JP2016216606A - 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 especially excellent in barrier property to corrosive gas to be formed by being cured.SOLUTION: The curable resin composition contains polyorganosiloxane (A-1) having two or more alkenyl groups in a molecule, organosiloxane (A-2) having two or more hydrosilyl groups in a molecule and a fluorine-based surfactant (B). The curable resin composition preferably further contains ladder type polyorganosilsesquioxane (A-3).SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition and a cured product thereof, a sealant using the curable resin composition, and a semiconductor device obtained by sealing a semiconductor element using the sealant.

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.

  At present, as a sealing material in an optical semiconductor device, a phenyl silicone-based sealing material having a relatively good barrier property against corrosive gas is widely used (Patent Document 1).

Patent No. 4409160

  However, although the phenyl silicone-based sealing material has a higher barrier property against corrosive gas than the conventionally used methyl silicone-based sealing material, its characteristics are still insufficient. Actually, even when a phenyl silicone-based sealing material is used, there is a problem in that the corrosion of the electrode by the corrosive gas proceeds with time in the optical semiconductor device, and the energization characteristics deteriorate.

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

  As a result of intensive studies to solve the above problems, the present inventor has found that a polyorganosiloxane having two or more alkenyl groups in the molecule, a polyorganosiloxane having two or more hydrosilyl groups in the molecule, and a fluorine-based interface It has been found that when a curable resin composition containing an activator as an essential component is cured, a cured product having particularly excellent barrier properties against corrosive gas can be formed. The present invention has been completed based on these findings.

  That is, the present invention relates to a polyorganosiloxane (A-1) having two or more alkenyl groups in the molecule, a polyorganosiloxane (A-2) having two or more hydrosilyl groups in the molecule, A curable resin composition containing a surfactant (B) is provided.

  The present invention also provides the curable resin composition further comprising a ladder type polyorganosilsesquioxane (A-3).

  The present invention also provides the above curable resin composition further comprising a silicone-based surfactant (C).

  The present invention also provides the curable resin composition described above further comprising a hydrosilylation catalyst (D).

［式（１）中、Ｒ^a、Ｒ^b、及びＲ^cは、同一又は異なって、下記式（１ａ）で表される基、下記式（１ｂ）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、下記式（１ａ）で表される基である。

（式中、Ｒ^d、Ｒ^eは、同一又は異なって、水素原子又は炭素数１〜８の直鎖状若しくは分岐鎖状のアルキル基を示す。ｓ、ｔは、同一又は異なって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。 The present invention further includes the following formula (1):

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

(Wherein R ^d and R ^e are the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. S and t are the same or different and represent 1 to 10) Indicates an integer)]]
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（A-3-1）を含む前記の硬化性樹脂組成物を提供する。 In the present invention, as the ladder-type polyorganosilsesquioxane (A-3), 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 (A-3-1) 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、カルボキシル基、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、ヒドロキシル基、ヒドロパーオキシ基、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、カルボキシル基、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、ヒドロキシル基、ヒドロパーオキシ基、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（A-3-2）を含む前記の硬化性樹脂組成物を提供する。 In the present invention, as the ladder-type polyorganosilsesquioxane (A-3), 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, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxyl group, hydroperoxy 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, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxyl group , A hydroperoxy group, an amino group or a substituted amino group, a mercapto group, or a sulfo group]
The group represented by these is shown. n represents an integer of 1 to 100]
A unit structure represented by the following formula (VIII)

[In the formula (VIII), R ¹⁰ are the same or different and each represents a hydrocarbon group]
The curable resin composition comprising a ladder-type silsesquioxane (A-3-2) having a polyorganosilsesquioxane residue containing a unit structure represented by the formula:

  In the present invention, the ladder-type polyorganosilsesquioxane (A-3) is a ladder-type polyorganosilsesquioxane (A-) in which part or all of the side chain is a substituted or unsubstituted aryl group. The curable resin composition is 3).

  The present invention also provides the curable resin composition further containing a silane coupling agent (F).

  The present invention also provides a cured product obtained by curing the curable resin composition.

  The present invention also provides the curable resin composition, which is a sealant.

  The present invention also provides 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. provide.

  The present invention also provides the above semiconductor device which is an optical semiconductor device.

  Since the curable resin composition of the present invention has the above-described configuration, a cured product having particularly excellent barrier properties against corrosive gas (for example, SOx gas) can be formed 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 (encapsulant) for forming an encapsulant for an optical semiconductor element (for example, an 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.

  The curable resin composition of the present invention is a siloxane compound [a compound having a siloxane (Si—O—Si) bond], which is a polyorganosiloxane (A-1) having two or more alkenyl groups in the molecule (simply “ Polyorganosiloxane (A-1) ”and polyorganosiloxane (A-2) having two or more hydrosilyl groups in the molecule (simply referred to as“ polyorganosiloxane (A-2) ”) In some cases) and further contains a fluorosurfactant (B).

[Polyorganosiloxane (A-1)]
The polyorganosiloxane (A-1) is a polyorganosiloxane having two or more alkenyl groups in the molecule. That is, the polyorganosiloxane (A-1) is a polysiloxane having an alkenyl group and a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, polyorganosiloxane (A-2) described later). . However, the polyorganosiloxane (A-1) does not include a compound corresponding to “ladder type polyorganosilsesquioxane (A-3)” described later.

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

  Examples of the alkenyl group that the polyorganosiloxane (A-1) has in the molecule include substituted or unsubstituted alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group. Examples of the substituent include a halogen atom, a hydroxyl group, and a carboxyl group. As the alkenyl group, a vinyl group is preferable. Further, the polyorganosiloxane (A-1) may have one type of alkenyl group, or may have two or more types of alkenyl groups. The alkenyl group of the polyorganosiloxane (A-1) is preferably a group bonded to a silicon atom.

The polyorganosiloxane (A-1) may have a group other than an alkenyl group as a group bonded to a silicon atom, and examples thereof include a hydrogen atom and an organic group. 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-substituted 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 Halogenated alkyl group such as propyl group], hydroxyl group, alkoxy group Preferably the C _1-6 alkoxy groups, more preferably C _1-4 alkoxy group). In the present specification, the “group bonded to a silicon atom” does not include a silicon atom.

  The property of the polyorganosiloxane (A-1) is not particularly limited, and may be liquid or solid.

As polyorganosiloxane (A-1), 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, such as an alkyl group [eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, Hexyl group etc.], cycloalkyl group [eg cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclododecyl group etc.], cycloalkyl-alkyl group [eg cyclohexylmethyl group, methylcyclohexyl group etc.], carbonization Halogenated hydrocarbon group in which one or more hydrogen atoms in the hydrogen group are substituted with a halogen atom [for example, halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. ], An alkenyl group [for example, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, etc.換又 the like unsubstituted alkenyl group, an aryl group [e.g., a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and aralkyl groups [e.g., benzyl group, phenethyl group, etc.] is. However, a part of R ¹ is an alkenyl group (particularly a vinyl group), and the ratio thereof is in a range of 2 or more in the molecule, and the ratio of the alkenyl group to the total amount (100 mol%) of R ¹ is For example, 0.1 to 40 mol%. By controlling the ratio of the alkenyl group within the above range, an effect of improving the curability of the curable resin composition can be obtained. 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 average unit formula, a1 to a5 are the same or different and are 0 or a positive number, and (a1 + a2 + a3) is a positive number.

  An example of the polyorganosiloxane (A-1) is a linear polyorganosiloxane having two or more alkenyl groups in the molecule. As the alkenyl group of the linear polyorganosiloxane, a vinyl group is preferable. Moreover, as a group couple | bonded with silicon atoms other than the alkenyl group in the said linear polyorganosiloxane, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.

  In the linear polyorganosiloxane, the ratio of the alkenyl group to the total amount (100 mol%) of groups bonded to silicon atoms is preferably 0.1 to 40 mol%. Moreover, the ratio of the alkyl group to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 1 to 20 mol%. Furthermore, the ratio of the aryl group to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 30 to 90 mol%. In particular, as the linear polyorganosiloxane, one having a ratio of aryl groups to 40 mol% or more (for example, 45 to 80 mol%) based on the total amount of groups bonded to silicon atoms (100 mol%) is used. Therefore, there is a tendency that a cured product having a particularly excellent barrier property against corrosive gas can be obtained. Further, by using a material having a ratio of alkyl groups (particularly methyl groups) to 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 exists a tendency for the hardened | cured material excellent in impact property to be obtained.

［式中、Ｒ¹¹は同一又は異なって一価の置換若しく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、１〜１０００（好ましくは、５〜１０００）の整数である］ The linear polyorganosiloxane is represented by the following formula (I-1), for example.

[Wherein, 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 1-1000 (preferably 5-1000)]

Another example of the polyorganosiloxane (A-1) is a branched polysiloxane having two or more alkenyl groups in the molecule and having a siloxane unit (T unit) represented by [RSiO _3/2 ]. Organosiloxane is mentioned. However, the branched polyorganosiloxane does not include a compound corresponding to “ladder type polyorganosilsesquioxane (A-3)” described later. R is a monovalent substituted or unsubstituted hydrocarbon group. As the alkenyl group of the branched polyorganosiloxane, a vinyl group is preferable. Moreover, as a group couple | bonded with silicon atoms other than the alkenyl group in the said branched polyorganosiloxane, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable. 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 the alkenyl group to the total amount of groups bonded to silicon atoms (100 mol%) is preferably 0.1 to 40 mol% from the viewpoint of curability of the curable resin composition. . Further, the ratio of the alkyl group to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 10 to 40 mol%. Furthermore, the ratio of the aryl group to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 5 to 70 mol%. In particular, as the branched polyorganosiloxane, one having an aryl group ratio of 40 mol% or more (for example, 45 to 60 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms is used. Therefore, there is a tendency that a cured product having a particularly excellent barrier property against corrosive gas can be obtained. Further, by using a material in which the ratio of alkyl groups (particularly methyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 50 mol% or more (for example, 60 to 99 mol%), There exists a tendency for the hardened | cured material excellent in impact property to be obtained.

  Examples of the branched polyorganosiloxane include compounds represented by the above average unit formula, wherein a1 is a number of 1 or more. In this case, 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 from 0 to 0.4. It is preferable that it is the number of these. Further, the molecular weight of the branched polyorganosiloxane is preferably 500 to 10,000, more preferably 700 to 3000, in terms of weight average molecular weight (in terms of polystyrene by GPC).

Other examples of the polyorganosiloxane (A-1) include, for example, the following average unit formula:
(R ^1a ₂ R ^1b SiO _1/2 ) _a6 (R ^1a ₃ SiO _1/2 ) _a7 (SiO _4/2 ) _a8 (HO _1/2 ) _a9
The polyorganosiloxane represented by these is mentioned. In said average unit formula, R ^<1a> is the same or different and shows a C1-C10 alkyl group ( _C1-10 alkyl group), and a methyl group is preferable especially. 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 a viewpoint of the hardness and mechanical strength of the hardened | cured material obtained. 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 obtained 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.

  The polyorganosiloxane (A-1) may have two or more alkenyl groups in the molecule, and may further have a hydrosilyl group. In this case, the polyorganosiloxane (A-1) may be a polyorganosiloxane (A-2) described later.

  The content (blending amount) of polyorganosiloxane (A-1) in the curable resin composition of the present invention (the total amount when two or more are included) is the total amount (100% by weight) of the curable resin composition. On the other hand, it is preferably 50 to 99% by weight, 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.

  In addition, the content (blending amount) of polyorganosiloxane (A-1) in the curable resin composition of the present invention (the total amount when two or more are included) is the total amount of siloxane compound contained in the curable resin composition. 30 to 70% by weight of (100% by weight) is preferable, more preferably 35 to 65% by weight, and still more preferably 40 to 60% by weight.

[Polyorganosiloxane (A-2)]
The polyorganosiloxane (A-2) is a polyorganosiloxane having two or more hydrosilyl groups (Si—H) in the molecule. That is, the polyorganosiloxane (A-2) is a polysiloxane having a hydrosilyl group, and a component that causes a hydrosilylation reaction with a component having an alkenyl group (for example, polyorganosiloxane (A-1)). However, polyorganosiloxane (A-2) does not include those corresponding to “ladder type polyorganosilsesquioxane (A-3)” described later.

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

  The polyorganosiloxane (A-2) may have a group other than a hydrogen atom as a group bonded to a silicon atom. Examples thereof include specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above. . Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable. The polyorganosiloxane (A-2) may have an alkenyl group (for example, a vinyl group) as a group bonded to a silicon atom.

  The property of the polyorganosiloxane (A-2) is not particularly limited, and may be liquid or solid. Especially, it is preferable that it is liquid, and it is more preferable that it is a liquid whose viscosity in 25 degreeC is 0.1-1000000000 mPa * s.

As polyorganosiloxane (A-2), the following average unit formula:
(R ² SiO _3/2 ) _{b 1} (R ² ₂ SiO _2/2 ) _{b 2} (R ² ₃ SiO _1/2 ) _{b 3} (SiO _4/2 ) _{b 4} (X ² O _1/2 ) _{b 5}
The polyorganosiloxane represented by these is preferable. In the above average unit formula, R ² is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the hydrogen atom and the above monovalent substituted or unsubstituted hydrocarbon group An example is given. However, a part of R ² 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 ² (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. As R ² other than a hydrogen atom, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.

In the average unit formula, X ² 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 average unit formula, b1 to b5 are the same or different and are 0 or a positive number, and (b1 + b2 + b3) is a positive number.

  An example of the polyorganosiloxane (A-2) is a linear polyorganosiloxane having two or more hydrosilyl groups in the molecule. The group bonded to a silicon atom other than a hydrogen atom in the linear polyorganosiloxane is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

  In the linear polyorganosiloxane, the ratio of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount (100 mol%) of groups bonded to silicon atoms is preferably 0.1 to 40 mol%. Further, the ratio of the alkyl group to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 20 to 99 mol%. Furthermore, the ratio of the aryl group to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 40 to 80 mol%. In particular, as the above linear polyorganosiloxane, those having an aryl group ratio of 40 mol% or more (for example, 45 to 70 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms are used. Therefore, there is a tendency that a cured product having a particularly excellent barrier property against corrosive gas can be obtained. Further, by using a material having a ratio of alkyl groups (particularly methyl groups) to 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 exists a tendency for the hardened | cured material excellent in impact property to be obtained.

［式中、Ｒ³¹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、Ｒ³¹の少なくとも２個は水素原子である。ｍ２は１〜１０００（好ましくは、５〜１０００）の整数である］ The linear polyorganosiloxane is represented by the following formula (III-1), for example.

[Wherein, R ³¹ 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 ³¹ are hydrogen atoms. m2 is an integer of 1-1000 (preferably 5-1000)]

Another example of the polyorganosiloxane (A-2) is a branched polysiloxane having two or more hydrosilyl groups in the molecule and having a siloxane unit (T unit) represented by [RSiO _3/2 ]. Organosiloxane is mentioned. However, the branched polyorganosiloxane does not include a compound corresponding to “ladder type polyorganosilsesquioxane (A-3)” described later. R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. The group bonded to the silicon atom other than the hydrogen atom in the branched polyorganosiloxane is preferably 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. The ratio of the aryl group (particularly phenyl group) to the total amount of R in the T unit (100 mol%) is preferably 30 mol% or more from the viewpoint of the barrier property against the corrosive gas of the cured product.

  In the branched polyorganosiloxane, the ratio of the alkyl group to the total amount (100 mol%) of groups bonded to silicon atoms is preferably 70 to 95 mol%. Further, the ratio of the aryl group to the total amount (100 mol%) of the groups bonded to the silicon atom 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 certain thing, there exists a tendency for the hardened | cured material excellent in the barrier property with respect to corrosive gas to be obtained. Further, by using a material having a ratio of alkyl groups (particularly methyl groups) to 50 mol% or more (for example, 50 to 90 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms, There exists a tendency for the hardened | cured material excellent in impact property to be obtained.

  Examples of the branched polyorganosiloxane include compounds represented by the above average unit formula, wherein b1 is a positive number. In this case, b2 / b1 is a number from 0 to 10, b3 / b1 is a number from 0 to 0.5, b4 / (b1 + b2 + b3 + b4) is a number from 0 to 0.3, and b5 / (b1 + b2 + b3 + b4) is from 0 to 0.4. It is preferable that it is the number of these. The molecular weight of the branched polyorganosiloxane is preferably 300 to 10,000, more preferably 500 to 3,000, in terms of weight average molecular weight (in terms of polystyrene by GPC).

  The content (blending amount) of polyorganosiloxane (A-2) in the curable resin composition of the present invention (the total amount when two or more types are contained) is the total amount of siloxane compound contained in the curable resin composition (100 20 to 60% by weight, more preferably 25 to 55% by weight, still more preferably 30 to 50% by weight.

  The content (blending amount) of the polyorganosiloxane (A-2) in the curable resin composition of the present invention is 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of the polyorganosiloxane (A-1). Is preferred. By controlling the content of the polyorganosiloxane (A-2) within the above range, the curability of the curable resin composition tends to be further improved and a cured product can be efficiently formed. If the content of polyorganosiloxane (A-2) is out of the above range, the cured product's properties such as heat resistance, thermal shock resistance, and reflow resistance tend to decrease due to the reason that the curing reaction does not proceed sufficiently. There is.

  Further, the total content (total content) of the polyorganosiloxane (A-1) and the polyorganosiloxane (A-2) in the curable resin composition (100% by weight) of the present invention is 60 to 99% by weight. Is preferable, more preferably 70 to 96% by weight, still more preferably 80 to 90% by 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.

  Further, the curable resin composition of the present invention has 0.2 to 4 mol of an aliphatic carbon-carbon double bond (particularly, an alkenyl group) 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 becomes like this, 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.

[Ladder type polyorganosilsesquioxane (A-3)]
The curable resin composition of the present invention may further contain a ladder type polyorganosilsesquioxane (A-3) as a siloxane compound. The ladder-type polyorganosilsesquioxane (A-3) is a polyorganosilsesquioxane containing at least a ladder-like Si—O—Si structure (ladder structure).

When the curable resin composition of the present invention contains a ladder-type polyorganosilsesquioxane (A-3), an effect of further improving the barrier property against the corrosive gas of the cured product can be obtained. The ladder-type polyorganosilsesquioxane (A-3) is a polysiloxane represented by the empirical formula (Basic Structure) RSiO _1.5, at least comprising polyorganosilsesquioxane ladder structure in the molecule is there.

As the ladder-type polyorganosilsesquioxane (A-3), known or conventional polyorganosilsesquioxane having the above structure can be used, and one or more (especially two or more) in the molecule. Those having an aliphatic carbon-carbon double bond and those having one or more (particularly two or more) hydrosilyl groups in the molecule are preferred. In addition, the ladder-type polyorganosilsesquioxane (A-3) is a polyorganosyl having a ladder structure that is a side chain [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 sesquioxane skeleton (a skeleton formed by a Si—O bond) is preferably a substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted aryl group include aryl groups such as a phenyl group and a naphthyl group (for example, a C _6-14 aryl group, particularly a C _6-10 aryl group).

  Among these, the ladder-type polyorganosilsesquioxane (A-3) is a ladder-type silsesquioxane (A-) described below from the viewpoint of barrier properties against the corrosive gas of the cured product, mechanical strength, and the like. 3-1) and ladder type silsesquioxane (A-3-2) are particularly preferable.

・ Ladder-type silsesquioxane (A-3-1)
Ladder-type silsesquioxane (A-3-1) has a formula (V) described below in part or all of the molecular chain terminal of polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) having a ladder structure. ) And a polyorganosilsesquioxane residue containing the unit structure represented by formula (VI) (sometimes referred to as “polyorganosilsesquioxane residue (a)”). Polyorganosilsesquioxane.

The polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) in the ladder-type silsesquioxane (A-3-1) is a polysiloxane represented by an empirical formula (basic structural formula) R ⁵ SiO _1.5. . R ⁵ in the polyorganosilsesquioxane is the same or different and is 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 Although a sulfur atom containing group is shown, at least one part is a monovalent organic group.

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. Group, alkenylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, etc. It is done.

  Examples of the hydrocarbon group (monovalent hydrocarbon group) 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 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 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 a C _3-12 cyclohexane such as a cyclohexenyl group. An alkenyl group; a C _4-15 bridged cyclic hydrocarbon group such as a bicycloheptanyl group and a bicycloheptenyl group.

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

Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Examples of the group 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-substituted C _2-6 alkenyl groups and tolyl groups, and C _2-4 alkenyl-substituted aryl groups such as styryl groups.

0-20 are preferable and, as for carbon number of the substituent which the said hydrocarbon group may have, More preferably, it is 0-10. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl 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; an aryloxy group (preferably a C _6-14 aryloxy group); a benzyloxy group, an aralkyl group (preferably such as phenethyloxy _7-18 aralkyloxy group); acetyloxy group, propionyloxy group, (meth) acryloyloxy group, an acyloxy group such as a benzoyloxy group (preferably a C _1-12 acyloxy group); a mercapto group; methylthio group, ethylthio group, etc. An alkylthio group (preferably a C _1-6 alkylthio group, more preferably a C _1-4 alkylthio group); an alkenylthio group such as an allylthio group (preferably a C _2-6 alkenylthio group, more preferably a C _2-4 alkenyl group). Thio group); phenylthio group, tolylthio group, naphthylthio group and the like, and aromatic rings have substituents such as C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. which may arylthio group (preferably a C _6-14 arylthio groups); benzylthio group, aralkylthio group such as a phenethylthio group (preferably _7-18 aralkylthio group); a carboxyl group; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an alkoxycarbonyl group (preferably C _1-6 alkoxy such as butoxycarbonyl group - carbonyl group); phenoxycarbonyl group, tolyloxy Aryloxycarbonyl groups such as carbonyl group and naphthyloxycarbonyl group (preferably C _6-14 aryloxy-carbonyl group); aralkyloxycarbonyl groups such as benzyloxycarbonyl group (preferably C _7-18 aralkyloxy-carbonyl group) Amino group; mono- or dialkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (preferably mono- or di-C _1-6 alkylamino group); acetylamino group, propionylamino group, benzoic acid; An acylamino group such as a ruamino 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.

Examples of the monovalent oxygen atom-containing group in R ⁵ include a hydroxyl 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 in R ⁵ include an amino group or substituted amino group (mono- or dialkylamino group, acylamino group, etc.), cyano group, isocyanate group, isothiocyanate group, carbamoyl group, and the like. Can be mentioned.

Examples of the monovalent sulfur atom-containing group in R ⁵ 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.

R ⁵¹ in the above formula (s) is the same or different and is 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-containing group. 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 _{2− 4} alkenyl group); C _3-12 cycloalkyl group; C _3-12 cycloalkenyl group; substitution of aromatic ring with C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. An optionally _substituted C _6-14 aryl group; a C _7-18 aralkyl group; a C _6-10 aryl-C _2-6 alkenyl group; a hydroxyl group; a C _1-6 alkoxy group; Are preferred.

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).

The polyorganosilsesquioxane in ladder type silsesquioxane (A-3-1) is represented by the following formula (L), for example.

In the above formula (L), v is an integer of 1 or more (for example, 1 to 5000, preferably 1 to 2000, more preferably 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 (A-3-1), the group directly bonded to the silicon atom in the polyorganosilsesquioxane (R ⁵ in the above empirical formula, R ⁵ (side chain) in the formula (L)) The ratio of the substituted or unsubstituted hydrocarbon group to the total amount (100 mol%) is preferably 50 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more. In particular, a substituted or unsubstituted linear or branched C _1-10 alkyl group (especially a linear or branched chain such as a methyl group or an ethyl group) with respect to the total amount (100 mol%) of the above group. C _1-4 alkyl group), substituted or unsubstituted C _6-10 aryl group (particularly phenyl group), substituted or unsubstituted C _7-10 aralkyl group (particularly benzyl group) % Or more, more preferably 80 mol% or more, still more preferably 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 (A-3-1) is a polyorganosilsesquioxy having a ladder structure which is a side chain [main skeleton (main chain). The part branched from the sun skeleton, 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 (A-3-1) includes at least a polyorganosilsesquioxane residue (a) on part or all of the molecular chain terminals of the polyorganosilsesquioxane having the ladder structure. It is preferable to have. When the polyorganosilsesquioxane having the ladder structure is represented by the above formula (L), the ladder type silsesquioxane (A-3-1) is a part or all of T in the formula (L). Is preferably substituted with the following polyorganosilsesquioxane 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)

Unit structure (siloxane unit structure) represented by 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 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. R ⁶ is preferably an alkenyl group, more preferably a C _2-20 alkenyl group, 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. 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. For example, a hydrogen atom, a halogen atom, a monovalent organic group excluding a group having an aliphatic carbon-carbon double bond, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom-containing group Groups and the like.

  In the polyorganosilsesquioxane residue (a), the ratio of silicon atoms to which three oxygen atoms represented by formula (V) are bonded is determined by the silicon atoms constituting the polyorganosilsesquioxane residue (a). 20 to 80 mol% is preferable with respect to the total amount (100 mol%), more preferably 25 to 60 mol%. When the ratio is less than 20 mol%, the amount of aliphatic carbon-carbon double bonds (particularly alkenyl groups) possessed by the ladder-type silsesquioxane (A-3-1) becomes insufficient, and the cured product May not be sufficient. On the other hand, when the ratio exceeds 80 mol%, a large amount of silanol groups and hydrolyzable silyl groups remain in the ladder-type silsesquioxane (A-3-1). -1) may not be obtained in liquid form. Furthermore, since the condensation reaction proceeds and the molecular weight tends to change, the storage stability may decrease.

  The ratio of silicon atoms to which one oxygen atom represented by formula (VI) in the polyorganosilsesquioxane residue (a) is bonded is determined by the silicon atoms constituting the polyorganosilsesquioxane residue (a). 20-85 mol% is preferable with respect to the whole quantity (100 mol%), More preferably, it is 30-75 mol%. When the ratio is less than 20 mol%, silanol groups and hydrolyzable silyl groups are likely to remain in the ladder-type silsesquioxane (A-3-1), and the ladder-type silsesquioxane (A-3-1) ) May not be obtained in liquid form. Furthermore, since the condensation reaction proceeds and the molecular weight tends to change, the storage stability may decrease. On the other hand, when the ratio exceeds 85 mol%, the amount of the aliphatic carbon-carbon double bond (particularly, alkenyl group) possessed by the ladder-type silsesquioxane (A-3-1) becomes insufficient, and curing occurs. In some cases, the hardness of the object cannot be obtained sufficiently.

  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 (A-3-1) can be represented, for example, by the following formula (L ^a ). 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 hydroxyl group, a halogen atom, an alkoxy group, or an acyloxy group. Oxan residue (a). When a plurality (2 to 4) of A in the formula (L ^a ) are polyorganosilsesquioxane residues (a), each A is represented by each other or another formula (L ^a ). The molecule A may be bonded to one or more Si-O-Si bonds.

  The polyorganosilsesquioxane residue (a) in the ladder-type silsesquioxane (A-3-1) is further represented by the formula (VII in the ladder-type silsesquioxane (A-3-2) described later. It may have a unit structure represented by In this case, ladder-type silsesquioxane (A-3-1) can also be used as ladder-type silsesquioxane (A-3-2).

  The method for producing the ladder-type silsesquioxane (A-3-1) is not particularly limited. For example, the ladder-type silsesquioxane (A-3-1) has a ladder structure and has silanol groups and / or hydrolyzable silyl groups (silanol groups and hydrolysates at the molecular chain terminals). The method of forming the said polyorgano silsesquioxane residue (a) with respect to the molecular chain terminal of the polyorgano silsesquioxane which has a decomposable silyl group or both) 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 (A-3-1), the number of aliphatic carbon-carbon double bonds (particularly alkenyl group) in the molecule 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.

  The content of the aliphatic carbon-carbon double bond in the ladder-type silsesquioxane (A-3-1) is preferably 0.7 to 5.5 mmol / g, more preferably 1.1 to 4.4 mmol. / G. Moreover, the ratio (weight basis) of the aliphatic carbon-carbon double bond contained in the ladder-type silsesquioxane (A-3-1) is preferably 2.0 to 15.0% by weight in terms of vinyl group. More preferably, it is 3.0 to 12.0% by weight.

  The molecular weight of the ladder type silsesquioxane (A-3-1) 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. When the molecular weight of the ladder-type silsesquioxane (A-3-1) is within this range, the liquid may easily become liquid at room temperature and the viscosity thereof tends to be relatively low, which may facilitate the handling. The ladder-type silsesquioxane (A-3-1) may be a mixture of those having various molecular weights within the above range. In addition, the said molecular weight is measured as a molecular weight of standard polystyrene conversion by GPC.

  The ladder-type silsesquioxane (A-3-1) has a weight average molecular weight (Mw) (in terms of polystyrene by GPC) of preferably from 100 to 800,000, more preferably from 200 to 100,000, still more preferably from 300 to 10,000. Preferably it is 500-8000. If the weight average molecular weight is less than 100, the heat resistance of the cured product may decrease. On the other hand, if the molecular weight exceeds 800,000, the compatibility with other components may decrease.

  The ladder-type silsesquioxane (A-3-1) is preferably liquid at normal temperature (about 25 ° C.). More specifically, the viscosity of the ladder-type silsesquioxane (A-3-1) 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. If the viscosity is less than 100 mPa · s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 100,000 mPa · s, it may be difficult to prepare and handle the curable resin composition. In addition, the viscosity in this specification uses 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. : Measured under the condition of 20 rpm.

  In the curable resin composition of the present invention, the ladder-type silsesquioxane (A-3-1) can be used singly or in combination of two or more.

  The content (blending amount) of the ladder-type silsesquioxane (A-3-1) in the curable resin composition of the present invention is, for example, 40% by weight or less with respect to the curable resin composition (100% by weight). More preferably, it is 1 to 40% by weight, further preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight. By setting the content to 1% by weight or more, a cured product having particularly excellent barrier properties against corrosive gas tends to be obtained. On the other hand, by setting the content to 40% by weight or less, there is a tendency that a cured product having excellent flexibility is obtained without becoming too hard.

  In addition, the content (blending amount) of ladder-type silsesquioxane (A-3-1) in the curable resin composition of the present invention (the total amount when two or more types are included) is determined in the curable resin composition. 0-30 weight% of the total amount (100 weight%) of the siloxane compound contained is preferable, More preferably, it is 5-20 weight%, More preferably, it is 10-20 weight%.

・ Ladder-type silsesquioxane (A-3-2)
Ladder-type silsesquioxane (A-3-2) is a compound represented by the formula (VII) described later on part or all of the molecular chain terminal of a polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) having a ladder structure. ) And a polyorganosilsesquioxane residue containing the unit structure represented by formula (VIII) (sometimes referred to as “polyorganosilsesquioxane residue (b)”). Polyorganosilsesquioxane.

The polyorganosilsesquioxane in the ladder-type silsesquioxane (A-3-2) 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 (A-3-2) include polyorganosilsesquioxanes in the ladder-type silsesquioxane (A-3-1) (for example, the above formula (L The same thing as the polyorganosilsesquioxane represented by) is illustrated.

  Ladder-type silsesquioxane (A-3-2), like ladder-type silsesquioxane (A-3-1), is part of the side chain from the viewpoint of the barrier property against the corrosive gas of the cured product. Or it is preferable that all are substituted or unsubstituted aryl groups.

  In the case where the polyorganosilsesquioxane is represented by the above formula (L), the ladder-type silsesquioxane (A-3-2) is a polymer in which part or all of T in the formula (L) is It has a structure substituted with an organosilsesquioxane 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。尚、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)

A unit structure represented by the formula (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), and a group in which a plurality of these are linked.

  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 cycloalkylene groups (including cycloalkylidene groups) such as a silene group, 1,4-cyclohexylene group, and cyclohexylidene group.

R ⁸ and R ⁹ in the above formula (VII) are the same or different and are 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 A sulfur atom-containing group is exemplified, and the same groups as those exemplified as R ⁵ are exemplified. 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. Especially, as R < ⁸ >, a hydrogen atom or a substituted or unsubstituted hydrocarbon group is respectively preferable, More preferably, it is a hydrogen atom. R ⁹ is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group, and still more preferably an aliphatic hydrocarbon group (particularly a methyl group). And an aromatic hydrocarbon group (particularly a 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 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. 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, R ¹⁰ in formula (VIII) is preferably a methyl group.

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

  Three oxygen atoms in the formula (VII) in the polyorganosilsesquioxane residue (b) with respect to the total amount (100 mol%) of the silicon atoms constituting the polyorganosilsesquioxane residue (b) The proportion of silicon atoms bonded to (not including silicon atoms in the SiH-containing group) is preferably 20 to 80 mol%, more preferably 25 to 60 mol%. When the ratio is less than 20 mol%, the amount of hydrosilyl group contained in the ladder-type silsesquioxane (A-3-2) becomes insufficient, and sufficient hardness of the cured product may not be obtained. On the other hand, when the ratio exceeds 80 mol%, a large amount of silanol groups and hydrolyzable silyl groups remain in the ladder-type silsesquioxane (A-3-2). -2) may not be obtained in liquid form. Furthermore, since the condensation reaction proceeds and the molecular weight tends to change, the storage stability may decrease.

  One oxygen atom in formula (VIII) in the polyorganosilsesquioxane residue (b) with respect to the total amount (100 mol%) of silicon atoms constituting the polyorganosilsesquioxane residue (b) The proportion of silicon atoms bonded to is preferably 20 to 85 mol%, more preferably 30 to 75 mol%. When the ratio is less than 20 mol%, silanol groups and hydrolyzable silyl groups are likely to remain in the ladder-type silsesquioxane (A-3-2), and the ladder-type silsesquioxane (A-3-2). ) May not be obtained in liquid form. Furthermore, since the condensation reaction proceeds and the molecular weight tends to change, the storage stability may decrease. On the other hand, when the ratio exceeds 85 mol%, the amount of hydrosilyl group contained in the ladder-type silsesquioxane (A-3-2) 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.

Ladder type silsesquioxane (A-3-2) 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 hydroxyl 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). When a plurality (2 to 4) of R ^b in the formula (L ^b ) are polyorganosilsesquioxane residues (b), each B is represented by each other or another 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 (A-3-2) is further represented by the formula (V) in the ladder-type silsesquioxane (A-3-1) described above. It may have a unit structure represented by In this case, the ladder-type silsesquioxane (A-3-2) may be used as the ladder-type silsesquioxane (A-3-1).

  A method for producing a ladder-type silsesquioxane (A-3-2) is, for example, a polyorganosilsesquioxane (raw material) having a ladder structure and having a silanol group and / or a hydrolyzable silyl group at the molecular chain end. The method of forming the said polyorgano silsesquioxane residue (b) with respect to the molecular chain terminal of a 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 (A-3-2), the number of the SiH-containing groups in the molecule (in one molecule) is preferably 2 or more (for example, 2 to 50), more preferably 2 to 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.

The hydrosilyl group content of the ladder-type silsesquioxane (A-3-2) is preferably 0.01 to 0.5 mmol / g, more preferably 0.08 to 0.28 mmol / g. In addition, the content of the hydrosilyl group based on the weight of the ladder-type silsesquioxane (A-3-2) is 0.01 to 0.50 in terms of the weight of H (hydride) in the hydrosilyl group (in terms of H). % By weight is preferable, and more preferably 0.08 to 0.28% by 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, when there is too much content of a hydrosilyl group (for example, when exceeding 0.50 mmol / g and exceeding 0.50 weight% in H conversion), the hardness of hardened | cured material may become high and it may become easy to crack. The content of the hydrosilyl group in the ladder type silsesquioxane (A-3-2) can be calculated by, for example, ¹ H-NMR spectrum measurement.

  The ratio of SiH-containing groups to the total amount of hydrosilyl groups (100 mol%) of ladder type silsesquioxane (A-3-2) is preferably 50 to 100 mol%, more preferably from the viewpoint of the degree of curing. Is 80 to 100 mol%.

  The molecular weight of the ladder-type silsesquioxane (A-3-2) 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 (A-3-2) is within this range, it is easy to handle because it tends to be liquid at room temperature and the viscosity tends to be relatively low. The ladder-type silsesquioxane (A-3-2) may be a mixture having various molecular weights within the above range. In addition, the said molecular weight is measured as a molecular weight of standard polystyrene conversion by GPC.

  The ladder-type silsesquioxane (A-3-2) has a weight average molecular weight (Mw) (in terms of polystyrene by GPC) of preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 10,000, Preferably it is 500-9000. If the weight average molecular weight is less than 100, the heat resistance of the cured product may decrease. On the other hand, if the molecular weight exceeds 800,000, the compatibility with other components may decrease.

  The ladder-type silsesquioxane (A-3-2) is preferably liquid at normal temperature (about 25 ° C.). More specifically, the viscosity of the ladder-type silsesquioxane (A-3-2) 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. If the viscosity is less than 100 mPa · s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 100,000 mPa · s, it may be difficult to prepare and handle the curable resin composition.

  In the curable resin composition of the present invention, ladder-type silsesquioxane (A-3-2) can be used alone or in combination of two or more.

  The content (blending amount) of the ladder-type silsesquioxane (A-3-2) in the curable resin composition of the present invention is 1 to 30% by weight with respect to the curable resin composition (100% by weight). Is more preferable, more preferably 3 to 20% by weight, still more preferably 5 to 15% by weight. By setting the content to 1% by weight or more, a cured product having particularly excellent barrier properties against corrosive gas tends to be obtained. 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 (A-3-3)
The ladder-type polyorganosilsesquioxane (A-3) is a ladder type other than the ladder-type silsesquioxane (A-3-1) and ladder-type silsesquioxane (A-3-2). Silsesquioxane (sometimes referred to as “other ladder-type silsesquioxane (A-3-3)”) can also be used. Other ladder-type silsesquioxanes (A-3-3) are preferably used in combination with ladder-type silsesquioxanes (A-3-1) and ladder-type silsesquioxanes (A-3-2). .

  Other ladder-type silsesquioxanes (A-3-3) are, for example, ladder-type silsesquioxanes that are solid at 25 ° C. and have an aliphatic carbon-carbon double bond (particularly an alkenyl group). (Sometimes referred to as “ladder-type silsesquioxane (S1)”); a ladder-type silsesquioxane that is solid at 25 ° C. and has a hydrosilyl group (“ladder-type silsesquioxane (S2)”) In some cases). 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 group) in the molecule is preferably 2 or more (for example, 2 to 50), more preferably 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. .

  In the ladder-type silsesquioxane (S2), the number of hydrosilyl groups in the molecule 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.

  Each of the ladder-type silsesquioxanes (S1) and (S2) has a weight average molecular weight (Mw) (in terms of polystyrene by GPC) of preferably from 2000 to 800000, more preferably from 6000 to 100,000. When the weight average molecular weight is less than 2000, the barrier property against the corrosive gas of the cured product may be lowered. On the other hand, if the molecular weight exceeds 800,000, the compatibility with other components may decrease.

  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).

  Each content of ladder type silsesquioxane (S1) and (S2) is not specifically limited, For example, 0.1-30 weight% with respect to curable resin composition (100 weight%), Preferably Can be suitably adjusted in the range of 0.1 to 15% by weight.

  Examples of the other ladder-type silsesquioxane (A-3-3) include, for example, two or more aliphatic carbon-carbon double bonds (particularly, disclosed in International Publication No. 2013/176238). , An alkenyl group) or two or more hydrosilyl groups in the molecule, the number average molecular weight (Mn) in terms of standard polystyrene by GPC is 500-1500, and the molecular weight dispersity (Mw / Mn) is 1.00-1. Ladder type silsesquioxane which is 40 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.

  In the curable resin composition of the present invention, the ladder-type polyorganosilsesquioxane (A-3) can be used singly or in combination of two or more. In particular, it is preferable to use a ladder type silsesquioxane (A-3-1) and a ladder type silsesquioxane (A-3-2) from the viewpoint of the barrier property against the corrosive gas of the cured product.

  The content of ladder-type polyorganosilsesquioxane (A-3) in the curable resin composition of the present invention (the total amount when containing two or more types) is based on the curable resin composition (100 wt%). The content is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight. By setting the content of the ladder-type polyorganosilsesquioxane (A-3) to 1% by weight or more, a cured product particularly excellent in barrier properties against corrosive gas tends to be obtained. On the other hand, when the content of the ladder-type polyorganosilsesquioxane (A-3) 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 particularly suitable from the viewpoint of remarkably increasing the barrier property against the corrosive gas of the cured product, and the ladder-type polyorganosilsesquioxane (A-3) and an isocyanurate compound (E described later). It is preferable that at least one selected from the group consisting of:

[Fluorosurfactant (B)]
The fluorosurfactant in the present invention is a compound having a polar group selected from a nonionic group (or nonionic group), an anionic group, and a cationic group, and a fluorinated alkyl group as a nonpolar group It is. In the present invention, a compound having a nonionic group as a polar group is preferable in terms of excellent compatibility with the above siloxane compound, and a compound having a polyoxyalkylene group as the nonionic group is preferable. A fluorine-type surfactant can be used individually by 1 type or in combination of 2 or more types.

The fluorinated alkyl group includes, for example, the following formula (b-1)
-C _m F _{2m + 1} (b-1)
It is represented by In said formula, m shows the integer of 1-30, Preferably it is 1-25, Most preferably, it is 1-20.

The polyoxyalkylene group includes, for example, the following formula (b-2)
_{^{- (A 1 O) p -H}} (b-2)
It is represented by In the above formula, A ¹ represents a linear or branched alkylene group having 1 to 20 carbon atoms (preferably 2 to 5 carbon atoms). p shows the integer of 1-5000, Preferably it is 2-2000, Most preferably, it is 5-1000.

  The weight average molecular weight (in terms of polystyrene by GPC) of the fluorosurfactant is, for example, 500 to 100,000, preferably 1000 to 50000, particularly preferably 2000 to 15000, and most preferably 2000 to 10,000. When the weight average molecular weight exceeds the above range, the compatibility with the polyorganosiloxane tends to decrease. On the other hand, when the weight average molecular weight is below the above range, it volatilizes during curing, and the addition effect tends to be difficult to obtain.

  The fluorosurfactant is, for example, copolymerized (meth) acrylic acid ester having a fluorinated alkyl group and (meth) acrylic acid ester having a polyoxyalkylene group (block copolymerization, graft copolymerization, random copolymerization). Or alternating copolymerization). Further, the fluorosurfactant may have a structural unit other than the structural unit derived from the monomer, and the monomer and another monomer copolymerizable with the monomer (for example, styrene, vinyltoluene, etc.). It may be a copolymer obtained by copolymerizing a styrene derivative, a vinyl copolymer such as butadiene or acrylic acid, or the like.

  Examples of the fluorosurfactant include trade names “Megafac F-444”, “Megafac F-477”, “Megafac F-553”, “Megafac F-554”, “Megafac F-−”. Commercially available products such as “556” (manufactured by DIC Corporation), trade names “FC-4430”, “FC-4432” (manufactured by Sumitomo 3M Ltd.) can be used.

  The amount of the fluorosurfactant used (when two or more types are contained, the total amount) is, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the siloxane compound contained in the curable resin composition of the present invention. , Preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight, and most preferably 0.3 to 2 parts by weight. When the fluorosurfactant is contained in the above range, a cured product having excellent barrier properties against corrosive gas can be obtained.

（式中、ａは１〜１００の整数を示す）
で表されるシリコーン鎖と、下記式（c-2）
−（Ａ²Ｏ）_b−Ｈ （c-2）
［式中、Ａ²は炭素数１〜２０（好ましくは、２〜５）の直鎖状又は分岐鎖状アルキレン基を示し、ｂは１〜５０００（好ましくは２〜２０００、特に好ましくは５〜１０００）の整数を示す］
で表されるポリオキシアルキレン鎖を有する共重合体である。 [Silicone surfactant (C)]
The silicone-based surfactant in the present invention has the following formula (c-1)

(Wherein, a represents an integer of 1 to 100)
And a silicone chain represented by the following formula (c-2)
_{^{- (A 2 O) b -H}} (c-2)
[Wherein, A ² represents a linear or branched alkylene group having 1 to 20 carbon atoms (preferably 2 to 5 carbon atoms), and b is 1 to 5000 (preferably 2 to 2000, particularly preferably 5 to 5). 1000)
Is a copolymer having a polyoxyalkylene chain represented by the formula:

  Examples of the bonding method of the silicone chain and the polyoxyalkylene chain include block copolymerization, graft copolymerization, random copolymerization, and alternating copolymerization. That is, the silicone surfactant includes a block copolymer, a graft copolymer, a random copolymer, or an alternating copolymer.

  The silicone-based surfactant has a weight average molecular weight (in terms of polystyrene by GPC) of, for example, 500 to 100,000, preferably 1,000 to 50,000, and particularly preferably 2,000 to 10,000. When the weight average molecular weight exceeds the above range, the compatibility tends to decrease. On the other hand, when the weight average molecular weight is below the above range, it volatilizes during curing, and the addition effect tends to be difficult to obtain.

  The silicone surfactant can be produced, for example, by copolymerizing a silicone monomer having a radical polymerizable group at the terminal of a silicone polymer such as polydimethylsiloxane.

  Examples of the silicone surfactant include trade names “BYK-307”, “BYK-310”, “BYK-330”, “BYK-333”, “BYK-377”, “BYK-378” (and above). , Manufactured by Big Chemie Japan), trade names “ACFS180”, “ACFS360”, “ACS20” (manufactured by Alginchemie), trade names “Polyflow KL-400X”, “Polyflow KL-400HF”, “Polyflow KL-401”, “Polyflow KL-402”, “Polyflow KL-403”, “Polyflow KL-404” (manufactured by Kyoeisha Chemical Co., Ltd.), trade names “KP-323”, “KP-326”, “KP-341” "KP-104", "KP-110", "KP-112" (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name "LP-700 ”,“ LP-7002 ”,“ L-7604 ”,“ FZ-2110 ”,“ FZ-2105 ”,“ 3 ADDITIVE ”,“ 56 ADDITIVE ”,“ 57 ADDITIVE ”,“ 67 ADDITIVE ”,“ 8032 ADDITIVE ” , "8618 ADDITIVE" (above, manufactured by Toray Dow Corning Co., Ltd.) can be used.

  The silicone surfactant is used in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the siloxane compound contained in the curable resin composition of the present invention. , Preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight, and most preferably 0.3 to 2 parts by weight. When the silicone surfactant is contained in the above range, a cured product having excellent barrier properties against corrosive gas can be obtained.

  Moreover, when using together the said fluorine-type surfactant and silicone type surfactant, the usage-ratio (the former / latter: weight ratio) is 30 / 70-70 / 30, for example, Preferably 40 / 60-60 / 40 Particularly preferred is 45/55 to 55/45. It is preferable to use the fluorosurfactant and the silicone surfactant in the above ranges in that a cured product having particularly excellent barrier properties against corrosive gas can be obtained.

[Hydrosilylation catalyst (D)]
The curable resin composition of the present invention may contain one or more hydrosilylation catalysts. When the curable resin composition of the present invention contains a hydrosilylation catalyst, a hydrosilylation reaction between an aliphatic carbon-carbon double bond (particularly, an alkenyl group) and a hydrosilyl group in the curable resin composition is caused by heating. It is possible to 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 these, 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.

The content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is 1 mol of the total amount of aliphatic carbon-carbon double bonds (particularly alkenyl groups) contained in the curable resin composition. 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol is preferable, and 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻³ mol is more preferable. 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, by setting the content to 1 × 10 ⁻² mol or less, a cured product having a more excellent hue (less coloring) tends to be obtained.

  Further, the content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is, for example, platinum, palladium, or rhodium in the hydrosilylation catalyst in a range of 0.01 to 1000 ppm by weight. An amount that falls within the range of 0.1 to 500 ppm is more preferable. 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 better hue tends to be obtained.

[Isocyanurate compound (E)]
The curable resin composition of the present invention preferably further contains an isocyanurate compound (E). When the curable resin composition of the present invention contains the isocyanurate compound (E), the isocyanurate skeleton in the isocyanurate compound (E) in the cured product regardless of the state reacted with other components and the unreacted state. However, it is possible to trap the corrosive gas such as SOx gas or to further improve the barrier property against the corrosive gas. Moreover, since the isocyanurate compound (E) has good solubility in the curable resin composition of the present invention, it does not precipitate as a solid even when the amount is increased or when the curable resin composition is not heated.

The isocyanurate compound (E) is a compound represented by the following formula (1).

（式中、Ｒ^d、Ｒ^eは、同一又は異なって、水素原子又は炭素数１〜８の直鎖状若しくは分岐鎖状のアルキル基を示す。ｓ、ｔは、同一又は異なって１〜１０の整数を示す） In the above formula (1), R ^a , R ^b , and R ^c are the same or different and represent a group represented by the following formula (1a), a group represented by the following formula (1b), a hydrogen atom, or an alkyl Indicates a group. However, at least one of R ^a , R ^b and R ^c is a group represented by the following formula (1a).

(Wherein R ^d and R ^e are the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. S and t are the same or different and represent 1 to 10) Indicates an integer)

Examples of the linear or branched alkyl group having 1 to 8 carbon atoms (linear or branched C _1-8 alkyl group) include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples include butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group and the like. Of these, 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.

R ^d and R ^e are particularly preferably hydrogen atoms.

The alkyl group as R ^a , R ^b and R ^c may be linear, branched or cyclic, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group , S-butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group, etc., linear or branched alkyl group (for example, linear or branched C _1-8 alkyl group) A cyclic alkyl group (that is, a cycloalkyl group) which may have a linear alkyl group (for example, a C _1-3 alkyl group) as a substituent such as a cyclohexyl group, a methylcyclohexyl group, or a dimethylcyclohexyl group; Is mentioned.

In addition, when two or three of R ^a , R ^b and R ^{c in} the formula (1) are groups represented by the formula (1a), the groups represented by these formulas (1a) are: They may be the same or different.

Further, when two of R ^a , R ^b and R ^c in the formula (1) are groups represented by the formula (1b), the groups represented by the formula (1b) are the same. It may be different or different. Furthermore, the isocyanurate compound (E) may not have the group represented by the formula (1b).

  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.

  The content of the isocyanurate compound (E) (when two or more are contained, the total amount thereof) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the siloxane compound contained in the curable resin composition. Preferably it is 0.03-3 weight part, More preferably, it is 0.05-1 weight part, Most preferably, it is 0.1-0.5 weight part. By containing the isocyanurate compound (E) in the above range, the effect of remarkably improving the barrier property against the corrosive gas of the cured product can be obtained without causing a problem of solid precipitation.

In the present invention, as the isocyanurate compound (E), among them, the group represented by the formula (1a) in the formula (1) is a group represented by the following formula (1a ′), and the formula (1b ) Is a group represented by the following formula (1b ′), and R ^a , R ^b , and R ^c are represented by the group represented by the formula (1a ′) and the formula (1b ′). It is preferable that at least the isocyanurate compound (E-1) having a group to be formed has an effect of improving the adhesion to the adherend of the cured product and improving the barrier property against corrosive gas. . In the following formula, R ^d and R ^e are the same as described above.

That is, the isocyanurate compound (E-1) is represented by the above formula (1), and in the formula (1), R ^a , R ^b and R ^c are the same or different and represented by the formula (1a ′). A group represented by formula (1b ′), a hydrogen atom, or an alkyl group. However, at least one of R ^a , R ^b , and R ^c is a compound represented by the formula (1a ′), and at least one is a compound represented by the formula (1b ′). .

Examples of the isocyanurate compound (E-1) include compounds in which one of R ^a , R ^b and R ^{c in} the formula (1) is a group represented by the formula (1b ′) (“monoallyl A glycidyl isocyanurate compound), a compound in which two of R ^a , R ^b and R ^c in formula (1) are represented by formula (1b ′) (“diallyl monoglycidyl isocyanurate compound”) May be referred to).

  Examples of the monoallyl diglycidyl isocyanurate compound include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methylpropenyl) -3, Examples include 5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate.

  Examples of the diallyl monoglycidyl isocyanurate compound include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3-bis (2-methylpropenyl) -5. Examples thereof include glycidyl isocyanurate and 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate.

  In the curable resin composition of this invention, an isocyanurate compound (E-1) can be used individually by 1 type or in combination of 2 or more types. Moreover, as isocyanurate compound (E-1), you may use commercial items, such as a brand name "MA-DGIC" (Shikoku Chemicals Co., Ltd. product), for example.

  Since the isocyanurate compound (E-1) has a group represented by the formula (1b ′), 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 the aforementioned ladder-type silsesquioxane (A-3-2) in the presence of a hydrosilylation catalyst is used for the curable resin composition of the present invention. It can also be used as a constituent.

  From the viewpoint of improving compatibility with other components, the isocyanurate compound (E-1) can be mixed with the silane coupling agent (F) described later before blending with other components.

  The content (blending amount) of the isocyanurate compound (E-1) is preferably 0.01 to 10 parts by weight, more preferably 0.03 with respect to 100 parts by weight of the siloxane compound contained in the curable resin composition. -3 parts by weight, more preferably 0.05-1 part by weight. When the content of the isocyanurate compound (E-1) is 0.01 parts by weight or more, the barrier property against the corrosive gas of the cured product and the adhesion to the adherend tend to be further improved. On the other hand, the problem of solid precipitation in the curable resin composition can be suppressed by setting the content of the isocyanurate compound (E-1) to 10 parts by weight or less.

  In the curable resin composition of the present invention, the group represented by the formula (1a) in the formula (1) is a group represented by the following formula (1a ″) together with the isocyanurate compound (E-1). It is preferable to contain some isocyanurate compound (E-2) in combination.

That is, the isocyanurate compound (E-2) is represented by the above formula (1), and in the formula (1), R ^a , R ^b and R ^c are the same or different and represented by the formula (1a ″). A group represented by formula (1b), a hydrogen atom, or an alkyl group, provided that at least one of R ^a , R ^b , and R ^c is represented by formula (1a ″). It is a compound that is a group.

  S ′ in the formula (1a ″) represents an integer of 2 to 10 (preferably 2 to 8, particularly preferably 2 to 6, most preferably 2 to 4). T in the formula (1b) is 1 to 10. It is an integer, preferably an integer of 1-6.

  Isocyanurate compound (E-2) has a group represented by the above formula (1a ") in the molecule or does not have the group (for example, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate) Other components in the curable resin composition of the present invention (especially polyorgano) compared with those not having the above group while having an effect of improving the barrier property against corrosive gas equal to or higher than The compatibility with the siloxane (A-1) and the polyorganosiloxane (A-2)) is very good, so that the isocyanurate compound (E-2) is added to the curable resin composition of the present invention. Therefore, the barrier property against the corrosive gas of the cured product can be remarkably improved without causing the problem of solid precipitation.

Examples of the isocyanurate compound (E-2) include compounds in which one of R ^a , R ^b , and R ^{c in} the formula (1) is a group represented by the formula (1a ″), the formula (1) A compound in which two of R ^a , R ^b and R ^c in formula (1a ″) are a group represented by formula (1a ″), and all of R ^a , R ^b and R ^c in formula (1) are represented by formula (1a ″) In particular, two or three of R ^a , R ^b , and R ^c in the formula (1) are represented by the formula (1a ″) in that the problem of solid precipitation hardly occurs. The compound which is group represented by this is preferable, More preferably, it is a compound in which all of R ^<a> , R ^<b > and R ^<c > in Formula (1) are group represented by Formula (1a ").

  When the isocyanurate compound (E-2) has a group represented by the formula (1b), 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 above-mentioned ladder type silsesquioxane (A-3-2) 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 this invention, an isocyanurate compound (E-2) can be used individually by 1 type or in combination of 2 or more types. As the isocyanurate compound (E-2), a commercial product such as a trade name “TEPIC-VL” (manufactured by Nissan Chemical Industries, Ltd.) may be used.

  The content (blending amount) of the isocyanurate compound (E-2) is preferably 0.01 to 10 parts by weight, more preferably 0.03 with respect to 100 parts by weight of the siloxane compound contained in the curable resin composition. -3 parts by weight, more preferably 0.05-1 part by weight. When the content of the isocyanurate compound (E-2) is 0.01 parts by weight or more, a cured product having particularly excellent barrier properties against corrosive gas tends to be obtained. On the other hand, by setting the content of the isocyanurate compound (E-2) to 10 parts by weight or less, a cured product that is superior in heat resistance, toughness, transparency, and the like tends to be obtained.

[Silane coupling agent (F)]
The curable resin composition of the present invention may contain a silane coupling agent (F). By containing the silane coupling agent (F), the effect of further improving the adhesion of the cured product to the adherend can be obtained. Furthermore, the silane coupling agent (F) has good compatibility with isocyanurate compounds (E) (especially monoallyl diglycidyl isocyanurate compounds) and ladder-type silsesquioxanes (A-3-2). Therefore, when the isocyanurate compound (E) is used, for example, when a composition of the isocyanurate compound (E) and the silane coupling agent (F) is formed in advance and then blended with other components. A uniform curable resin composition is easily obtained.

  As the silane coupling agent (F), a known or conventional silane coupling agent can be used. For example, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy group-containing silane coupling agents such as silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N- (1,3-dimethyl-butylide ) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (β-aminoethyl) -γ- Amino group-containing silane coupling agents such as aminopropylmethyldiethoxysilane; tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (Methoxyethoxysilane), phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxy Silane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, mercaptopropylenetrimethoxysilane, mercaptopropylenetriethoxysilane, alkoxy oligomer (for example, trade name “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 be used individually by 1 type or in combination of 2 or more types. Moreover, as a silane coupling agent (F), commercial items, such as a brand name "XIAMETER OFS-6040" (made by Dow Corning), can be used, for example.

  The content (blending amount) of the silane coupling agent (F) in the curable resin composition of the present invention is preferably 0.01 to 15% by weight relative to the curable resin composition (100% by weight), and more. Preferably it is 0.1 to 10 weight%, More preferably, it is 0.5 to 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 (E) 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.

  Furthermore, the curable resin composition of the present invention may contain components other than the above-mentioned components (sometimes referred to as “other components”). Examples of other components include siloxane compounds other than those described above (for example, cyclic siloxane compounds, low molecular weight linear or branched siloxane compounds, etc.), hydrosilylation reaction inhibitors, 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 can be used individually by 1 type or in combination of 2 or more types. 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.

  The curable resin composition of the present invention can be prepared, for example, by stirring and mixing the above components 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 preferably 300 to 20000 mPa · s, more preferably 500 to 10000 mPa · s, and still more preferably 1000 to 8000 mPa · s. By setting the viscosity to 300 mPa · s or more, the heat resistance of the cured product tends to be further improved. On the other hand, by setting the viscosity to 20000 mPa · s or less, the curable resin composition can be easily prepared, the productivity and handleability are further improved, and bubbles are less likely to remain in the cured product. There exists a tendency for the productivity and quality of a thing (especially sealing material) to improve more.

<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 that seals 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 conventional method. For example, the sealing agent of the present invention can be injected into a predetermined mold and cured by heating under predetermined conditions. The curing temperature and the curing time can be set in the same range as at the time of preparing the cured product. The encapsulant of the present invention is particularly effective when the semiconductor device is an optical semiconductor device, that is, when it is used as an encapsulant for optical semiconductor elements in an optical semiconductor device (encapsulant for optical semiconductors). . 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). The number average molecular weight and weight average molecular weight of the product and product were measured under the following conditions.
Alliance HPLC system 2695 (manufactured by Waters)
Refractive Index Detector 2414 (manufactured by Waters)
Column: Tskel GMH _HR- M (manufactured by Tosoh Corporation) × 2 guard columns: Tskel guard column H _HR L (manufactured by Tosoh Corporation)
Column oven: COLUMN HEATER U-620 (manufactured by Sugai)
Solvent: THF
Measurement conditions: 40 ° C

Production Example 1
[Synthesis of Ladder Type Polyorganosilsesquioxane (A-3-1) 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 (A-3-1) having a vinyl group and a TMS group at the terminal [A ladder described above] 19.0 g of a colorless transparent liquid product was obtained, which corresponds to type silsesquioxane (A-3-1).
The ladder-type polyorganosilsesquioxane (A-3-1) having a vinyl group and a TMS group at the terminal has a weight average molecular weight (Mw) of 3000. Content of vinyl groups per molecule (average content) Was 4.00% by weight, the phenyl group content (average content) was 3.85% by weight, and the phenyl group / methyl group / vinyl group (molar ratio) was 5/80/15.
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)

Production Example 2
[Synthesis of Ladder Type Polyorganosilsesquioxane (A-3-2) Having SiH-containing Group and TMS Group at Terminal]
In a reaction vessel, 12 g of ladder-type polyorganosilsesquioxane (A-3-1) obtained in Production Example 1 and 1,1,3,3-tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) 24 g and a 2.0% platinum-cyclovinylsiloxane complex vinylcyclosiloxane solution (manufactured by Wako Pure Chemical Industries, Ltd.) 10 μL were charged. Subsequently, the reaction was completed by heating at 70 ° C. for 8 hours. Subsequently, after concentrating with an evaporator, the pressure is reduced at 0.2 Torr for 3 hours using a vacuum pump, and a ladder-type polyorganosilsesquioxane (A-3-2) having a SiH-containing group and a TMS group at the end (A-3-2) [ Corresponding to the ladder-type silsesquioxane (A-3-2) described above] was obtained as a liquid product.
The ladder-type polyorganosilsesquioxane (A-3-2) has a weight average molecular weight (Mw) of 3300, and the content of hydrosilyl groups per molecule (average content) is the amount of H (hydride) in the hydrosilyl group. It was 0.12% by weight in terms of weight.
¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )): δ 0.3-0.3 ppm (br), 4.7 ppm (s), 7.1-7.7 ppm (br)

Example 1
[Production of curable resin composition]
First, as shown in Table 1, GD1012A (50 parts by weight), F-556 (1 part by weight), and BYK-333 (1 part by weight) are mixed and stirred at 80 ° C. for 1 hour to prepare agent A. did.
Next, GD1012B (50 parts by weight) as the B agent was mixed with the A agent (50.3 parts by weight) obtained above and stirred at room temperature for 1 hour. As a result, a uniform liquid curable resin composition was obtained. Product (viscosity at 23 ° C .: 3200 mPa · s) 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 2-11, Comparative Examples 1-2
[Production of curable resin composition]
A curable resin composition was produced in the same manner as in Example 1 except that the composition of the curable resin composition was changed as shown in Table 1.

[Manufacture of optical semiconductor devices]
Moreover, the optical semiconductor device was manufactured like Example 1 except having used each curable resin composition obtained above.

(Evaluation)
The following evaluation was performed about the optical semiconductor device obtained above. The evaluation results are shown in Table 1.
[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 of the curable resin compositions (for each example and comparative example), the luminous intensity maintenance rate was measured and calculated for 10 optical semiconductor devices. Table 1 shows an average value of these luminous intensity maintenance rates (N = 10).

In the examples and comparative examples, the following components were used.
[Siloxane compound]
<Polyorganosiloxane (A-1)>
GD1012A: Trade name “ETERLED GD1012A”, manufactured by Changko Material Industries, vinyl group content 1.33% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride conversion) 0% by weight, number average molecular weight 5108, weight Average molecular weight 23385, including hydrosilylation catalyst.
KER-2500A: trade name “KER-2500A”, manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.53% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride conversion) 0.03% %, Number average molecular weight 4453, weight average molecular weight 19355, and a hydrosilylation catalyst.
<Polyorganosiloxane (A-2)>
GD-1012B: Trade name “ETERLED GD1012B”, manufactured by Changxing Materials Industry, vinyl group content 1.65% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride conversion) 0.19% by weight, number average Molecular weight 4563, weight average molecular weight 21873
KER-2500B: trade name “KER-2500B”, manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.08 wt%, phenyl group content 0 wt%, hydrosilyl group content (hydride conversion) 0.13 wt %, Number average molecular weight 4636, weight average molecular weight 18814
<Ladder-type silsesquioxane (A-3)>
A-3-1: Compound obtained in Production Example 1
A-3-2: Compound obtained in Production Example 2 [Fluorosurfactant (B)]
F-556: Nonionic, weight average molecular weight 9000, trade name “Megafac F-556”, manufactured by DIC Corporation F-477: Nonionic, weight average molecular weight 12000, trade name “Megafac F-477”, DIC [Silicone surfactant (C)]
BYK-307: weight average molecular weight 12000, trade name “BYK-307”, manufactured by BYK Japan Japan BYK-310: weight average molecular weight 3500, product name “BYK-310”, manufactured by BYK Japan Japan BYK-330: weight average molecular weight 12000 , Trade name “BYK-330”, BYK-333 manufactured by BYK Japan: weight average molecular weight 5000, trade name “BYK-333”, manufactured by BYK Japan Japan BYK-377: weight average molecular weight 18000, trade name “BYK-377” BYK-378 manufactured by Big Chemie Japan: weight average molecular weight 5000, trade name “BYK-378”, manufactured by Big Chemie Japan [isocyanurate compound (E)]
MA-DGIC: Monoallyl diglycidyl isocyanurate, trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd. TEPIC-VL: Tris- (4,5-epoxypentyl) -isocyanurate, trade name “TEPIC-VL "Nissan Chemical Industry Co., Ltd. [Silane coupling agent (F)]
OFS-6040: γ-glycidoxypropyltrimethoxysilane, trade name “XIAMETER OFS-6040”, manufactured by Dow Corning

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

Claims (13)

  A polyorganosiloxane (A-1) having two or more alkenyl groups in the molecule, a polyorganosiloxane (A-2) having two or more hydrosilyl groups in the molecule, and a fluorosurfactant (B) A curable resin composition comprising:   Furthermore, the curable resin composition of Claim 1 containing ladder type polyorgano silsesquioxane (A-3).   Furthermore, the curable resin composition of Claim 1 or 2 containing a silicone type surfactant (C).   Furthermore, the curable resin composition of any one of Claims 1-3 containing a hydrosilylation catalyst (D). Further, the following formula (1)

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

(Wherein R ^d and R ^e are the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. S and t are the same or different and represent 1 to 10) Indicates an integer)]]
The curable resin composition of any one of Claims 1-4 containing the isocyanurate compound (E) represented by these. As the ladder-type polyorganosilsesquioxane (A-3), 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 according to any one of claims 2 to 5, comprising a ladder-type silsesquioxane (A-3-1) having a polyorganosilsesquioxane residue containing a unit structure represented by: object. As the ladder-type polyorganosilsesquioxane (A-3), 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, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxyl group, hydroperoxy 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, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group, hydroxyl group , A hydroperoxy group, an amino group or a substituted amino group, a mercapto group, or a sulfo group]
The group represented by these is shown. n represents an integer of 1 to 100]
A unit structure represented by the following formula (VIII)

[In the formula (VIII), R ¹⁰ are the same or different and each represents a hydrocarbon group]
The curable resin composition according to any one of claims 2 to 6, comprising a ladder-type silsesquioxane (A-3-2) having a polyorganosilsesquioxane residue containing a unit structure represented by the formula: object.   The ladder-type polyorganosilsesquioxane (A-3) is a ladder-type polyorganosilsesquioxane (A-3) in which part or all of the side chain is a substituted or unsubstituted aryl group. The curable resin composition according to any one of 2 to 7.   Furthermore, the curable resin composition of any one of Claims 1-8 containing a silane coupling agent (F).   A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9.   It is a sealing agent, The curable resin composition of any one of Claims 1-9.   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 according to claim 11.   The semiconductor device according to claim 12, which is an optical semiconductor device.

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