JP2021012202A - Curable resin composition, method for manufacturing the same and method for measuring tack on surface of viscoelastic material - Google Patents

Abstract

To provide a method for measuring tack on the surface of a viscoelastic material, having high accuracy of measurement in a low tack region and capable of quantitatively measuring the tack from the low tack region to a high tack region.SOLUTION: A method for measuring tack on the surface of a viscoelastic material comprises steps of: contacting an adherend 303 to a viscoelastic material 300 so as to form a contact area of 50 mm2 or more to apply a load and relax a stress; applying a displacement in a separation direction to separate the adherend 303 from the viscoelastic material 300; and recording a stress change on the contact surface from the contact to the separation to quantify the tack from a curve obtained using the x-axis as a displacement and the y-axis as a stress.SELECTED DRAWING: Figure 3

Description

The present invention is obtained by sealing a semiconductor element (particularly an optical semiconductor element) using a curable resin composition and a cured product thereof, a sealing agent using the curable resin composition, and the sealing agent. The present invention relates to semiconductor devices (particularly optical semiconductor devices). The present invention also relates to a method for producing a curable resin composition. Furthermore, the present invention relates to a method for measuring tack on the surface of a viscoelastic material.

Various resin materials are used as a sealing material for coating and protecting a semiconductor element in a semiconductor device. In particular, the sealing material in the optical semiconductor device, to be excellent in barrier properties against corrosive gas typified by sulfur compounds such as SO _X or H ₂ S is determined.

Methyl silicone (methyl silicone-based encapsulant), which has excellent heat resistance, is mainly used as an encapsulant in optical semiconductor devices, especially for lighting applications. For example, it is known that the sulfurization resistance to SO _X is improved by using a resin composition containing a ladder-type silsesquioxane, an isocyanurate compound, and a silane coupling agent in methyl silicone as a sealing agent. (See, for example, Patent Document 1).

International Publication No. 2014/109349

By the way, silicone-based encapsulants often have tackiness. For this reason, when picking an LED using a silicone-based encapsulant, the portion where the encapsulant is exposed on the surface may adhere to the pickup tool, or the LEDs may stick to each other in the production line, resulting in workability. There was a problem of lowering. Further, the LED using the silicone-based sealing material has a problem that dust easily adheres to the portion where the sealing material is exposed on the surface.

Therefore, an object of the present invention is to provide a curable resin composition capable of forming a material (cured product) having low tack property and to which dust does not easily adhere by curing.
Another object of the present invention is to provide a material (cured product) having low tackiness and to which dust does not easily adhere.
Further, another object of the present invention is a sealing agent using the curable resin composition, and a quality obtained by sealing a semiconductor element (particularly an optical semiconductor element) using the sealing agent. The purpose is to provide semiconductor devices (particularly optical semiconductor devices) having excellent durability.
Furthermore, an object of the present invention is a method for producing a curable resin composition capable of producing a curable resin composition having an idea of the tackiness of the cured product of the curable resin composition and the adhesion of dust. To provide.

Further, conventionally, the curable resin composition for forming a silicone-based encapsulant has actually been used to determine the tackiness and the adhesion of dust when the LED element is sealed with the cured material. It was the first thing that could be confirmed after manufacturing. Even in the past, it has been possible to evaluate the tackiness of a cured product obtained by curing a curable resin composition under predetermined conditions by a conventional method before actually manufacturing the LED.

As a conventional tackiness evaluation, for example, a tilted ball tack test is defined in JIS Z 0237, and related to this, there is a JIS Z 0237-related supplement (rolling ball tack test, probe tack test). For the ball tack test, J. The Dow method may also be used. In the ball tack test, a steel ball is rolled on an inclined test piece adhesive surface and evaluated based on the rolling distance. The balance between the kinetic energy of the steel ball rolling on the slope and the adhesive force is valued by the sliding distance or the size of the steel ball. In the probe tack test, the tack is measured by pressing the needle-shaped adherend against the test piece.

However, the conventional evaluation of tackiness as described above is suitable for evaluation of a pressure-sensitive adhesive having high tackiness, but not suitable for a viscoelastic material having low tackiness such as a silicone-based encapsulant. For example, in the ball tack test, accuracy in quantitativeness and reproducibility could not be expected in the evaluation of adhesiveness with low tackiness. The probe tack test was not always a sufficient measurement because the test piece was deformed by the adherend and the evaluation results varied due to the small contact area between the adherend and the test piece. In addition, since the probe tack test targets the evaluation of tape adhesives and the like, the detection ability and measurement stability may be lacking in a low tack region in order to quantify the surface tack of a viscoelastic body.

Therefore, another object of the present invention is to provide a method for measuring the tack on the surface of a viscoelastic material, which has high measurement accuracy in a low tack region and can quantitatively measure from a low tack region to a high tack region. ..

The present inventors have a silicone having a specific composition containing a specific polysiloxane having two or more alkenyl groups in the molecule and a specific polysiloxane having two or more hydrosilyl groups in the molecule as essential components. According to a curable resin composition containing a resin and the peel strength and the total peel load obtained by a specific peel load evaluation for a cured product are equal to or less than a specific value, the tack property is low and dust adheres to the cured product. It was found that a difficult cured product can be formed. Further, the present inventors contact the viscoelastic material with the adherend so as to have a specific contact area, apply a load to the viscoelastic material, relax the stress, and then release the adherend and the viscoelastic material. According to the measurement method of separating and quantifying the tack by recording the stress change of the contact surface from this contact to the separation, the measurement accuracy in the low tack region is high, and the quantitative measurement is performed from the low tack region to the high tack region. Found that is possible. The present invention has been completed based on these findings.

That is, the present invention is selected from the group consisting of polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and polyorganosyloxysylalkylene (A2) having two or more alkenyl groups in the molecule. From at least one polysiloxane (A), polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule, and polyorganosyloxysylalkylene (B2) having two or more hydrosilyl groups in the molecule. A curable resin composition containing at least one polysiloxane (B) selected from the above group, and the polysiloxane (A) is a polyorgano represented by the following average unit formula (a-1). It contains at least one selected from the group consisting of siloxane and polyorganosyloxysylalkylene represented by the following average unit formula (a-2), and the polysiloxane (B) is represented by the following average unit formula (b-1). All containing at least one selected from the group consisting of the polyorganosiloxane represented and the polyorganosyloxysylalkylene represented by the following average unit formula (b-2), and contained in the curable resin composition. Of the silicon atoms, the ratio of the number of silicon atoms in the siloxane unit represented by (R ₃ SiO _1/2 ) is M, and the ratio of the number of silicon atoms in the siloxane unit represented by (R ₂ SiO _2/2 ). the D, T a ratio of the number of silicon atoms in the siloxane units represented by (RSiO _3/2), when the ratio of the number of silicon atoms in the siloxane units represented by (SiO _4/2) and is Q, For 1 mol of aliphatic carbon-carbon double bond present in the curable resin composition, which satisfies (T + Q) / D> 0.3 and M + D + T + Q = 1 (where R indicates a monovalent group). The hydrosilyl group is 0.9 to 5.0 mol, and the curable resin composition is heated at at least one curing condition selected from the conditions of 25 to 180 ° C. and 1 to 720 minutes. The peel strength per 1 mm ² obtained by the following peel load evaluation of the cured product when cured is 0.40 N or less, and / or the total peel load per 1 mm ² obtained by the following peel load evaluation is 0.018 N. Provided is a curable resin composition having a size of mm or less.
Peeling load evaluation: The adherend made of SUS and the cured product are brought into contact with the adherend and the cured product by moving at least one of the adherend and the cured product from a state in which they are vertically separated from each other. After contacting them so that they have an area of 50 to 800 mm ² and pressing them with a load of 100 N for 2 minutes, the stress change of the contact surface when separated in the vertical direction is recorded, and the adherend and the cured product are separated. The value obtained by dividing the maximum stress value from the start of separation to the complete separation by the contact area is defined as the peel strength, and the stress curve and baseline from the start of separation of the adherend and the cured product to the complete separation. The value obtained by dividing the area surrounded by and by the contact area is defined as the total peeling load. However, the peel strength and the total peel load can be separated from each other at any 10 points within the range of 5 to 500 mm / min (however, the speed difference between the two adjacent points is 5 mm / min or more). It is the maximum value of the value obtained by measuring with).
Average unit formula (a-1):
(R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5
[In the average unit formula (a-1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, which is the same or different. However, a part of R ¹ is an alkenyl group, which is in the range of two or more in the molecule. X ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a1, a2, a3, a4, and a5 are 1> a1 ≧ 0, 1> a2 ≧ 0, 1>a3> 0, 1> a4 ≧ 0, 0.05 ≧ a5 ≧ 0, a1 + a2 + a4> 0, respectively. And a numerical value satisfying a1 + a2 + a3 + a4 + a5 = 1 is shown. ]
Average unit formula (a-2):
(R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 (SiO _4/2 ) _b4 ( ^RA ) _b5 (X ² O _1/2 ) _b6
[In the average unit formula (a-2), R ² represents the same or different alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, or alkenyl group having 2 to 8 carbon atoms. However, a part of R ² is an alkenyl group, which is in the range of two or more in the molecule. ^RA represents the same or different alkylene group having 1 to 14 carbon atoms. X ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. b1, b2, b3, b4, b5, and b6 are 1> b1 ≧ 0, 1>b2> 0, 1> b3 ≧ 0, 1> b4 ≧ 0, 0.7>b5> 0, 0, respectively. The numerical values satisfying 05 ≧ b6 ≧ 0, b1 + b3 + b4> 0, and b1 + b2 + b3 + b4 + b5 + b6 = 1 are shown. ]
Average unit formula (b-1):
(R ³ SiO _3/2 ) _c1 (R ³ ₂ SiO _2/2 ) _c2 (R ³ ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (X ³ O _1/2 ) _c5
[In the average unit formula (b-1), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which are the same or different. However, a part of R ³ is a hydrogen atom, which is a range of two or more in the molecule. X ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. c1, c2, c3, c4, and c5 are 1> c1 ≧ 0, 1> c2 ≧ 0, 1>c3> 0, 1> c4 ≧ 0, 0.05 ≧ c5 ≧ 0, c1 + c2 + c4> 0, respectively. And c1 + c2 + c3 + c4 + c5 = 1 are shown. ]
Average unit formula (b-2):
(R ⁴ ₂ SiO _2/2 ) _d1 (R ⁴ ₃ SiO _1/2 ) _d2 (R ⁴ SiO _3/2 ) _d3 (SiO _4/2 ) _d4 ( ^RA ) _d5 (X ⁴ O) _d6
[In the average unit formula (b-2), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which is the same or different. However, a part of R ⁴ is a hydrogen atom, which is a range of two or more in the molecule. ^RA represents the same or different alkylene group having 1 to 14 carbon atoms. X ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. d1, d2, d3, d4, d5, and d6 are 1> d1 ≧ 0, 1>d2> 0, 1> d3 ≧ 0, 1> d4 ≧ 0, 0.5>d5> 0, 0, respectively. The numerical values satisfying 05 ≧ d6 ≧ 0, d1 + d3 + d4> 0, and d1 + d2 + d3 + d4 + d5 + d6 = 1 are shown. ]

It is preferable that the curable resin composition further satisfies 0.9> T ≧ 0.4 or 0.9> Q ≧ 0.2.

The curable resin composition preferably further contains a ladder-type polyorganosylsesquioxane (C).

［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（Ｃ１）を含むことが好ましい。 As the ladder-type polyorganosylsesquioxane (C), a part or all of the molecular chain ends of the polyorganosylsesquioxane having a ladder structure has the following formula (V).

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

[In formula (VI), R ⁷ represents the same or different hydrocarbon group. ]
It is preferable to contain a ladder-type silsesquioxane (C1) having a polyorganosilsesquioxane residue containing a unit structure represented by.

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

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

［式（VIII）中、Ｒ¹⁰は、同一又は異なって、炭化水素基を示す。］
で表される単位構造を含むポリオルガノシルセスキオキサン残基を有するラダー型シルセスキオキサン（Ｃ２）を含むことが好ましい。 As the ladder-type polyorganosylsesquioxane (C), a part or all of the molecular chain ends of the polyorganosylsesquioxane having a ladder structure is 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, hydrogen atom, halogen atom, substituted or unsubstituted hydrocarbon group, alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, acyloxy group, alkylthio group, alkenylthio. Group, arylthio group, aralkylthio group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanato group, carbamoyl group, isothiocyanate group, hydroxy group, hydroperoxy Group, sulfo group, amino group or substituted amino group, mercapto group, sulfo group, or the following formula (s)

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

[In formula (VIII), R ¹⁰ represents the same or different hydrocarbon group. ]
It is preferable to contain a ladder-type silsesquioxane (C2) having a polyorganosilsesquioxane residue containing a unit structure represented by.

It is preferable that the ladder-type polyorganosylsesquioxane (C) is a ladder-type polyorganosylsesquioxane having an aryl group in which a part or all of the side chain is substituted or unsubstituted.

The ratio of the aryl group to the total amount of the monovalent substituted or unsubstituted hydrocarbon group bonded to the silicon atom in all the polysiloxanes contained in the curable resin composition is preferably 10 mol% or more.

The curable resin composition preferably further contains compound (D) containing an isocyanuric skeleton.

［式（１）中、Ｒ^x、Ｒ^y、及びＲ^zは、同一又は異なって、式（１ａ）で表される基、又は式（１ｂ）で表される基を示す。

［式（１ａ）中、Ｒ¹³は、水素原子又は炭素数１〜８の直鎖若しくは分岐鎖状のアルキル基を示す。］

［式（１ｂ）中、Ｒ¹⁴は、水素原子又は炭素数１〜８の直鎖若しくは分岐鎖状のアルキル基を示す。］］
で表される化合物であることが好ましい。 The compound (D) containing the isocyanuric skeleton has the following formula (1).

[In the formula (1), R ^x , R ^y , and R ^z represent the same or different groups represented by the formula (1a) or the groups represented by the formula (1b).

[In formula (1a), R ¹³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]

[In formula (1b), R ¹⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
It is preferably a compound represented by.

Regarding the compound represented by the formula (1), it is preferable that any one or more of R ^x , R ^y , and R ^z in the formula (1) is a group represented by the formula (1b).

The curable resin composition preferably further contains a silane coupling agent (E).

The present invention also provides a cured product of the curable resin composition.

The present invention also provides a sealing agent containing the curable resin composition.

Further, the present invention is a semiconductor device having a semiconductor element and a sealing material for sealing the semiconductor element, wherein the sealing material is a cured product of the sealing agent. Provide the device.

Furthermore, the present invention is selected from the group consisting of polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and polyorganosyloxysylalkylene (A2) having two or more alkenyl groups in the molecule. From at least one polysiloxane (A), polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule, and polyorganosyloxysylalkylene (B2) having two or more hydrosilyl groups in the molecule. A composition (I) containing at least one polysiloxane (B) selected from the above group, and the polysiloxane (A) is a polyorgano represented by the following average unit formula (a-1). It contains at least one selected from the group consisting of siloxane and polyorganosyloxysylalkylene represented by the following average unit formula (a-2), and the polysiloxane (B) is represented by the following average unit formula (b-1). All containing at least one selected from the group consisting of the polyorganosiloxane represented and the polyorganosyloxysylalkylene represented by the following average unit formula (b-2), and contained in the composition (I). Of the silicon atoms, the ratio of the number of silicon atoms in the siloxane unit represented by (R ₃ SiO _1/2 ) is M, and the ratio of the number of silicon atoms in the siloxane unit represented by (R ₂ SiO _2/2 ). the D, T a ratio of the number of silicon atoms in the siloxane units represented by (RSiO _3/2), when the ratio of the number of silicon atoms in the siloxane units represented by (SiO _4/2) and is Q, For 1 mol of aliphatic carbon-carbon double bond present in the composition (I), which satisfies (T + Q) / D> 0.3 and M + D + T + Q = 1 (where R indicates a monovalent group). Then, a cured product of the composition (I) having a hydrosilyl group of 0.9 to 5.0 mol is formed, and the peeling strength and / or the total peeling load of the cured product is obtained by the following peeling load evaluation. Provided is a method for producing a curable resin composition, which comprises a step of determining the composition of the curable resin composition.
Peeling load evaluation: The adherend is moved from a state in which the adherend and the cured product are vertically separated from each other, and at least one of the adherend and the cured product is moved so that the contact area is 50 mm ² or more. The stress change of the contact surface when the body and the cured product are brought into contact with each other, pressed under a load, and then separated in the vertical direction is recorded, and the adherend and the cured product are completely separated after they start to separate. The value obtained by dividing the maximum stress value until separation by the contact area between the adherend and the cured product is defined as the peel strength, and the stress from when the adherend and the cured product begin to separate to when they are completely separated. The value obtained by dividing the area surrounded by the curve and the baseline by the contact area is defined as the total peel load.
Average unit formula (a-1):
(R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5
[In the average unit formula (a-1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, which is the same or different. However, a part of R ¹ is an alkenyl group, which is in the range of two or more in the molecule. X ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a1, a2, a3, a4, and a5 are 1> a1 ≧ 0, 1> a2 ≧ 0, 1>a3> 0, 1> a4 ≧ 0, 0.05 ≧ a5 ≧ 0, a1 + a2 + a4> 0, respectively. And a numerical value satisfying a1 + a2 + a3 + a4 + a5 = 1 is shown. ]
Average unit formula (a-2):
(R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 (SiO _4/2 ) _b4 ( ^RA ) _b5 (X ² O _1/2 ) _b6
[In the average unit formula (a-2), R ² represents the same or different alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, or alkenyl group having 2 to 8 carbon atoms. However, a part of R ² is an alkenyl group, which is in the range of two or more in the molecule. ^RA represents the same or different alkylene group having 1 to 14 carbon atoms. X ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. b1, b2, b3, b4, b5, and b6 are 1> b1 ≧ 0, 1>b2> 0, 1> b3 ≧ 0, 1> b4 ≧ 0, 0.7>b5> 0, 0, respectively. The numerical values satisfying 05 ≧ b6 ≧ 0, b1 + b3 + b4> 0, and b1 + b2 + b3 + b4 + b5 + b6 = 1 are shown. ]
Average unit formula (b-1):
(R ³ SiO _3/2 ) _c1 (R ³ ₂ SiO _2/2 ) _c2 (R ³ ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (X ³ O _1/2 ) _c5
[In the average unit formula (b-1), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which are the same or different. However, a part of R ¹ is a hydrogen atom, which is a range of two or more in the molecule. X ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. c1, c2, c3, c4, and c5 are 1> c1 ≧ 0, 1> c2 ≧ 0, 1>c3> 0, 1> c4 ≧ 0, 0.05 ≧ c5 ≧ 0, c1 + c2 + c4> 0, respectively. And c1 + c2 + c3 + c4 + c5 = 1 are shown. ]
Average unit formula (b-2):
(R ⁴ ₂ SiO _2/2 ) _d1 (R ⁴ ₃ SiO _1/2 ) _d2 (R ⁴ SiO _3/2 ) _d3 (SiO _4/2 ) _d4 ( ^RA ) _d5 (X ⁴ O) _d6
[In the average unit formula (b-2), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which is the same or different. However, a part of R ⁴ is a hydrogen atom, which is a range of two or more in the molecule. ^RA represents the same or different alkylene group having 1 to 14 carbon atoms. X ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. d1, d2, d3, d4, d5, and d6 are 1> d1 ≧ 0, 1>d2> 0, 1> d3 ≧ 0, 1> d4 ≧ 0, 0.5>d5> 0, 0, respectively. The numerical values satisfying 05 ≧ d6 ≧ 0, d1 + d3 + d4> 0, and d1 + d2 + d3 + d4 + d5 + d6 = 1 are shown. ]

Further, the present invention includes a step A in which the adherend and the viscoelastic material are brought into contact with each other so that the contact area is 50 mm ² or more, a load is applied, and then stress relaxation is performed, and the adherence is displaced in the separation direction. Step B for separating the body and the viscoelastic material and the stress change of the contact surface from the contact to the separation were recorded to obtain a curve with the x-axis as the displacement and the y-axis as the stress, and the obtained curve. Provided is a method for measuring the tack on the surface of a viscoelastic material having the step C for quantifying the tack from the above.

In the step A, a stress detection mechanism having a pedestal and an adherend is used to arrange a flat plate-shaped viscoelastic material on the pedestal so that the contact surface between the viscoelastic material and the adherend becomes flat. It is preferable that the adherend is pressed against the viscoelastic material to continuously apply a load and then stress relaxation.

In the step C, the maximum stress value in the curve can be obtained as the tack value of the viscoelastic material. Further, in the step C, the area surrounded by the curve and the baseline and including the maximum stress value in the curve can be obtained as the tack value of the viscoelastic material.

In the step A, the value obtained by dividing the load applied by bringing the adherend into contact with the viscoelastic material by the contact area is preferably 0.1 to 4 MPa.

In the step A, the time for applying the load after the adherend is brought into contact with the viscoelastic material is preferably 0.5 to 10 minutes.

In the step B, the speed at which the adherend and the viscoelastic material are separated is 5 mm / min, 10 mm / min, 20 mm / min, 30 mm / min, 50 mm / min, 70 mm / min, 100 mm / min, 150 mm. It is preferable to set 10 points of / min, 300 mm / min, and 500 mm / min.

The thickness of the viscoelastic material is preferably 0.5 to 5 mm.

It is preferable that the surface of the adherend in contact with the viscoelastic material is flat, and the area of the plane of the adherend is larger than the area of the contact portion between the viscoelastic material and the adherend. ..

The method for measuring the tack on the surface of the viscoelastic material is preferably carried out in an environment of a temperature of 10 to 30 ° C. and a humidity of 30 to 70% RH.

Since the curable resin composition of the present invention has the above-mentioned structure, it is possible to form a cured product having low tack property and less dust adhered by curing. Therefore, when the cured product is used as a sealing material for a semiconductor element in a semiconductor device, workability during handling of the semiconductor device is improved, and dust is less likely to adhere. Therefore, the curable resin composition of the present invention can be preferably used as a material (sealing agent) for forming a sealing material for an optical semiconductor element (LED element) in an optical semiconductor device. The optical semiconductor device obtained by using the curable resin composition of the present invention as a sealing agent has excellent quality and durability.

Further, according to the method for producing a curable resin composition of the present invention, it is possible to produce a curable resin composition having an idea of the tackiness and the adhesion of dust of the cured product of the obtained curable resin composition. it can. Therefore, even if a product using the cured product of the curable resin composition is not actually produced, a curable resin composition having a low tack property of the cured product and to which dust does not easily adhere can be produced. be able to.

Further, according to the method for measuring the tack of a viscoelastic material of the present invention, the measurement accuracy is high even in a low tack region, and quantitative measurement is possible from a low tack region to a high tack region. Therefore, it becomes easy to consistently make a relative comparison of tackiness for various viscoelastic bodies from a low tack region to a high tack region, including a viscoelastic material having a low tack property.

It is a schematic diagram which shows one Embodiment of the optical semiconductor device which sealed the optical semiconductor element by the cured product of the curable resin composition of this invention. The left side view (a) is a perspective view, and the right side view (b) is a cross-sectional view. It is a graph which shows an example of the state of the change of the stress amount of the contact surface between an adherend and a cured material at the time of evaluation of a peeling load. It is a schematic block diagram of the testing machine used for the peeling load evaluation in an Example.

<Curable resin composition>
The curable resin composition of the present invention is a group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganosyloxysylalkylene (A2) having two or more alkenyl groups in the molecule. Polysiloxane (A), which is at least one selected from the above (sometimes referred to simply as "polysiloxane (A)"), polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule, and a molecule. Polysiloxane (B), which is at least one selected from the group consisting of polyorganosyloxysylalkylene (B2) having two or more hydrosilyl groups within (sometimes simply referred to as "polysiloxane (B)"). And, is a curable composition containing as an essential component. In addition to the above-mentioned essential components, the curable resin composition of the present invention further includes, for example, a ladder-type polyorganosylsesquioxane (C) described later, a compound containing an isocyanuric skeleton (D), a hydrosilylation catalyst, and the like. May contain the components of.

Further, the curable resin composition of the present invention has a polyorganosiloxane represented by the following average unit formula (a-1) as a polysiloxane (A) and a polyorgano represented by the following average unit formula (a-2). It contains at least one selected from the group consisting of siloxysil alkylene. Further, the curable resin composition of the present invention is a polyorganosiloxane represented by the following average unit formula (b-1) as a polysiloxane (B) and a polyorgano represented by the following average unit formula (b-2). It contains at least one selected from the group consisting of siloxysil alkylene. The polyorganosiloxane represented by the following average unit formula (a-1) corresponds to the polyorganosiloxane (A1), and the polyorganosyloxysylalkylene represented by the following average unit formula (a-2) corresponds to the polyorgano. Corresponds to siloxysil alkylene (A2). The polyorganosiloxane represented by the following average unit formula (b-1) corresponds to the polyorganosiloxane (B1), and the polyorganosyloxysylalkylene represented by the following average unit formula (b-2) corresponds to the polyorgano. Corresponds to siloxysil alkylene (B2).
Average unit formula (a-1):
(R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5
Average unit formula (a-2):
(R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 (SiO _4/2 ) _b4 ( ^RA ) _b5 (X ² O _1/2 ) _b6
Average unit formula (b-1):
(R ³ SiO _3/2 ) _c1 (R ³ ₂ SiO _2/2 ) _c2 (R ³ ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (X ³ O _1/2 ) _c5
Average unit formula (b-2):
(R ⁴ ₂ SiO _2/2 ) _d1 (R ⁴ ₃ SiO _1/2 ) _d2 (R ⁴ SiO _3/2 ) _d3 (SiO _4/2 ) _d4 ( ^RA ) _d5 (X ⁴ O) _d6

Of all the silicon atoms contained in the curable resin composition of the present invention, the ratio of the number of silicon atoms in the siloxane unit represented by (R ₃ SiO _1/2 ) is M, (R ₂ SiO _2/2). The ratio of the number of silicon atoms in the siloxane unit represented by) is D, the ratio of the number of silicon atoms in the siloxane unit represented by (RSiO _3/2 ) is T, and the ratio of the number of silicon atoms in the siloxane unit (SiO _4/2 ) is siloxane. When the ratio of the number of silicon atoms in the unit is Q, M, D, T, and Q satisfy (T + Q) / D> 0.3 and M + D + T + Q = 1, respectively. As a result, the tackiness of the cured product is low, and dust tends to be less likely to adhere. In particular, it is preferable to satisfy 5> (T + Q) / D> 0.3. The above R indicates a monovalent group, such as 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. Can be mentioned. Examples of the monovalent organic group include an alkenyl group and a monovalent substituted or unsubstituted hydrocarbon group described later.

Further, among all the silicon atoms contained in the curable resin composition of the present invention, 0.9> T ≧ 0.4 or 0.9> Q ≧ 0.2 is satisfied for the above T or Q. Is preferable. As a result, dust is less likely to adhere to the cured product, and the toughness of the cured product tends to be improved.

Of all the silicon atoms contained in the curable resin composition of the present invention, the above M, D, T, and Q are 1> M ≧ 0, 1>D> 0, 1>T> 0, respectively. And 1>Q> 0 are preferably satisfied. The above M, D, T, and Q can be calculated by, for example, ²⁹ Si-NMR spectrum measurement or the like. In the present specification, the ratios of M, D, T, and Q are the ratios to all the silicon atoms contained in the curable resin composition of the present invention, respectively. Examples of the compound containing a silicon atom contained in the curable resin composition of the present invention include polysiloxane (A), polysiloxane (B), and ladder-type polyorganosylsesquioxane (C) described later.

The curable resin composition of the present invention contains 0.9 to 5.0 mol of hydrosilyl groups with respect to 1 mol of aliphatic carbon-carbon double bonds (particularly alkenyl groups) present in the curable resin composition. It is a composition (blending composition) such that, preferably 0.9 to 4.0 mol, more preferably 0.9 to 3.0 mol, still more preferably 0.9 to 2.5 mol. By controlling the ratio of the hydrosilyl group to the aliphatic carbon-carbon double bond (particularly the alkenyl group) within the above range, the uncured components in the cured product (particularly, the uncured polysiloxane (A) and the uncured The residual amount of the polysiloxane (B)) in the above tends to decrease, and the peeling strength tends to decrease. Further, the heat resistance, transparency, heat impact resistance and reflow resistance of the cured product, and the barrier property against corrosive gas (for example, SOx gas) tend to be improved. The number of moles of the hydrosilyl group with respect to 1 mole of the aliphatic carbon-carbon double bond (particularly the alkenyl group) can be calculated by, for example, ¹ H-NMR spectrum measurement or the like.

Further, the curable resin composition of the present invention is peeled off from the cured product when it is cured by heating under at least one curing condition selected from the conditions of 25 to 180 ° C. and 1 to 720 minutes. A curable resin composition having a peel strength of 0.40 N or less per 1 mm ² obtained by load evaluation and / or a total peel load of 0.018 N · mm or less per 1 mm ² obtained by the following peel load evaluation. .. Therefore, in the curable resin composition of the present invention, the peel strength per 1 mm ² obtained by the following peel load evaluation is 0.40 N or less, and the total peel load per 1 mm ² obtained by the following peel load evaluation is 0. It may be a curable resin composition satisfying only one of 018 N · mm or less, or it may be a curable resin composition satisfying both. In addition, in this specification, the following peeling load evaluation may be referred to as "peeling load evaluation (X)".
Peeling load evaluation: The adherend made of SUS and the cured product are brought into contact with the adherend and the cured product by moving at least one of the adherend and the cured product from a state in which they are vertically separated from each other. After contacting them so that they have an area of 50 to 800 mm ² and pressing them with a load of 100 N for 2 minutes, the stress change of the contact surface when separated in the vertical direction is recorded, and the adherend and the cured product are separated. The value obtained by dividing the maximum stress value from the start of separation to the complete separation by the contact area is defined as the peel strength, and the stress curve and baseline from the start of separation of the adherend and the cured product to the complete separation. The value obtained by dividing the area surrounded by and by the contact area is defined as the total peeling load. However, the peel strength and the total peel load can be separated from each other at any 10 points within the range of 5 to 500 mm / min (however, the speed difference between the two adjacent points is 5 mm / min or more). It is the maximum value of the value obtained by measuring with).

The curable resin composition of the present invention has a peel strength of 0.40 N or less per 1 mm ² obtained by the peel load evaluation of the cured product obtained by curing under the above specific conditions, and / or. Satisfy that the total peeling load per 1 mm ² obtained by the peeling load evaluation is 0.018 N · mm or less. As a result, the curable resin composition of the present invention tends to reduce both the tackiness of the cured product and the adhesion of dust.

Conventionally, a curable resin composition for forming a silicone-based encapsulant actually manufactures an LED in terms of tackiness and dust adhesion when the LED element is sealed with a cured material. It was only possible to confirm it. Even in the past, it has been possible to evaluate the tackiness of a cured product obtained by curing a curable resin composition under predetermined conditions by a tacking tester or the like before actually manufacturing the LED. However, the correlation between the evaluation result obtained by the tackability evaluation using the tacking tester and the tackiness and the adhesion of dust of the actually manufactured LED was not high. Further, if the tackiness is low, it is not always difficult for dust to adhere, and even if the tackiness is low, dust is likely to adhere, or even if the tackiness is high, dust is difficult to adhere. As described above, the tackiness and the adhesion of dust of the material obtained by curing the curable resin composition could not be confirmed until an LED using the material as a sealing material was actually manufactured. .. Furthermore, until now, there have been only qualitative methods for evaluating the tackiness and the adhesion of dust to manufactured LEDs.

On the other hand, for a curable resin composition having a specific composition, the curable resin composition is used as a sealing agent by performing the peeling load evaluation (X) to obtain the peeling strength and the total peeling load. The tackiness and the adhesion of dust of the optical semiconductor device can be evaluated in advance at a stage before the optical semiconductor device is actually manufactured by using the optical semiconductor device. In addition, the tackiness and dust adhesion of the manufactured LED can be quantitatively evaluated by the peeling load evaluation (X). The curable resin composition of the present invention is cured when it has a specific composition and the peel strength and / or the total peel load determined by the peel load evaluation (X) is within a specific range. As a result, it is possible to form a cured product having low tackiness and to which dust does not easily adhere.

The curable resin composition of the present invention preferably has a peel strength of 0.40 N or less per 1 mm ² obtained by the peel load evaluation of the cured product obtained by curing under the above specific conditions, more preferably. Is 0.10 N or less. When the peel strength is 0.40 N or less, the tackiness of the cured product tends to decrease.

In the curable resin composition of the present invention, the total peeling load per 1 mm ² obtained by the peeling load evaluation of the cured product obtained by curing under the above specific conditions is preferably 0.018 N · mm or less. , More preferably 0.016 N · mm or less, still more preferably 0.010 N · mm or less. When the total peeling load is 0.018 N · mm or less, dust tends to be less likely to adhere to the cured product.

The polysiloxane (A) and polysiloxane (B) contained in the curable resin composition are important in order to keep the peel strength and the total peel load within the specific ranges. More specifically, the ratio of the linear polysiloxane and the branched polysiloxane in the polysiloxane (A) and the polysiloxane (B) in the curable resin composition, and the ratio of the alkyl group bonded to the silicon atom. By adjusting the ratio of the aryl group bonded to the silicon atom and the ratio of the alkenyl group to the hydrosilyl group, the peel strength and the total peel load can be easily set within the specific ranges. For example, when a linear polysiloxane is used, the peel strength tends to be small, and when a branched chain polysiloxane is used, the total peel load tends to be small. Further, if there are many alkyl groups (particularly methyl groups) as groups bonded to silicon atoms other than the alkenyl group and the hydrosilyl group in the polysiloxane, the peel strength tends to be small, and there are many aryl groups (particularly phenyl groups). Then, the total peeling load tends to be small. In addition, since the peel strength tends to increase when the amount of uncured components in the cured product is large, the ratio of alkenyl groups to hydrosilyl groups is adjusted so that the amount of uncured components in the cured product is small (especially for vinyl groups). It is effective to adjust the ratio so that it does not become excessive.

(Peeling load evaluation (X))
The peeling load evaluation (X) is when the curable resin composition of the present invention is heated and cured under at least one curing condition selected from the conditions of 25 to 180 ° C. and 1 to 720 minutes. Carry out for cured products. That is, the cured product obtained by curing the curable resin composition of the present invention by heating it at an arbitrary temperature in the range of 25 to 180 ° C. for an arbitrary time in the range of 1 to 720 minutes is described above. Evaluate the peeling load. Therefore, the peel strength and / or the total peel load obtained by the peel load evaluation of the cured product obtained by curing the curable resin composition of the present invention is within the above range at least one point under the above curing conditions. It is sufficient that the cured product cured in is filled. The temperature at the time of the above curing (curing temperature) is preferably 60 to 170 ° C, more preferably 80 to 150 ° C. The heating time (curing time) at the time of curing is preferably 3 to 600 minutes, more preferably 60 to 480 minutes. The curing may be performed in one step or in multiple steps. When performed in multiple stages, the curing temperature in each stage is within the above-mentioned curing temperature range, and the total curing time is within the above-mentioned curing time. Above all, it is preferable to heat at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours. The peeling load evaluation (X) corresponds to the measurement method of the present invention described later.

In the peeling load evaluation, first, the adherend made of SUS and the cured product of the curable resin composition are separated from each other in the vertical direction (vertical direction), and at least one of the adherend and the cured product is moved to be covered. The adherend and the cured product are brought into contact with each other so as to have a contact area of 50 to 800 mm ² . From the viewpoint that the contact area does not easily change even when a load is applied and pressed, the contact surface between the adherend and the cured product is preferably flat.

The adherend and the cured product in contact with each other are then pressed vertically with a load of 100 N for 2 minutes. The load may be applied from the adherend side or the cured product side, but it is preferable to apply the load from the cured product side. The load may be applied from the upper side in the vertical direction or from the lower side.

After applying the load, the adherend and the cured product are separated in the vertical direction. During a series of operations of contacting, pressing, and separating the adherend and the cured product, the stress change of the contact surface is recorded. Then, the value obtained by dividing the maximum stress value from the start of separation between the adherend and the cured product to the complete separation by the contact area between the adherend and the cured product is defined as the peel strength, and the adherend and the cured product are separated from each other. The total peeling is the value obtained by dividing the area surrounded by the stress curve and the baseline (the line where the stress on the contact surface is 0) from the start of separation to the complete separation by the contact area between the adherend and the cured product. Let it be a load. FIG. 2 is a graph showing an example of a change in the amount of stress on the contact surface between the adherend and the cured product during the evaluation of the peeling load. In FIG. 2, 200 is the maximum stress value, and 201 is the area surrounded by the stress curve and the baseline from when the adherend and the cured product start to separate from each other to when they are completely separated. The peel strength and the total peel load are the maximum values obtained by measuring the speed at the time of separation at any 10 points within the range of 5 to 500 mm / min. However, the speed difference between the two adjacent points is 5 mm / min or more. This is because the separation speed when the peel strength and the total peel load are maximized may differ depending on the composition of the curable resin composition. Among the above arbitrary 10 points, 5 mm / min, 10 mm / min, 20 mm / min, 30 mm / min, 50 mm / min, 70 mm / min, 100 mm / min, 150 mm / min, 300 mm / min, and 500 mm / min. 10 points are preferable.

The peeling load evaluation (X) can be performed using a commercially available universal testing machine (for example, "Tencilon universal material testing machine RTC-1310A", manufactured by A & D Co., Ltd.).

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

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

In the present specification, the polyorganosyloxysylalkylene (A2) means -Si- ^RA -Si- (silalkylene bond: ^RA is alkylene) in addition to -Si-O-Si- (siloxane bond) as the main chain. It is a polysiloxane containing (showing a group). The polyorganosiloxane (A1) in the present specification is a polysiloxane that does not contain the above-mentioned silalkylene bond as a main chain.

(Polyorganosiloxane (A1))
Examples of the polyorganosiloxane (A1) include those having a linear, partially branched linear, branched chain, and network-like molecular structure. As the polyorganosiloxane (A1), one type may be used alone, or two or more types may be used in combination. Specifically, two or more types of polyorganosiloxane (A1) having different molecular structures can be used in combination, for example, a linear polyorganosiloxane (A1) and a branched chain polyorganosiloxane (A1). Can also be used together.

Examples of the alkenyl group contained in the molecule of the polyorganosiloxane (A1) include a substituted or unsubstituted alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group and the like. Of these, a vinyl group is preferable. Further, the polyorganosiloxane (A1) may have only one type of alkenyl group, or may have two or more types of alkenyl groups. The alkenyl group contained in the polyorganosiloxane (A1) is not particularly limited, but is preferably one bonded to a silicon atom.

The group other than the alkenyl group contained in the polyorganosiloxane (A1) is not particularly limited, and examples thereof include an organic group. Examples of the organic group include an alkyl group [for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.] and a cycloalkyl group [for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.] , Cyclododecyl group, etc.], aryl group [eg, phenyl group, tolyl group, xsilyl group, naphthyl group, etc.], cycloalkyl-alkyl group [eg, cyclohexylmethyl group, methylcyclohexyl group, etc.], aralkyl group [eg, Benzyl group, phenethyl group, etc.], a halogenated hydrocarbon group in which one or more hydrogen atoms in the hydrocarbon group are replaced with a halogen atom [for example, chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoro A monovalent substituted or unsubstituted hydrocarbon group such as an alkyl halide group such as a propyl group] can be mentioned. In addition, in this specification, a "group bonded to a silicon atom" usually refers to a group containing no silicon atom.

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

The properties of the polyorganosiloxane (A1) are not particularly limited, and may be in a liquid state or a solid state at, for example, 25 ° C.

As the polyorganosiloxane (A1), the following average unit formula (a-1):
(R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _a2 (R ¹ ₃ SiO _1/2 ) _a3 (SiO _4/2 ) _a4 (X ¹ O _1/2 ) _a5 (a-1)
Polyorganosiloxane represented by is preferable. In the above average unit formula (a-1), R ¹ represents the same or different alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, or alkenyl group having 2 to 8 carbon atoms. However, a part of R ¹ is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of two or more in the molecule. For example, the ratio of alkenyl groups to the total amount of R ¹ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the proportion of alkenyl groups within the above range, the curability of the curable resin composition tends to be improved. Further, the alkyl group having 1 to 10 carbon atoms is particularly preferably a methyl group, and the aryl group having 6 to 14 carbon atoms is particularly preferably a phenyl group.

In the above average unit formula (a-1), X ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, and a methyl group is particularly preferable.

In the above average unit formula (a-1), a1, a2, a3, a4, and a5 are 1> a1 ≧ 0, 1> a2 ≧ 0, 1> a3> 0, 1> a4 ≧ 0, 0, respectively. It is a numerical value satisfying .05 ≧ a5 ≧ 0, a1 + a2 + a4> 0, and a1 + a2 + a3 + a4 + a5 = 1.

An example of the polyorganosiloxane (A1) is a linear polyorganosiloxane having two or more alkenyl groups in the molecule. Examples of the alkenyl group contained in this linear polyorganosiloxane include the above-mentioned specific examples of the alkenyl group, and among them, the vinyl group is preferable. In addition, it may have only one alkenyl group, or may have two or more alkenyl groups. Examples of the group bonded to a silicon atom other than the alkenyl group in the linear polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group (particularly the number of carbon atoms). (1 to 10 alkyl groups) and aryl groups (particularly aryl groups having 6 to 14 carbon atoms) are preferable, and methyl groups and phenyl groups are particularly preferable.

The ratio of the alkenyl group to the total amount (100 mol%) of the groups bonded to the silicon atom in the linear polyorganosiloxane is not particularly limited, but is preferably 0.1 to 40 mol%. The ratio of the alkyl group (particularly the methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 1 to 20 mol%. Further, the ratio of the aryl group (particularly the phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 30 to 90 mol%. In particular, as the linear polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 80 mol%). By using the one, the barrier property of the cured product against corrosive gas tends to be improved. Further, by using a cured product in which the ratio of alkyl groups (particularly methyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 90 mol% or more (for example, 95 to 99 mol%). The thermal shock resistance of the material tends to improve.

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

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

Another example of the polyorganosiloxane (A1) is a branched chain polyorganosiloxane having two or more alkenyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO _3/2. Be done. However, as described above, the branched-chain polyorganosiloxane does not include the one corresponding to the ladder-type polyorganosylsesquioxane (C) described later. In addition, R is a monovalent substituted or unsubstituted hydrocarbon group. Examples of the alkenyl group contained in this branched-chain polyorganosiloxane include the above-mentioned specific examples of the alkenyl group, and among them, the vinyl group is preferable. In addition, it may have only one alkenyl group, or may have two or more alkenyl groups. Examples of the group bonded to a silicon atom other than the alkenyl group in the branched polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group (particularly a methyl group). ), Aryl group (particularly phenyl group) is preferable. Further, as R in the T unit, an alkyl group (particularly an alkyl group having 1 to 10 carbon atoms) and an aryl group (particularly an aryl group having 6 to 14 carbon atoms) are preferable, and a methyl group and a phenyl group are particularly preferable. preferable.

The ratio of the alkenyl group to the total amount (100 mol%) of the groups bonded to the silicon atom in the branched chain polyorganosiloxane is not particularly limited, but is 0.1 to 1 from the viewpoint of curability of the curable resin composition. 40 mol% is preferable. The ratio of the alkyl group (particularly the methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 10 to 40 mol%. Further, the ratio of the aryl group (particularly the phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 5 to 70 mol%. In particular, as the branched chain polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 60 mol%). By using one, the barrier property of the cured product against corrosive gas tends to be improved. Further, by using a cured product in which the ratio of the alkyl group (particularly the methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is 50 mol% or more (for example, 60 to 99 mol%). The thermal shock resistance of the material tends to improve.

The branched chain polyorganosiloxane can be represented by the average unit formula (a-1) in which a1 is a positive number. In this case, although not particularly limited, a2 / a1 is a number from 0 to 10, a3 / a1 is a number from 0 to 0.5, a4 / (a1 + a2 + a3 + a4) is a number from 0 to 0.3, and a5 / (a1 + a2 + a3 + a4) is. The number is preferably 0 to 0.4. The molecular weight of the branched-chain polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, more preferably 700 to 5000.

As yet another example of the polyorganosiloxane (A1), for example, in the above average unit formula, a1 and a2 are 0 and X ¹ is a hydrogen atom.
(R ^1a ₂ R ^1b SiO _1/2 ) _a6 (R ^1a ₃ SiO _1/2 ) _a7 (SiO _4/2 ) _a8 (HO _1/2 ) _a9
Examples thereof include polyorganosiloxane represented by. In the above average unit formula, R ^1a represents an alkyl group having 1 to 10 carbon atoms (C _1-10 alkyl group), which is the same or different, and represents, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. , Hexyl group, cyclopentyl group, cyclohexyl group, and methyl group is preferable. Further, R ^1b shows the same or different alkenyl group, and 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. Further, from the viewpoint of hardness and mechanical strength of the cured product, a8 / (a6 + a7 + a8) is preferably 0.55 to 0.60. Examples of such a polyorganosiloxane include a polyorganosiloxane 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 unit and (CH ₃ ) ₃ SiO _1/2 unit can be mentioned.

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

The alkylene group ( ^RA ) in the silalkylene bond of the polyorganosyloxysylalkylene (A2) in the molecule includes, for example, a linear or branched C _1-14 alkylene such as a methylene group, an ethylene group, or a propylene group. Groups and the like are mentioned, and among them, a C _2-4 alkylene group (particularly an ethylene group) is preferable. When the above polyorganosyloxysylalkylene (A2) is used, the sulfurization resistance of the cured product tends to be improved.

Examples of the polyorganosyloxysylalkylene (A2) include those having a linear, partially branched linear, branched chain, and network-like molecular structure. As the polyorganosyloxysylalkylene (A2), one type may be used alone, or two or more types may be used in combination. Specifically, two or more types of polyorganosyloxysylalkylene (A2) having different molecular structures can be used in combination. For example, linear polyorganosyloxysylalkylene (A2) and branched-chain polyorganosyloxy It can also be used in combination with silalkylene (A2).

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

The group bonded to a silicon atom other than the alkenyl group of the polyorganosyloxysylalkylene (A2) is not particularly limited, and examples thereof include an organic group. Examples of the organic group include the above-mentioned organic groups (for example, substituted or unsubstituted hydrocarbons such as alkyl group, cycloalkyl group, aryl group, cycloalkyl-alkyl group, aralkyl group and halogenated hydrocarbon group). Be done.

Further, the polyorganosyloxysylalkylene (A2) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.

The properties of the polyorganosyloxysylalkylene (A2) are not particularly limited, and may be in a liquid state or a solid state at, for example, 25 ° C.

As the polyorganosyloxysylalkylene (A2), the following average unit formula (a-2):
(R ² ₂ SiO _2/2 ) _b1 (R ² ₃ SiO _1/2 ) _b2 (R ² SiO _3/2 ) _b3 (SiO _4/2 ) _b4 ( ^RA ) _b5 (X ² O _1/2 ) _b6 (A-2)
Polyorganosyloxysylalkylene represented by is preferable. In the above average unit formula (a-2), R ² represents the same or different alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, or alkenyl group having 2 to 8 carbon atoms. However, a part of R ² is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of two or more in the molecule. For example, the ratio of alkenyl groups to the total amount of R ² (100 mol%) is preferably 0.1 to 40 mol%. By controlling the proportion of alkenyl groups within the above range, the curability of the curable resin composition tends to be improved.

In the above average unit formula (a-2), ^RA is an alkylene group having 1 to 14 carbon atoms. Ethylene groups are particularly preferred.

In the above average unit formula (a-2), X ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, like the above X ¹ . Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, and a methyl group is particularly preferable.

In the above average unit formula (a-2), b1, b2, b3, b4, b5, and b6 are 1> b1 ≧ 0, 1> b2> 0, 1> b3 ≧ 0, 1> b4 ≧ 0, respectively. , 0.7> b5> 0, 0.05 ≧ b6 ≧ 0, b1 + b3 + b4> 0, and b1 + b2 + b3 + b4 + b5 + b6 = 1. In particular, when b3 + b4> 0, the polyorganosyloxysylalkylene (A2) has a branched chain (branched main chain), and the mechanical strength of the cured product tends to be improved.

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

In formula (I-2) above, R ¹² is the same, different, or monovalent substituted or unsubstituted hydrocarbon group. Examples of R ¹² include specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (for example, an alkyl group, an aryl group, an aralkyl group, a halogenated hydrocarbon group, etc.), and the alkenyl group described above. However, at least two of R ¹² are alkenyl groups (particularly vinyl groups). Further, as R ¹² other than the alkenyl group, an alkyl group (particularly an alkyl group having 1 to 10 carbon atoms) and an aryl group (particularly an aryl group having 6 to 14 carbon atoms) are preferable, and a methyl group and a phenyl group are particularly preferable.

In the above formula (I-2), ^RA represents an alkylene group as described above, and among them, a C _1-14 alkylene group is preferable, and a C _2-4 alkylene group (particularly an ethylene group) is more preferable. When a plurality of R ^A are present, they may be the same or may be different.

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

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

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

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

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

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

The terminal structure of the polyorganosyloxysylalkylene having the structure represented by the formula (I-2) is not particularly limited, but is, for example, a silanol group, an alkoxysilyl group, or a trialkylsilyl group (for example, parentheses with r5). Internal structure, trimethylsilyl group, etc.) and the like. Various groups such as an alkenyl group and a hydrosilyl group may be introduced into the terminal of the polyorganosyloxysylalkylene.

The polyorganosyloxysylalkylene (A2) can be produced by a known or conventional method, and the production method thereof is not particularly limited, but can be produced, for example, by the method described in JP2012-140617A. Further, as products containing polyorganosyloxysylalkylene (A2), for example, trade names "ETERLED GD1130", "ETERLED GD1125", "ETERLED GS5145", "ETERLED GS5135", "ETERLED GS5120" (all manufactured by Choko Materials Industry Co., Ltd.) ) Etc. are available.

In the curable resin composition of the present invention, one type of polysiloxane (A) may be used alone, or two or more types may be used in combination.

The content (blending amount) (total amount) of the polysiloxane (A) in the curable resin composition of the present invention is not particularly limited, but is 50 to 99 with respect to the total amount (100% by weight) of the curable resin composition. The weight is preferably%, more preferably 60 to 97% by weight, 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 improved.

As the polysiloxane (A) in the curable resin composition of the present invention, only polyorganosiloxane (A1) can be used, only polyorganosyloxysylalkylene (A2) can be used, or only polyorganosyloxysylalkylene (A2) can be used. , Polyorganosiloxane (A1) and polyorganosyloxysylalkylene (A2) can also be used in combination. When the polyorganosiloxane (A1) and the polyorganosyloxysylalkylene (A2) are used in combination, the ratios thereof are not particularly limited and can be appropriately set. Similarly, as the polysiloxane (A) in the curable resin composition of the present invention, only the polyorganosiloxane represented by the above average unit formula (a-1) can be used, or the above average unit formula ( Only the polyorganosyloxysylalkylene represented by a-2) can be used, or the polyorganosiloxane represented by the average unit formula (a-1) and the average unit formula (a-2) can be used. It can also be used in combination with the polyorganosyloxysylalkylene represented by.

The polyorganosiloxane represented by the average unit formula (a-1) and the polyorganosyloxysyl represented by the average unit formula (a-2) in the polysiloxane (A) in the curable resin composition of the present invention. The content (blending amount) (total amount) of the alkylene is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 60% by weight or more, based on the total amount (100% by weight) of the polysiloxane (A). It is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. When the content is 50% by weight or more, the tackiness of the cured product tends to be lower and dust tends to be less likely to adhere. In the curable resin composition of the present invention, only one of the polyorganosiloxane represented by the average unit formula (a-1) and the polyorganosyloxysylalkylene represented by the average unit formula (a-2) is contained. When is contained, the above-mentioned content is the content of one of them.

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

Polysiloxane (B) is a polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule (sometimes simply referred to as "polyorganosiloxane (B1)") and two or more hydrosilyl groups in the molecule. It is a polysiloxane which is at least one selected from the group consisting of polyorganosyloxysylalkylene (B2) having (sometimes referred to simply as "polyorganosyloxysylalkylene (B2)").

In the present specification, the polyorganosyloxysylalkylene (B2) means -Si- ^RA -Si- (silalkylene bond: ^RA is alkylene) in addition to -Si-O-Si- (siloxane bond) as the main chain. It is a polysiloxane containing (showing a group). The polyorganosiloxane (B1) in the present specification is a polysiloxane that does not contain the above-mentioned silalkylene bond as a main chain. As the ^RA (alkylene group) in the silalkylene bond, for example, a linear or branched C _1-14 alkylene group can be mentioned, preferably a linear or branched C _{2 -4} alkylene groups (particularly ethylene groups).

(Polyorganosiloxane (B1))
Examples of the polyorganosiloxane (B1) include those having a linear, partially branched linear, branched chain, and network-like molecular structure. As the polyorganosiloxane (B1), one type may be used alone, or two or more types may be used in combination. Specifically, two or more types of polyorganosiloxane (B1) having different molecular structures can be used in combination, for example, a linear polyorganosiloxane (B1) and a branched chain polyorganosiloxane (B1). Can also be used together.

Among the groups bonded to the silicon atom of the polyorganosiloxane (B1), the group other than the hydrogen atom is not particularly limited, but for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, more specifically, an alkyl group, etc. Examples thereof include an aryl group, an aralkyl group, and a halogenated hydrocarbon group. Of these, alkyl groups (particularly methyl groups) and aryl groups (particularly phenyl groups) are preferable.

The properties of the polyorganosiloxane (B1) are not particularly limited, and may be in a liquid state or a solid state at, for example, 25 ° C. Of these, a liquid is preferable, and a liquid having a viscosity at 25 ° C. of 0.1 to 1 billion mPa · s is more preferable.

As the polyorganosiloxane (B1), the following average unit formula (b-1):
(R ³ SiO _3/2 ) _c1 (R ³ ₂ SiO _2/2 ) _c2 (R ³ ₃ SiO _1/2 ) _c3 (SiO _4/2 ) _c4 (X ³ O _1/2 ) _c5 (b-1)
Polyorganosiloxane represented by is preferable. In the above average unit formula (b-1), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which are the same or different. However, a part of R ³ is a hydrogen atom (hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled within a range in which the number of hydrosilyl groups is two or more in the molecule. For example, the ratio of hydrogen atoms to the total amount of R ³ (100 mol%) is preferably 0.1 to 50 mol%. By controlling the ratio of hydrogen atoms within the above range, the curability of the curable resin composition tends to be improved.

In the above average unit formula (b-1), X ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, and a methyl group is particularly preferable.

In the above average unit formula (b-1), c1, c2, c3, c4, and c5 are 1> c1 ≧ 0, 1> c2 ≧ 0, 1> c3> 0, 1> c4 ≧ 0, 0, respectively. It is a numerical value satisfying .05 ≧ c5 ≧ 0, c1 + c2 + c4> 0, and c1 + c2 + c3 + c4 + c5 = 1.

An example of a polyorganosiloxane (B1) is a linear polyorganosiloxane having two or more hydrosilyl groups in the molecule. Examples of the group bonded to a silicon atom other than the hydrogen atom in the linear polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, among which alkyl groups (particularly those having 1 to 1 carbon atoms) are used. An alkyl group of 10) and an aryl group (particularly an aryl group having 6 to 14 carbon atoms) are preferable, and a methyl group and a phenyl group are particularly preferable.

The ratio of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount (100 mol%) of groups bonded to silicon atoms in the linear polyorganosiloxane is not particularly limited, but is 0.1 to 50 mol%. Is preferable. The ratio of the alkyl group (particularly the methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 20 to 99 mol%. Further, the ratio of the aryl group (particularly the phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 40 to 80 mol%. In particular, as the linear polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 70 mol%). By using the one, the barrier property of the cured product against corrosive gas tends to be further improved. Further, by using a cured product in which the ratio of alkyl groups (particularly methyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 90 mol% or more (for example, 95 to 99 mol%). The thermal shock resistance of the material tends to improve.

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

[In the above formula, R ²¹ is the same or different, a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R ²¹ are hydrogen atoms. m2 is an integer of 1 to 1000. ]

Another example of the polyorganosiloxane (B1) is a branched chain polyorganosiloxane having two or more hydrosilyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO _3/2. Be done. However, as described above, the branched-chain polyorganosiloxane does not include the one corresponding to the ladder-type polyorganosylsesquioxane (C) described later. In addition, R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of the group bonded to a silicon atom other than the hydrogen atom in the branched polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, among which alkyl groups (particularly methyl groups) and groups. Aaryl groups (particularly phenyl groups) are preferred. Further, examples of R in the T unit include hydrogen atoms, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups, among which alkyl groups (particularly alkyl groups having 1 to 10 carbon atoms) and aryl groups (particularly alkyl groups having 1 to 10 carbon atoms) and aryl groups ( Aryl groups having 6 to 14 carbon atoms) are particularly preferable, and methyl groups and phenyl groups are particularly preferable. The ratio of the aryl group (particularly the phenyl group) to the total amount (100 mol%) of R in the T unit is not particularly limited, but is preferably 30 mol% or more from the viewpoint of the barrier property of the cured product against the corrosive gas.

The ratio of the alkyl group (particularly the methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom in the branched chain polyorganosiloxane is not particularly limited, but is preferably 70 to 95 mol%. Further, the ratio of the aryl group (particularly the phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 10 to 70 mol%. In particular, as the branched chain 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 one, the barrier property of the cured product against corrosive gas tends to be improved. Further, by using a cured product in which the ratio of the alkyl group (particularly the methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is 50 mol% or more (for example, 50 to 90 mol%). The thermal shock resistance of the material tends to improve.

The branched chain polyorganosiloxane can be represented by, for example, the average unit formula (b-1) in which c1 is a positive number. In this case, although not particularly limited, c2 / c1 is a number of 0 to 10, c3 / c1 is a number of 0 to 0.5, c4 / (c1 + c2 + c3 + c4) is a number of 0 to 0.3, and c5 / (c1 + c2 + c3 + c4) is a number. The number is preferably 0 to 0.4. The molecular weight of the branched-chain polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 300 to 10,000, more preferably 500 to 5000.

(Polyorganosyloxysylalkylene (B2))
As described above, polyorganosyloxysylalkylene (B2) is a polysiloxane having two or more hydrosilyl groups in the molecule and containing a sylalkylene bond in addition to a siloxane bond as a main chain. As the alkylene group in the silalkylene bond, for example, a C _2-4 alkylene group (particularly an ethylene group) is preferable.

Examples of the polyorganosyloxysylalkylene (B2) include those having a linear, partially branched linear, branched chain, and network-like molecular structure. As the polyorganosyloxysylalkylene (B2), one type may be used alone, or two or more types may be used in combination. Specifically, two or more types of polyorganosyloxysylalkylene (B2) having different molecular structures can be used in combination. For example, linear polyorganosyloxysylalkylene (B2) and branched-chain polyorganosyloxy It can also be used in combination with sylalkylene (B2).

The group bonded to a silicon atom other than the hydrogen atom of the polyorganosyloxysylalkylene (B2) is not particularly limited, and examples thereof include an organic group. Examples of the organic group include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group. Of these, alkyl groups (particularly methyl groups) and aryl groups (particularly phenyl groups) are preferable.

The properties of the polyorganosyloxysylalkylene (B2) are not particularly limited, and may be in a liquid state or a solid state at, for example, 25 ° C.

As the polyorganosyloxysylalkylene (B2), the following average unit formula (b-2):
(R ⁴ ₂ SiO _2/2 ) _d1 (R ⁴ ₃ SiO _1/2 ) _d2 (R ⁴ SiO _3/2 ) _d3 (SiO _4/2 ) _d4 ( ^RA ) _d5 (X ⁴ O) _d6 (b− 2)
Polyorganosyloxysylalkylene represented by is preferable. In the above average unit formula (b-2), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which are the same or different. However, a part of R ⁴ is a hydrogen atom, and its ratio is controlled within a range of two or more in the molecule. For example, the ratio of hydrogen atoms to the total amount (100 mol%) of R ⁴ is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%. By controlling the ratio of hydrogen atoms within the above range, the curability of the curable resin composition tends to be improved.

In the above average unit formula (b-2), ^RA is an alkylene group having 1 to 14 carbon atoms. Ethylene groups are particularly preferred.

In the above average unit formula (b-2), X ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, like the above X ³ . Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, and a methyl group is particularly preferable.

In the above average unit formula (b-2), d1, d2, d3, d4, d5, and d6 are 1> d1 ≧ 0, 1> d2> 0, 1> d3 ≧ 0, 1> d4 ≧ 0, respectively. , 0.5> d5> 0, 0.05 ≧ d6 ≧ 0, d1 + d3 + d4> 0, and d1 + d2 + d3 + d4 + d5 + d6 = 1.

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

In the above formula (II-2), R ²² is the same or different, a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group. Examples of R ²² include a hydrogen atom and specific examples of the above-mentioned monovalent or unsubstituted hydrocarbon group (for example, alkyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.). However, at least two of R ²² are hydrogen atoms. Further, as R ²² other than the hydrogen atom, an alkyl group (particularly an alkyl group having 1 to 10 carbon atoms) and an aryl group (particularly an aryl group having 6 to 14 carbon atoms) are preferable, and a methyl group and a phenyl group are particularly preferable.

In the formula (II-2), R ^A, like R ^A in formula (I-2), an alkylene group, among them, C _2-4 alkylene group (in particular, an ethylene group) is preferable. When a plurality of R ^A are present, they may be the same or may be different.

In the above equation (II-2), q1 represents an integer of 1 or more (for example, 1 to 100). When q1 is an integer of 2 or more, the structures in parentheses with q1 may be the same or different.

In the above equation (II-2), q2 represents an integer of 1 or more (for example, 1 to 400). When q2 is an integer of 2 or more, the structures in parentheses with q2 may be the same or different.

In the above equation (II-2), q3 represents an integer of 0 or 1 or more (for example, 0 to 50). When q3 is an integer of 2 or more, the structures in parentheses with q3 may be the same or different.

In the above formula (II-2), q4 represents an integer of 0 or 1 or more (for example, 0 to 50). When q4 is an integer of 2 or more, the structures in parentheses with q4 may be the same or different.

In the above formula (II-2), q5 represents an integer of 0 or 1 or more (for example, 0 to 50). When q5 is an integer of 2 or more, the structures in parentheses with q5 may be the same or different.

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

The terminal structure of the polyorganosyloxysylalkylene having the structure represented by the formula (II-2) is not particularly limited, but is, for example, a silanol group, an alkoxysilyl group, or a trialkylsilyl group (for example, parentheses with q5). Internal structure, trimethylsilyl group, etc.) and the like. Various groups such as a hydrosilyl group may be introduced at the end of the polyorganosyloxysylalkylene.

Polyorganosyloxysylalkylene (B2) can be produced by a known or commonly used method, and the production method thereof is not particularly limited, but can be produced, for example, by the method described in JP2012-140617A.

In the curable resin composition of the present invention, one type of polysiloxane (B) may be used alone, or two or more types may be used in combination.

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

As the polysiloxane (B) in the curable resin composition of the present invention, only polyorganosiloxane (B1) can be used, only polyorganosyloxysylalkylene (B2) can be used, or only polyorganosyloxysylalkylene (B2) can be used. , Polyorganosiloxane (B1) and polyorganosyloxysylalkylene (B2) can also be used in combination. When the polyorganosiloxane (B1) and the polyorganosyloxysylalkylene (B2) are used in combination, the ratios thereof are not particularly limited and can be set as appropriate. Similarly, as the polysiloxane (B) in the curable resin composition of the present invention, only the polyorganosiloxane represented by the above average unit formula (b-1) can be used, or the above average unit formula ( Only the polyorganosyloxysylalkylene represented by b-2) can be used, or the polyorganosiloxane represented by the average unit formula (b-1) and the average unit formula (b-2) can be used. It can also be used in combination with the polyorganosyloxysylalkylene represented by.

The polyorganosiloxane represented by the average unit formula (b-1) and the polyorganosyloxysyl represented by the average unit formula (b-2) in the polysiloxane (B) in the curable resin composition of the present invention. The content (blending amount) (total amount) of the alkylene is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more, and further, with respect to the total amount (100% by weight) of the polysiloxane (B). It is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. When the content is 50% by weight or more, the tackiness of the cured product is lower and dust tends to be less likely to adhere. In the curable resin composition of the present invention, only one of the polyorganosiloxane represented by the average unit formula (b-1) and the polyorganosyloxysylalkylene represented by the average unit formula (b-2) is contained. When is contained, the above-mentioned content is the content of one of them.

The curable resin composition of the present invention contains, among others, a combination in which (i) polysiloxane (A) contains a branched polyorganosiloxane (A1) and polysiloxane (B) contains a polyorganosiloxane (B1). And / or (ii) a combination in which the polysiloxane (A) contains a polyorganosyloxysylalkylene (A2) having a phenyl group bonded to a silicon atom and the polysiloxane (B) contains a polyorganosyloxysylalkylene (B2). Is particularly preferable.

The total content (total content) of the polysiloxane (A) and the polysiloxane (B) in the curable resin composition (100% by weight) of the present invention is not particularly limited, but is preferably 60 to 99% by weight. It is 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 improved.

[Ladder-type polyorganosylsesquioxane (C)]
The curable resin composition of the present invention may contain a ladder-type polyorganosylsesquioxane (C). When the curable resin composition of the present invention contains a ladder-type polyorganosylsesquioxane (C), the barrier property of the cured product against corrosive gas tends to be high. The ladder-type polyorganosyl sesquioxane (C) is a polysiloxane represented by the empirical formula (basic structural formula) RSiO _1.5 , and has at least a ladder-like Si—O—Si structure (ladder structure) in the molecule. Contains polyorganosylsesquioxane. The ladder-type polyorganosylsesquioxane (C) has a siloxane unit represented by (RSiO _3/2 ), a siloxane unit represented by (R ₂ SiO _2/2 ), and (SiO _4/2 ). It is preferably a polysiloxane having no siloxane unit represented by. In this case, it may or may not have the siloxane unit represented by (R ₃ SiO _1/2 ).

As the ladder-type polyorganosylsesquioxane (C), a known or commonly used polyorganosylsesquioxane having the above structure can be used, and is not particularly limited, but is 1 or more (particularly 2 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 preferable. The ladder-type polyorganosylsesquioxane (C) is a polyorganosylsesquioxane having a ladder structure which is a side chain [main skeleton (main chain)) from the viewpoint of barrier property against corrosive gas of the cured product. Part or all of the skeleton (the portion branched from the skeleton (skeleton formed by the Si—O bond)] is preferably a substituted or unsubstituted aryl group (aromatic hydrocarbon group). Examples of the substituted or unsubstituted aryl group include a substituted or unsubstituted aryl group exemplified as R ⁵ described later.

Among them, the ladder-type polyorganosilsesquioxane is the ladder-type silsesquioxane (C1) and the ladder-type silsesquioxia described below from the viewpoints of barrier property against corrosive gas of the cured product, mechanical strength, and the like. Sun (C2) is particularly preferred.

(Ladder type silsesquioxane (C1))
Ladder-type silsesquioxane (C1) as rudder-type polyorganosilsesquioxane (C) is a part of the molecular chain terminal of polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) having a ladder structure. Or all of them contain a unit structure represented by the formula (V) described later and a unit structure represented by the formula (VI) (“polyorganosyl sesquioxane residue (a)). It is a polyorganosilsesquioxane having (sometimes referred to as).

The polyorganosilsesquioxane (polyorganosilsesquioxane skeleton) in the ladder type silsesquioxane (C1) is a polysiloxane represented by the empirical formula (basic structural formula) R ⁵ SiO _1.5 . R ⁵ represents 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, and R ⁵ (the above poly). at least a portion of the R ⁵⁾ organo silsesquioxane is a monovalent organic group. R ⁵ in the polyorganosylsesquioxane may be the same or different.

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

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

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

Examples of the alicyclic hydrocarbon group in R ⁵ include a cycloalkyl group of C _3-12 such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclododecyl group; and a C _{3- of a} cyclohexenyl group and the like. ₁₂ cycloalkenyl groups; C _4-15 crosslinked cyclic hydrocarbon groups such as bicycloheptanyl group and bicycloheptenyl group can be mentioned.

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

Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group in R ⁵ 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 a C _7-18 aralkyl group such as a benzyl group and a phenethyl group (particularly, a C _7-10 aralkyl group) and a C such as a cinnamyl group. _Examples thereof include a C _1-4 alkyl-substituted aryl group such as a _6-10 aryl-C _2-6 alkenyl group and a tolyl group, and a C _2-4 alkenyl-substituted aryl group such as a styryl group.

The hydrocarbon group in R ⁵ may be a hydrocarbon group having a substituent (substituted hydrocarbon group). The number of carbon atoms of the substituent in the above-mentioned substituted hydrocarbon group is preferably 0 to 20, more preferably 0 to 10. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group. (Preferably C _1-6 alkoxy group, more preferably C _1-4 alkoxy group); Alkenyloxy group such as allyloxy group (preferably C _2-6 alkenyloxy group, more preferably C _2-4 alkenyloxy group) The aromatic ring may have a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, or a C _1-4 alkoxy group, such as a phenoxy group, a triloxy group, or a naphthyloxy group. Aryloxy group (preferably C _6-14 aryloxy group); aralkyloxy group such as benzyloxy group, phenethyloxy group (preferably C _7-18 aralkyloxy group); acetyloxy group, propionyloxy group, (meth) Acryloxy groups such as acryloyloxy group and benzoyloxy group (preferably C _1-12 acyloxy group); mercapto group; alkylthio group such as methylthio group and ethylthio group (preferably C _1-6 alkylthio group, more preferably C _{1- 4} Alkylthio group); Alkenylthio group such as allylthio group (preferably C _2-6 alkenylthio group, more preferably C _2-4 alkenylthio group); C in aromatic ring such as phenylthio group, trilthio group, naphthylthio group _An arylthio group (preferably a C _6-14 arylthio group) which may have a substituent such as a _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, or a C _1-4 alkoxy group; a benzylthio group, a phenethyl Aralkylthio groups such as thio groups (preferably C _7-18 aralkylthio groups); carboxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups, butoxycarbonyl groups (preferably C _1-6 alkoxy) -Carbonyl group); aryloxycarbonyl group such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group (preferably C _6-14 aryloxy-carbonyl group); aralkyloxycarbonyl group such as benzyloxycarbonyl group (preferably) Is a C _7-18 aralkyloxy-carbonyl group); amino group; methylamino group, ethylamino group, dimethylamino group, diethylamino group, etc. No or dialkylamino group (preferably mono or di-C _1-6 alkylamino group); acylamino group such as acetylamino group, propionylamino group, benzoylamino group (preferably C _1-11 acylamino group); glycidyloxy group Epoxy group-containing groups such as; oxetanyl group-containing groups such as ethyloxetanyloxy group; acyl groups such as acetyl group, propionyl group, benzoyl group; oxo group; two or more of these groups may be _{added as} required. Examples thereof include groups bonded via. The number of substituents contained in the substituted hydrocarbon group is not particularly limited.

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

Further, as the above R ⁵ , a group represented by the following formula (s) can be mentioned.

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

In the group represented by the above formula (s), each R ⁵¹ includes a hydrogen atom; a C _1-10 alkyl group (particularly, a C _1-4 alkyl group); a C _2-10 alkenyl group (particularly, C). _2-4 alkenyl group); C _3-12 cycloalkyl group; C _3-12 cycloalkenyl group; C _1-4 alkyl group on aromatic ring, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group, etc. C _6-14 aryl group which may have a substituent of C _6-14 aryl group; C _7-18 aralkyl group; C _6-10 aryl-C _2-6 alkenyl group; hydroxy group; C _1-6 alkoxy group; preferable.

Among the above, as R ⁵ , a hydrogen atom or a substituted or unsubstituted hydrocarbon group is preferable, a substituted or unsubstituted hydrocarbon group is more preferable, and an aliphatic hydrocarbon group (particularly, an alkyl group) is more preferable. ), Aromatic hydrocarbon groups (particularly phenyl groups).

Generally, the structure of polyorganosyl sesquioxane includes a ladder-like Si—O—Si structure (ladder structure), a cage-like Si—O—Si structure (cage structure), and a random Si—O—Si structure. (Random structure) and the like can be mentioned, but the polyorganosilsesquioxane in the ladder-type silsesquioxane (C1) is a polyorganosilsesquioxane containing at least the rudder structure (polyorganosilsesquioxane having a ladder structure). Sun).

The polyorganosilsesquioxane in the ladder type silsesquioxane (C1) is represented by, for example, the following formula (L).

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

Ladder silsesquioxane polyorganosilsesquioxane directly bonded groups to the silicon atom in San in (C1) (R ⁵ in the above empirical formula, for example, R ⁵ in the formula (L) (side chain)), especially The ratio of the substituted or unsubstituted hydrocarbon group to the total amount (100 mol%) of the above groups is preferably 50 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol%. That is all. In particular, substituted or unsubstituted linear or branched C _1-10 alkyl groups (particularly, linear or branched C ₁ such as methyl group and ethyl group) with respect to the total amount (100 mol%) of the above groups. _-4 Alkyl groups), substituted or unsubstituted C _6-10 aryl groups (particularly phenyl groups), substituted or unsubstituted C _7-10 aralkyl groups (particularly benzyl groups) totaling 50 mol% or more. It is more preferably 80 mol% or more, still more preferably 90 mol% or more.

In particular, from the viewpoint of the barrier property of the cured product against corrosive gas, the ladder-type silsesquioxane (C1) is branched from the polyorganosilsesquioxane skeleton having a ladder structure which is a side chain [main skeleton (main chain)). It is preferable that a part or all of the portion, for example, R ⁵ ] in the above formula (L), is a substituted or unsubstituted aryl group (aromatic hydrocarbon group).

The ladder-type silsesquioxane (C1) has at least a polyorganosilsesquioxane residue (a) at a part or all of the molecular chain ends of the polyorganosilsesquioxane having the ladder structure. When the polyorganosilsesquioxane is represented by the above formula (L), the ladder type silsesquioxane (C1) is a polyorganosilsesquioxane in which a part or all of T in the formula (L) is as follows. It has a structure substituted with the 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 polyorganosylsesquioxane residue (a) is represented by the following formula (V).

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

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

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, an allyl group, a metallicyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group and a 3-butenyl group. C _2-20 alkenyl groups such as 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 5-hexenyl group (preferably C _2-10 alkenyl group, more preferably C _2-4 alkenyl group Group); C _3-12 cycloalkenyl group such as cyclohexenyl group; C _4-15 crosslinked unsaturated hydrocarbon group such as bicycloheptenyl group; C _2-4 alkenyl-substituted aryl group such as styryl group; cinnamyl The group etc. can be mentioned. In addition, in the group having the aliphatic carbon-carbon double bond, in the group represented by the above formula (s), at least one of three R ⁵¹ is the above C _2-20 alkenyl group, C _{3- 12} cycloalkenyl groups, C _4-15 crosslinked unsaturated hydrocarbon groups, C _2-4 alkenyl-substituted aryl groups, cinnamyl groups and the like are also included. Among them, R ⁶ is preferably an alkenyl group, more preferably a C _2-20 alkenyl group, and even more preferably a vinyl group.

R ⁷ in the above formula (VI) represents a hydrocarbon group (monovalent hydrocarbon group), which is the same or different. Examples of the hydrocarbon group, a hydrocarbon group similar to those exemplified as the R ⁵ can be exemplified. Among them, as R ⁷ , a C _1-20 alkyl group is preferable, a C _1-10 alkyl group is more preferable, a C _1-4 alkyl group is more preferable, and a methyl group is particularly preferable. In particular, it is preferred that R ⁷ in formula (VI) are 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。 The polyorganosylsesquioxane residue (a) has, for example, the following formula (V') in addition to the unit structure represented by the formula (V) and the unit structure represented by the formula (VI).

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

'R ⁶ in the formula (V)' is aliphatic carbon - indicates a monovalent group excluding the group having a carbon-carbon double bond. Specifically, for example, a monovalent organic group excluding a hydrogen atom, a halogen atom, and a group having an aliphatic carbon-carbon double bond, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent group. Examples include valent sulfur atom-containing groups.

The amount of the silicon atom to which the three oxygen atoms represented by the formula (V) in the polyorganosylsesquioxane residue (a) is bonded is not particularly limited, but the polyorganosylsesquioxane residue (a) It is preferably 20 to 80 mol%, more preferably 25 to 60 mol%, based on the total amount (100 mol%) of silicon atoms constituting the above. If the content is less than 20 mol%, the amount of aliphatic carbon-carbon double bonds (particularly alkenyl groups) possessed by the ladder-type silsesquioxane (C1) becomes insufficient, and the hardness of the cured product becomes insufficient. You may not get enough. On the other hand, when the content exceeds 80 mol%, a large amount of silanol groups and hydrolyzable silyl groups remain in the ladder-type silsesquioxane (C1), so that the ladder-type silsesquioxane (C1) is obtained in liquid form. It may not be possible. Further, the condensation reaction proceeds and the molecular weight is likely to change, so that the storage stability may deteriorate.

The amount of the silicon atom to which one oxygen atom represented by the formula (VI) in the polyorganosylsesquioxane residue (a) is bonded is not particularly limited, but the polyorganosylsesquioxane residue (a) 20 to 85 mol% is preferable, and more preferably 30 to 75 mol% with respect to the total amount (100 mol%) of silicon atoms constituting. If the content is less than 20 mol%, silanol groups and hydrolyzable silyl groups are likely to remain in the ladder-type silsesquioxane (C1), and the ladder-type silsesquioxane (C1) cannot be obtained in liquid form. In some cases. Further, the condensation reaction proceeds and the molecular weight is likely to change, so that the storage stability may deteriorate. On the other hand, when the content exceeds 85 mol%, the amount of the aliphatic carbon-carbon double bond (particularly the alkenyl group) possessed by the ladder type silsesquioxane (C1) becomes insufficient, and the hardness of the cured product becomes insufficient. May not be obtained sufficiently.

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

Ladder silsesquioxane (C1) is, for example, can be represented by the following formula (L ^a). V in the formula (L ^a), as it is R ^5, those similar to the above formula (L) can be exemplified. The A in the formula (L ^a), polyorganosilsesquioxane residues (a), or a hydroxy group, a halogen atom, an alkoxy group, or shows an acyloxy group, a part or all polyorganosilsesquioxane of A It is an oxane residue (a). Incidentally, represented by formula If (L ^a) A plurality (two to four) in is polyorganosilsesquioxane residues (a), each A is each other or other formula (L ^a) It may be bonded to A of the molecule via one or more Si—O—Si bonds.

The polyorganosilsesquioxane residue (a) in the ladder-type silsesquioxane (C1) further has a unit structure represented by the formula (VII) in the ladder-type silsesquioxane (C2) described later. It may have. In this case, the ladder-type silsesquioxane (C1) may also be used as the ladder-type silsesquioxane (C2).

The method for producing the rudder-type silsesquioxane (C1) is not particularly limited, but for example, it has a rudder structure and has a silanol group and / or a hydrolyzable silyl group (silanol group and hydrolyzable silyl group) at the end of the molecular chain. A method of forming the polyorganosylsesquioxane residue (a) at the end of the molecular chain of the polyorganosylsesquioxane having either one or both of the above is mentioned. Specifically, it can be produced by the method disclosed in the literature such as International Publication No. 2013/176238.

The number of aliphatic carbon-carbon double bonds (particularly alkenyl groups) in the molecule in the ladder-type silsesquioxane (C1) is not particularly limited, but is preferably 2 or more (for example, 2 to 50). , More preferably 2 to 30 pieces. By having an aliphatic carbon-carbon double bond (particularly an alkenyl group) in the above range, it tends to be easy to obtain a cured product having various physical properties such as heat resistance, crack resistance, and a barrier property against corrosive gas. There is.

The content of the aliphatic carbon-carbon double bond in the ladder-type silsesquioxane (C1) is not particularly limited, but is preferably 0.7 to 5.5 mmol / g, more preferably 1.1 to 4. It is 4 mmol / g. The proportion of aliphatic carbon-carbon double bonds (weight basis) contained in the ladder-type silsesquioxane (C1) is not particularly limited, but is 2.0 to 15.0% by weight in terms of vinyl group. It is preferable, more preferably 3.0 to 12.0% by weight.

The molecular weight of the ladder-type silsesquioxane (C1) is not particularly limited, but is preferably 1 to 800,000, more preferably 2 to 100,000, still more preferably 300 to 10,000, and particularly preferably 500 to 8000. When the molecular weight of the ladder-type silsesquioxane (C1) is in this range, it tends to become a liquid at room temperature and its viscosity tends to be relatively low, so that it tends to be easy to handle. The ladder-type silsesquioxane (C1) may be a mixture of those having various molecular weights in the above range. The molecular weight is measured as a standard polystyrene-equivalent molecular weight by gel permeation chromatography.

The weight average molecular weight (Mw) of the ladder-type silsesquioxane (C1) is not particularly limited, but is preferably 1 to 800,000, more preferably 2 to 100,000, still more preferably 300 to 10,000, and particularly preferably 500. ~ 8000. When the weight average molecular weight is 100 or more, the heat resistance of the cured product tends to improve. On the other hand, when the molecular weight is 800,000 or less, the compatibility with other components tends to be improved. The weight average molecular weight is calculated from the standard polystyrene-equivalent molecular weight obtained by gel permeation chromatography.

The ladder type silsesquioxane (C1) is not particularly limited, but is preferably a liquid at room temperature (about 25 ° C.). More specifically, the viscosity of the ladder type silsesquioxane (C1) at 23 ° C. is preferably 1 to 100,000 mPa · s, more preferably 500 to 10,000 mPa · s, still more preferably 1000 to 8000 mPa · s. s. When the viscosity is 100 mPa · s or more, the heat resistance of the cured product tends to improve. On the other hand, when the viscosity is 100,000 mPa · s or less, the curable resin composition tends to be easily prepared and handled. The viscosity at 23 ° C. was determined by using a leometer (trade name "PhysicaUDS-200", manufactured by AntonioPaar) and a cone plate (cone diameter: 16 mm, taper angle = 0 °), temperature: 23 ° C., rotation speed: It is measured under the condition of 20 rpm.

In the curable resin composition of the present invention, one type of ladder-type silsesquioxane (C1) may be used alone, or two or more types may be used in combination.

When the curable resin composition of the present invention contains a ladder-type silsesquioxane (C1), the content (blending amount) of the rudder-type silsesquioxane (C1) in the curable resin composition of the present invention is particularly high. Although not limited, it is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, still more preferably 10 to 20% by weight, based on the curable resin composition (100% by weight). When the content is 1% by weight or more, the barrier property of the cured product against corrosive gas tends to be further improved. On the other hand, when the content is 40% by weight or less, the cured product does not become too hard, and a cured product having excellent flexibility tends to be obtained.

(Ladder type silsesquioxane (C2))
The rudder-type silsesquioxane (C2) in the curable resin composition of the present invention has a rudder structure, and the rudder-type silsesquioxane (polyorganosylsesquioxane skeleton) has a part or all of the molecular chain ends. A polyorganosylsesquioxane residue containing a unit structure represented by the formula (VII) described later and a unit structure represented by the formula (VIII) (when referred to as "polyorganosylsesquioxane residue (b)"). Is a polyorganosilsesquioxane having).

The polyorganosilsesquioxane in the ladder type silsesquioxane (C2) is a polysiloxane represented by the empirical formula (basic structural formula) R ⁵ SiO _1.5 . The polyorganosilsesquioxane in the ladder-type silsesquioxane (C2) is a polyorganosylsesquioxane in the ladder-type silsesquioxane (C1) (for example, the polyorganosyl represented by the above formula (L)). The same as sesquioxane) is exemplified.

Like the ladder-type silsesquioxane (C1), the ladder-type silsesquioxane (C2) is partially or completely absent of the side chain, particularly from the viewpoint of the barrier property of the cured product against corrosive gas. It is preferably a substituted aryl group.

When the polyorganosilsesquioxane is represented by the above formula (L), the ladder type silsesquioxane (C2) is a polyorganosilsesquioxan in which a part or all of T in the formula (L) is as follows. It has a structure substituted with the sun residue (b).

で表される単位構造（シロキサン単位構造）及び下記式（VIII）

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

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

It is a residue containing at least a unit structure (siloxane unit structure) represented by. 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 referred to.

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). Bonding), groups in which a plurality of these are linked, and the like can be mentioned.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group and the like. 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 and 1,3-cyclohexyl group. Examples thereof include a divalent cycloalkylene group (including a cycloalkylidene group) such as a silene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

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

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

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

In the above formula (VII), n represents an integer of 1 to 100, preferably an integer of 1 to 30, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 5. If n is too large, the barrier property against the gas (particularly corrosive gas) of the cured product tends to decrease, so that it may not be suitable as a sealing agent for, for example, an optical semiconductor element.

R ¹⁰ in the above formula (VIII) represents a hydrocarbon group (monovalent hydrocarbon group), which is the same or different. Examples of the hydrocarbon group, a hydrocarbon group similar to those exemplified in the above R ⁵ is exemplified. Among them, as R ¹⁰ , a C _1-20 alkyl group is preferable, a C _1-10 alkyl group is more preferable, a C _1-4 alkyl group is more preferable, and a methyl group is particularly preferable. In particular, it is preferable that all R ^10s in the formula (VIII) are methyl groups.

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

The amount of the silicon atom (excluding the silicon atom in the SiH-containing group) to which the three oxygen atoms in the formula (VII) in the polyorganosylsesquioxane residue (b) are bonded is not particularly limited, but is poly. It is preferably 20 to 80 mol%, more preferably 25 to 60 mol%, based on the total amount (100 mol%) of silicon atoms constituting the organosilsesquioxane residue (b). If the content is less than 20 mol%, the amount of hydrosilyl groups contained in the ladder-type silsesquioxane (C2) may be insufficient, and sufficient hardness of the cured product may not be obtained. On the other hand, when the content exceeds 80 mol%, a large amount of silanol groups and hydrolyzable silyl groups remain in the ladder-type silsesquioxane (C2), so that the ladder-type silsesquioxane (C2) is obtained in liquid form. It may not be possible. Further, the condensation reaction proceeds and the molecular weight is likely to change, so that the storage stability may deteriorate.

The amount of the silicon atom to which one oxygen atom is bonded in the formula (VIII) in the polyorganosylsesquioxane residue (b) is not particularly limited, but constitutes the polyorganosylsesquioxane residue (b). It is preferably 20 to 85 mol%, more preferably 30 to 75 mol%, based on the total amount of silicon atoms (100 mol%). If the content is less than 20 mol%, silanol groups and hydrolyzable silyl groups are likely to remain in the ladder-type silsesquioxane (C2), and the ladder-type silsesquioxane (C2) cannot be obtained in liquid form. In some cases. Further, the condensation reaction proceeds and the molecular weight is likely to change, so that the storage stability may deteriorate. On the other hand, if the content exceeds 85 mol%, the amount of hydrosilyl groups contained in the ladder-type silsesquioxane (C2) becomes insufficient, and the hardness of the cured product may not be sufficiently obtained.

The Si—O—Si structure (skeleton) contained in the polyorganosylsesquioxane residue (b) is not particularly limited, and examples thereof include a ladder structure, a basket structure, and a random structure.

Polyorganosylsesquioxane (C2) can be represented by, for example, the following formula (L ^b ). 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 polyorganosyl sesquioxane residue (b) or a hydroxy group, a halogen atom, an alkoxy group, or an acyloxy group, and is a part of B in the formula (L ^b ). Or all are polyorganosylsesquioxane residues (b). When a plurality (2 to 4) Bs in the formula (L ^b ) are polyorganosylsesquioxane residues (b), each B is represented by each other or another formula (L ^b ). It may be bonded to B of the molecule via one or more Si—O—Si bonds.

The polyorganosilsesquioxane residue (b) in the ladder-type silsesquioxane (C2) further has a unit structure represented by the formula (V) in the ladder-type silsesquioxane (C1) described above. It may have. In this case, the ladder-type silsesquioxane (C2) may also be used as the ladder-type silsesquioxane (C1).

The method for producing the rudder-type silsesquioxane (C2) is not particularly limited, but for example, a polyorganosylsesquioxane having a rudder structure and having a silanol group and / or a hydrolyzable silyl group at the end of the molecular chain ( A method of forming the polyorganosylsesquioxane residue (b) at the end of the molecular chain of the raw material ladder polymer) can be mentioned. Specifically, it can be produced by the method disclosed in the literature such as International Publication No. 2013/176238.

The number of the SiH-containing groups in the molecule (in one molecule) in the ladder type silsesquioxane (C2) is not particularly limited, but is preferably 2 or more (for example, 2 to 50), and more preferably 2. ~ 30 pieces. Having the SiH-containing group in the above range tends to improve the heat resistance of the cured product of the curable resin composition.

The content of the hydrosilyl group contained in the ladder-type silsesquioxane (C2) is not particularly limited, but is preferably 0.01 to 0.5 mmol / g, and more preferably 0.08 to 0.28 mmol / g. The weight-based content of the hydrosilyl group of the ladder-type silsesquioxane (C2) is not particularly limited, but the weight-equivalent (H-equivalent) of H (hydride) in the hydrosilyl group is 0.01 to 0. It is preferably 50% by weight, 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), the curing of the curable resin composition may not proceed. On the other hand, if the content of the hydrosilyl group is too large (for example, when it exceeds 0.50 mmol / g and exceeds 0.50% by weight in terms of H), the hardness of the cured product becomes high and it may be easily cracked. The content of the hydrosilyl group in the ladder-type silsesquioxane (C2) can be calculated by, for example, ¹ H-NMR spectrum measurement or the like.

The molecular weight of the ladder-type silsesquioxane (C2) is not particularly limited, but is preferably 1 to 800,000, more preferably 2 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 (C2) is in this range, it tends to become a liquid at room temperature and its viscosity tends to be relatively low, so that it tends to be easy to handle. The ladder-type silsesquioxane (C2) may be a mixture of those having various molecular weights in the above range. The molecular weight is measured as a standard polystyrene-equivalent molecular weight by gel permeation chromatography.

The weight average molecular weight (Mw) of the ladder-type silsesquioxane (C2) is not particularly limited, but is preferably 1 to 800,000, more preferably 2 to 100,000, still more preferably 300 to 10,000, and particularly preferably 500. ~ 9000. When the weight average molecular weight is 100 or more, the heat resistance of the cured product tends to improve. On the other hand, when the molecular weight is 800,000 or less, the compatibility with other components tends to be improved. The weight average molecular weight is calculated from the standard polystyrene-equivalent molecular weight obtained by gel permeation chromatography.

The ladder-type silsesquioxane (C2) is not particularly limited, but is preferably a liquid at room temperature (about 25 ° C.). More specifically, the viscosity of the ladder-type silsesquioxane (C2) at 23 ° C. is preferably 1 to 100,000 mPa · s, more preferably 500 to 10,000 mPa · s, still more preferably 1000 to 8000 mPa · s. s. When the viscosity is 100 mPa · s or more, the heat resistance of the cured product tends to improve. On the other hand, when the viscosity is 100,000 mPa · s or less, the curable resin composition tends to be easily prepared and handled. The viscosity at 23 ° C. is measured by the same method as the viscosity of the ladder type silsesquioxane (C1).

In the curable resin composition of the present invention, one type of ladder-type silsesquioxane (C2) may be used alone, or two or more types may be used in combination.

When the curable resin composition of the present invention contains rudder-type silsesquioxane (C2), the content (blending amount) of rudder-type silsesquioxane (C2) in the curable resin composition of the present invention is particularly high. Although not limited, it is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, still more preferably 5 to 15% by weight, based on the curable resin composition (100% by weight). When the content is 1% by weight or more, the barrier property of the cured product against corrosive gas tends to be further improved. In addition, the amount of hydrosilyl groups in the curable resin composition increases, and the curing reaction proceeds sufficiently, so that a cured product having high hardness tends to be obtained. On the other hand, when the content is 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 silsesquioxane)
Examples of the ladder-type polyorganosilsesquioxane (C) include ladder-type silsesquioxane (C1) and ladder-type silsesquioxane (C2) other than the above-mentioned ladder-type silsesquioxane (“other ladder-type silses”). (Sometimes referred to as "sesquioxane") can also be used. In particular, the other ladder-type silsesquioxane is preferably used in combination with the ladder-type silsesquioxane (C1) or the ladder-type silsesquioxane (C2).

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

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

The number of hydrosilyl groups in the molecule of the ladder-type silsesquioxane (S2) is not particularly limited, but is preferably 2 or more (for example, 2 to 50), and more preferably 2 to 30. 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.

The weight average molecular weight (Mw) of each of the ladder-type silsesquioxane (S1) and (S2) is not particularly limited, but is preferably 2000 to 800,000, more preferably 6000 to 100,000. When the weight average molecular weight is 2000 or more, the barrier property of the cured product against corrosive gas tends to be further improved. On the other hand, when the molecular weight is 800,000 or less, the compatibility with other components tends to be improved. The weight average molecular weight is calculated from the standard polystyrene-equivalent molecular weight obtained by gel permeation chromatography.

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

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

Examples of the other ladder-type silsesquioxane include two or more aliphatic carbon-carbon double bonds (particularly alkenyl groups) in the molecule or intramolecularly disclosed in International Publication No. 2013/176238. Has two or more hydrosilyl groups, has a standard polystyrene-equivalent number average molecular weight (Mn) of 500 to 1500 by gel permeation chromatography, and a molecular weight dispersion (Mw / Mn) of 1.00 to 1.40. Ladder type silsesquioxane and the like can also be used. By using such a ladder type silsesquioxane, the barrier property of the cured product against corrosive gas tends to be remarkably improved. The content of the ladder-type silsesquioxane is not particularly limited, and can be appropriately adjusted in the range of 0.1 to 15% by weight with respect to the curable resin composition (100% by weight), for example.

In the curable resin composition of the present invention, one type of ladder-type polyorganosylsesquioxane may be used alone, or two or more types may be used in combination. In particular, from the viewpoint of the barrier property of the cured product against the corrosive gas, it is preferable to use the ladder type silsesquioxane (C1) and the ladder type silsesquioxane (C2) in combination.

When the curable resin composition of the present invention contains a ladder-type polyorganosylsesquioxane (C), the content (blending amount) of the ladder-type polyorganosylsesquioxane (C) in the curable resin composition of the present invention. ) Is not particularly limited, but is preferably 0.1 to 50% by weight, more preferably 0.5 to 40% by weight, still more preferably 0.5 to 50% by weight, based on the curable resin composition (100% by weight). It is 30% by weight. By setting the content of the ladder-type polyorganosylsesquioxane (C) to 0.1% by weight or more, the barrier property of the cured product against corrosive gas tends to be further improved. On the other hand, when the content of the ladder-type polyorganosylsesquioxane (C) is 50% by weight or less, the mechanical strength such as toughness of the cured product tends to be improved.

[Compound (D) containing an isocyanuric skeleton]
The curable resin composition of the present invention may contain a compound (D) containing an isocyanuric skeleton. When the curable resin composition of the present invention contains the compound (D) containing an isocyanul skeleton, the barrier property of the cured product to corrosive gas is improved, and the adhesion to the adherend tends to be improved. Further, when used in combination with a ladder-type polyorganosylsesquioxane (C), the barrier property against corrosive gas becomes even higher. In particular, the compound (D) containing an isocyanuric skeleton is preferably a compound represented by the following formula (1).

In the formula (1), R ^x , R ^y , and R ^z represent the same or different groups represented by the formula (1a) or the groups represented by the formula (1b). Among them, at least one of R ^x , R ^y , and R ^z is preferably a group represented by the formula (1b).

In formula (1a), R ¹³ represents a hydrogen atom or a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms (straight-chain or branched C _1-8 alkyl group). Examples of the linear or branched C _1-8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples thereof include an octyl group and an ethylhexyl group. Among the above alkyl groups, linear or branched C _1-3 alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group are preferable. Of these, a hydrogen atom is particularly preferable as R ¹³ .

If two or three of R ^x , R ^y , and R ^{z in} the formula (1) are groups represented by the formula (1a), the groups represented by these formulas (1a) are It may be the same or different. Further, the compound represented by the formula (1) does not have to have the group represented by the formula (1a).

In formula (1b), R ¹⁴ represents a hydrogen atom or a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms (straight-chain or branched C _1-8 alkyl group). Examples of the linear or branched C _1-8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples thereof include an octyl group and an ethylhexyl group. Among the above alkyl groups, linear or branched C _1-3 alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group are preferable. Of these, a hydrogen atom is particularly preferable as R ¹⁴ .

If two or three of R ^x , R ^y , and R ^z in the formula (1) are groups represented by the formula (1b), the groups represented by these formulas (1b) are It may be the same or different. Further, the compound represented by the formula (1) does not have to have the group represented by the formula (1b).

Examples of the compound represented by the formula (1) include a compound in which one of R ^x , R ^y , and R ^{z in} the formula (1) is a group represented by the formula (1b) (“monoallyldi). (Sometimes referred to as "glycidyl isocyanurate compound"), two of R ^x , R ^y , and R ^z in formula (1) are represented by formula (1b) (as "diallyl monoglycidyl isocyanurate compound"). A compound in which all of R ^x , R ^y , and R ^z in the formula (1) are represented by the formula (1b) (sometimes referred to as a "triallyl isocyanurate compound") and the like can be mentioned. ..

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

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

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

The compound (D) containing an isocyanuric skeleton in the curable resin composition of the present invention may be used alone or in combination of two or more. The compound (D) containing an isocyanuric skeleton can be obtained as a commercially available product, for example.

When the compound represented by the formula (1) has a group represented by the formula (1a), it is modified by reacting with a compound that reacts with an epoxy group such as alcohol or acid anhydride. It can also be used in.

When the compound represented by the formula (1) has a group represented by the formula (1b), for example, it can be used after reacting with a compound having a hydrosilyl group in advance (hydrosilylation reaction). For example, a reaction of the monoallyl diglycidyl isocyanurate compound and a ladder-type silsesquioxane (C2) in the presence of a hydrosilylation catalyst is used as a constituent component of the curable resin composition of the present invention. You can also.

From the viewpoint of improving compatibility with other components, the compound (D) containing an isocyanuric skeleton may be mixed with the silane coupling agent (E) in advance and then blended with the other components, as will be described later. it can.

When the curable resin composition of the present invention contains the compound (D) containing an isocyanul skeleton, the content (blending amount) of the compound (D) containing an isocyanul skeleton in the curable resin composition of the present invention is not particularly limited. However, it is preferably 0.01 to 6% by weight, more preferably 0.05 to 4% by weight, still more preferably 0.08 to 3% by weight, based on the curable resin composition (100% by weight). By setting the content of the compound (D) containing the isocyanuric skeleton to 0.01% by weight or more, the barrier property of the cured product to the corrosive gas and the adhesion to the adherend tend to be further improved. On the other hand, when the content of the compound (D) containing an isocyanuric skeleton is 6% by weight or less, the precipitation of solids caused by the compound (D) containing an isocyanuric skeleton tends to be easily suppressed in the curable resin composition. is there.

[Silane Coupling Agent (E)]
The curable resin composition of the present invention may contain a silane coupling agent (E). When the silane coupling agent (E) is contained, the adhesion of the cured product to the adherend tends to be improved. Further, the silane coupling agent (E) has good compatibility with the compound (D) containing an isocyanul skeleton (particularly, a monoallyl diglycidyl isocyanurate compound), a ladder-type silsesquioxane (C2), and the like. In particular, it makes it possible to improve the compatibility with other components such as the compound (D) containing an isocyanate skeleton. Specifically, for example, when the compound (D) containing an isocyanuric skeleton is used, a composition of the compound (D) containing an isocyanuric skeleton and the silane coupling agent (E) is formed in advance, and then other components are used. When blended with the above components, a uniform curable resin composition can be easily obtained.

As the silane coupling agent (E), a known or commonly used silane coupling agent can be used, and is not particularly limited, but for example, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxy). Epoxy group-containing silane coupling agents such as cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-3 Amino group-containing silane coupling agent such as hydrochloride of aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane; tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyl Diethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxysilane), phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloyloxypropyltriethoxy. Silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, mercaptopropylene trimethoxysilane, mercaptopropylene triethoxysilane , Alkoxy oligomers (for example, trade names "KR-513", "X-41-1059A", "KR-516", "X-41-1085", "X-41-1818", "X-411-1810". , "X-40-2651", "X-40-2665A", "KR-513", "KC-89S", "KR-500", "X-40-9225", "X-40-9246" , "X-40-9250"; above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like. Among them, an epoxy group-containing silane coupling agent (particularly, 3-glycidoxypropyltrimethoxysilane) can be preferably used.

In the curable resin composition of the present invention, one type of silane coupling agent (E) may be used alone, or two or more types may be used in combination. Further, as the silane coupling agent (E), a commercially available product can also be used.

When the curable resin composition of the present invention contains a silane coupling agent (E), the content (blending amount) of the silane coupling agent (E) in the curable resin composition of the present invention is not particularly limited. 0.01 to 15% by weight is preferable, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 5% by weight, and particularly preferably 0, based on the curable resin composition (100% by weight). .3 to 0.5% by weight. By setting the content of the silane coupling agent (E) to 0.01% by weight or more, the adhesion of the cured product to the adherend tends to be improved. Further, since the solubility of the compound (D) containing the isocyanuric skeleton in the curable resin composition can be improved, the barrier property of the cured product to the corrosive gas may be further improved. On the other hand, when the content of the silane coupling agent (E) 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 improved. ..

[Hydrosilylation catalyst]
The curable resin composition of the present invention may contain a hydrosilylation catalyst. By heating the curable resin composition of the present invention by containing a hydrosilylation catalyst, a hydrosilyl between an aliphatic carbon-carbon double bond (particularly an alkenyl group) and a hydrosilyl group in the curable resin composition can be obtained. There is a tendency for the chemical reaction to proceed more efficiently.

Examples of the hydrosilylation catalyst include well-known hydrosilylation reaction catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Specific examples thereof include platinum fine powder, platinum black, platinum-supported silica fine powder, and platinum. Supported activated charcoal, platinum chloride acid, complex of platinum chloride acid with alcohol, aldehyde, ketone, etc., platinum olefin complex, platinum carbonyl complex such as platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex or platinum- Platinum vinyl methyl siloxane complex such as cyclovinyl methyl siloxane complex, platinum-based catalyst such as platinum-phosphine complex, platinum-phosphite complex, and palladium-based catalyst containing palladium atom or rhodium atom instead of platinum atom in the platinum-based catalyst. Examples thereof include catalysts and rhodium-based catalysts. Among them, as the hydrosilylation catalyst, a platinum-vinylmethylsiloxane complex, a platinum-carbonylvinylmethyl complex, or a complex of platinum chloride acid with an alcohol or an aldehyde is preferable because the reaction rate is good.

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

When the curable resin composition of the present invention contains a hydrosilylation catalyst, the content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited, but is included in the curable resin composition. 1 × 10 ^-8 to 1 × 10 ⁻² mol is preferable, and 1.0 × 10 ^-6 to 1 is more preferable, based on 1 mol of the total amount of the aliphatic carbon-carbon double bond (particularly, the alkenyl group). It is 0 × 10 ^-3 mol. By setting the content to 1 × 10 ^-8 mol or more, the cured product tends to be formed more efficiently. On the other hand, when the content is 1 × 10 ⁻² mol or less, a cured product having a better hue (less coloring) tends to be obtained.

The content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited, but for example, platinum, palladium, or rhodium in the hydrosilylation catalyst is 0.01 to 0.01 by weight. An amount in the range of 1000 ppm is preferable, and an amount in 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 more excellent hue tends to be obtained.

Furthermore, the curable resin composition of the present invention may contain components other than the above-mentioned components (sometimes referred to as "other components"). Other components are not particularly limited, but are, for example, siloxane compounds other than polysiloxanes (A) and (B) (for example, cyclic siloxane compounds, low molecular weight linear or branched chain siloxane compounds, etc.), and inhibition of hydrosilylation reaction. Examples include agents, solvents, and various additives. As additives, for example, 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, etc. Inorganic fillers such as boron nitride, inorganic fillers obtained by treating these fillers with organic silicon compounds such as organohalosilane, organoalkoxysilane, and organosilazane; organic resins such as silicone resins, epoxy resins, and fluororesins other than those described above. Fine powder; fillers such as conductive metal powders such as silver and copper, solvents, stabilizers (antioxidants, ultraviolet absorbers, light-resistant stabilizers, heat stabilizers, etc.), flame retardants (phosphorus flame retardants, etc.) Halogen-based flame retardants, inorganic flame retardants, etc.), flame retardants, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents, lubricants, waxes, plasticizers, mold release agents, impact resistance improving agents , Color improver, fluidity improver, colorant (dye, pigment, etc.), dispersant, defoamer, defoamer, antibacterial agent, preservative, viscosity modifier, thickener, phosphor, etc. .. One of these other components may be used alone, or two or more thereof may be used in combination. The content (blending amount) of other components can be appropriately selected within a range that does not impair the effects of the present invention.

The curable resin composition of the present invention contains, among others, a combination in which (i) polysiloxane (A) contains a branched polyorganosiloxane (A1) and polysiloxane (B) contains a polyorganosiloxane (B1). And / or (ii) a combination in which the polysiloxane (A) contains a polyorganosyloxysylalkylene (A2) having a phenyl group bonded to a silicon atom and the polysiloxane (B) contains a polyorganosyloxysylalkylene (B2). The total content of the polysiloxane (A) and the polysiloxane (B) in the curable resin composition (100% by weight) of the present invention is 60 to 99% by weight (more preferably 70 to 96% by weight, and further. The content is preferably 80 to 90% by weight), and the content of the ladder-type polyorganosylsesquioxane (C) is 0.1 to 50% by weight (more preferably 0.5 to 40% by weight, still more preferably 0. 5 to 30% by weight), and the content of the compound (D) containing an isocyanul skeleton is 0.01 to 6% by weight (more preferably 0.05 to 4% by weight, still more preferably 0.08 to 3% by weight). ), And the content of the silane coupling agent (E) is 0.01 to 15% by weight (more preferably 0.1 to 10% by weight, still more preferably 0.2 to 5% by weight, and particularly preferably 0. 3 to 0.5% by weight) is particularly preferable.

In the present specification, each component contained in the curable resin composition of the present invention (for example, polysiloxane (A), polysiloxane (B), ladder-type polyorganosylsesquioxane (C), isocyanuric skeleton) is used. The content of the compound (D), the silane coupling agent (E), etc.) to be contained can be appropriately selected from the range described so that the total content is 100% by weight or less.

One bonded to a silicon atom in all the polysiloxanes (polysiloxane (A), polysiloxane (B), ladder-type polyorganosylsesquioxane (C), etc.) contained in the curable resin composition of the present invention. The ratio of the aryl group (particularly the phenyl group) to the total amount (100 mol%) of the substituted or unsubstituted hydrocarbon group is not particularly limited, but is preferably 1 mol% or more (for example, 1 to 90 mol%). It is preferably 5 mol% or more (for example, 5 to 80 mol%), more preferably 10 mol% or more (for example, 10 to 70 mol%, particularly preferably 30 mol% or more (for example, 30 to 50 mol%)). When the ratio of the aryl group is 1 mol% or more (particularly, 10 mol% or more), the hydrocarbon resistance of the cured product tends to be more excellent. The ratio of the aryl group (particularly, phenyl group) is , It can be calculated based on the ¹ H-NMR spectrum measurement result of each polysiloxane contained in the curable resin composition and the blending amount of each polysiloxane.

The curable resin composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components at room temperature. The curable resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance and is used as it is. For example, two or more separately stored compositions can be used. 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 a liquid at room temperature (about 25 ° C.).

The viscosity of the curable resin composition of the present invention at 23 ° C. is not particularly limited, but is preferably 300 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, still more preferably 1000 to 8000 mPa · s. is there. By setting the viscosity to 300 mPa · s or more, the heat resistance of the cured product tends to be improved. On the other hand, when the viscosity is set to 20,000 mPa · s or less, the curable resin composition can be easily prepared, the productivity and handleability thereof are improved, and bubbles are less likely to remain in the cured product. The productivity and quality of cured products (particularly encapsulants) tend to improve. The viscosity of the curable resin composition is measured by the same method as the viscosity of the ladder type silsesquioxane (C) described above.

<Cured product>
By curing the curable resin composition of the present invention (particularly, curing by a hydrosilylation reaction), a cured product (sometimes referred to as "cured product of the present invention") can be obtained. The conditions for curing (particularly curing by a 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 to. 180 ° C. (more preferably 60 to 150 ° C.) is preferable, and the time (curing time) is preferably 1 to 720 minutes. The curing can be carried out in one step or in multiple steps. The cured product of the present invention not only has high heat resistance and transparency peculiar to polysiloxane-based materials, but also has low tackiness and is resistant to dust adhesion.

<Sealant>
The curable resin composition of the present invention can be preferably used as a composition (sealing agent) for encapsulating a semiconductor element in a semiconductor device (sometimes referred to as "the encapsulant of the present invention"). Specifically, the encapsulant of the present invention can be particularly preferably used for encapsulation of an optical semiconductor element (LED element) in an optical semiconductor device (that is, as a sealant for an optical semiconductor). The encapsulant (cured product) obtained by curing the encapsulant of the present invention not only has high heat resistance and transparency peculiar to polysiloxane-based materials, but also has particularly low tackiness and dust. Hard to adhere. Therefore, the encapsulant of the present invention can be particularly preferably used as an encapsulant for high-luminance, short-wavelength optical semiconductor devices and the like.

<Semiconductor device>
By encapsulating a semiconductor element using the encapsulant of the present invention, a semiconductor device (sometimes referred to as "semiconductor device of the present invention") can be obtained. That is, the semiconductor device of the present invention is a semiconductor device having at least a semiconductor element and a sealing material for sealing the semiconductor element, and the sealing material is a cured product of the sealing agent of the present invention. .. The semiconductor device of the present invention can be manufactured by a known or conventional method, and is not particularly limited. For example, the sealing agent of the present invention is injected into a predetermined molding mold and heat-cured under predetermined conditions. it can. The curing temperature and curing time are not particularly limited, but can be set in the same range as when preparing the cured product. The sealant of the present invention is particularly described above when the semiconductor device is an optical semiconductor device, that is, when it is used as a sealant (encapsulant for an optical semiconductor) for an optical semiconductor device in an optical semiconductor device. It is possible to effectively exert an advantageous effect. By using the sealing agent of the present invention as a sealing agent for an optical semiconductor, an optical semiconductor device (sometimes referred to as "the optical semiconductor device of the present invention") can be obtained. An example of the optical semiconductor device of the present invention is shown in FIG. In FIG. 1, 100 is a reflector (resin composition for light reflection), 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 used for forming a sealing material for coating an optical semiconductor element in a high-brightness, short-wavelength optical semiconductor device, which has been difficult to handle with conventional resin materials. It can be preferably used as a sealant, a sealant for forming a sealant for coating a semiconductor element in a semiconductor device (power semiconductor, etc.) having high heat resistance and high withstand voltage.

The curable resin composition of the present invention is not limited to the above-mentioned encapsulant applications (particularly, encapsulant applications for optical semiconductor devices), and includes, for example, functional coating agents, heat-resistant plastic lenses, transparent devices, and adhesives (adhesives). Heat-resistant transparent adhesive, etc.), electrical insulating material (insulating film, etc.), laminate, coating, ink, paint, sealant, resist, composite material, transparent base material, transparent sheet, transparent film, optical element, optical lens, optical member It can also be preferably used for optical-related and semiconductor-related applications such as optical modeling, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, and holographic memories.

[Method for producing curable resin composition of the present invention]
The method for producing a curable resin composition of the present invention (sometimes simply referred to as "the method for producing the present invention") contains polysiloxane (A) and polysiloxane (B), and is referred to as polysiloxane (A). It contains at least one selected from the group consisting of the polyorganosiloxane represented by the average unit formula (a-1) and the polyorganosyloxysylalkylene represented by the average unit formula (a-2), and is a polysiloxane. As (B), at least one selected from the group consisting of the polyorganosiloxane represented by the average unit formula (b-1) and the polyorganosyloxysylalkylene represented by the average unit formula (b-2) is selected. It contains (T + Q) / D> 0.3 and M + D + T + Q = 1 and contains 0.9-5.0 mol of hydrosilyl group for 1 mol of aliphatic carbon-carbon double bond present in the composition. A method for producing a curable resin composition.

The production method of the present invention contains a polysiloxane (A) and a polysiloxane (B), and as the polysiloxane (A), a polyorganosiloxane represented by the above average unit formula (a-1) and the above average unit formula. The polyorganosiloxane represented by the above average unit formula (b-1) and the polyorganosiloxane represented by the above average unit formula (b-1) as the polysiloxane (B) containing at least one selected from the group consisting of the polyorganosyloxysylalkylene represented by (a-2). It contains at least one selected from the group consisting of polyorganosyloxysylalkylene represented by the above average unit formula (b-2), satisfies (T + Q) / D> 0.3 and M + D + T + Q = 1 in the composition. A cured product of the composition (I) having a hydrosilyl group of 0.9 to 5.0 mol was formed with respect to 1 mol of the aliphatic carbon-carbon double bond present in the above-mentioned cured product by the following peeling load evaluation. Includes the step of determining the composition of the desired curable resin composition by determining the peel strength and / or the total peel load of. The following peeling load evaluation may be referred to as "peeling load evaluation (Y)".
Peeling load evaluation: The adherend is moved from a state in which the adherend and the cured product are vertically separated from each other, and at least one of the adherend and the cured product is moved so that the contact area is 50 mm ² or more. The stress change of the contact surface when the body and the cured product are brought into contact with each other, pressed under a load, and then separated in the vertical direction is recorded, and the adherend and the cured product are completely separated after they start to separate. The maximum stress value until separation is divided by the contact area between the adherend and the cured product, and the peel strength is defined as the peel strength from when the adherend and the cured product begin to separate to when they are completely separated. The value obtained by dividing the area surrounded by the stress curve and the baseline by the above contact area is defined as the total peeling load.

That is, in the production method of the present invention, the polysiloxane (A) and the polysiloxane (B) are contained before the curable resin composition is produced, and the polysiloxane (A) is represented by the above average unit formula (a-1). ) And at least one selected from the group consisting of the polyorganosyloxysylalkylene represented by the above average unit formula (a-2), and the above average unit formula as the polysiloxane (B). It contains at least one selected from the group consisting of the polyorganosiloxane represented by (b-1) and the polyorganosyloxysylalkylene represented by the above average unit formula (b-2), and contains (T + Q) / D>. A composition satisfying 0.3 and M + D + T + Q = 1 and having 0.9 to 5.0 mol of a hydrosilyl group with respect to 1 mol of an aliphatic carbon-carbon double bond present in the composition ("Composition (" Composition (" The composition (I) may be referred to as "I)" to form a cured product, and the cured product is subjected to the peeling load evaluation (Y) to determine the peeling strength and / or the total peeling load. Ask. Then, the composition of the curable resin composition capable of forming a cured product having desired tackiness and dust adhesion is determined from the obtained peel strength and / or total peel load, and the curability of the determined composition is determined. Manufacture a resin composition.

The production method of the present invention includes the above steps, and the curable resin composition is obtained after estimating the tackiness and the adhesion of dust of the cured resin composition obtained by the production method of the present invention. Can be manufactured. Therefore, even if a product using a cured product of the curable resin composition is not actually produced, a curable resin composition having low tackiness of the product and less likely to adhere dust can be produced. Can be done.

The peeling load evaluation (Y) corresponds to the measuring method of the present invention described later. The curing of the curable resin composition when forming the cured product to be subjected to the peeling load evaluation (Y) is not particularly limited, but at least one point selected from the conditions of 25 to 180 ° C. and 1 to 720 minutes. It is preferable to carry out under the curing conditions of. The curing can be carried out in one step or in multiple steps. The preferable curing conditions are the same as the curing conditions in the peeling load evaluation (X).

The adherend in the peeling load evaluation (Y) is not particularly limited, but is preferably made of SUS. Contact area when contacting the cured product adherend is a so 50 mm ² or more as described above, preferably 50~800mm ^2. The load at the time of pressing is not particularly limited, but 100 N is preferable. The pressing time is preferably 2 minutes.

In the peeling load evaluation (Y), the speed at which the adherend and the cured product are separated is not particularly limited, but is preferably at least any one point of 5 to 500 mm / min. Above all, the peeling load is evaluated at any 10 points out of at least 5 to 500 mm / min, and the maximum value obtained by measuring at the above 10 points is adopted as the peeling strength and the total peeling load, respectively. Is preferable. However, the speed difference between the two adjacent points is 5 mm / min or more. The above 10 points are 5 mm / min, 10 mm / min, 20 mm / min, 30 mm / min, 50 mm / min, 70 mm / min, 100 mm / min, 150 mm / min, 300 mm / min, and 500 mm / min. Is preferable.

The more preferable evaluation conditions in the peeling load evaluation (Y) are the same as the evaluation conditions in the peeling load evaluation (X).

The curable resin composition before the peel load evaluation (Y) is produced by the same method as the curable resin composition of the present invention.

[Method for measuring tack on the surface of viscoelastic material of the present invention]
In the method for measuring the tack on the surface of the viscoelastic material of the present invention, the adherend and the viscoelastic material are brought into contact with each other so that the contact area is 50 mm ² or more, a load is applied, and then stress relaxation is performed. (Sometimes referred to as "step A"), and step B (hereinafter, may be simply referred to as "step B") in which the adherend and the viscoelastic material are separated by applying a displacement in the separation direction. Step C (hereinafter, simply "step C") of recording the stress change of the contact surface from the contact to the separation, obtaining a curve with the x-axis as the displacement and the y-axis as the stress, and quantifying the tack from the obtained curve. ”), And. In addition, in this specification, "the method of measuring the tack of the surface of a viscoelastic material of this invention" may be referred to as "the measuring method of this invention". According to the measuring method of the present invention, even for a low-tack viscoelastic material such as a silicone-based encapsulant, the obtained tack property can be measured with high accuracy and quantitative measurement becomes possible. Therefore, it becomes easy to make a relative comparison of tackiness even for a viscoelastic material having low tackiness, and it becomes easy to make a consistent relative comparison of tackiness from a low tack region to a high tack region.

(Step A)
The measuring method of the present invention is a method for evaluating the tackiness of a viscoelastic material. The step A includes a means for applying a load by bringing the adherend into contact with the viscoelastic material so that the contact area is 50 mm ² or more, and a means for stress relaxation. In step A, the direction in which the adherend and the viscoelastic material are brought into contact with each other and the direction in which the load is applied are preferably the vertical direction (vertical direction). Further, the load may be applied from the adherend side or the viscoelastic material side. That is, at least one of the adherend and the viscoelastic material is moved in the direction of contact, but either of them may be moved. When the contacting direction and the load applying direction are the vertical directions, the contacting direction may be vertically upward or vertically downward. It should be noted that the direction of movement when making contact in step A and the direction of moving when separating in step B are opposite.

In the above stress relaxation means, after the adherend and the viscoelastic material come into contact with each other, the stress generated by applying a load to the viscoelastic material is relaxed by holding the stress for a certain period of time while the load is applied.

In step A, it is preferable to use a stress detection mechanism having a pedestal and an adherend as a means for applying a load by bringing the adherend into contact with a viscoelastic material. Further, in this case, a flat plate-shaped viscoelastic material is arranged on the pedestal, and the adherend is pressed against the viscoelastic material so that the contact surface between the viscoelastic material and the adherend is flat, and the load is continued. It is preferable that it is a means for adding.

In the step A, the value (pressure) obtained by dividing the load applied by contacting the adherend with the viscoelastic material by the contact area is not particularly limited, but is preferably 0.1 to 4 MPa, more preferably 0.1 to 1. It is 2 MPa, more preferably 0.2 to 2 MPa. When the pressure is within the above range, the pressure tends to be appropriate for measuring the tack property.

The time (pressurization time) of holding the load in the applied state (pressurized state) is not particularly limited, but is preferably 0.5 to 10 minutes, more preferably 1 to 3 minutes. When the pressurizing time is within the above range, it is possible to secure a sufficient time for promoting stress relaxation after the surface of the viscoelastic material and the surface of the adherend are brought into close contact with each other, and the elastic force at the time of measuring the tack property can be secured. The impact tends to be small.

The shape of the viscoelastic material is not particularly limited, but a flat plate shape is preferable. The thickness of the viscoelastic material is not particularly limited, but is preferably 0.5 to 5 mm, more preferably 1 to 3 mm.

The shape of the adherend is not particularly limited, but it is preferable that the surface in contact with the viscoelastic material is flat. Further, in this case, it is preferable that the area of the plane of the adherend is larger than the area of the contact portion between the viscoelastic material and the adherend. That is, it is preferable that the area of the surface of the adherend in contact with the viscoelastic material is larger than the contact area. As an example of such a case, for example, 300 shown in FIG. 3 is a viscoelastic material and 303 is an adherend. In the probe tack test, the area of the surface of the adherend (probe) that comes into contact with the viscoelastic material is smaller than the contact area between the viscoelastic material and the adherend, so that the contact surface at the outer peripheral edge of the tip surface of the probe Stress is concentrated and the viscoelastic material is deformed, which causes unevenness in the measurement result and deteriorates the quantitativeness and quality of the measurement result. On the other hand, in the measuring method of the present invention, by making the area of the plane of the adherend larger than the area of the contact portion between the viscoelastic material and the adherend, the influence of the edge portion in the probe tack test is extremely large. It can be made smaller.

Contact area between the viscoelastic material and the adherend is a so 50 mm ² or more as described above, preferably 50～800Mm ^2, more preferably 100 to 400 mm ^2. When the contact area is 50 mm ² or more, the measurement area is narrow and local in the conventional probe tack test, whereas the measurement area of the viscoelastic material is wide in the measurement method of the present invention, so that the low tack region The detected value in is increased, and a wide range of average measured values can be obtained. Further, for example, as in the case where 300 shown in FIG. 3 is a viscoelastic material and 303 is an adherend, the area of the surface of the flat plate-shaped viscoelastic material in contact with the adherend and the contact area. Is preferably the same.

The material of the adherend is not particularly limited, and a material used for a known or commonly used adherend for evaluation of tackiness can be used. Of these, SUS is preferable.

(Step B)
In step B, the adherend and the viscoelastic material are separated by applying a displacement in the separation direction. The target to which the displacement is applied may be either a viscoelastic material or an adherend, but is the same as the target to which the displacement is applied when the contact and the load are applied in the step A. Further, the direction of separation is preferably the vertical direction (vertical direction).

In step B, the speed at which the adherend and the viscoelastic material are separated is not particularly limited, but is preferably 1 to 1000 mm / min, and more preferably 5 to 30 mm / min. In particular, the speed at the time of separation is 5 mm / min, 10 mm / min, 20 mm / min, 30 mm / min, 50 mm / min, 70 mm / min, 100 mm / min, 150 mm / min, 300 mm / min, and 500 mm / min. It is preferably any of the 10 points, and more preferably all of the above 10 points (that is, measurement at the speed of all the above 10 points).

(Step C)
In step C, the stress change of the contact surface from the contact in step A to the separation in step B is recorded, and a curve with the x-axis as the displacement (distance between the adherend and the viscoelastic material) and the y-axis as the stress is obtained. .. Then, the tack is quantified from the obtained curve. FIG. 2 is also an example showing a curve in which the x-axis is the displacement and the y-axis is the stress.

In step C, the maximum stress value in the curve can be obtained as the tack value of the viscoelastic material. The maximum stress value is the difference between the stress 0 that changes from compression to tension of the curve and the maximum stress value (for example, the value shown by 200 in FIG. 2).

Further, the area on the side surrounded by the curve and the baseline (axis with zero stress) and including the maximum stress value in the curve (for example, the area of the region shown as 201 in FIG. 2) is viscoelastic. It can also be obtained as the tack value of the material. The area can be calculated as an integral value of the function when the curve is used as a function.

The speed at the time of separation is 10 points of 5 mm / min, 10 mm / min, 20 mm / min, 30 mm / min, 50 mm / min, 70 mm / min, 100 mm / min, 150 mm / min, 300 mm / min, and 500 mm / min. In the case of all, it is particularly preferable to obtain the maximum value of the above 10 points as the tack value. That is, the above curves are obtained for each of the above 10 separation speeds, and the maximum value among the maximum stress values in the obtained 10 curves is obtained as the tack value, or the maximum in the obtained 10 curves. It is preferable to obtain the maximum value of the area including the stress value as the tack value.

Since the maximum stress value and the area are indexes for obtaining different tackiness, it is preferable to consider both tackiness according to the evaluation purpose.

The measuring method of the present invention is not particularly limited, but is preferably carried out in an environment of a temperature of 10 to 30 ° C. and a humidity of 30 to 70% RH (preferably a temperature of 15 to 25 ° C. and a humidity of 40 to 60% RH). ..

The measuring method of the present invention can be carried out using a commercially available universal testing machine. The peeling load evaluation (X) and the peeling load evaluation (Y) are examples of evaluation methods that employ the measurement method of the present invention. Therefore, FIG. 3 is also a schematic view showing a specific example of the measurement method of the present invention. As a more preferable evaluation condition in the measurement method of the present invention, each evaluation condition in the peeling load evaluation (X) and the peeling load evaluation (Y) can be appropriately adopted in consideration of each evaluation condition.

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 products and products was performed by JEOL ECA500 (500 MHz). In addition, ²⁹ Si-NMR analysis of products and products was performed by JEOL ECA500 (500 MHz). In addition, the number average molecular weight and weight average molecular weight of products and products were measured by Alliance HPLC system 2695 (manufactured by Waters), Refractometer Index 2414 (manufactured by Waters), column: Tskgel GMH _HR- M × 2 (Tosoh Co., Ltd.). Ltd.), guard column: Tskgel guard column H _HR manufactured L (Tosoh Corporation), column oven: cOLUMN HEATER U-620 (Sugai Ltd.), solvent: THF, measuring conditions: 40 ° C., by been.

Manufacturing example 1
[Synthesis of ladder-type polyorganosylsesquioxane having a vinyl group and a trimethylsilyl group (TMS group) at the ends]
In a 200 ml four-necked flask, 42.61 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 6.76 g of phenyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and methyl isobutyl ketone (MIBK) 17. 69 g was charged and the mixture was cooled to 10 ° C. 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 to the mixture over 1 hour. After the dropping, the mixture was kept at 10 ° C. for 1 hour. Then, 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 it reached 70 ° C., 606 mmol (10.91 g) of water was added, and the polycondensation reaction was carried out under nitrogen for 9 hours at the same temperature. Further, 2.08 g of vinyltriethoxysilane was added, and the reaction (aging) was carried out at the same temperature for 3 hours.
Subsequently, 15.0 g of hexamethyldisiloxane was added to the obtained reaction solution, and the silylation reaction was carried out at 70 ° C. for 3 hours. Then, the reaction solution was cooled, washed with water until the lower layer liquid became neutral, and then the upper layer liquid was separated. Next, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 60 ° C., and a ladder-type polyorganosylsesquioxane having a vinyl group and a TMS group at the ends was used as a colorless and transparent liquid product. I got 0g. The ladder-type polyorganosilsesquioxane obtained in Production Example 1 corresponds to the above-mentioned ladder-type silsesquioxane (C1).
The weight average molecular weight (Mw) of the ladder-type polyorganosylsesquioxane having a vinyl group and a TMS group at the terminal is 2700, and the content of phenyl group (average content) per molecule is 4 mol%, vinyl group. The content (average content) of was 2 mol%.
( ¹ H-NMR spectrum of a ladder-type polyorganosylsesquioxane having a vinyl group and a TMS group at the ends)
^{1 1} H-NMR (JEOL ECA500 (500MHz, CDCl ₃ )): δ-0.3-0.3ppm (br), 5.7-6.2ppm (br), 7.1-7.7ppm (br)

Manufacturing example 2
[Synthesis of ladder-type polyorganosylsesquioxane having a vinyl group and a TMS group at the end]
In a 200 ml four-necked flask, 34.07 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 11.49 g of phenyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and methyl isobutyl ketone (MIBK) 17. 69 g was charged and the mixture was cooled to 10 ° C. 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 to the mixture over 1 hour. After the dropping, the mixture was kept at 10 ° C. for 1 hour. Then, 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 it reached 70 ° C., 606 mmol (10.91 g) of water was added, and the polycondensation reaction was carried out under nitrogen for 9 hours at the same temperature. Further, 6.25 g of vinyltriethoxysilane was added, and the reaction (aging) was carried out at the same temperature for 3 hours.
Subsequently, 15.0 g of hexamethyldisiloxane was added to the obtained reaction solution, and the silylation reaction was carried out at 70 ° C. for 3 hours. Then, the reaction solution was cooled, washed with water until the lower layer liquid became neutral, and then the upper layer liquid was separated. Next, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 60 ° C., and a ladder-type polyorganosylsesquioxane having a vinyl group and a TMS group at the ends was used as a colorless and transparent liquid product 36. I got 8g. The ladder-type polyorganosilsesquioxane obtained in Production Example 2 corresponds to the above-mentioned ladder-type silsesquioxane (C1).
The weight average molecular weight (Mw) of the ladder-type polyorganosylsesquioxane having a vinyl group and a TMS group at the terminal is 3400, and the content of phenyl group (average content) per molecule is 8 mol%, vinyl group. The content (average content) of was 6 mol%.
( ¹ H-NMR spectrum of a ladder-type polyorganosylsesquioxane having a vinyl group and a TMS group at the ends)
^{1 1} H-NMR (JEOL ECA500 (500MHz, CDCl ₃ )): δ-0.3-0.3ppm (br), 5.7-6.2ppm (br), 7.1-7.7ppm (br)

Manufacturing example 3
[Synthesis of ladder-type polyorganosylsesquioxane having a TMS group at the end]
In a 200 ml four-necked flask, 30.06 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 21.39 g of vinyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and methyl isobutyl ketone (MIBK) 17. 69 g was charged and the mixture was cooled to 10 ° C. To the above mixture, 281 mmol (5.06 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 dropping, the mixture was kept at 10 ° C. for 1 hour. Then, 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 it reached 70 ° C., 703 mmol (12.64 g) of water was added, and the polycondensation reaction was carried out under nitrogen for 12 hours at the same temperature.
Subsequently, 15.0 g of hexamethyldisiloxane was added to the obtained reaction solution, and the silylation reaction was carried out at 70 ° C. for 3 hours. Then, the reaction solution was cooled, washed with water until the lower layer liquid became neutral, and then the upper layer liquid was separated. Next, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 60 ° C. to obtain 22.0 g of a ladder-type polyorganosylsesquioxane having a TMS group at the terminal as a colorless and transparent solid product. .. The ladder-type polyorganosilsesquioxane obtained in Production Example 3 corresponds to the above-mentioned ladder-type silsesquioxane (C1).
The weight average molecular weight (Mw) of the ladder-type polyorganosylsesquioxane having a TMS group at the terminal is 5000, the content of vinyl groups per molecule (average content) is 16 mol%, and the content of phenyl groups (Mw). The average content) was 0 mol% (not observed).
( ¹ H-NMR spectrum of ladder-type polyorganosylsesquioxane having a TMS group at the end)
^{1 1} H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )): δ 0-0.3 ppm (br), 5.8-6.1 ppm (br)

Manufacturing example 4
[Synthesis of ladder-type polyorganosylsesquioxane having a vinyl group at the end]
15.86 g of phenyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 6.16 g of methyl isobutyl ketone (MIBK) were placed in a 200 ml four-necked flask, and the mixture thereof was cooled to 10 ° C. To the above mixture, 4.32 g of water and 0.16 g of 5N hydrochloric acid (2.4 mmol as hydrogen chloride) were added dropwise over 1 hour. After the dropping, the mixture was kept at 10 ° C. for 1 hour. Then, 26.67 g of MIBK was added to dilute the reaction solvent.
Next, the temperature of the reaction vessel was raised to 70 ° C., and when the temperature reached 70 ° C., 0.16 g of 5N hydrochloric acid (25 mmol as hydrogen chloride) was added, and the polycondensation reaction was carried out under nitrogen for 4 hours. ..
Subsequently, 11.18 g of divinyltetramethyldisiloxane and 3.25 g of hexamethyldisiloxane were added to the obtained reaction solution, and the silylation reaction was carried out at 70 ° C. for 4 hours. Then, the reaction solution was cooled, washed with water until the lower layer liquid became neutral, and then the upper layer liquid was separated. Next, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 40 ° C. to obtain a colorless and transparent liquid reaction product (ladder type silsesquioxane having a vinyl group at the terminal, 13.0 g). .. The ladder-type polyorganosilsesquioxane obtained in Production Example 4 corresponds to the above-mentioned ladder-type silsesquioxane (C1).
The number average molecular weight (Mn) of the ladder-type polyorganosylsesquioxane having a vinyl group at the terminal was 840, and the molecular weight dispersion was 1.06.

A description of each component shown in Table 1 is shown below.
(Agent A)
AS-9070A: Made by Changxing Materials Industries, trade name "AS-9070A" (including polyorganosiloxane represented by the average unit formula (a-1)), content of vinyl groups with respect to the total amount (100% by weight) of the product. It contains 1.20% by weight, 0% by weight of phenyl group, 0% by weight of hydrosilyl group (hydride equivalent), number average molecular weight 2517, weight average molecular weight 14505, and hydrosilylation catalyst.
GS5145A: Made by Changxing Materials Industries, trade name "ETERLED GS5145A" (including polyorganosyloxysylalkylene represented by average unit formula (a-2)), aryl group (phenyl group) ratio of about 24 mol%, hydrosilylation Includes catalyst.
KER-2500A: manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KER-2500A" (including polyorganosiloxane represented by the average unit formula (a-1)), vinyl group based on the total amount of the product (100% by weight). Content 1.53% by weight, methyl group content 94.29% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride equivalent) 0.03% by weight, number average molecular weight 4453, weight It has an average molecular weight of 19355 and contains a hydrosilylation catalyst.
OE-6351A: manufactured by Toray Dow Corning Co., Ltd., trade name "OE-6351A" (including polyorganosiloxane represented by the average unit formula (a-1)), vinyl group content 0.67% by weight, It contains 0% by weight of phenyl group, 0% by weight of hydrosilyl group (hydride equivalent), number average molecular weight of 4900, weight average molecular weight of 20900, and hydrosilylation catalyst.
OE-6630A: manufactured by Toray Dow Corning Co., Ltd., trade name "OE-6630A" (including polyorganosiloxane represented by the average unit formula (a-1)), vinyl group content 2.17% by weight, It contains 51.94% by weight of phenyl group, 0% by weight of hydrosilyl group content (hydride equivalent), 2532 number average molecular weight, 4490 weight average molecular weight, and hydrosilylation catalyst.
DMS-V35: Made by Gelest, trade name "DMS-V35", polydimethylsiloxane MA-DGIC having vinyl groups at both ends: manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name "MA-DGIC", monoallyl diglycidyl Isocyanurate OFS-6040: manufactured by Dow Corning, trade name "XIAMETER OFS-6040", 3-glycidoxypropyltrimethoxysilane

(Agent B)
AS-9070B: Made by Changxing Materials Industries, trade name "AS-9070B" (including polyorganosiloxane represented by the average unit formula (b-1)), content of vinyl groups with respect to the total amount (100% by weight) of the product. 1.15% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride equivalent) 0.150% by weight, number average molecular weight 2371, weight average molecular weight 14526
GS5145B: Product name "ETERLED GS5145B" (including polyorganosyloxysylalkylene represented by the average unit formula (b-2)), KER-2500B manufactured by Choko Materials Industry Co., Ltd ., Product name ""KER-2500B" (including polyorganosiloxane represented by the average unit formula (b-1)), vinyl group content 1.08% by weight, methyl group content 95 to the total amount of the product (100% by weight) .63% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride equivalent) 0.13% by weight, number average molecular weight 4636, weight average molecular weight 18814
OE-6351B: manufactured by Toray Dow Corning Co., Ltd., trade name "OE-6351B" (including polyorganosiloxane represented by the average unit formula (b-1)), vinyl group content 0.71% by weight, Phenyl group content 0% by weight, hydrosilyl group content (hydride equivalent) 0.08% by weight, number average molecular weight 6100, weight average molecular weight 20900
OE-6630B: manufactured by Toray Dow Corning Co., Ltd., trade name "OE-6630B" (including polyorganosiloxane represented by the average unit formula (b-1)), vinyl group content 3.87% by weight, Phenyl group content 50.11% by weight, hydrosilyl group content (hydride equivalent) 0.17% by weight, number average molecular weight 783, weight average molecular weight 133
HMS-991: Made by Gelest, trade name "HMS-991", polymethylhydrosiloxane having TMS groups at both ends

Example 1
[Manufacturing of curable resin composition]
First, as shown in Table 1, AS-9070A (50 parts by weight), ladder-type polyorganosylsesquioxane (15 parts by weight) obtained in Production Example 3, MA-DGIC (0.2 parts by weight), And OFS-6040 (0.4 parts by weight) were mixed and stirred at 80 ° C. for 1 hour to prepare Agent A.
Next, AS-9070B (45 parts by weight) and HMS-991 (5 parts by weight) as the agent B were mixed with the agent A (65.6 parts by weight) obtained above, and stirred at room temperature for 10 minutes. As a result, a curable resin composition which was a uniform liquid was obtained.

[Manufacturing of optical semiconductor devices]
The curable resin composition obtained above is injected into the LED package (InGaN device, 5.0 mm × 5.0 mm) of the embodiment shown in FIG. 1, and heated at 100 ° C. for 1 hour, and then at 150 ° C. for 5 hours. By doing so, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable resin composition was manufactured.

Examples 2-7, Comparative Examples 1-5
A curable resin composition and an optical semiconductor device were produced in the same manner as in Example 1 except that the compounding composition of the curable resin composition was changed as shown in Table 1.

(Evaluation)
The curable resin composition and the optical semiconductor device obtained above were evaluated as follows. The evaluation results are shown in Table 1.

[ ²⁹ Si-NMR spectrum measurement, ^{1 1} H-NMR spectrum measurement]
For the curable resin compositions obtained in Examples and Comparative Examples, M, D, T, and Q were calculated by ²⁹ Si-NMR spectrum measurement, and (T + Q) / D was calculated using the obtained values. did. In addition, the number of moles of hydrosilyl group per 1 mole of aliphatic carbon-carbon double bond was calculated by ¹ H-NMR spectrum measurement. Further, from ¹ H-NMR spectrum measurement and the blending amount of each polysiloxane used, the total amount of monovalent substituted or unsubstituted hydrocarbon groups bonded to silicon atoms in all the polysiloxanes in the curable resin composition was obtained. The proportion of aryl groups was calculated. In the above ¹ H-NMR spectrum measurement, the presence of an aryl group other than the phenyl group could not be confirmed. The results are shown in Table 1.

[Peeling strength, total peeling load]
Each of the curable resin compositions obtained in Examples and Comparative Examples is injected into a square mold having a thickness of 3 mm, a width of 80 mm, and a length of 80 mm, and heated at 100 ° C. for 1 hour, and then at 150 ° C. for 5 hours. A cured product (thickness 3 mm) of the curable resin composition was produced. This was punched with a circular cutter having a diameter of 16 mm to prepare a test piece for measuring peel strength and total peel load.
The peel strength was evaluated using a universal testing machine (trade name "Tencilon universal material testing machine RTC-1310A", manufactured by A & D Co., Ltd.). The evaluation method will be described with reference to FIG. The measurement test piece 300 was fixed on the crosshead 306 with a double-sided adhesive tape 304, and an adherend 303 (a plate made of SUS having a smooth surface) was attached to the load cell 302.
Next, the cross head 300 is slowly moved upward in the vertical direction (D direction), and the measurement test piece 300 is pressed against the adherend 303 under the conditions of a pressing load of 100 N and a pressing time of 2 minutes, and then the cross head 306. Was moved downward in the vertical direction (in the direction opposite to the D direction) at a separation speed of 5 mm / min and separated, and the measurement test piece 300 was separated from the adherend 303. The stress applied at this time was detected by the load cell 302 and recorded on a chart with a recorder to obtain a stress curve in which the vertical axis is the peel strength (stress) (N) and the horizontal axis is the displacement (mm). Then, among the obtained measured values, the value obtained by dividing the maximum stress value by the contact area (that is, 201 mm ² ) between the measurement test piece 300 and the adherend 303 is used as the peel strength at the separation rate. The area surrounded by the stress curve and the baseline from the start of separation of the test piece and the adherend to the complete separation was divided by the contact area (that is, 201 mm ² ) between the test piece 300 for measurement and the adherend 303. The value was taken as the total peeling load at the separation speed.
Further, when the separation speed is 10 mm / min, 20 mm / min, 30 mm / min, 50 mm / min, 70 mm / min, 100 mm / min, 150 mm / min, 300 mm / min, and 500 mm / min, the peeling is performed in the same manner. Strength and total peel load were obtained. Then, the largest values of the obtained peel strength and the total peel load were taken as the values of the peel strength and the total peel load of the cured product of the curable resin composition, respectively. The results are shown in Table 1. In Table 1, the unit of peel strength is [N], and the unit of total peel load is [N · mm].

[Adhesion test]
Each optical semiconductor device manufactured in Examples and Comparative Examples was used as a sample.
After the surface of the cured product in the above-mentioned optical semiconductor device and a SUS plate (made of SUS304; thickness 1 mm, surface mirror finish) that has been washed with acetone in advance are brought into close contact with each other and rubbed against each other, the SUS plate is on the lower side. It was confirmed whether the optical semiconductor device spontaneously peeled off due to gravity within 10 seconds when the SUS plate was held and lifted vertically and the top and bottom were turned upside down. Then, those peeled off within 10 seconds were evaluated as having no tackiness, and those that had been adhered for more than 10 seconds were evaluated as having tackiness. The results are shown in Table 1.

[Dust adhesion test]
Each curable resin composition obtained in Examples and Comparative Examples is injected into a rectangular mold having a thickness of 3 mm, a width of 10 mm, and a length of 50 mm, and heated at 100 ° C. for 1 hour, and then at 150 ° C. for 5 hours. Then, a cured product (thickness 3 mm) of the curable resin composition was produced, and this was used as a test piece for a dust adhesion test.
The above test piece was attached to a stand (height 1 m, inclination 45 °) installed on the site of Daicel Co., Ltd. in Otake City, Hiroshima Prefecture, and an exposure test was conducted for 2 weeks to evaluate the ease of dust adhesion according to the following criteria. .. The results are shown in Table 1.
⊚: Almost no dust adheres.
◯: Although a small amount of dust is observed, it can be easily removed by washing with running water.
X: A considerable amount of dust adheres and cannot be removed even by washing with running water.

[Sulfur corrosion test (sulfurization resistance)]
The optical semiconductor devices manufactured in Examples and Comparative Examples were used as samples.
First, for 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 (multi-spectral radiometry system "OL771" manufactured by Optronic Laboratories). Was defined as "total luminous flux before the corrosiveness 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. The total luminous flux of the heated sample was measured in the same manner as above, and this was defined as the "total luminous flux after the corrosiveness test". Then, the maintenance rate (%) of the total luminous flux before and after the corrosiveness test [= 100 × (total luminous flux after the corrosiveness test (lm)) / (total luminous flux before the corrosiveness test (lm))] was calculated.
The higher the luminous intensity retention rate, the better the barrier property of the cured product (encapsulant) against corrosive gas. The luminous intensity retention rates were measured and calculated for 10 optical semiconductor devices for each curable silicone resin composition (for each example and comparative example), and Table 1 shows the average value (N) of these luminous intensity retention rates. = 10) was shown.

Example 8
[Tackiness evaluation]
A 3 mm thick sheet of silicone resin (trade name "OE6630", manufactured by Toray Dow Corning Co., Ltd.) and silicone resin (trade name "OE7660", manufactured by Toray Dow Corning Co., Ltd.) is circular with a diameter of 15 mm. A test piece for measurement was obtained. For each of the obtained measurement test pieces, the measurement test piece was attached to the center of a smooth surface having a diameter of 50 mm of the test piece mounting jig of the measuring device with double-sided tape. Then, the adherend was moved downward in the vertical direction at a very low speed to come into contact with the surface of the measurement sample. Then, it was compressed with a load of 100 N (0.57 MPa), held at a load of 100 ± 10 N for 120 seconds, and then the adherend was moved and separated at a speed of 20 mm / min. The stress applied at this time was detected and recorded on a chart with a recorder to obtain a stress curve in which the vertical axis is the peel strength (stress) (N) and the horizontal axis is the displacement (mm). From the obtained stress curve, the maximum value of stress was obtained. This was performed 10 times (N = 10), and the maximum value of the obtained stress is shown in Table 2.

Comparative Example 6
The tackiness of the measurement test piece used in Example 8 was evaluated by a probe tack test (N = 10). The results are shown in Table 2. The measuring machine used in the probe tack test is the probe tack tester "TAC-II" (probe: SUS, diameter 5 mm) manufactured by Resuka Co., Ltd. Further, the preload is 200 gf, the holding time of the compressed state is 20 seconds, and the speed at the time of pulling is 120 mm / min.

100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor element 103: Bonding wire 104: Hardened product (encapsulant)
200: Maximum stress value 201: Area surrounded by stress curve and baseline from when the adherend and the cured product start to separate completely 300: Specimen for measurement 301: Universal tester 302: Load cell 303: Adhesive body 304: Double-sided adhesive tape 305: SUS plate 306: Crosshead D: Vertically upward

Claims (10)

Step A in which the adherend and the viscoelastic material are brought into contact with each other so that the contact area is 50 mm ² or more, a load is applied, and then stress relaxation is performed.
Step B, in which the adherend and the viscoelastic material are separated by applying a displacement in the separation direction,
A viscoelastic material having a step C of recording the stress change of the contact surface from the contact to the separation, obtaining a curve with the x-axis as the displacement and the y-axis as the stress, and quantifying the tack from the obtained curve. How to measure surface tack. In the step A, a stress detection mechanism having a pedestal and an adherend is used to arrange a flat plate-shaped viscoelastic material on the pedestal so that the contact surface between the viscoelastic material and the adherend becomes flat. The method for measuring the tack on the surface of a viscoelastic material according to claim 1, wherein the adherend is pressed against the viscoelastic material to continuously apply a load and then stress relaxation. The method for measuring the tack on the surface of a viscoelastic material according to claim 1 or 2, wherein in the step C, the maximum stress value in the curve is obtained as the tack value of the viscoelastic material. The surface of the viscoelastic material according to claim 1 or 2, wherein in the step C, the area surrounded by the curve and the baseline and including the maximum stress value in the curve is obtained as the tack value of the viscoelastic material. Tack measurement method. The method according to any one of claims 1 to 4, wherein in the step A, the value obtained by dividing the load applied by contacting the adherend with the viscoelastic material by the contact area is 0.1 to 4 MPa. A method for measuring the tack on the surface of a viscoelastic material. The viscoelasticity according to any one of claims 1 to 5, wherein in the step A, the time for applying the load after contacting the adherend with the viscoelastic material is 0.5 to 10 minutes. How to measure the tack on the material surface. In the step B, the speed at which the adherend and the viscoelastic material are separated is 5 mm / min, 10 mm / min, 20 mm / min, 30 mm / min, 50 mm / min, 70 mm / min, 100 mm / min, 150 mm. The method for measuring the tack on the surface of a viscoelastic material according to any one of claims 1 to 6, wherein the points are 10 points of / min, 300 mm / min, and 500 mm / min. The method for measuring tack on the surface of a viscoelastic material according to any one of claims 1 to 7, wherein the thickness of the viscoelastic material is 0.5 to 5 mm. The claim that the surface of the adherend in contact with the viscoelastic material is a flat surface, and the area of the plane of the adherend is larger than the area of the contact portion between the viscoelastic material and the adherend. The method for measuring the tack on the surface of a viscoelastic material according to any one of 1 to 8. The method for measuring tack on the surface of a viscoelastic material according to any one of claims 1 to 9, which is carried out in an environment of a temperature of 10 to 30 ° C. and a humidity of 30 to 70% RH.

Images