferred are groups. Examples of the substituent in the hydrocarbon group which may have a substituent include specific examples of the substituent in the hydrocarbon group which may have a substituent as R ³³ described above. Among these, a hydroxy group and an alkoxy group (more preferably a linear or branched alkoxy group having 1 to 30 carbon atoms, and still more preferably a linear or branched alkoxy group having 1 to 20 carbon atoms) are preferable. Therefore, R ³⁵ is preferably an alkyl group which may have a hydroxy group and / or an alkoxy group.

In the above formula (1b), R ³⁶ and R ³⁷ are the same or different and each represents an aryl group which may have a substituent. Examples of the aromatic ring of the aryl group which may have a substituent include an aromatic hydrocarbon ring (for example, a benzene ring and a naphthalene ring), an aromatic heterocyclic ring (for example, a furan ring, a thiophene ring, and a pyrrole ring). Etc.). Among them, an aromatic hydrocarbon ring is preferable, a benzene ring or a naphthalene ring is more preferable, and a benzene ring is more preferable. Examples of the substituent that the aryl group that may have the above-described substituent include a halogen atom, a hydroxy group, a carboxy group, and a hydrocarbon that may include a linking group. Examples of the hydrocarbon group include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.). . As the hydrocarbon group containing a linking group, two or more of the monovalent substituted or unsubstituted hydrocarbon groups in R ³³ described above are linking groups such as an ether bond, a thioether bond, an ester bond, an amide bond, and a carbonyl group. And a group bonded via the. Examples of the substituent that the aryl group which may have the above substituent include a linear or branched C _1-8 alkyl group, a hydroxy group, and an alkoxy group having 1 to 8 carbon atoms (C _{1- 8} alkoxy groups) are preferred. In addition, the bonding position of the substituent in the aryl group which may have the substituent is not particularly limited, but is in the ortho position and / or the para position with respect to the position bonded to the triazine ring in the formula (1b). Are more preferable, and ortho-position and para-position are more preferable. Further, the number of substituents in the aryl group which may have the above substituent is not particularly limited.

Specific examples of R ³⁶ and R ^{37 in} the above formula (1b) are not particularly limited, but include xylyl group (particularly 2,4-xylyl group), 4- (C _1-8 alkoxy) -2-hydroxyphenyl. The group 2,4-di (C _1-8 alkoxy) phenyl is preferred.

Among the compounds represented by the above formula (1b), among others, R ³⁵ is an alkyl group optionally having a hydroxy group and / or an alkoxy group, and R ³⁶ and R ³⁷ are the same or different, Particularly preferred are compounds that are xylyl groups (particularly 2,4-xylyl groups), 4- (C _1-8 alkoxy) -2-hydroxyphenyl groups, or 2,4-di (C _1-8 alkoxy) phenyl groups. .

Specific examples of the compound represented by the formula (1b) include compounds represented by the following formulas (1b-I) to (1b-III).

In the above formula (1c), R ³⁸ represents a hydrocarbon group that may contain a linking group. Examples of the hydrocarbon group include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.). . As the hydrocarbon group containing a linking group, two or more of the monovalent substituted or unsubstituted hydrocarbon groups in R ³³ described above are linking groups such as an ether bond, a thioether bond, an ester bond, an amide bond, and a carbonyl group. And a group bonded via the. Among them, R ³⁸ is preferably a C _1-10 alkyl group (particularly a C _1-8 alkyl group) or an alkoxy group having 1 to 10 carbon atoms (particularly an alkoxy group having 1 to 8 carbon atoms).

In the above formula (1c), R ³⁹ represents a divalent organic group. Examples of the divalent organic group include alkylene groups such as methylene, ethylene, propylene, and butylene (particularly alkylene groups having 1 to 20 carbon atoms); alkenylene groups such as vinylene (particularly those having 2 to 20 carbon atoms). Alkenylene group); cycloalkenylene group such as cyclopentylene and cyclohexylene group; arylene group such as phenylene group; two or more of these are directly or a linking group (for example, ether bond, thioether bond, ester bond, amide bond, carbonyl) A divalent organic group bonded via a group or the like). These exemplified groups may have a substituent. In addition, these exemplified groups may be substituted with a halogen atom (particularly a fluorine atom).

In the above formula (1c), R ⁴⁰ represents an organic group which may have a substituent. Examples of the organic group which may have a substituent in R ⁴⁰ include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, Halogenated hydrocarbon groups, etc.), and substituted or unsubstituted heterocyclic groups. Moreover, as a substituent in the organic group which may have a substituent, the specific example of the substituent in the hydrocarbon group which may have a substituent as the above-mentioned R ^<33 > is mentioned.

  As the heterocyclic ring in the substituted or unsubstituted heterocyclic group, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, imidazoline ring, pyrazine ring, triazine ring, morpholine ring, indole ring, Nitrogen-containing heterocycles such as isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, pteridine ring, acridine ring, carbazole ring, benzo [c] cinnoline ring, pyrimidine ring, triazole ring A ring is preferable, and a nitrogen atom-containing heterocyclic ring (c) is more preferable. Among the above heterocyclic rings, a piperidine ring is preferable. That is, the above-mentioned substituent or unsubstituted heterocyclic group is preferably a piperidinyl group (for example, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, etc.). The piperidinyl group may have a substituent. The bonding position of the substituent in the piperidinyl group may be on a nitrogen atom or a carbon atom.

Among the compounds represented by the above formula (1c), R ³⁸ is a C _1-10 alkyl group (particularly a C _1-8 alkyl group) or an alkoxy group having 1 to 10 carbon atoms (particularly a carbon number). 1 to 8 alkoxy groups), and R ⁴⁰ preferably includes at least a piperidinyl group optionally having a substituent.

Specific examples of the compound represented by the formula (1c) include compounds represented by the following formulas (1c-I) to (1c-IV).

In the above formula (1d), R ⁴¹ represents an may contain a linking group hydrocarbon group. Examples of the hydrocarbon group include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.). . As the hydrocarbon group containing a linking group, two or more of the monovalent substituted or unsubstituted hydrocarbon groups in R ³³ described above are linking groups such as an ether bond, a thioether bond, an ester bond, an amide bond, and a carbonyl group. And a group bonded via the.

Specific examples of the hydrocarbon group that may contain the linking group in R ⁴¹ include, for example, a hydrocarbon group that may have a substituent, a hydrocarbon group-substituted carbamoyl group (amide bond (—CO A group to which a hydrocarbon group which may have a substituent is bonded via —NH—), a hydrocarbon group-substituted oxycarbonyl group (having a substituent via an ester bond (—CO—O—)). And a hydrocarbon group-substituted oxy group (a group to which a hydrocarbon group which may have a substituent is bonded via an ether bond (—O—)) and the like. It is done. Specific examples of the hydrocarbon group which may have a substituent include the above-described hydrocarbon groups which may have a substituent as R ³³ . As the hydrocarbon group which may contain the linking group, a hydrocarbon group-substituted carbamoyl group is particularly preferable.

Examples of the hydrocarbon group in the hydrocarbon group-substituted carbamoyl group include specific examples of the monovalent substituted or unsubstituted hydrocarbon group as R ³³ described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated group). Hydrocarbon group, etc.), among which an alkyl group (particularly a C _1-8 alkyl group) is preferred. That is, the hydrocarbon group-substituted carbamoyl group is preferably an alkyl group (particularly a C _1-8 alkyl group) -substituted carbamoyl group. In addition, the alkyl group in the substituted carbamoyl group optionally having the substituent may have a substituent, and the substituent has the substituent as R ³³ described above. Specific examples of the substituent in the good hydrocarbon group are mentioned, and among them, an acyloxy group is preferable. The acyloxy group is represented by (—O—CO—R), and R represents a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent in the acyloxy group include saturated aliphatic hydrocarbon groups such as alkyl groups; unsaturated aliphatic hydrocarbon groups such as alkenyl groups; aryl groups and aralkyl groups. An aromatic hydrocarbon group such as an unsaturated aliphatic hydrocarbon group (for example, an alkenyl group such as a vinyl group or an isopropenyl group) is preferable, and an alkenyl group is more preferable. That is, the acyloxy group is preferably an unsaturated aliphatic acyloxy group. Therefore, R ⁴¹ is preferably a group in which an unsaturated aliphatic acyloxy group-substituted alkyl group is bonded via an amide bond.

In the above formula (1d), R ⁴² and R ⁴³ are the same or different and represent a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have the above-described substituent include specific examples of the monovalent substituted or unsubstituted hydrocarbon group as R ³³ described above (for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, Halogenated hydrocarbon group, etc.). Examples of the substituent in the hydrocarbon group which may have a substituent include specific examples of the substituent in the hydrocarbon group which may have a substituent as R ³³ described above. Among these, R ⁴² and R ⁴³ are preferably a C _1-8 alkyl group (particularly a C _1-3 alkyl group).

Among the compounds represented by the above formula (1d), R ⁴¹ is a group in which an unsaturated aliphatic acyloxy group-substituted alkyl group is bonded via an amide bond, and R ⁴² and R ⁴³ are the same or different. A compound having a C _1-8 alkyl group (particularly a C _1-3 alkyl group) is preferred.

Specific examples of the compound represented by the formula (1d) include compounds represented by the following formula (1d-I).

In the above formula (1e), R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the same or different and represent a hydrocarbon group which may contain a linking group. Examples of the hydrocarbon group include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.). . As the hydrocarbon group containing a linking group, two or more of the monovalent substituted or unsubstituted hydrocarbon groups in R ³³ described above are linking groups such as an ether bond, a thioether bond, an ester bond, an amide bond, and a carbonyl group. And a group bonded via the.

Specific examples of the hydrocarbon group that may contain the linking group for R ⁴⁴ include a hydrocarbon group that may have a substituent. Specific examples of the hydrocarbon group which may have a substituent include the above-described hydrocarbon groups which may have a substituent as R ³³ . As the hydrocarbon group which may contain the linking group, an aliphatic hydrocarbon group having an acyl group is preferable, and a saturated aliphatic hydrocarbon group having an acyl group is more preferable. The saturated aliphatic hydrocarbon group is preferably a linear or branched C _1-10 alkyl group. Moreover, as said acyl group, a saturated aliphatic acyl group is preferable and C1-C10 saturated aliphatic acyl groups, such as an acetyl group, a propionyl group, a butyryl group, are more preferable. Accordingly, R ⁴⁴ is preferably a linear or branched C _1-10 alkyl group which may have a saturated aliphatic acyl group (particularly a saturated aliphatic acyl group having 1 to 10 carbon atoms).

Specific examples of the hydrocarbon group that may contain the linking group in R ⁴⁵ and R ⁴⁶ include a hydrocarbon group that may have a substituent. Specific examples of the hydrocarbon group which may have a substituent include the above-described hydrocarbon groups which may have a substituent as R ³³ . As the hydrocarbon group which may contain the linking group, a linear or branched C _1-10 alkyl group (particularly, a linear or branched C _1-3 alkyl group) is particularly preferable. .

As the compound represented by the above formula (1e), among them, R ⁴⁴ may have a saturated aliphatic acyl group (particularly a saturated aliphatic acyl group having 1 to 10 carbon atoms), which may be a straight chain or branched. A linear C _1-10 alkyl group, and R ⁴⁵ and R ⁴⁶ are the same or different and are each a linear or branched C _1-10 alkyl group (particularly a linear or branched C _1-3 alkyl group). The compound which is an alkyl group) is preferable.

Specific examples of the compound represented by the formula (1e) include compounds represented by the following formula (1e-I).

In the above formula (1f), R ⁴⁷ and R ⁴⁸ are the same or different and represent a hydrocarbon group which may contain a linking group. Examples of the hydrocarbon group include specific examples of the monovalent substituted or unsubstituted hydrocarbon group in R ³³ described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.). . As the hydrocarbon group containing a linking group, two or more of the monovalent substituted or unsubstituted hydrocarbon groups in R ³³ described above are linking groups such as an ether bond, a thioether bond, an ester bond, an amide bond, and a carbonyl group. And a group bonded via the.

Specific examples of the hydrocarbon group that may contain the linking group in R ⁴⁷ and R ⁴⁸ include a hydrocarbon group that may have a substituent. Specific examples of the hydrocarbon group which may have a substituent include the above-described hydrocarbon groups which may have a substituent as R ³³ . As the hydrocarbon group which may contain the linking group, a linear or branched C _1-10 alkyl group (particularly, a linear or branched C _1-3 alkyl group) is particularly preferable. Accordingly, in the compound represented by the above formula (1f), R ⁴⁷ and R ⁴⁸ are the same or different and each represents a linear or branched C _1-10 alkyl group (particularly a linear or branched C 1 _1-3 alkyl groups) are preferred.

Specific examples of the compound represented by the formula (1f) include compounds represented by the following formula (1f-I).

  The heterocyclic compound (C) is not particularly limited, but preferably does not have a heterocyclic ring containing a nitrogen atom to which a hydrogen atom is directly bonded. In this case, there is a tendency that the inhibition of curing at the time of curing the curable resin composition hardly occurs.

  The heterocyclic compound (C) is not particularly limited, but preferably does not have a heterocyclic ring containing a sulfur atom. In this case, there is a tendency that the inhibition of curing at the time of curing the curable resin composition hardly occurs.

  In the curable resin composition of the present invention, the heterocyclic compound (C) can be used alone or in combination of two or more. Further, the heterocyclic compound (C) has the trade names “TINUVIN PS”, “TINUVIN 99-2”, “TINUVIN 384-2”, “TINUVIN 900”, “TINUVIN 928”, “TINUVIN 1130” (formula, (Compound represented by (1a)), “TINUVIN 400”, “TINUVIN 405”, “TINUVIN 460” (the compound represented by formula (1b) above), “TINUVIN 123”, “TINUVIN 292”, “TINUVIN” 144 "(compound represented by formula (1c) above) (above, manufactured by BASF Japan Ltd.)," Karenz MOI-BP "(produced by Showa Denko KK, compound represented by formula (1d)) Commercial products such as these can also be obtained.

  When the curable resin composition of the present invention contains the heterocyclic compound (C), the cured product can exhibit a barrier property against corrosive gas on the nitrogen atom contained in the heterocyclic compound (C). This is presumed to prevent the reaction between the electrode and the corrosive gas by coordinate bonding of the unshared electron pairs to silver atoms on the electrode surface of the semiconductor device.

  The content (blending amount) of the heterocyclic compound (C) in the curable resin composition of the present invention is not particularly limited, but is 0.001 to 10 weights with respect to the curable resin composition (100 wt%). % Is preferable, more preferably 0.005 to 5% by weight, and still more preferably 0.01 to 1% by weight. By setting the content of the heterocyclic compound (C) to 0.001% by weight or more, the barrier property against the corrosive gas of the cured product tends to be further improved. On the other hand, when the content of the heterocyclic compound (C) is 10% by weight or less, the heat resistance of the cured product tends to be improved.

[Isocyanurate Compound (D)]
The curable resin composition of the present invention may contain an isocyanurate compound represented by the following formula (2) (sometimes referred to as “isocyanurate compound (D)”). When the curable resin composition of the present invention contains an isocyanurate compound (D), the adhesion of the cured product to the adherend is further improved, and the barrier property against corrosive gas tends to be higher. .

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

In formula (2a), R ⁱ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C _1-8 alkyl group). Examples of the linear or branched C _1-8 alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group, etc. are mentioned. Among the above alkyl groups, linear or branched C _1-3 alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. Among these, as R ⁱ , a hydrogen atom is particularly preferable.

In addition, when two of R ^f , R ^g , and R ^{h in} the formula (2) are groups represented by the formula (2a), these groups represented by the formula (2a) are the same. It may be different or different. Further, the isocyanurate compound (D) may not have the group represented by the formula (2a).

In the formula (2b), R ^j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C _1-8 alkyl group). Examples of the linear or branched C _1-8 alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group, etc. are mentioned. Among the above alkyl groups, linear or branched C _1-3 alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. Among these, as R ^j , a hydrogen atom is particularly preferable.

In addition, when two or three of R ^f , R ^g , and R ^h in the formula (2) are groups represented by the formula (2b), the groups represented by these formulas (2b) are: They may be the same or different.

As the isocyanurate compound (D), for example, one of R ^f , R ^g , and R ^h in the formula (2) is a group represented by the formula (2b) (“monoallyl diglycidyl isocyanurate”). 2) out of R ^f , R ^g , and R ^h in formula (2) (sometimes referred to as a “diallyl monoglycidyl isocyanurate compound”). And a compound in which R ^f , R ^g and R ^h in formula (2) are all represented by formula (2b) (sometimes referred to as “triallyl isocyanurate compound”).

  Specific examples of the monoallyl diglycidyl isocyanurate compound include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, and 1- (2-methyl). Propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, and the like.

  Specific examples of the diallyl monoglycidyl isocyanurate compound include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, and 1,3-bis (2-methyl). And propenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate, and the like.

  Specific examples of the triallyl isocyanurate compound include triallyl isocyanurate and tris (2-methylpropenyl) isocyanurate.

  In the curable resin composition of the present invention, the isocyanurate compound (D) can be used alone or in combination of two or more. The isocyanurate compound (D) can be obtained as a commercial product, for example.

  When the isocyanurate compound (D) has a group represented by the formula (2a), it is used after being modified by reacting with a compound that reacts with an epoxy group such as an alcohol or an acid anhydride. You can also.

  Since the isocyanurate compound (D) has a group represented by the formula (2b), for example, it can be used after previously reacting with a compound having a hydrosilyl group (hydrosilylation reaction). For example, a product obtained by reacting the monoallyl diglycidyl isocyanurate compound with a ladder-type silsesquioxane (H) described below in the presence of a hydrosilylation catalyst is used as a constituent of the curable resin composition of the present invention. You can also

  From the viewpoint of improving the compatibility with other components, the isocyanurate compound (D) can be mixed with the silane coupling agent (F) in advance and then blended with other components as described later.

  When the curable resin composition of the present invention contains an isocyanurate compound (D), the content (blending amount) of the isocyanurate compound (D) in the curable resin composition of the present invention is not particularly limited, but is curable. 0.01-6 weight% is preferable with respect to a resin composition (100 weight%), More preferably, it is 0.05-4 weight%, More preferably, it is 0.08-3 weight%. By setting the content of the isocyanurate compound (D) to 0.01% by weight or more, there is a tendency that the barrier property against the corrosive gas of the cured product and the adhesion to the adherend are further improved. On the other hand, by setting the content of the isocyanurate compound (D) to 6% by weight or less, solid precipitation due to the isocyanurate compound (D) tends to be suppressed in the curable resin composition.

[Isocyanurate compound (E)]
The curable resin composition of the present invention may contain an isocyanurate compound represented by the following formula (3) (sometimes referred to as “isocyanurate compound (E)”). When the curable resin composition of this invention contains an isocyanurate compound (E), the hardened | cured material excellent in the barrier property with respect to corrosive gas can be formed. Moreover, although it is thought that the isocyanurate compound (E) has good solubility in the curable resin composition of the present invention, it is precipitated as a solid even when the amount is increased or when the curable resin composition is not heated. Is less likely to occur.

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

In the formula (3a), R ^d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C _1-8 alkyl group). Examples of the linear or branched C _1-8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, a heptyl group, An octyl group, an ethylhexyl group, etc. are mentioned. Among the above alkyl groups, linear or branched C _1-3 alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. Among these, as R ^d , a hydrogen atom is particularly preferable.

  In formula (3a), s represents an integer of 2 to 10. Especially, the integer of 2-8 is preferable, More preferably, it is an integer of 2-6, More preferably, it is an integer of 2-4. When s is in the above range, suppression of solid precipitation in the curable resin composition and excellent barrier properties against the corrosive gas of the cured product tend to be compatible at a higher level.

In addition, when two or three of R ^a , R ^b and R ^{c in} the formula (3) are groups represented by the formula (3a), the groups represented by these formulas (3a) are: They may be the same or different.

In formula (3b), R ^e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C _1-8 alkyl group). Examples of the linear or branched C _1-8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, a heptyl group, An octyl group, an ethylhexyl group, etc. are mentioned. Among the above alkyl groups, linear or branched C _1-3 alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. Of these examples of R ^e, hydrogen atom is particularly preferred.

  T in Formula (3b) represents an integer of 1 to 10. Among these, an integer of 1 to 6 is preferable.

In addition, when two of R ^a , R ^b and R ^{c in} the formula (3) are groups represented by the formula (3b), the groups represented by the formula (3b) are the same. It may be different or different. Further, the isocyanurate compound (E) may not have the group represented by the formula (3b).

The alkyl group as R ^a , R ^b and R ^c may be linear, branched or cyclic, and is not particularly limited. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl Group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group and the like linear or branched alkyl groups (for example, linear or branched C _1-8 alkyl Group); cyclic alkyl groups (cycloalkyl groups) such as a cyclohexyl group, a methylcyclohexyl group, and a dimethylcyclohexyl group.

  When the curable resin composition of the present invention contains an isocyanurate compound (E), the cured product can exhibit a barrier property against a corrosive gas regardless of a state reacted with other components and an unreacted state. The isocyanurate skeleton in the isocyanurate compound (E) is supposed to trap corrosive gases such as SOx gas in the cured product.

Examples of the isocyanurate compound (E) include a compound in which one of R ^a , R ^b and R ^{c in} the formula (3) is a group represented by the formula (3a), and R ^a in the formula (3) , R ^b , and R ^c are compounds in which two are groups represented by the formula (3a), and all of R ^a , R ^b , and R ^{c in} the formula (3) are represented by the formula (3a) The compound which is group is mentioned. In particular, a compound in which two or three of R ^a , R ^b , and R ^{c in} the formula (3) are groups represented by the formula (3a) is preferable in that solid precipitation is less likely to occur. Is a compound in which all of R ^a , R ^b and R ^{c in} the formula (3) are groups represented by the formula (3a).

  The isocyanurate compound (E) is presumed to have a group represented by the above formula (3a) as an essential group in the molecule, but does not have the group (for example, triglycidyl isocyanate). Other components in the curable resin composition of the present invention compared with those not having the above group, while having an effect of improving the barrier property against corrosive gas equivalent to or better than that of nurate, monoallyl diglycidyl isocyanurate, etc. (In particular, the compatibility with polysiloxane (A) and polysiloxane (B)) is very good. As a result, there is no problem of solid precipitation in the curable resin composition. It can be easily dissolved in these components. For this reason, the productivity of the curable resin composition is improved. In addition, even when the content of the isocyanurate compound (E) is increased, the above-described problem of solid precipitation does not occur. Therefore, the barrier property against the corrosive gas of the cured product due to the increased amount of the isocyanurate compound (E) is remarkable. Improvement is possible.

  The isocyanurate compound (E) can be used after being modified by reacting with a compound that reacts with an epoxy group such as alcohol or acid anhydride.

  When the isocyanurate compound (E) has a group represented by the formula (3b), for example, it can be used after previously reacting with a compound having a hydrosilyl group (hydrosilylation reaction). For example, what was made to react with the ladder type silsesquioxane (H) mentioned later in presence of a hydrosilylation catalyst can also be used as a structural component of the curable resin composition of this invention.

  In the curable resin composition of the present invention, the isocyanurate compound (E) can be used alone or in combination of two or more. The isocyanurate compound (E) can also be obtained from commercial products such as trade name “TEPIC-VL” (manufactured by Nissan Chemical Industries, Ltd.).

  When the curable resin composition of the present invention contains the isocyanurate compound (E), the content (blending amount) of the isocyanurate compound (E) in the curable resin composition of the present invention is not particularly limited, but is curable. The amount is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight, still more preferably 0.05 to 3% by weight, particularly preferably 0.1 to the resin composition (100% by weight). ~ 2% by weight. By setting the content of the isocyanurate compound (E) to 0.01% by weight or more, the barrier property against the corrosive gas of the cured product tends to be further improved. On the other hand, by setting the content of the isocyanurate compound (E) to 10% by weight or less, a cured product that is superior in heat resistance, toughness, transparency, and the like tends to be obtained.

  When the curable resin composition of the present invention contains the isocyanurate compound (D) and the isocyanurate compound (E), the total content (total content) of the isocyanurate compound (D) and the isocyanurate compound (E) is Although not particularly limited, it is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 3% by weight, particularly preferably, based on the curable resin composition. 0.3 to 2% by weight. By making the total content 0.01% by weight or more, the barrier property against the corrosive gas of the cured product tends to be remarkably improved. On the other hand, by setting the content of the total content to 15% by weight or less, the problem of solid precipitation in the curable resin composition tends to be further suppressed.

[Silane coupling agent (F)]
The curable resin composition of the present invention may contain a silane coupling agent (F). When the silane coupling agent (F) is included, the adhesion of the cured product to the adherend tends to be further improved. Furthermore, since the silane coupling agent (F) has good compatibility with the isocyanurate compound (D) (particularly monoallyl diglycidyl isocyanurate compound), ladder type silsesquioxane (H), etc. It is possible to improve the compatibility with other components such as the isocyanurate compound (D). Specifically, for example, when the isocyanurate compound (D) is used, a composition of the isocyanurate compound (D) and the silane coupling agent (F) is formed in advance and then blended with other components. When it is made, a uniform curable resin composition is easy to be obtained.

  As the silane coupling agent (F), a known or conventional silane coupling agent can be used, and is not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxy group-containing silane coupling agent such as 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N- (1,3 Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (β-aminoethyl) -Amino group-containing silane coupling agent such as γ-aminopropylmethyldiethoxysilane; tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxy Silane, vinyltris (methoxyethoxysilane), phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxy Propyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, mercaptopropylenetrimethoxysilane, mercaptopropylenetriethoxysilane, alkoxy oligomer (for example, “ X-41-1053, X-41-1059A, X-41-1056, X-41-1085, X-41-1818, X-41-1810, X- 40-2651 "," X-40-2665A "," KR-513 "," KC-89S "," KR-500 "," X-40-9225 "," X-40-9246 "," X- 40-9250 "; Shin-Etsu Chemical Co., Ltd.) and the like. Among these, an epoxy group-containing silane coupling agent (particularly 3-glycidoxypropyltrimethoxysilane) can be preferably used.

  In the curable resin composition of this invention, a silane coupling agent (F) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, a commercial item can also be used as a silane coupling agent (F).

  When the curable resin composition of the present invention contains a silane coupling agent (F), the content (blending amount) of the silane coupling agent (F) in the curable resin composition of the present invention is not particularly limited, 0.01-15 weight% is preferable with respect to curable resin composition (100 weight%), More preferably, it is 0.1-10 weight%, More preferably, it is 0.5-5 weight%. By setting the content of the silane coupling agent (F) to 0.01% by weight or more, the adhesiveness of the cured product to the adherend tends to be further improved. Moreover, since the solubility in the curable resin composition of an isocyanurate compound (D) can be improved, the further improvement of the barrier property with respect to the corrosive gas of hardened | cured material may be attained. On the other hand, when the content of the silane coupling agent (F) is 15% by weight or less, the curing reaction proceeds sufficiently, and the toughness, heat resistance, and barrier property against corrosive gas of the cured product tend to be further improved. is there.

[Ladder type polyorganosilsesquioxane]
The curable resin composition of the present invention may contain a ladder type polyorganosilsesquioxane. When the curable resin composition of this invention contains ladder type polyorgano silsesquioxane, there exists a tendency for the barrier property with respect to the corrosive gas of hardened | cured material to become higher. The ladder-type polyorganosilsesquioxane is a polysiloxane represented by the empirical formula (Basic Structure) RSiO _1.5, including at least a ladder-like Si-O-Si structure (ladder structure) in a molecule of poly Organosilsesquioxane.

As the ladder-type polyorganosilsesquioxane, known or conventional polyorganosilsesquioxane having the above structure can be used, and is not particularly limited, but one or more (particularly two or more) fats in the molecule. Those having a group carbon-carbon double bond and those having one or more (particularly two or more) hydrosilyl groups in the molecule are preferred. The ladder-type polyorganosilsesquioxane is a side chain [polyorganosilsesquioxane skeleton having a ladder structure that is a main skeleton (main chain) from the viewpoint of barrier properties against the corrosive gas of the cured product ( A part or all of a portion branched from a skeleton formed by a Si—O bond is preferably a substituted or unsubstituted aryl group (aromatic hydrocarbon group). Examples of the substituted or unsubstituted aryl group include a substituted or unsubstituted aryl group exemplified as R ⁵ described later.

  Among these, as the ladder-type polyorganosilsesquioxane, ladder-type silsesquioxane (G) and ladder-type silsesquioxane, which will be described below, from the viewpoints of barrier properties against corrosive gas of cured products, mechanical strength, and the like. Sun (H) is particularly preferred.

(Ladder type silsesquioxane (G))
The ladder-type silsesquioxane (G) as the ladder-type polyorganosilsesquioxane is a part or all of the molecular chain terminal of the polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) having a ladder structure. And a polyorganosilsesquioxane residue (“polyorganosilsesquioxane residue (a)”) containing a unit structure represented by the following formula (V) and a unit structure represented by the formula (VI): A polyorganosilsesquioxane having a composition).

The polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) in the ladder-type silsesquioxane (G) is a polysiloxane represented by an empirical formula (basic structural formula) R ⁵ SiO _1.5 . Incidentally, R ⁵ is a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen-containing group, and monovalent nitrogen-containing group, or a sulfur atom-containing monovalent radical, R ⁵ (the poly At least a part of R ⁵ ) in the organosilsesquioxane is a monovalent organic group. R ⁵ in the polyorganosilsesquioxane may be the same or different.

Examples of the halogen atom in R ⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the monovalent organic group in R ⁵ include a substituted or unsubstituted hydrocarbon group (monovalent hydrocarbon group), an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, and an alkylthio group. Groups, alkenylthio groups, arylthio groups, aralkylthio groups, carboxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, epoxy groups, cyano groups, isocyanate groups, carbamoyl groups, isothiocyanate groups, etc. It is done.

Examples of the hydrocarbon group for R ⁵ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

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

Examples of the alicyclic hydrocarbon group in R ⁵ include C _3-12 cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group; and C ₃₋ groups such as a cyclohexenyl group. ₁₂ cycloalkenyl groups; C _4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl group and bicycloheptenyl group.

Examples of the aromatic hydrocarbon group for R ⁵ include aryl groups such as phenyl group and naphthyl group (for example, C _6-14 aryl group, particularly C _6-10 aryl group).

In addition, examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group in R ⁵ are bonded to each other include a cyclohexylmethyl group, a methylcyclohexyl group, and the like. Examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded include, for example, C _7-18 aralkyl groups such as benzyl group and phenethyl group (particularly C _7-10 aralkyl groups), and C such as cinnamyl group. _Examples thereof include C _1-4 alkyl-substituted aryl groups such as _6-10 aryl-C _2-6 alkenyl groups and tolyl groups, and C _2-4 alkenyl-substituted aryl groups such as styryl groups.

The hydrocarbon group in R ⁵ may be a hydrocarbon group having a substituent (substituted hydrocarbon group). As for carbon number of the substituent in the said substituted hydrocarbon group, 0-20 are preferable, More preferably, it is 0-10. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C _1-6 alkoxy group, more preferably C _1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C _2-6 alkenyloxy group, more preferably C _2-4 alkenyloxy group) The aromatic ring may have a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group, such as a phenoxy group, a tolyloxy group, or a naphthyloxy group; Aryloxy groups (preferably C _6-14 aryloxy groups); aralkyloxy groups such as benzyloxy groups and phenethyloxy groups (preferably C _{7-1 8} aralkyloxy groups); acyloxy groups such as acetyloxy groups, propionyloxy groups, (meth) acryloyloxy groups, and benzoyloxy groups (preferably C _1-12 acyloxy groups); mercapto groups; alkylthio groups such as methylthio groups and ethylthio groups Group (preferably C _1-6 alkylthio group, more preferably C _1-4 alkylthio group); alkenylthio group such as allylthio group (preferably C _2-6 alkenylthio group, more preferably C _2-4 alkenylthio group) ); Aromatic ring such as phenylthio group, tolylthio group, naphthylthio group and the like may have a substituent such as C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. Arylthio groups (preferably C _6-14 arylthio groups); aralkylthio groups such as benzylthio groups and phenethylthio groups (preferably C _{7-1 8} aralkylthio group); carboxy group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group (preferably C _1-6 alkoxy-carbonyl group); phenoxycarbonyl group, tolyloxycarbonyl group An aryloxycarbonyl group such as a naphthyloxycarbonyl group (preferably a C _6-14 aryloxy-carbonyl group); an aralkyloxycarbonyl group such as a benzyloxycarbonyl group (preferably a C _7-18 aralkyloxy-carbonyl group); Groups: mono- or dialkylamino groups (preferably mono- or di-C _1-6 alkylamino groups) such as methylamino group, ethylamino group, dimethylamino group, diethylamino group; acetylamino group, propionylamino group, benzoylamino An acylamino group such as a cyano group (preferably a C _1-11 acylamino group); an epoxy group-containing group such as a glycidyloxy group; an oxetanyl group-containing group such as an ethyloxetanyloxy group; an acyl group such as an acetyl group, a propionyl group, or a benzoyl group An oxo group; a group in which two or more of these are bonded via a C _1-6 alkylene group as necessary. The number of substituents that the substituted hydrocarbon group has is not particularly limited.

Examples of the monovalent oxygen atom-containing group in R ⁵ include a hydroxy group, a hydroperoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an isocyanate group, a sulfo group, and a carbamoyl group. Can be mentioned. Examples of the monovalent nitrogen atom-containing group include an amino group or a substituted amino group (mono or dialkylamino group, acylamino group, etc.), a cyano group, an isocyanate group, an isothiocyanate group, a carbamoyl group, and the like. Examples of the monovalent sulfur atom-containing group include a mercapto group (thiol group), a sulfo group, an alkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, and an isothiocyanate group. The monovalent organic group, the monovalent oxygen atom-containing group, the monovalent nitrogen atom-containing group, and the monovalent sulfur atom-containing group described above can overlap each other.

Furthermore, as said R < ⁵ >, group represented by a following formula (s) is mentioned.

The formula R ⁵¹ (3 one R ⁵¹⁾ in (s) are the same or different, a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen-containing group, Alternatively, a monovalent sulfur atom-containing group is shown, and examples of these groups include the same groups as those exemplified as R ⁵ above.

In the group represented by the formula (s), each R ⁵¹ is a hydrogen atom; a C _1-10 alkyl group (particularly a C _1-4 alkyl group); a C _2-10 alkenyl group (particularly a C 1 _2-4 alkenyl group); C _3-12 cycloalkyl group; C _3-12 cycloalkenyl group; C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. on the aromatic ring A C _6-14 aryl group which may have a substituent of C _6-18 aralkyl group; a C _6-10 aryl-C _2-6 alkenyl group; a hydroxy group; a C _1-6 alkoxy group; preferable.

Among the above, R ⁵ is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group, still more preferably an aliphatic hydrocarbon group (particularly an alkyl group). ), An aromatic hydrocarbon group (particularly a phenyl group).

  Generally, polyorganosilsesquioxane has a ladder-like Si—O—Si structure (ladder structure), a cage-like Si—O—Si structure (cage structure), and a random-like Si—O—Si structure. (Random structure) and the like. The polyorganosilsesquioxane in the ladder-type silsesquioxane (G) is a polyorganosilsesquioxane containing at least the ladder structure (polyorganosilsesquioxane having a ladder structure). Sun).

The polyorganosilsesquioxane in ladder type silsesquioxane (G) is represented by the following formula (L), for example.

In the above formula (L), v represents an integer of 1 or more (for example, 1 to 5000), preferably an integer of 1 to 2000, and more preferably an integer of 1 to 1000. R ⁵ in the formula (L) represents the same as R ⁵ described above. T represents a terminal group.

In the ladder-type silsesquioxane (G), a group directly bonded to a silicon atom in the polyorganosilsesquioxane (R ⁵ in the above empirical formula, for example, R ⁵ (side chain) in the formula (L)) is particularly Although not limited, the ratio of the substituted or unsubstituted hydrocarbon group to the total amount (100 mol%) of the above group is preferably 50 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol%. That's it. In particular, a substituted or unsubstituted linear or branched C _1-10 alkyl group (especially a linear or branched C ₁ such as a methyl group or an ethyl group) with respect to the total amount (100 mol%) of the above group. _-4 alkyl group), substituted or unsubstituted C _6-10 aryl group (particularly phenyl group), substituted or unsubstituted C _7-10 aralkyl group (particularly benzyl group) is 50 mol% or more More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more.

In particular, from the viewpoint of the barrier property against the corrosive gas of the cured product, the ladder-type silsesquioxane (G) is branched from a polyorganosilsesquioxane skeleton having a ladder structure that is a side chain [main skeleton (main chain)]. For example, part or all of R ⁵ ] in the above formula (L) is preferably a substituted or unsubstituted aryl group (aromatic hydrocarbon group).

  The ladder-type silsesquioxane (G) has at least a polyorganosilsesquioxane residue (a) at a part or all of the molecular chain ends of the polyorganosilsesquioxane having the ladder structure. When the polyorganosilsesquioxane is represented by the above formula (L), the ladder-type silsesquioxane (G) is a polyorganosilsesquioxane in which a part or all of T in the formula (L) is It has a structure substituted with a sun residue (a).

で表される単位構造（シロキサン単位構造）及び下記式（VI）

で表される単位構造（シロキサン単位構造）を少なくとも含む残基である。 The polyorganosilsesquioxane residue (a) is represented by the following formula (V)

The unit structure represented by (siloxane unit structure) and the following formula (VI)

Is a residue containing at least a unit structure represented by (siloxane unit structure).

R ⁶ in the above formula (V) represents a group having an aliphatic carbon-carbon double bond. Examples of the group having an aliphatic carbon-carbon double bond include a vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-4 alkenyl groups) such as 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and 5-hexenyl group Group); C _3-12 cycloalkenyl group such as cyclohexenyl group; C _4-15 bridged cyclic unsaturated hydrocarbon group such as bicycloheptenyl group; C _2-4 alkenyl-substituted aryl group such as styryl group; cinnamyl Groups and the like. In the group having an aliphatic carbon-carbon double bond, in the group represented by the above formula (s), at least one of three R ⁵¹ is the above C _2-20 alkenyl group, C _3- Also included are groups such as ₁₂ cycloalkenyl groups, C _4-15 bridged cyclic unsaturated hydrocarbon groups, C _2-4 alkenyl substituted aryl groups, cinnamyl groups, and the like. Among them, R ⁶ is preferably an alkenyl group, more preferably a C _2-20 alkenyl group, and still more preferably a vinyl group.

R ⁷ in the above formula (VI) is the same or different and represents a hydrocarbon group (monovalent hydrocarbon group). Examples of the hydrocarbon group include the same hydrocarbon groups as those exemplified as R ⁵ above. Among them, R ⁷ is preferably a C _1-20 alkyl group, more preferably a C _1-10 alkyl group, still more preferably a C _1-4 alkyl group, and particularly preferably a methyl group. In particular, it is preferable that all R ⁷ in the formula (VI) is a methyl group.

で表される単位構造（シロキサン単位構造）を有していてもよい。 In addition to the unit structure represented by the formula (V) and the unit structure represented by the formula (VI), the polyorganosilsesquioxane residue (a) includes, for example, the following formula (V ′):

It may have a unit structure represented by (siloxane unit structure).

R ⁶ ′ in the above formula (V ′) represents a monovalent group excluding a group having an aliphatic carbon-carbon double bond. Specifically, for example, a monovalent organic group excluding a hydrogen atom, a halogen atom, a group having an aliphatic carbon-carbon double bond, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or one And valent sulfur atom-containing groups.

  The amount of the silicon atom bonded to the three oxygen atoms represented by the formula (V) in the polyorganosilsesquioxane residue (a) is not particularly limited, but the polyorganosilsesquioxane residue (a) The amount is preferably 20 to 80 mol%, more preferably 25 to 60 mol%, based on the total amount of silicon atoms (100 mol%). If the content is less than 20 mol%, the amount of aliphatic carbon-carbon double bonds (particularly alkenyl groups) possessed by the ladder-type silsesquioxane (G) becomes insufficient, and the hardness of the cured product is reduced. You may not get enough. On the other hand, when the content exceeds 80 mol%, since many silanol groups and hydrolyzable silyl groups remain in the ladder-type silsesquioxane (G), the ladder-type silsesquioxane (G) is obtained in a liquid state. It may not be possible. Furthermore, since the condensation reaction proceeds and the molecular weight easily changes, the storage stability may deteriorate.

  The amount of silicon atom bonded to one oxygen atom represented by the formula (VI) in the polyorganosilsesquioxane residue (a) is not particularly limited, but the polyorganosilsesquioxane residue (a) It is preferably 20 to 85 mol%, more preferably 30 to 75 mol%, based on the total amount (100 mol%) of silicon atoms constituting the. If the content is less than 20 mol%, silanol groups and hydrolyzable silyl groups are likely to remain in the ladder-type silsesquioxane (G), and the ladder-type silsesquioxane (G) cannot be obtained in liquid form. There is a case. Furthermore, since the condensation reaction proceeds and the molecular weight easily changes, the storage stability may deteriorate. On the other hand, if the content exceeds 85 mol%, the amount of aliphatic carbon-carbon double bonds (particularly alkenyl groups) possessed by the ladder-type silsesquioxane (G) becomes insufficient, and the hardness of the cured product May not be sufficient.

  The Si—O—Si structure (skeleton) of the polyorganosilsesquioxane residue (a) is not particularly limited, and examples thereof include a ladder structure, a cage structure, and a random structure.

Ladder type silsesquioxane (G) can be represented by the following formula (L ^a ), for example. V in the formula (L ^a), as is R ^5, those similar to the above formula (L) can be exemplified. A in the formula (L ^a ) represents a polyorganosilsesquioxane residue (a), or a hydroxy group, a halogen atom, an alkoxy group, or an acyloxy group. Oxan residue (a). Incidentally, represented by formula If (L ^a) A plurality (two to four) in is polyorganosilsesquioxane residues (a), each A is each other or other formula (L ^a) May be bonded to A of one molecule through one or more Si—O—Si bonds.

  The polyorganosilsesquioxane residue (a) in the ladder-type silsesquioxane (G) further has a unit structure represented by the formula (VII) in the ladder-type silsesquioxane (H) described later. You may have. In this case, the ladder-type silsesquioxane (G) may be used as the ladder-type silsesquioxane (H).

  The method for producing the ladder-type silsesquioxane (G) is not particularly limited. For example, the ladder-type silsesquioxane (G) has a ladder structure and has a silanol group and / or a hydrolyzable silyl group (silanol group and hydrolyzable silyl group at the molecular chain terminal). The method of forming the said polyorgano silsesquioxane residue (a) with respect to the molecular chain terminal of the polyorgano silsesquioxane which has any one or both of these is mentioned. Specifically, it can be produced by a method disclosed in a document such as International Publication No. 2013/176238.

  In the ladder-type silsesquioxane (G), the number of aliphatic carbon-carbon double bonds (particularly alkenyl groups) in the molecule is not particularly limited, but is preferably 2 or more (for example, 2 to 50). More preferably, it is 2-30. By having an aliphatic carbon-carbon double bond (especially an alkenyl group) within the above-mentioned range, a cured product excellent in various physical properties such as heat resistance, crack resistance, and barrier properties against corrosive gas tends to be obtained. There is.

  Although content of the aliphatic carbon-carbon double bond in ladder type silsesquioxane (G) is not specifically limited, 0.7-5.5 mmol / g is preferable, More preferably, 1.1-4. 4 mmol / g. Moreover, the ratio (weight basis) of the aliphatic carbon-carbon double bond contained in the ladder-type silsesquioxane (G) is not particularly limited, but is 2.0 to 15.0% by weight in terms of vinyl group. Preferably, it is 3.0 to 12.0% by weight.

  The molecular weight of the ladder-type silsesquioxane (G) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 10,000, and particularly preferably 500 to 8,000. If the molecular weight of the ladder-type silsesquioxane (G) is in this range, it tends to be liquid at room temperature and its viscosity tends to be relatively low, and therefore it tends to be easy to handle. The ladder-type silsesquioxane (G) may be a mixture of those having various molecular weights within the above range. The molecular weight is measured as a molecular weight in terms of standard polystyrene by gel permeation chromatography.

  The weight average molecular weight (Mw) of the ladder type silsesquioxane (G) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 10,000, and particularly preferably 500. ~ 8000. There exists a tendency for the heat resistance of hardened | cured material to improve that a weight average molecular weight is 100 or more. On the other hand, when the molecular weight is 800,000 or less, the compatibility with other components tends to be improved. In addition, the said weight average molecular weight is computed from the molecular weight of standard polystyrene conversion by gel permeation chromatography.

  The ladder type silsesquioxane (G) is not particularly limited, but is preferably liquid at room temperature (about 25 ° C.). More specifically, the viscosity of the ladder-type silsesquioxane (G) at 23 ° C. is preferably 100 to 100,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1000 to 8000 mPa · s. s. There exists a tendency for the heat resistance of hardened | cured material to improve that a viscosity is 100 mPa * s or more. On the other hand, when the viscosity is 100,000 mPa · s or less, the curable resin composition tends to be easily prepared and handled. The viscosity at 23 ° C. was measured using a rheometer (trade name “PhysicaUDS-200”, manufactured by Anton Paar) and a cone plate (cone diameter: 16 mm, taper angle = 0 °), temperature: 23 ° C., rotational speed: It is measured at 20 rpm.

  In the curable resin composition of the present invention, the ladder-type silsesquioxane (G) can be used alone or in combination of two or more.

  When the curable resin composition of the present invention contains a ladder-type silsesquioxane (G), the content (blending amount) of the ladder-type silsesquioxane (G) in the curable resin composition of the present invention is particularly Although not limited, 1-40 weight% is preferable with respect to curable resin composition (100 weight%), More preferably, it is 5-30 weight%, More preferably, it is 10-20 weight%. By making the content 1% by weight or more, the barrier property against the corrosive gas of the cured product tends to be further improved. On the other hand, by setting the content to 40% by weight or less, the cured product does not become too hard, and a cured product having excellent flexibility tends to be obtained.

(Ladder type silsesquioxane (H))
The ladder-type silsesquioxane (H) in the curable resin composition of the present invention is a part or all of the molecular chain terminal of the polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) having a ladder structure. A polyorganosilsesquioxane residue containing a unit structure represented by the formula (VII) and a unit structure represented by the formula (VIII) (hereinafter referred to as “polyorganosilsesquioxane residue (b)”) Is a polyorganosilsesquioxane.

The polyorganosilsesquioxane in the ladder-type silsesquioxane (H) is a polysiloxane represented by an empirical formula (basic structural formula) R ⁵ SiO _1.5 . Examples of the polyorganosilsesquioxane in the ladder type silsesquioxane (H) include polyorganosilsesquioxanes in the ladder type silsesquioxane (G) (for example, polyorganosyl represented by the above formula (L)). Examples thereof are similar to those of sesquioxane).

  The ladder-type silsesquioxane (H) is similar to the ladder-type silsesquioxane (G), particularly in terms of the barrier property against the corrosive gas of the cured product, in which part or all of the side chain is substituted or absent. It is preferably a substituted aryl group.

  When the polyorganosilsesquioxane is represented by the above formula (L), the ladder-type silsesquioxane (H) is a polyorganosilsesquioxane in which a part or all of T in the formula (L) is It has a structure substituted with a sun residue (b).

で表される単位構造（シロキサン単位構造）及び下記式（VIII）

で表される単位構造（シロキサン単位構造）を少なくとも含む残基である。なお、上記式（VII）で表される単位構造中の有機基（−Ｘ−ＣＨＲ⁸−ＣＲ⁸ ₂−［ＳｉＲ⁹ ₂−Ｏ−］_n−ＳｉＨＲ⁹ ₂）を、「ＳｉＨ含有基」と称する場合がある。 The polyorganosilsesquioxane residue (b) is represented by the following formula (VII)

The unit structure represented by (siloxane unit structure) and the following formula (VIII)

Is a residue containing at least a unit structure represented by (siloxane unit structure). The organic group (—X—CHR ⁸ —CR ⁸ ₂ — [SiR ⁹ ₂ —O—] _n —SiHR ⁹ ₂ ) in the unit structure represented by the above formula (VII) is referred to as “SiH containing group”. Sometimes called.

  In the above formula (VII), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether group (ether bond), a thioether group (thioether bond), an ester group (ester bond), a carbonate group (carbonate bond), and an amide group (amide). Bond), a group in which a plurality of these are linked, and the like.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. And divalent cycloalkylene groups (including cycloalkylidene groups) such as a silylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

R ⁸ in the above formula (VII) is the same or different and contains a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom. Indicates a group. Examples of R ⁸ include the same groups as those exemplified as R ⁵ above. Among them, each R ⁸ is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a hydrogen atom.

R ⁹ in the above formula (VII) is the same or different and contains a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom Indicates a group. Examples of R ⁹ include the same groups as those exemplified as R ⁵ above. When n in the formula (VII) is an integer of 2 or more, R ⁹ in each parenthesis to which n is attached may be the same or different.

Among the above, each R ⁹ is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group, still more preferably an aliphatic hydrocarbon group (particularly, Methyl group) and aromatic hydrocarbon group (particularly phenyl group).

  N in the formula (VII) represents an integer of 1 to 100, preferably an integer of 1 to 30, more preferably an integer of 1 to 10, and further preferably an integer of 1 to 5. When n is too large, the barrier property against the gas (particularly corrosive gas) of the cured product tends to be lowered, and therefore, for example, it may not be suitable as a sealant for an optical semiconductor element.

R ¹⁰ in the above formula (VIII) is the same or different and represents a hydrocarbon group (monovalent hydrocarbon group). As said hydrocarbon group, the hydrocarbon group similar to what was illustrated in said R < ⁵ > is illustrated. Among them, R ¹⁰ is preferably a C _1-20 alkyl group, more preferably a C _1-10 alkyl group, still more preferably a C _1-4 alkyl group, and particularly preferably a methyl group. In particular, it is preferred that all of R ¹⁰ in formula (VIII) are methyl groups.

  The polyorganosilsesquioxane residue (b) is represented by, for example, the above formula (V ′) in addition to the unit structure represented by the formula (VII) and the unit structure represented by the formula (VIII). It may have a unit structure.

  The amount of silicon atoms (not including silicon atoms in the SiH-containing group) to which the three oxygen atoms in formula (VII) are bonded in the polyorganosilsesquioxane residue (b) is not particularly limited. 20-80 mol% is preferable with respect to the total amount (100 mol%) of the silicon atom which comprises an organosilsesquioxane residue (b), More preferably, it is 25-60 mol%. If the content is less than 20 mol%, the amount of hydrosilyl group contained in the ladder-type silsesquioxane (H) becomes insufficient, and sufficient hardness of the cured product may not be obtained. On the other hand, when the content exceeds 80 mol%, since many silanol groups and hydrolyzable silyl groups remain in the ladder-type silsesquioxane (H), the ladder-type silsesquioxane (H) is obtained in a liquid state. It may not be possible. Furthermore, since the condensation reaction proceeds and the molecular weight easily changes, the storage stability may deteriorate.

  The amount of the silicon atom bonded to one oxygen atom in the formula (VIII) in the polyorganosilsesquioxane residue (b) is not particularly limited, but constitutes the polyorganosilsesquioxane residue (b). The amount is preferably 20 to 85 mol%, more preferably 30 to 75 mol%, based on the total amount of silicon atoms (100 mol%). When the content is less than 20 mol%, silanol groups and hydrolyzable silyl groups are likely to remain in the ladder-type silsesquioxane (H), and the ladder-type silsesquioxane (H) cannot be obtained in liquid form. There is a case. Furthermore, since the condensation reaction proceeds and the molecular weight easily changes, the storage stability may deteriorate. On the other hand, if the content exceeds 85 mol%, the amount of hydrosilyl group contained in the ladder-type silsesquioxane (H) becomes insufficient, and the hardness of the cured product may not be sufficiently obtained.

  The Si—O—Si structure (skeleton) of the polyorganosilsesquioxane residue (b) is not particularly limited, and examples thereof include a ladder structure, a cage structure, and a random structure.

Polyorganosilsesquioxane (H) can be represented by the following formula (L ^b ), for example. Examples of v and R ⁵ in the formula (L ^b ) are the same as those in the above formula (L). B in the formula (L ^b ) represents a polyorganosilsesquioxane residue (b), or a hydroxy group, a halogen atom, an alkoxy group, or an acyloxy group, and a part of B in the formula (L ^b ) Or all are polyorganosilsesquioxane residues (b). Note that Table in formula (L ^b) a plurality of in case R ^b in (2-4) is a polyorganosilsesquioxane residues (b), each B is each other or other formula (L ^b) May be bonded to B of the molecule to be bonded through one or more Si—O—Si bonds.

  The polyorganosilsesquioxane residue (b) in the ladder-type silsesquioxane (H) further has a unit structure represented by the formula (V) in the ladder-type silsesquioxane (G). You may have. In this case, the ladder-type silsesquioxane (H) may be used as the ladder-type silsesquioxane (G).

  Although the manufacturing method of ladder type silsesquioxane (H) is not specifically limited, For example, polyorgano silsesquioxane which has a ladder structure and has a silanol group and / or a hydrolyzable silyl group at the molecular chain terminal ( The method of forming the said polyorgano silsesquioxane residue (b) with respect to the molecular chain terminal of (raw material ladder polymer) is mentioned. Specifically, it can be produced by a method disclosed in a document such as International Publication No. 2013/176238.

  In the ladder type silsesquioxane (H), the number of the SiH-containing groups in the molecule (in one molecule) is not particularly limited, but is preferably 2 or more (for example, 2 to 50), more preferably 2 ~ 30. By having the SiH-containing group within the above range, the heat resistance of the cured product of the curable resin composition tends to be improved.

Although content of the hydrosilyl group which ladder type silsesquioxane (H) has is not specifically limited, 0.01-0.5 mmol / g is preferable, More preferably, it is 0.08-0.28 mmol / g. In addition, the content of the hydrosilyl group based on the weight of the ladder-type silsesquioxane (H) is not particularly limited, but is 0.01 to 0. 50 weight% is preferable, More preferably, it is 0.08 to 0.28 weight%. If the content of the hydrosilyl group is too small (for example, less than 0.01 mmol / g and less than 0.01% by weight in terms of H), curing of the curable resin composition may not proceed. On the other hand, if the content of the hydrosilyl group is too large (for example, exceeding 0.50 mmol / g, exceeding 0.50% by weight in terms of H), the hardness of the cured product becomes high and may be easily cracked. The content of hydrosilyl group in the ladder-type silsesquioxane (H), for example, can be calculated by ¹ H-NMR spectrum measurement and the like.

  In addition, the ratio of the SiH-containing group with respect to the total amount (100 mol%) of the hydrosilyl group of the ladder-type silsesquioxane (H) is not particularly limited, but is preferably 50 to 100 mol% from the viewpoint of the degree of curing. Preferably it is 80-100 mol%.

  The molecular weight of the ladder-type silsesquioxane (H) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 10,000, and particularly preferably 500 to 9000. When the molecular weight of the ladder-type silsesquioxane (H) is within this range, it tends to be liquid at room temperature and its viscosity tends to be relatively low, so that it tends to be easy to handle. The ladder-type silsesquioxane (H) may be a mixture of those having various molecular weights within the above range. The molecular weight is measured as a molecular weight in terms of standard polystyrene by gel permeation chromatography.

  The weight average molecular weight (Mw) of the ladder type silsesquioxane (H) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 10,000, and particularly preferably 500. ~ 9000. There exists a tendency for the heat resistance of hardened | cured material to improve that a weight average molecular weight is 100 or more. On the other hand, when the molecular weight is 800,000 or less, the compatibility with other components tends to be improved. In addition, the said weight average molecular weight is computed from the molecular weight of standard polystyrene conversion by gel permeation chromatography.

  The ladder type silsesquioxane (H) is not particularly limited, but is preferably liquid at room temperature (about 25 ° C.). More specifically, the viscosity of the ladder-type silsesquioxane (H) at 23 ° C. is preferably 100 to 100,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1000 to 8000 mPa · s. s. There exists a tendency for the heat resistance of hardened | cured material to improve that a viscosity is 100 mPa * s or more. On the other hand, when the viscosity is 100,000 mPa · s or less, the curable resin composition tends to be easily prepared and handled. The viscosity at 23 ° C. is measured by the same method as that for the ladder type silsesquioxane (G).

  In addition, ladder type silsesquioxane (H) can also be used individually by 1 type in the curable resin composition of this invention, and can also be used in combination of 2 or more type.

  When the curable resin composition of the present invention contains a ladder-type silsesquioxane (H), the content (blending amount) of the ladder-type silsesquioxane (H) in the curable resin composition of the present invention is particularly Although not limited, 1-30 weight% is preferable with respect to curable resin composition (100 weight%), More preferably, it is 3-20 weight%, More preferably, it is 5-15 weight%. By making the content 1% by weight or more, the barrier property against the corrosive gas of the cured product tends to be further improved. Moreover, there exists a tendency for the hardened | cured material with higher hardness to be obtained because the quantity of the hydrosilyl group in curable resin composition increases and hardening reaction fully advances. On the other hand, by setting the content to 30% by weight or less, the cured product does not become too hard, and a cured product having excellent flexibility tends to be obtained.

(Other ladder-type silsesquioxanes)
Examples of the ladder-type polyorganosilsesquioxane include ladder-type silsesquioxanes (G) and ladder-type silsesquioxanes other than the ladder-type silsesquioxane (H) (“other ladder-type silsesquioxanes”). May also be used). In particular, the other ladder-type silsesquioxane is preferably used in combination with ladder-type silsesquioxane (G) or ladder-type silsesquioxane (H).

  Examples of the other ladder-type silsesquioxanes include ladder-type silsesquioxanes (“ladder-type silsesquioxanes” which are solid at 25 ° C. and have an aliphatic carbon-carbon double bond (particularly an alkenyl group). Oxane (S1) ”); a ladder-type silsesquioxane that is solid at 25 ° C. and has a hydrosilyl group (sometimes referred to as“ ladder-type silsesquioxane (S2) ”). Can be mentioned. When the curable resin composition of the present invention contains ladder-type silsesquioxane (S1) and / or (S2), the barrier property against the corrosive gas of the cured product is improved, and the toughness ( In particular, the crack resistance tends to be improved.

  In the ladder-type silsesquioxane (S1), the number of aliphatic carbon-carbon double bonds (particularly alkenyl groups) in the molecule is not particularly limited, but is preferably 2 or more (for example, 2 to 50). More preferably, it is 2-30. Further, the position of the aliphatic carbon-carbon double bond (particularly, alkenyl group) in the ladder-type silsesquioxane (S1) is not particularly limited, and may be a side chain or a terminal. .

  The number of hydrosilyl groups in the molecule in the ladder-type silsesquioxane (S2) is not particularly limited, but is preferably 2 or more (for example, 2 to 50), more preferably 2 to 30. In addition, the position of the hydrosilyl group in the ladder-type silsesquioxane (S2) is not particularly limited, and may be a side chain or a terminal.

  Although each weight average molecular weight (Mw) of ladder type silsesquioxane (S1) and (S2) is not specifically limited, 2000-800,000 are preferable, More preferably, it is 6000-100,000. When the weight average molecular weight is 2000 or more, the barrier property against the corrosive gas of the cured product tends to be further improved. On the other hand, when the molecular weight is 800,000 or less, the compatibility with other components tends to be improved. In addition, the said weight average molecular weight is computed from the molecular weight of standard polystyrene conversion by gel permeation chromatography.

  Ladder-type silsesquioxanes (S1) and (S2) can be produced by a known or conventional method for producing ladder-type silsesquioxanes (for example, a sol-gel method using a trifunctional silane compound as a raw material).

  When the curable resin composition of the present invention includes a ladder-type silsesquioxane (S1), the content of the ladder-type silsesquioxane (S1) is not particularly limited. For example, the curable resin composition (100 % By weight) can be appropriately adjusted within a range of 0.1 to 30% by weight. Further, the content of the ladder-type silsesquioxane (S2) when the curable resin composition of the present invention contains the ladder-type silsesquioxane (S2) is not particularly limited, and for example, the curable resin composition It can be suitably adjusted in the range of 0.1 to 30% by weight with respect to (100% by weight).

  Examples of the other ladder-type silsesquioxanes include, for example, two or more aliphatic carbon-carbon double bonds (particularly, alkenyl groups) or intramolecularly disclosed in International Publication No. 2013/176238. Having a number average molecular weight (Mn) of 500 to 1500 in terms of standard polystyrene by gel permeation chromatography, and a molecular weight dispersity (Mw / Mn) of 1.00 to 1.40. Ladder type silsesquioxane or the like can also be used. By using such ladder-type silsesquioxane, there is a tendency that the barrier property against the corrosive gas of the cured product is remarkably improved. Content of the said ladder type silsesquioxane is not specifically limited, For example, it can adjust suitably in 0.1-15 weight% with respect to curable resin composition (100 weight%).

  In the curable resin composition of the present invention, the ladder-type polyorganosilsesquioxane can be used alone or in combination of two or more. In particular, it is preferable to use a ladder type silsesquioxane (G) and a ladder type silsesquioxane (H) in combination from the viewpoint of the barrier property against the corrosive gas of the cured product.

  When the curable resin composition of the present invention contains a ladder-type polyorganosilsesquioxane, the content (blending amount) of the ladder-type polyorganosilsesquioxane in the curable resin composition of the present invention is not particularly limited. However, it is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight with respect to the curable resin composition (100% by weight). By setting the content of the ladder-type polyorganosilsesquioxane to 1% by weight or more, the barrier property against the corrosive gas of the cured product tends to be further improved. On the other hand, when the content of the ladder-type polyorganosilsesquioxane is 50% by weight or less, the mechanical strength such as toughness of the cured product tends to be further improved.

  The curable resin composition of the present invention is selected from the group consisting of the ladder-type polyorganosilsesquioxane and the isocyanurate compound (D), particularly from the viewpoint of significantly increasing the barrier property against the corrosive gas of the cured product. It is preferable to include at least one (the ladder-type polyorganosilsesquioxane and / or isocyanurate compound (D)).

[Hydrosilylation catalyst]
The curable resin composition of the present invention may contain a hydrosilylation catalyst. When the curable resin composition of the present invention contains a hydrosilylation catalyst, the hydrosilyl group between the aliphatic carbon-carbon double bond (particularly, alkenyl group) and the hydrosilyl group in the curable resin composition is heated by heating. There is a tendency that the chemical reaction can proceed more efficiently.

  Examples of the hydrosilylation catalyst include known hydrosilylation reaction catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Specifically, platinum fine powder, platinum black, platinum-supported silica fine powder, platinum Supported activated carbon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, platinum olefin complexes, platinum carbonyl complexes such as platinum-carbonylvinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes and platinum- Platinum-based catalysts such as platinum-vinylmethylsiloxane complexes such as cyclovinylmethylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, etc., and palladium-based catalysts containing palladium atoms or rhodium atoms instead of platinum atoms in the platinum-based catalysts A catalyst or a rhodium-type catalyst is mentioned. Among them, as the hydrosilylation catalyst, a platinum-vinylmethylsiloxane complex, a platinum-carbonylvinylmethyl complex, or a complex of chloroplatinic acid, an alcohol, and an aldehyde is preferable because the reaction rate is good.

  In the curable resin composition of the present invention, the hydrosilylation catalyst can be used alone or in combination of two or more.

When the curable resin composition of the present invention includes a hydrosilylation catalyst, the content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited, but is included in the curable resin composition. 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol is preferable with respect to 1 mol of the total amount of aliphatic carbon-carbon double bonds (particularly alkenyl groups), and more preferably 1.0 × 10 ⁻⁶ to 1. 0 × 10 ⁻³ mol. By setting the content to 1 × 10 ⁻⁸ mol or more, there is a tendency that a cured product can be formed more efficiently. On the other hand, when the content is 1 × 10 ⁻² mol or less, there is a tendency that a cured product having a more excellent hue (less coloring) can be obtained.

  Further, the content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited. For example, platinum, palladium, or rhodium in the hydrosilylation catalyst is 0.01 to An amount that falls within the range of 1000 ppm is preferred, and an amount that falls within the range of 0.1 to 500 ppm is more preferred. When the content of the hydrosilylation catalyst is in such a range, a cured product can be formed more efficiently, and a cured product having a more excellent hue tends to be obtained.

  Furthermore, the curable resin composition of the present invention may contain components other than the above-mentioned components (sometimes referred to as “other components”). Other components are not particularly limited. For example, siloxane compounds other than polysiloxanes (A) and (B) (for example, cyclic siloxane compounds, low molecular weight linear or branched siloxane compounds, etc.), hydrosilylation reaction inhibition Agents, solvents, various additives and the like. Examples of the additive include precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, Inorganic fillers such as boron nitride, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; organic resins such as silicone resins, epoxy resins, and fluororesins other than those described above Fine powder: Filler such as conductive metal powder such as silver and copper, solvent, stabilizer (antioxidant, ultraviolet absorber, light stabilizer, heat stabilizer, etc.), flame retardant (phosphorous flame retardant, Halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents, lubricants, waxes, Plasticizer, mold release agent, impact resistance improver, hue improver, fluidity improver, colorant (dye, pigment, etc.), dispersant, antifoaming agent, defoaming agent, antibacterial agent, preservative, viscosity adjustment Agents, thickeners, phosphors and the like. These other components can also be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, it is possible to select suitably content (blending amount) of another component in the range which does not impair the effect of this invention.

  In the curable resin composition of the present invention, the content of the compound having a heterocyclic ring containing a sulfur atom other than the components (A) to (H) is not particularly limited, but the curable resin composition (100% by weight) ) Is preferably 1% by weight or less (for example, 0 to 1% by weight), more preferably 0.5% by weight or less (for example, 0 to 0.5% by weight), and still more preferably 0.1% by weight. Or less (for example, 0 to 0.1% by weight), particularly preferably 0.05% by weight or less (for example, 0 to 0.05% by weight). When the content is 1% by weight or less, there is a tendency that curing inhibition is difficult to occur when the curable resin composition is cured.

  In the curable resin composition of the present invention, the content of the compound having a heterocyclic ring containing a nitrogen atom to which a hydrogen atom is directly bonded, other than the components (A) to (H), is not particularly limited. 1% by weight or less (for example, 0 to 1% by weight) is preferable with respect to the composition (100% by weight), more preferably 0.5% by weight or less (for example, 0 to 0.5% by weight), and still more preferably. Is 0.1 wt% or less (for example, 0 to 0.1 wt%), particularly preferably 0.05 wt% or less (for example, 0 to 0.05 wt%). When the content is 1% by weight or less, there is a tendency that curing inhibition is difficult to occur when the curable resin composition is cured.

  The curable resin composition of the present invention is not particularly limited, but an aliphatic carbon-carbon double bond (particularly an alkenyl group) is 0.2 with respect to 1 mol of a hydrosilyl group present in the curable resin composition. It is preferable that it is a composition (formulation composition) which will be -4 mol, More preferably, it is 0.5-3.0 mol, More preferably, it is 0.8-2.0 mol. By controlling the ratio of hydrosilyl group and aliphatic carbon-carbon double bond (especially alkenyl group) within the above range, the heat resistance, transparency, thermal shock resistance, reflow resistance and corrosive gas of the cured product There is a tendency that the barrier property against (for example, SOx gas) is further improved.

  Although the curable resin composition of this invention is not specifically limited, It can prepare by stirring and mixing said each component at room temperature. In addition, the curable resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately. It can also be used as a multi-component (for example, two-component) composition in which the components are mixed at a predetermined ratio before use.

  The curable resin composition of the present invention may have either a solid state or a liquid state, and is not particularly limited, but is usually liquid at room temperature (about 25 ° C.).

  The viscosity at 23 ° C. of the curable resin composition of the present invention is not particularly limited, but is preferably 300 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1000 to 8000 mPa · s. is there. There exists a tendency for the heat resistance of hardened | cured material to improve more by making the said viscosity into 300 mPa * s or more. On the other hand, by setting the viscosity to 20,000 mPa · s or less, it is easy to prepare a curable resin composition, the productivity and handleability are further improved, and bubbles are less likely to remain in the cured product. The productivity and quality of the cured product (especially the sealing material) tend to be further improved. In addition, the viscosity of curable resin composition is measured by the same method as the viscosity of the above-mentioned ladder type silsesquioxane (G).

<Hardened product>
By curing the curable resin composition of the present invention (particularly, curing by hydrosilylation reaction), a cured product (sometimes referred to as “cured product of the present invention”) is obtained. Conditions for curing (particularly, curing by hydrosilylation reaction) are not particularly limited and can be appropriately selected from conventionally known conditions. For example, from the viewpoint of reaction rate, the temperature (curing temperature) is 25 to 25. 180 ° C. (more preferably 60 to 150 ° C.) is preferable, and the time (curing time) is preferably 5 to 720 minutes. Curing can be performed in one stage or in multiple stages. The cured product of the present invention not only has high heat resistance and transparency unique to polysiloxane materials, but is particularly excellent in barrier properties against corrosive gases (for example, SOx gas).

<Sealant>
The curable resin composition of the present invention can be preferably used as a composition (sealing agent) for sealing a semiconductor element in a semiconductor device (sometimes referred to as “sealing agent of the present invention”). Specifically, the sealing agent of the present invention can be particularly preferably used for sealing an optical semiconductor element (LED element) in an optical semiconductor device (that is, as an optical semiconductor sealing agent). The encapsulant (cured product) obtained by curing the encapsulant of the present invention has not only high heat resistance and transparency peculiar to polysiloxane materials, but particularly corrosive gas (for example, SOx gas). Etc.). For this reason, the sealing agent of this invention can be preferably used especially as a sealing agent etc. of a high-intensity, short wavelength optical semiconductor element.

<Semiconductor device>
By sealing the semiconductor element using the sealing agent of the present invention, a semiconductor device (sometimes referred to as “the semiconductor device of the present invention”) is obtained. That is, the semiconductor device of the present invention is a semiconductor device having at least a semiconductor element and a sealing material for sealing the semiconductor element, and the sealing material is a cured product of the sealing agent of the present invention. . The production of the semiconductor device of the present invention can be carried out by a known or commonly used method, and is not particularly limited. it can. The curing temperature and the curing time are not particularly limited, but can be set in the same range as in the preparation of the cured product. The encapsulant of the present invention is particularly suitable for the case where the semiconductor device is an optical semiconductor device, that is, when used as an encapsulant for an optical semiconductor element (an encapsulant for optical semiconductors) in an optical semiconductor device. An advantageous effect can be exhibited effectively. By using the sealing agent of the present invention as an optical semiconductor sealing agent, an optical semiconductor device (sometimes referred to as “optical semiconductor device of the present invention”) is obtained. An example of the optical semiconductor device of the present invention is shown in FIG. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring (electrode), 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).

  In particular, the curable resin composition of the present invention is for forming a sealing material that covers an optical semiconductor element in an optical semiconductor device having a high luminance and a short wavelength, which has been difficult to cope with with a conventional resin material. It can be preferably used for applications such as an encapsulant and an encapsulant for forming an encapsulant covering a semiconductor element in a semiconductor device (such as a power semiconductor) having high heat resistance and high withstand voltage.

  The curable resin composition of the present invention is not limited to the above-described encapsulant application (particularly, an encapsulant application for an optical semiconductor element). For example, a functional coating agent, a heat-resistant plastic lens, a transparent device, an adhesive ( Heat-resistant transparent adhesives, etc.), electrical insulating materials (insulating films, etc.), laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members , Optical modeling, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, and other optical and semiconductor applications.

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

¹ H-NMR analysis of the product and product was performed by JEOL ECA500 (500 MHz). In addition, the number average molecular weight and the weight average molecular weight of the product and the product are measured by Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (Tosoh Corp.) Manufactured), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corp.), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C.

Production Example 1
[Synthesis of Ladder Type Polyorganosilsesquioxane Having Vinyl Group and Trimethylsilyl Group (TMS Group) at Terminal]
In a 200 ml four-necked flask, 40.10 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 3.38 g of phenyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and 17.17 g of methyl isobutyl ketone (MIBK). 69 g was charged and the mixture was cooled to 10 ° C. To the above mixture, 240 mmol (4.33 g) of water and 0.48 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) were simultaneously added dropwise over 1 hour. After the addition, these mixtures were kept at 10 ° C. for 1 hour. Thereafter, 80.0 g of MIBK was added to dilute the reaction solution.
Next, the temperature of the reaction vessel was raised to 70 ° C., and when the temperature reached 70 ° C., 606 mmol (10.91 g) of water was added, and polycondensation reaction was performed at the same temperature under nitrogen for 9 hours. Furthermore, 6.25 g of vinyltriethoxysilane was added, and a reaction (aging) was performed at the same temperature for 3 hours.
Subsequently, 15.0 g of hexamethyldisiloxane was added to the obtained reaction solution, and a silylation reaction was performed at 70 ° C. for 3 hours. Thereafter, the reaction solution was cooled, washed with water until the lower layer solution became neutral, and then the upper layer solution was collected. Next, the solvent is distilled off from the upper layer liquid under the conditions of 1 mmHg and 60 ° C., and a ladder-type polyorganosilsesquioxane having a vinyl group and a TMS group at the end is used as a colorless and transparent liquid product. 0 g was obtained. The ladder type polyorganosilsesquioxane obtained in Production Example 1 corresponds to the ladder type silsesquioxane (G) described above.
The ladder type polyorganosilsesquioxane having a vinyl group and a TMS group at the terminal has a weight average molecular weight (Mw) of 3000, and a vinyl group content (average content) per molecule of 4.00% by weight. Yes, and the phenyl group / methyl group / vinyl group (molar ratio) was 5/80/15.
⁽¹ H-NMR spectrum of ladder-type polyorganosilsesquioxane 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)

The following products were used as polyorganosiloxane (A1) and polyorganosiloxane (B1).
KER-2500A: manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.53% by weight, methyl group content 94.29% by weight, phenyl group content 0% by weight, hydrosilyl based on the total amount (100% by weight) of the product Group content (in terms of hydride) 0.03% by weight, number average molecular weight 4453, weight average molecular weight 19355, and hydrosilylation catalyst.
KER-2500B: manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.08% by weight, methyl group content 95.63% by weight, phenyl group content 0% by weight, hydrosilyl with respect to the total amount (100% by weight) of the product Group content (in terms of hydride) 0.13% by weight, number average molecular weight 4636, weight average molecular weight 18814
ETERLED GD1012A: manufactured by Changxing Materials Industrial Co., Ltd., vinyl group content 1.33% by weight, methyl group content 96.34% by weight, phenyl group content 0% by weight, hydrosilyl group content (100% by weight) (Hydride conversion) 0% by weight, number average molecular weight 5108, weight average molecular weight 23385, and hydrosilylation catalyst.
ETERLED GD1012B: manufactured by Changxing Materials Co., Ltd., vinyl group content 1.65% by weight, methyl group content 91.16% by weight, phenyl group content 0% by weight, hydrosilyl group content (based on the total amount (100% by weight) of the product ( Hydride conversion) 0.19% by weight, number average molecular weight 4563, weight average molecular weight 21873

１，３−Ｄｉｍｅｔｈｙｌｂｕｒｂｉｔｕｒｉｃ Ａｃｉｄ：１，３−ジメチルバルビツール酸［ピリミジン誘導体］（下記式で表される化合物）

ＴＩＮＵＶＩＮ ３８４−２：ＢＡＳＦジャパン（株）製、商品名「ＴＩＮＵＶＩＮ ３８４−２」［ベンゾトリアゾール誘導体］
ＴＩＮＵＶＩＮ ４００：ＢＡＳＦジャパン（株）製、商品名「ＴＩＮＵＶＩＮ ４００」［トリアジン誘導体］
ＴＩＮＵＶＩＮ １２３：ＢＡＳＦジャパン（株）製、商品名「ＴＩＮＵＶＩＮ １２３」［ピペリジン誘導体］
ＴＩＮＵＶＩＮ ２９２：ＢＡＳＦジャパン（株）製、商品名「ＴＩＮＵＶＩＮ ２９２」［ピペリジン誘導体］ The following compounds were used as the heterocyclic compound (C).
MOI-BP: manufactured by Showa Denko KK, trade name “Karenz MOI-BP”, [pyrazole derivative]
Pentoxylline: Pentoxifylline [purine derivative] (compound represented by the following formula)

1,3-Dimethylburbituric Acid: 1,3-dimethylbarbituric acid [pyrimidine derivative] (compound represented by the following formula)

TINUVIN 384-2: BASF Japan K.K., trade name “TINUVIN 384-2” [benzotriazole derivative]
TINUVIN 400: manufactured by BASF Japan, trade name “TINUVIN 400” [triazine derivative]
TINUVIN 123: manufactured by BASF Japan Ltd., trade name “TINUVIN 123” [piperidine derivative]
TINUVIN 292: manufactured by BASF Japan Ltd., trade name “TINUVIN 292” [piperidine derivative]

As the isocyanurate compound (D), the following compound was used.
MA-DGIC: manufactured by Shikoku Kasei Kogyo Co., Ltd., monoallyl diglycidyl isocyanurate (compound represented by the following formula)

As the isocyanurate compound (E), the following compound was used.
TEPIC-VL: Nissan Chemical Industries, Ltd. (compound represented by the following formula)

  As a silane coupling agent, the brand name "Z-6040" (made by Toray Dow Corning Co., Ltd.) was used.

Example 1
[Production of curable resin composition]
First, as shown in Table 1, ETERLED GD1012A (50 parts by weight) and MOI-BP (0.1 parts by weight) were mixed and stirred at 80 ° C. for 1 hour to prepare agent A.
Next, E agent LED GD1012B (50 parts by weight) as agent B was mixed with agent A (50.1 parts by weight) obtained above and stirred at room temperature for 10 minutes. A resin composition was obtained.

[Manufacture of optical semiconductor devices]
The curable resin composition obtained above is injected into the LED package (InGaN element, 3.5 mm × 2.8 mm) of the embodiment shown in FIG. 1 and heated at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours. Thus, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable resin composition was manufactured.

Examples 2-30, Comparative Examples 1-4
A curable resin composition and an optical semiconductor device were produced in the same manner as in Example 1 except that the composition of the curable resin composition was changed as shown in Tables 1 to 3.

(Evaluation)
The following evaluation was performed about the optical semiconductor device obtained above. The evaluation results are shown in Tables 1-3. In Comparative Examples 2 and 3, since no cured product was obtained, the following evaluation using an optical semiconductor device was not performed.

[Sulfur corrosion test]
Each optical semiconductor device manufactured above was used as a sample.
First, with respect to the above sample, the total luminous flux (unit: lm) when a current of 20 mA was passed was measured using a total luminous flux measuring machine (manufactured by Optronic Laboratories, Inc., multispectral radiation measurement system “OL771”). Was defined as “total luminous flux before test”.
Next, the sample and 0.3 g of sulfur powder (manufactured by Kishida Chemical Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was further placed in an aluminum box. Subsequently, the aluminum box was placed in an oven at 80 ° C. (manufactured by Yamato Scientific Co., Ltd., model number “DN-64”) and taken out after 8 hours. With respect to the sample thus obtained, the total luminous flux (unit: lm) was measured in the same manner as described above, and this was designated as “total luminous flux after test”.
From the value of the total luminous flux measured above, the luminous intensity maintenance factor was calculated according to the following formula.
Luminance maintenance rate (%) = (total luminous flux after test / total luminous flux before test) × 100
It shows that hardened | cured material (sealing material) is excellent in the barrier property with respect to corrosive gas, so that a luminous intensity maintenance factor is high.
In addition, for each curable resin composition (for each example / comparative example), the luminous intensity maintenance rate was measured and calculated for 10 optical semiconductor devices, and Tables 1 to 3 show the average values of these luminous intensity maintenance rates ( N = 10).

100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor element 103: Bonding wire 104: Cured material (sealing material)

Claims (14)

  A poly at least one selected from the group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganosiloxysilalkylene (A2) having two or more alkenyl groups in the molecule Selected from the group consisting of siloxane (A), polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule, and polyorganosiloxysilalkylene (B2) having two or more hydrosilyl groups in the molecule Comprising at least one polysiloxane (B) and a heterocyclic compound (C), wherein the heterocyclic compound (C) has at least one nitrogen atom and no sulfur atom; And a heterocyclic compound (C) having a heterocyclic ring which does not have a nitrogen atom directly bonded to a hydrogen atom (excluding an isocyanurate compound) Curable resin composition characterized in that it.   Examples of the heterocyclic compound (C) include pyridine, oxazole, pyrazine, triazine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, benzo [c] cinnoline, pyrimidine, derivatives thereof, pyrrolidine derivatives, pyrrole derivatives, piperidine derivatives. At least one compound selected from the group consisting of imidazole derivatives, pyrazole derivatives, imidazoline derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, benzimidazole derivatives, purine derivatives, carbazole derivatives, triazole derivatives, and benzotriazole derivatives The curable resin composition according to claim 1. The heterocyclic compound (C) is represented by the following formula (1a)

[In the formula (1a), R ³¹ represents a hydrogen atom or a group represented by the formula (1a-I). R ³² represents a group represented by the formula (1a-I) or a group represented by the formula (1a-II).

[In the formula (1a-I), R ³³ are the same or different and each represents a hydrocarbon group which may have a substituent. ]

[In the formula (1a-II), R ³⁴ represents a hydrocarbon group which may have a substituent. p shows the integer of 1-20. ]]
A compound represented by formula (1b):

[In the formula (1b), R ³⁵ represents a hydrocarbon group which may have a substituent. R ³⁶ and R ³⁷ are the same or different and each represents an aryl group which may have a substituent. ]
A compound represented by formula (1c):

[In the formula (1c), R ³⁸ represents a hydrocarbon group which may contain a linking group. R ³⁹ represents a divalent organic group. R ⁴⁰ represents an organic group which may have a substituent. ]
A compound represented by formula (1d):

[In the formula (1d), R ⁴¹ represents a hydrocarbon group which may contain a linking group. R ⁴² and R ⁴³ are the same or different and each represents a hydrocarbon group which may have a substituent. ]
A compound represented by formula (1e):

[In the formula (1e), R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the same or different and each represents a hydrocarbon group which may contain a linking group. ]
And a compound represented by the following formula (1f)

[In formula (1f), R ⁴⁷ and R ⁴⁸ are the same or different and each represents a hydrocarbon group which may contain a linking group. ]
The curable resin composition according to claim 1, wherein the curable resin composition is one or more compounds selected from the group consisting of compounds represented by:   Furthermore, the curable resin composition of any one of Claims 1-3 containing a hydrosilylation catalyst. Furthermore, ladder-type polyorganosilsesquioxane and the following formula (2)

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

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

[In the formula (2b), R ^j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
The curable resin composition of any one of Claims 1-4 containing at least 1 sort (s) selected from the group which consists of isocyanurate compound (D) represented by these. Further, the following formula (3)

[In the formula (3), R ^a , R ^b and R ^c are the same or different and represent a group represented by the formula (3a), a group represented by the formula (3b), a hydrogen atom or an alkyl group. Show. However, at least one of R ^a , R ^b and R ^c is a group represented by the formula (3a).

[In the formula (3a), R ^d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. s shows the integer of 2-10. ]

[In formula (3b), R ^e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. t shows the integer of 1-10. ]]
The curable resin composition of any one of Claims 1-5 containing the isocyanurate compound (E) represented by these. As the ladder-type polyorganosilsesquioxane, a part or all of the molecular chain terminals of the polyorganosilsesquioxane having a ladder structure may be represented by the following formula (V):

[In the formula (V), R ⁶ represents a group having an aliphatic carbon-carbon double bond. ]
The unit structure represented by the following formula (VI)

[In Formula (VI), R ⁷ is the same or different and represents a hydrocarbon group. ]
The curable resin composition of Claim 5 or 6 containing the ladder type silsesquioxane (G) which has the polyorgano silsesquioxane residue containing the unit structure represented by these. As the ladder-type polyorganosilsesquioxane, a part or all of the molecular chain terminals of the polyorganosilsesquioxane having a ladder structure may be represented by the following formula (VII):

[In Formula (VII), X represents a single bond, a divalent hydrocarbon group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, an amide group, or a group in which a plurality of these are linked. R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an alkylthio group, an alkenylthio group. Group, arylthio group, aralkylthio group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxy group, hydroperoxy Group, sulfo group, amino group or substituted amino group, mercapto group, sulfo group, or the following formula (s)

[In formula (s), R ⁵¹ is the same or different and is a hydrogen atom, halogen atom, substituted or unsubstituted hydrocarbon group, alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, acyloxy group, alkylthio group. Group, alkenylthio group, arylthio group, aralkylthio group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxy group , A hydroperoxy group, a sulfo group, an amino group or a substituted amino group, a mercapto group, or a sulfo group. ]
The group represented by these is shown. n shows the integer of 1-100. ]
A unit structure represented by the following formula (VIII)

[In formula (VIII), R ¹⁰ is the same or different and represents a hydrocarbon group. ]
The curable resin composition of any one of Claims 5-7 containing the ladder type silsesquioxane (H) which has a polyorgano silsesquioxane residue containing the unit structure represented by these.   9. The ladder type polyorganosilsesquioxane according to claim 5, wherein the ladder type polyorganosilsesquioxane is a ladder type polyorganosilsesquioxane having a substituted or unsubstituted aryl group in a part or all of the side chain. Curable resin composition.   Furthermore, the curable resin composition of any one of Claims 1-9 containing a silane coupling agent (F).   Hardened | cured material obtained by hardening the curable resin composition of any one of Claims 1-10.   It is a sealing agent, The curable resin composition of any one of Claims 1-10. A semiconductor device having a semiconductor element and a sealing material for sealing the semiconductor element,
The semiconductor device, wherein the sealing material is a cured product of the curable resin composition according to claim 12.   The semiconductor device according to claim 13, which is an optical semiconductor device.

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