JP2016222850A - Curable silicone resin composition, cured product thereof, and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable silicone resin composition for forming materials (a sealing material, a lens, etc.) which hardly cause an increase in hardness, a reduction in weight, and a decrease in transparency.SOLUTION: The curable silicone resin composition contains the following components (A), (B), (C) and (D): (A) a polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturated group; (B) a branched polyorganosiloxane having one or more alkenyl groups in the molecule; (C) a hydrosilylation catalyst containing a platinum group metal; and (D) a rare earth metal compound.SELECTED DRAWING: None

Description

  The present invention relates to a curable silicone resin composition and a cured product thereof, an optical semiconductor device obtained by sealing an optical semiconductor element using the curable silicone resin composition, and the curable silicone resin composition. The present invention relates to an optical semiconductor device including a lens obtained by using an optical semiconductor element and an optical semiconductor element.

  In a semiconductor device such as an optical semiconductor device, a sealing material is used to cover and protect a semiconductor element. Various resin materials are used as such a sealing material.

  In recent years, the output of optical semiconductor devices has been increased, and the resin (encapsulant) that covers the optical semiconductor element in such an optical semiconductor device is required to have high transparency, heat resistance, and thermal shock resistance. Yes. Accordingly, a silicone resin having high transparency, heat resistance, and thermal shock resistance is used as the resin.

  As a composition for forming a silicone resin as described above, for example, a resin composition for sealing an optical element containing a liquid silsesquioxane having a cage structure as a resin component is known (Patent Document 1). reference). Also known are curable compositions containing organic compounds containing at least two carbon-carbon double bonds in one molecule, compounds containing at least two SiH groups in one molecule, and hydrosilylation catalysts. (See Patent Document 2). A curable resin composition containing a ladder-type polyorganosilsesquioxane and a specific isocyanurate compound is known (see Patent Document 3). In addition, a curable resin composition containing a polyorganosiloxane having an aryl group, an isocyanurate compound, and a silane coupling agent is known (see Patent Document 4).

JP 2007-031619 A JP 2002-314140 A Japanese Patent No. 5655163 International Publication No. 2014/125964

  In recent years, the size of an optical semiconductor device package (LED package) has been increased, and accordingly, a sealing material is also required to have flexibility. However, the cured product obtained by curing the resin composition described in Patent Document 1 or the curable composition described in Patent Document 2 is insufficient in flexibility, and seals of an enlarged LED package. When used as a stopping material, problems such as the occurrence of cracks (cracks) may occur when a thermal shock such as a cooling cycle (repeating heating and cooling periodically) is applied.

  The sealing material obtained by using the curable resin composition described in Patent Documents 3 and 4 is unlikely to crack when a thermal shock is applied. However, when exposed to a harsh environment such as high temperature for a long time, the flexibility is lost, and the hardness of the encapsulant may increase or the weight may decrease. When used as a sealing material, when a thermal shock severer than the conventional thermal shock is applied, problems such as the occurrence of cracks may occur. In addition, transparency may be reduced. For this reason, there is a need for a curable composition that can form a material having characteristics that are unlikely to cause an increase in hardness, a decrease in weight, and a decrease in transparency even when a more severe thermal shock is applied. is the current situation.

Accordingly, an object of the present invention is to provide a curable silicone resin composition for forming a material (such as a sealing material or a lens) that hardly causes an increase in hardness, a decrease in weight, and a decrease in transparency. .
Another object of the present invention is to provide a material (cured product) that hardly causes an increase in hardness, a decrease in weight, and a decrease in transparency.
Furthermore, another object of the present invention is to provide an optical semiconductor device excellent in durability (for example, resistance to thermal shock and harsh environment) obtained by sealing an optical semiconductor element with the cured product. There is.

  The inventors of the present invention provide a polyorganosiloxane having one or more hydrosilyl groups in the molecule and no aliphatic unsaturated group, a branched polyorganosiloxane having one or more alkenyl groups in the molecule, and According to a composition (curing silicone resin composition) containing a specific hydrosilylation catalyst and a rare earth metal compound as essential components, a material that does not easily increase in hardness, decrease in weight, and decrease in transparency (curing) The present invention was completed.

That is, this invention provides the curable silicone resin composition characterized by including the following (A) component, (B) component, (C) component, and (D) component.
(A): a polyorganosiloxane having one or more hydrosilyl groups in the molecule and no aliphatic unsaturated group (B): a branched polyorganosiloxane having one or more alkenyl groups in the molecule (C): Hydrosilylation catalyst containing platinum group metal (D): Rare earth metal compound

  Furthermore, the said curable silicone resin composition whose content of rare earth metal atoms is 0.1-500 ppm with respect to 100 weight% of said curable silicone resin compositions is provided.

Furthermore, the said curable silicone resin composition containing the following (E) component is provided.
(E): polyorganosiloxysilalkylene having two or more alkenyl groups and one or more aryl groups in the molecule

  Furthermore, the curable silicone resin composition containing a phosphor is provided.

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

  Furthermore, the said curable silicone resin composition which is a resin composition for optical semiconductor sealing is provided.

  Furthermore, the said curable silicone resin composition which is a resin composition for formation of the lens for optical semiconductors is provided.

  The present invention also includes an optical semiconductor element and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the curable silicone resin composition. A semiconductor device is provided.

  The present invention also provides an optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable silicone resin composition.

  Since the curable silicone resin composition of the present invention has the above-described configuration, it can be cured to be a cured product that hardly causes an increase in hardness, a decrease in weight, and a decrease in transparency. For this reason, durability (for example, tolerance with respect to a thermal shock or a severe environment) of an optical semiconductor device can be improved by using the said hardened | cured material as a sealing material of the optical semiconductor element in an optical semiconductor device. Accordingly, the curable silicone resin composition of the present invention is particularly preferably used as an encapsulant (an optical semiconductor encapsulating resin composition) or a lens forming composition (an optical semiconductor lens forming composition) in an optical semiconductor device. Accordingly, an optical semiconductor device having excellent durability can be obtained.

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

<Curable silicone resin composition>
The curable silicone resin composition of the present invention is a curable composition containing the following components (A), (B), (C), and (D) as essential components. That is, the curable silicone resin composition of the present invention is an addition-curable silicone resin composition that can be cured by a hydrosilylation reaction. In addition, the curable silicone resin composition of this invention may contain arbitrary components other than these essential components.
(A): a polyorganosiloxane having one or more hydrosilyl groups in the molecule and no aliphatic unsaturated group (B): a branched polyorganosiloxane having one or more alkenyl groups in the molecule (C): Hydrosilylation catalyst containing platinum group metal (D): Rare earth metal compound

[(A) component]
The component (A) in the curable silicone resin composition of the present invention is a polyorganosiloxane having one or more hydrosilyl groups (Si—H) in the molecule and no aliphatic unsaturated groups. Accordingly, in the curable silicone resin composition of the present invention, the component (A) is a component that causes a hydrosilylation reaction with a component having an alkenyl group (for example, the component (B)). When the curable silicone resin composition of the present invention contains the component (A), the curing reaction by the hydrosilylation reaction can be efficiently advanced. Further, the cured product tends to exhibit excellent gas barrier properties.

  The number of hydrosilyl groups that the component (A) has in the molecule is not particularly limited as long as it is 1 or more, but 2 or more (for example, 2 to 50) from the viewpoint of curability of the curable silicone resin composition. ) Is preferred.

The component (A) is a polysiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule and a main chain composed of siloxane bonds (Si—O—Si), It is a polysiloxane having no aliphatic unsaturated group and no silalkylene bond (—Si—R ^A —Si—: R ^A represents an alkylene group). The above R ^A represents the same as R ^A in the later component (E).

In addition, (A) component does not have an aliphatic unsaturated group in a molecule | numerator as mentioned above. The aliphatic unsaturated group is an aliphatic hydrocarbon group having a non-aromatic carbon-carbon unsaturated bond, and examples thereof include an ethylenically unsaturated group and an acetylenic unsaturated group. Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, and 5-hexenyl group (for example, C _2-20 alkenyl group (particularly C _2-10 alkenyl group)). An alkadienyl group such as a 1,3-butadienyl group (particularly a C _4-10 alkadienyl group); an alkenylcarbonyloxy group such as an acryloyloxy group or a methacryloyloxy group; an alkenylcarbonylamino group such as an acrylamide group; Examples of the acetylenically unsaturated group include an alkynyl group such as an ethynyl group and a propargyl group (for example, a C _2-20 alkynyl group (particularly a C _2-10 alkynyl group)); an alkynylcarbonyloxy group such as an ethynylcarbonyloxy group. An alkynylcarbonylamino group such as an ethynylcarbonylamino group;

  Examples of the component (A) include those having a molecular structure such as a straight chain or branched chain (a partially branched straight chain, branched chain, network, etc.). In addition, (A) component can also be used individually by 1 type, and can also be used in combination of 2 or more type. For example, two or more types of component (A) having different molecular structures can be used in combination, and specific examples include a mode in which a linear polyorganosiloxane and a branched polyorganosiloxane are used in combination. .

Among the groups bonded to the silicon atom of the component (A), groups other than hydrogen atoms are not particularly limited. For example, alkyl groups [for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group] Etc.], cycloalkyl groups [eg cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclododecyl group etc.], cycloalkyl-alkyl groups [eg cyclohexylmethyl group, methylcyclohexyl group etc.], aryl groups [ For example, a substituted or unsubstituted C _6-14 aryl group such as a phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group (eg, benzyl group, phenethyl group, etc.), one or more hydrogen atoms in a hydrocarbon group A halogenated hydrocarbon group substituted with a halogen atom [for example, chloromethyl group, 3-chloropropyl Propyl group, 3,3,3-trifluoropropyl halogenated alkyl group such as a group] monovalent substituted or unsubstituted hydrocarbon group such as (but aliphatic unsaturated groups excluded are) it includes. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable. In the present specification, the “group bonded to a silicon atom” usually means a group not containing a silicon atom.

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

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

As the component (A), the following average unit formula:
^{_{(R 1 SiO 3/2) a1 (}} R 1 2 SiO 2/2) a2 (R 1 3 SiO 1/2) a3 (SiO 4/2) a4 (X 1 O 1/2) a5
The polyorganosiloxane represented by these is mentioned. In the above average unit formula, R ¹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (excluding an aliphatic unsaturated group), such as a hydrogen atom, Specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (for example, an alkyl group, an aryl group, a halogenated alkyl group, etc.) can be mentioned. However, a part of R ¹ is a hydrogen atom (hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in a range in which one or more (preferably two or more) hydrosilyl groups are present in the molecule. For example, the ratio of hydrogen atoms to the total amount of R ¹ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. Moreover, as R < ¹ > other than a hydrogen atom, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.

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

  In the above average unit formula, a1 is 0 or positive, a2 is 0 or positive, a3 is 0 or positive, a4 is 0 or positive, a5 is 0 or positive, and (b1 + b2 + b3) is positive Is a number.

  As an example of (A) component, the linear polyorganosiloxane which has 1 or more (preferably 2 or more) hydrosilyl group in a molecule | numerator is mentioned, for example. Examples of the group bonded to a silicon atom other than a hydrogen atom in the linear polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (however, an aliphatic unsaturated group is excluded). However, among them, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.

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

［上記式中、Ｒ¹¹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（但し、脂肪族不飽和基は除かれる）である。但し、Ｒ¹¹の少なくとも１個（好ましくは少なくとも２個）は水素原子である。ｍ１は、５〜１０００の整数である。］ The linear polyorganosiloxane is represented by the following formula (I-1), for example.

[In the above formula, R ^{11 s} are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (excluding an aliphatic unsaturated group). However, at least one (preferably at least 2) of R ¹¹ is a hydrogen atom. m1 is an integer of 5 to 1000. ]

In the linear polyorganosiloxane represented by the formula (I-1), R ¹¹ may be a hydroxy group or an alkoxy group. Moreover, the monovalent substituted or unsubstituted hydrocarbon group in R ¹¹ (excluding the aliphatic unsaturated group) may have a hydroxy group or an alkoxy group.

Another example of the component (A) is a branched chain having one or more (preferably two or more) hydrosilyl groups in the molecule and a siloxane unit (T unit) represented by RSiO _3/2. Polyorganosiloxane is mentioned. This branched polyorganosiloxane also includes a polyorganosiloxane having a three-dimensional structure such as a network. R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (excluding an aliphatic unsaturated group). Examples of the group bonded to a silicon atom other than a hydrogen atom in the branched polyorganosiloxane include the monovalent substituted or unsubstituted hydrocarbon group described above, among which an alkyl group (particularly a methyl group), Aryl groups (particularly phenyl groups) are preferred. Furthermore, examples of R in the T unit include a hydrogen atom and the above-mentioned monovalent substituted or unsubstituted hydrocarbon group. Among them, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable. . The ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of R in the T unit is not particularly limited, but is preferably 30 mol% or more from the viewpoint of gas barrier properties of the cured product.

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

  The branched polyorganosiloxane can be represented by, for example, the average unit formula in which a1 is a positive number. In this case, although not particularly limited, a2 / a1 is a number from 0 to 10, a3 / a1 is a number from 0 to 0.5, a4 / (a1 + a2 + a3 + a4) is a number from 0 to 0.3, and a5 / (a1 + a2 + a3 + a4) is The number is preferably 0 to 0.4. The molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 300 to 10,000, more preferably 500 to 3000.

  The content (blending amount) of the component (A) in the curable silicone resin composition of the present invention is not particularly limited, but is preferably 1 to 60% by weight with respect to the curable silicone resin composition (100% by weight). More preferably, it is 5-55 weight%, More preferably, it is 10-50 weight%. By setting the content of the component (A) to 1% by weight or more, the curability of the curable silicone resin composition is further improved, and the gas barrier property tends to be further improved. Moreover, there exists a tendency for the surface adhesiveness (tack property) of hardened | cured material to reduce. On the other hand, when the content of the component (A) is 60% by weight or less, the thermal shock resistance of the cured product tends to be further improved.

[Component (B)]
As described above, the component (B) in the curable silicone resin composition of the present invention is a branched polyorganosiloxane having one or more alkenyl groups in the molecule (sometimes referred to as “(B) component”). Yes). In the curable silicone resin composition of the present invention, the component (B) is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (A)). When the curable silicone resin composition of the present invention contains the component (B), the heat resistance of the cured product is improved, and the hardness and the weight of the cured product are less likely to be increased. Moreover, the thermal shock resistance and gas barrier properties of the cured product may be improved.

  The component (B) is a branched polyorgano having one or more alkenyl groups in the molecule, having -Si-O-Si- (siloxane bond) as the main chain, and no silalkylene bond. Siloxane (polyorganosiloxane having a branched main chain). The component (B) includes a polyorganosiloxane having a three-dimensional structure such as a network. However, the ladder type polyorganosilsesquioxane described later is not included in the component (B).

  (B) As an alkenyl group which a component has in a molecule | numerator, substituted or unsubstituted alkenyl groups, such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, are mentioned. Examples of the substituent in the substituted alkenyl group include a halogen atom, a hydroxy group, and a carboxy group. Of these, the alkenyl group is preferably a vinyl group. Moreover, (B) component may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. Although the alkenyl group which (B) component has is not specifically limited, It is preferable that it is a thing couple | bonded with the silicon atom.

  The number of alkenyl groups that the component (B) has in the molecule is not particularly limited as long as it is 1 or more, but 2 or more (for example, 2 to 50) from the viewpoint of curability of the curable silicone resin composition. ) Is preferred.

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

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

  The property of (B) component is not specifically limited, For example, in 25 degreeC, it may be liquid and a solid form may be sufficient.

As the component (B), the following average unit formula:
(R ² SiO _3/2 ) _{b 1} (R ² ₂ SiO _2/2 ) _{b 2} (R ² ₃ SiO _1/2 ) _{b 3} (SiO _4/2 ) _{b 4} (X ² O _1/2 ) _{b 5}
The polyorganosiloxane represented by these is mentioned. In the above average unit formula, R ² is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the above monovalent substituted or unsubstituted hydrocarbon group (for example, alkyl group, aryl Group, halogenated hydrocarbon group and the like), and the above-mentioned alkenyl group. However, a part of R ² is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 1 or more (preferably 2 or more) in the molecule. For example, the ratio of the alkenyl group to the total amount of R ² (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of the alkenyl group to the above range, the curability of the curable silicone resin composition tends to be further improved. R ² other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

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

  In the above average unit formula, b1 is 0 or a positive number, b2 is 0 or a positive number, b3 is a positive number, b4 is 0 or a positive number, b5 is 0 or a positive number, and (b1 + b2 + b3) and (b1 + b4) Are positive numbers.

Specific examples of the component (B) include branched polyorganosiloxane having two or more alkenyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO _3/2 . R is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the alkenyl group described above can be given as examples of the alkenyl group of the branched polyorganosiloxane. Among them, a vinyl group is preferable. In addition, you may have only 1 type of alkenyl group, and you may have 2 or more types of alkenyl groups. Examples of the group bonded to the silicon atom other than the alkenyl group in the branched polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group (particularly a methyl group). ) Or an aryl group (particularly a phenyl group). Furthermore, as R in the T unit, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.

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

  The branched polyorganosiloxane can be represented by the above average unit formula wherein b1 is a positive number. In this case, although not particularly limited, b2 / b1 is a number from 0 to 10, b3 / b1 is a number from 0 to 0.5, b4 / (b1 + b2 + b3 + b4) is a number from 0 to 0.3, and b5 / (b1 + b2 + b3 + b4) is The number is preferably 0 to 0.4. The molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, more preferably 700 to 3000.

Specific examples of the component (B) include, for example, the following average unit formula in which b1 and b2 are 0 and X ² is a hydrogen atom in the above average unit formula:
(R ^2a ₂ R ^2b SiO _1/2 ) _b6 (R ^2a ₃ SiO _1/2 ) _b7 (SiO _4/2 ) _b8 (HO _1/2 ) _b9
The polyorganosiloxane represented by these is mentioned. In the above average unit formula, R ^2a is the same or different and represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group A hexyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and the like. Among them, a methyl group is preferable. R ^2b is the same or different and represents an alkenyl group, and among them, a vinyl group is preferable. Further, all of b6, b7, b8 and b9 are b6 + b7 + b8 = 1, b6 / (b6 + b7) = 0.15 to 0.35, b8 / (b6 + b7 + b8) = 0.53 to 0.62, b9 / (b6 + b7 + b8) = A positive number satisfying 0.005 to 0.03. Note that b7 may be 0. In view of curability of the curable silicone resin composition, b6 / (b6 + b7) is preferably 0.2 to 0.3. Moreover, it is preferable that b8 / (b6 + b7 + b8) is 0.55-0.60 from a viewpoint of the hardness and mechanical strength of hardened | cured material. Furthermore, it is preferable that b9 / (b6 + b7 + b8) is 0.01-0.025 from the viewpoint of adhesiveness and mechanical strength of the cured product. Examples of such polyorganosiloxanes include polyorganosiloxanes composed of SiO _4/2 units and (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 units, SiO _4/2 units and (CH ₃ ) Polyorganosiloxane composed of ₂ (CH ₂ ═CH) SiO _1/2 units and (CH ₃ ) ₃ SiO _1/2 units.

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

  The content (blending amount) of the component (B) in the curable silicone resin composition of the present invention is not particularly limited, but is preferably 50 to 300 parts by weight, more preferably 100 parts by weight of the component (A). It is 75-275 weight part, More preferably, it is 100-250 weight part. By controlling the content of the component (B) within the above range, an increase in hardness and a decrease in weight of the cured product are further suppressed, and the thermal shock resistance, gas barrier property, and heat resistance may be further improved.

[Component (C)]
The component (C) in the curable silicone resin composition of the present invention is a hydrosilylation catalyst containing a platinum group metal. That is, the component (C) is a hydrosilylation catalyst containing at least one metal (platinum group metal) selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum. When the curable silicone resin composition of the present invention contains the component (C), the hydrosilylation reaction between the alkenyl group and the hydrosilyl group in the curable silicone resin composition can be efficiently advanced by heating.

  As the component (C), a known or commonly used hydrosilylation catalyst (for example, a platinum-based catalyst, a rhodium-based catalyst, a palladium-based catalyst, etc.) can be used. Specifically, platinum fine powder, platinum black, platinum Supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, complexes of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum olefin complexes, platinum carbonyl complexes such as platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyl Platinum-based catalysts such as platinum-vinylmethylsiloxane complexes such as disiloxane complexes and platinum-cyclovinylmethylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, etc., and palladium atoms or Examples thereof include a palladium catalyst or a rhodium catalyst containing a rhodium atom. Among them, as the component (C), a platinum-based catalyst (platinum-containing hydrosilylation catalyst) is preferable, and in particular, a platinum-vinylmethylsiloxane complex, a platinum-carbonylvinylmethyl complex, a complex of chloroplatinic acid, an alcohol, and an aldehyde. , Which is preferable because the reaction rate is good.

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

The content (blending amount) of the component (C) in the curable silicone resin composition of the present invention is not particularly limited, but is 1 mol (per mol) of the total amount of alkenyl groups contained in the curable silicone resin composition. 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol is preferable, and 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻³ mol is more preferable. There exists a tendency which can form hardened | cured material more efficiently by making content of (C) component into 1 * 10 < ^-8 > mol or more. On the other hand, when the content of the component (C) is 1 × 10 ⁻² mol or less, there is a tendency that a cured product having a more excellent hue (less coloring) can be obtained.

  Further, the content (blending amount) of the component (C) in the curable silicone resin composition of the present invention is not particularly limited. For example, the platinum group metal in the hydrosilylation catalyst is 0.01 to 1000 ppm by weight. Is preferably in the range of 0.1 to 500 ppm. When content of (C) component exists in such a range, there exists a tendency which can form hardened | cured material more efficiently and can obtain hardened | cured material more excellent in hue.

[(D) component]
The component (D) in the curable silicone resin composition of the present invention is a rare earth metal compound. When the curable silicone resin composition of the present invention contains the component (D), an increase in hardness, a decrease in weight, and a decrease in transparency are hardly caused in the cured product. Moreover, there exists a tendency for the gas barrier property of hardened | cured material to improve.

  The component (D) is a compound containing a rare earth metal atom. That is, the component (D) is at least selected from the group consisting of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. It is a compound containing one kind of metal (rare earth metal). Among these, cerium is preferable from the viewpoint of the hardness of the cured product being increased, the weight being decreased, and the transparency being less likely to be decreased. That is, the component (D) is preferably a cerium compound. In addition, 1 type may be sufficient as the rare earth metal atom contained in (D) component, and 2 or more types may be sufficient as it.

  Examples of component (D) include oxides of rare earth metal atoms, hydroxides of rare earth metal atoms, borides of rare earth metal atoms, halides of rare earth atoms (for example, fluorides, chlorides, bromides, iodides, etc.) ), Rare earth metal atom complexes (complex salts), rare earth metal atom salts (including complex salts), and the like. Of these, complexes of rare earth metal atoms and salts of rare earth metal atoms are preferred. The oxides of rare earth metal atoms, hydroxides of rare earth metal atoms, borides of rare earth metal atoms, halides of rare earth atoms, complexes of rare earth metal atoms, and salts of rare earth metal atoms overlap each other. obtain.

  Examples of the rare earth metal complex (complex) include acetylacetonate, triflate, pyridine complex, bipyridyl complex, terpyridyl complex, pincer complex, imine complex, salen complex, tetramethylenediamine complex, ethylenediamine complex, ephedrine complex, carbonyl And a complex, a dienyl complex, and the like.

  Examples of the rare earth metal atom salt include, in addition to the above complex salt, an oxo acid salt of a carbon atom (for example, carbonate), an oxo acid salt of a sulfur atom (for example, sulfate), an oxo acid salt of a nitrogen atom. Inorganic salts (eg, nitrates, etc.), phosphorus oxoacid salts (eg, phosphates), chlorine atom oxoacid salts (eg, perchlorate); organic carboxylates (eg, acetic acid) Salt, stearate, and the like). One or more hydrogen atoms in the inorganic salt may be substituted with a monovalent organic group (for example, the above-described monovalent substituted or unsubstituted hydrocarbon group).

  Examples of the carboxylic acid constituting the organic carboxylate of the rare earth metal atom include known and commonly used carboxylic acids. Among these, a carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 15, more preferably 4 to 12, and further preferably 5 to 10) is preferable, and hexanoic acid such as 2-ethylhexanoic acid is more preferable. Among them, as the carboxylate of the rare earth metal atom, yttrium carboxylate, cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, neodymium carboxylate (particularly, yttrium carboxylate having 1 to 20 carbon atoms, 1 to 20 carbon atoms). Cerium carboxylate, lanthanum carboxylic acid having 1 to 20 carbon atoms, praseodymium having 1 to 20 carbon atoms, neodymium carboxylic acid having 1 to 20 carbon atoms, more preferably yttrium 2-ethylhexanoate, 2-ethyl (Cerium hexanoate, lanthanum 2-ethylhexanoate, praseodymium 2-ethylhexanoate, neodymium 2-ethylhexanoate) are preferred.

  The carboxylate of the rare earth metal atom is, for example, a carboxylate of a rare earth metal atom containing cerium (for example, one selected from the group consisting of cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, and neodymium carboxylate) A mixture of the above rare earth metal atoms with a carboxylate (such as a mixture of cerium carboxylate, lanthanum carboxylate, praseodymium carboxylate, and neodymium carboxylate), or only cerium carboxylate (single compound), or a carboxylic acid Preferred is a carboxylate of a rare earth metal atom containing yttrium (for example, only yttrium carboxylate, etc.), and 2-ethylhexanoate of a rare earth metal atom containing cerium (eg, cerium 2-ethylhexanoate and 2 -Lanthanum ethylhexanoate, 2-ethylhexane A mixture of one or more rare earth metal atoms selected from the group consisting of praseodymium acid and neodymium 2-ethylhexanoate with 2-ethylhexanoate (cerium 2-ethylhexanoate, lanthanum 2-ethylhexanoate, More preferably, it is a mixture of praseodymium 2-ethylhexanoate and neodymium 2-ethylhexanoate), or only cerium 2-ethylhexanoate (single compound), or yttrium 2-ethylhexanoate.

  As a product containing the component (D), for example, a trade name “Octope R” (manufactured by Hope Pharmaceutical Co., Ltd.) is available.

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

  The content of the rare earth metal atom in the curable silicone resin composition of the present invention is not particularly limited, but is preferably 0.1 to 500 ppm, more preferably 0 with respect to the curable silicone resin composition (100% by weight). .2 to 300 ppm, more preferably 0.5 to 200 ppm. When the content of the rare earth metal atom is 0.1 ppm or more, there is a tendency that an increase in hardness, a decrease in weight, and a decrease in transparency of the cured product are less likely to occur. Moreover, there exists a tendency for the gas barrier property of hardened | cured material to improve more. On the other hand, when it is 500 ppm or less, the transparency of the cured product tends to be further improved. The rare earth metal atom content in the curable silicone resin composition is measured by ICP-MS (inductively coupled plasma mass spectrometry).

  The content of the rare earth metal atom in the curable silicone resin composition of the present invention is not particularly limited, but is 0.00001 to 0.05 parts by weight with respect to 100 parts by weight as a total of the components (A) and (B). Is preferred, more preferably 0.00002 to 0.03 parts by weight, still more preferably 0.00005 to 0.02 parts by weight. When the content of the rare earth metal atom is 0.00001 part by weight or more, there is a tendency that an increase in hardness, a decrease in weight, and a decrease in transparency of the cured product are less likely to occur. Moreover, there exists a tendency for the gas barrier property of hardened | cured material to improve more. On the other hand, when it is 0.05 parts by weight or less, the transparency of the cured product tends to be further improved. The content of the rare earth metal atom is measured by ICP-MS (inductively coupled plasma mass spectrometry).

  Although content of (D) component in the curable silicone resin composition of this invention is not specifically limited, 1-5000 ppm is preferable with respect to curable silicone resin composition (100 weight%), More preferably, it is 5- 1000 ppm, more preferably 10 to 500 ppm. In particular, when the content of the rare earth metal atom is in the above range and the component (D) is in the above range, the hardness of the cured product, the weight, and the transparency are less likely to occur.

[(E) component]
The curable silicone resin composition of the present invention contains a polyorganosiloxysilalkylene having two or more alkenyl groups and one or more aryl groups in the molecule (sometimes referred to as “component (E)”). May be. In the curable silicone resin composition of the present invention, the component (E) is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (A)).

The component (E) has two or more alkenyl groups and one or more aryl groups in the molecule, and in addition to —Si—O—Si— (siloxane bond) as a main chain, —Si—R ^A — It is a polysiloxane (polyorganosiloxysilalkylene) containing Si- (silalkylene bond: R ^A represents an alkylene group). That is, the (E) component does not include a polyorganosiloxane having no silalkylene bond as in the above-described component (A). By including such a component (E), the curable silicone resin composition of the present invention is less likely to cause an increase in hardness, a decrease in weight, and a decrease in transparency of the cured product, and has a gas barrier property and thermal shock resistance. There is a tendency to be better. Furthermore, by curing, since it has a high gas barrier property and hardly yellows, it is difficult to cause a decrease in transparency, and a cured product with low or no tackiness can be obtained. Therefore, an optical semiconductor device using this as a sealing material There is a tendency for quality to improve.

(E) As an alkylene group in the silalkylene bond which a component has in a molecule | numerator, linear or branched _C1-12 alkylene groups, such as a methylene group, ethylene group, a propylene group, etc. are mentioned, for example, A C _2-4 alkylene group (particularly an ethylene group) is preferred. The component (E) has a main chain composed only of siloxane bonds, and is less likely to be decomposed by heating or the like to produce silanol groups (—SiOH) compared to polyorganosiloxanes having no silalkylene bonds. By using, there is a tendency that transparency is less likely to be lowered because it is more difficult to yellow.

  Examples of the component (E) include those having a molecular structure such as a straight chain or branched chain (for example, a partially branched straight chain, a branched chain, or a network). Among these, as the component (E), those having a branched molecular structure are preferable from the viewpoint of the mechanical strength of the cured product.

  (E) As an alkenyl group which a component has in a molecule | numerator, the above-mentioned substituted or unsubstituted alkenyl group is mentioned, Especially, a vinyl group is preferable. Moreover, (E) component may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. Although the alkenyl group which (E) component has is not specifically limited, It is preferable that it is the group couple | bonded with the silicon atom.

Examples of the aryl group that the component (E) has in the molecule include substituted or unsubstituted C _6-14 such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group (for example, benzyl group, phenethyl group). An aryl group etc. are mentioned. Examples of the substituent in the substituted aryl group include a substituted or unsubstituted C _1-8 alkyl group, a halogen atom, a hydroxy group, and a carboxy group. Of these, the aryl group is preferably a phenyl group. Moreover, (E) component may have only 1 type of aryl group, and may have 2 or more types of aryl groups. Although the aryl group which (E) component has is not specifically limited, It is preferable that it is the group couple | bonded with the silicon atom. Component (E) has one or more aryl groups in the molecule, so that a cured product having excellent gas barrier properties can be formed as compared with polyorganosiloxysilalkylene having no aryl group.

  Although it does not specifically limit as a group couple | bonded with silicon atoms other than the alkenyl group and aryl group which (E) component has in a molecule | numerator, For example, a hydrogen atom, an organic group, etc. are mentioned. As an organic group, the specific example (For example, an alkyl group, a halogenated alkyl group, etc.) of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group is mentioned, for example. Of these, an alkyl group (particularly a methyl group) is preferable.

  Moreover, (E) component may have a hydroxy group and an alkoxy group as a group couple | bonded with the silicon atom.

  The property of (E) component is not specifically limited, For example, in 25 degreeC, it may be liquefied and may be solid.

As the component (E), the following average unit formula:
(R ³ ₂ SiO _2/2 ) _{c 1} (R ³ ₃ SiO _1/2 ) _{c 2} (R ³ SiO _3/2 ) _{c 3} (SiO _4/2 ) _{c 4} (R ^A ) _{c 5} (X ³ O) _{c 6}
A polyorganosiloxysilalkylene represented by the formula is preferred. In the above average unit formula, R ³ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of the above monovalent substituted or unsubstituted hydrocarbon group (for example, alkyl group, aryl Group, halogenated alkyl group and the like) and the above-mentioned alkenyl group. However, a part of R ³ is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 or more in the molecule. For example, the ratio of the alkenyl group to the total amount of R ³ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of the alkenyl group to the above range, the curability of the curable silicone resin composition tends to be further improved. A part of R ³ is an aryl group (particularly a phenyl group), and the ratio thereof is controlled within a range of 1 or more in the molecule. For example, the ratio of the aryl group to the total amount of R ³ (100 mol%) is preferably 10 to 60 mol%. By controlling the ratio of the aryl group within the above range, the gas barrier property of the cured product tends to be further improved. R ³ other than an alkenyl group and an aryl group is preferably an alkyl group (particularly a methyl group).

In the average unit formula, R ^A is an alkylene group as described above. An ethylene group is particularly preferable.

In the above average unit formula, X ³ is a hydrogen atom or an alkyl group as in X ¹ above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

  In the above average unit formula, c1 is a positive number, c2 is a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is a positive number, and c6 is 0 or a positive number. Among these, c1 is preferably 1 to 200, c2 is preferably 1 to 200, c3 is preferably 0 to 10, c4 is preferably 0 to 5, and c5 is preferably 1 to 100. In particular, when (c3 + c4) is a positive number, the component (E) has a branched chain (branched main chain), and the mechanical strength of the cured product tends to be further improved.

More specific examples of the component (E) include polyorganosiloxysilalkylene having a structure represented by the following formula (II-1).

In the above formula (II-1), R ¹² are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of R ¹² include the specific examples of the monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, an aryl group, a halogenated hydrocarbon group, etc.) and the above-described alkenyl group. However, at least two of R ¹² are alkenyl groups (particularly vinyl groups), and at least one of R ¹² is an aryl group (particularly a phenyl group). Further, R ¹² other than the alkenyl group and aryl group is preferably an alkyl group (particularly a methyl group).

In the formula (II-1), R ^A represents an alkylene group as described above, and among them, a C _2-4 alkylene group (particularly an ethylene group) is preferable. In addition, when several ^RA exists, these may be the same and may differ.

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

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

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

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

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

  Moreover, the addition form of each structural unit in the formula (II-1) 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 polyorganosiloxysilalkylene having the structure represented by the formula (II-1) is not particularly limited, but for example, a silanol group, an alkoxysilyl group, a trialkylsilyl group (for example, parenthesis with r5 attached) Internal structure, trimethylsilyl group, etc.). Various groups such as an alkenyl group and a hydrosilyl group may be introduced at the terminal of the polyorganosiloxysilalkylene.

  The component (E) can be produced by a known or conventional method, and the production method is not particularly limited. For example, the component (E) can be produced by the method described in JP2012-140617A. In addition, as products containing the component (E), for example, trade names “ETERLED GD1130”, “ETERLED GD1125”, “ETERLED GS5155”, “ETERLED GS5145”, “ETERLED GS5135”, “ETERLED GS5120” (all manufactured by Changxing Material Industries) ) Etc. are available.

  In addition, in the curable silicone resin composition of this invention, (E) component can also be used individually by 1 type, and can also be used in combination of 2 or more type. For example, two or more types of (E) components having different molecular structures can be used in combination, and specifically, an embodiment in which a linear (E) component and a branched (E) component are used in combination. Can be mentioned.

  When the curable silicone resin composition of the present invention contains the component (E), the content (blending amount) of the component (E) in the curable silicone resin composition of the present invention is not particularly limited, but (A) 0.1-150 weight part is preferable with respect to a total of 100 weight part of a component and (B) component, More preferably, it is 0.1-120 weight part, More preferably, it is 0.1-100 weight part. There exists a tendency for the gas barrier property of hardened | cured material to improve more by making content of (E) component into 0.1 weight part or more. Further, since yellowing resistance is improved, the quality and durability of the optical semiconductor device also tend to be improved. On the other hand, when the content of the component (E) is 150 parts by weight or less, an increase in the hardness of the cured product and a decrease in the weight are further suppressed, and the thermal shock resistance tends to be further improved, and (A) There is a tendency that the effect (for example, improvement of curability, improvement of gas barrier property, improvement of adhesion, etc.) due to the increase of the component (D) can be efficiently obtained.

[Other polysiloxanes]
The curable silicone resin composition of the present invention has other polysiloxane having an alkenyl group in the molecule in addition to the components (B) and (E) described above (sometimes referred to as “other polysiloxane”). May be included. By containing other polysiloxanes, the viscosity of the curable silicone resin composition may be adjusted, or the balance of physical properties (eg, mechanical properties) of the cured product may be adjusted.

  Examples of other polysiloxanes include linear polyorganosiloxane having one or more alkenyl groups in the molecule, ladder-type polyorganosilsesquioxane having one or more alkenyl groups in the molecule, and the like. .

  The above-mentioned linear polyorganosiloxane having one or more alkenyl groups in the molecule has one or more alkenyl groups in the molecule, has a siloxane bond as the main chain, and does not have a silalkylene bond. It is a chain polyorganosiloxane.

  In the curable silicone resin composition of the present invention, the linear polyorganosiloxane can be used singly or in combination of two or more.

  Examples of the alkenyl group in the molecule of the linear polyorganosiloxane include the above-mentioned substituted or unsubstituted alkenyl groups, and among them, a vinyl group is preferable. Moreover, the said linear polyorganosiloxane may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. The alkenyl group of the linear polyorganosiloxane is not particularly limited, but is preferably bonded to a silicon atom.

  The number of alkenyl groups that the linear polyorganosiloxane has in the molecule is not particularly limited as long as it is 1 or more, but 2 or more (for example, 2 to 2) from the viewpoint of curability of the curable silicone resin composition. 50) is preferable.

  Although the group couple | bonded with silicon atoms other than the alkenyl group which the said linear polyorganosiloxane has is not specifically limited, For example, a hydrogen atom, an organic group, etc. are mentioned. Examples of the organic group include the above-described monovalent substituted or unsubstituted hydrocarbon groups (for example, substituted or unsubstituted carbon groups such as alkyl groups, cycloalkyl groups, cycloalkyl-alkyl groups, aryl groups, and halogenated hydrocarbon groups). Hydrogen group, etc.).

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

  The property of the linear polyorganosiloxane is not particularly limited, and may be liquid or solid at 25 ° C., for example.

As said linear polyorganosiloxane, the following average unit formula:
(R ⁴ ₂ SiO _2/2 ) _d1 (R ⁴ ₃ SiO _1/2 ) _d2 (X ⁴ O _1/2 ) _d3
The polyorganosiloxane represented by these is mentioned. In the above average unit formula, R ⁴ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the above monovalent substituted or unsubstituted hydrocarbon group (for example, alkyl group, aryl Group, halogenated hydrocarbon group and the like) and the above-mentioned alkenyl group. However, a part of R ⁴ is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 1 or more (preferably 2 or more) in the molecule. For example, the ratio of the alkenyl group to the total amount of R ⁴ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of the alkenyl group to the above range, the curability of the curable silicone resin composition tends to be further improved. R ⁴ other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

In the above average unit formula, X ⁴ is a hydrogen atom or an alkyl group as in X ¹ above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

  In the above average unit formula, d1 is a positive number, d2 is 0 or a positive number, and d3 is 0 or a positive number.

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

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

［上記式中、Ｒ³¹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、Ｒ³¹の少なくとも１個（好ましくは少なくとも２個）はアルケニル基である。ｍ２は、５〜１０００の整数である。］ The linear polyorganosiloxane is represented by, for example, the following formula (III-1).

[In the above formula, R ³¹ are the same or different and each represents a monovalent substituted or unsubstituted hydrocarbon group. However, at least one (preferably at least two) of R ³¹ is an alkenyl group. m2 is an integer of 5 to 1000. ]

  When the curable silicone resin composition of the present invention contains the linear polyorganosiloxane, the content (blending amount) of the linear polyorganosiloxane in the curable silicone resin composition of the present invention is particularly limited. However, it is preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight, based on the curable silicone resin composition (100% by weight). By controlling the content of the linear polyorganosiloxane within the above range, it may be possible to adjust the balance of the viscosity of the curable silicone resin composition and the physical properties of the cured product.

  The ladder-type polyorganosilsesquioxane having one or more alkenyl groups in the molecule has one or more (preferably two or more) alkenyl groups in the molecule, and has a ladder structure -Si- A polyorganosilsesquioxane having an O—Si— skeleton can be used and is not particularly limited. When the curable silicone resin composition of the present invention contains the ladder-type polyorganosilsesquioxane, the gas barrier property of the cured product tends to be remarkably improved. In the curable silicone resin composition of the present invention, the ladder-type polyorganosilsesquioxane can be used alone or in combination of two or more.

The ladder-type polyorganosilsesquioxane has a ladder structure, this near 1050 cm ^-1 in the FT-IR spectrum (e.g., 1000～1100Cm ^-1) and 1150cm around ^-1 (e.g., exceed 1100 cm ^-1 1200 cm ^-1 or less) each having a unique absorption peak (i.e., having at least two absorption peaks at 1000 to 1200 ^-1) is confirmed by the fact that [ref: R. H. Raney, M.M. Itoh, A.D. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. In addition, an FT-IR spectrum can be measured with the following apparatus and conditions, for example.
Measuring device: Trade name “FT-720” (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Measurement wavenumber range: 400 to 4000 cm ⁻¹
Integration count: 16 times

  When the curable silicone resin composition of the present invention contains the ladder-type polyorganosilsesquioxane, the content (blending amount) of the ladder-type polyorganosilsesquioxane in the curable silicone resin composition of the present invention. Is not particularly limited, but is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 45 parts by weight, and still more preferably 0 to 100 parts by weight of the total of the components (A) and (B). 0.01 to 40 parts by weight. Although not particularly limited, the content (blending amount) of the ladder-type polyorganosilsesquioxane is preferably 0.1 to 20% by weight with respect to the curable silicone resin composition (100% by weight). Preferably it is 0.1 to 15 weight%, More preferably, it is 0.2 to 10 weight%. By controlling the content of the ladder-type polyorganosilsesquioxane within the above range, the gas barrier property of the cured product tends to be remarkably improved.

[Isocyanurate compounds]
The curable silicone resin composition of the present invention is a group represented by the following formula (Y) and / or a group represented by the following formula (Z) (group and formula represented by the formula (Y) ( It may contain an isocyanurate compound (sometimes simply referred to as “isocyanurate compound”) having at least one of or both of the groups represented by Z). When the curable silicone resin composition of the present invention contains the isocyanurate compound, the sulfur barrier property of the cured product is remarkably improved, and the adhesion of the cured product to the adherend tends to be improved. In the curable silicone resin composition of the present invention, the isocyanurate compound can be used alone or in combination of two or more. Moreover, the said isocyanurate compound may mix | blend with other components after previously mixing with a silane coupling agent and its partial condensate from a viewpoint of improving compatibility with another component. .

In formula (Y) and formula (Z), R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.

The isocyanurate compound is a compound having an isocyanuric acid skeleton and having at least one group represented by the formula (Y) and / or one group represented by the formula (Z) in the molecule. I just need it. Among these, the isocyanurate compound is preferably a compound represented by the following formula (X).

In the formula (X), R ^x , R ^y , and R ^z are the same or different and each represents an alkyl group, a group represented by the formula (Y), or a group represented by the formula (Z). However, at least one of R ^x , R ^y , and R ^z is a group selected from the group consisting of a group represented by the formula (Y) and a group represented by the formula (Z).

  Specific examples of the isocyanurate compound include monoallyl dimethyl isocyanurate, diallyl monomethyl isocyanurate, triallyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, triglycidyl isocyanurate, 1- Allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methylpropenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis ( 2-methylepoxypropyl) isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3-bis (2-methylpropenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpro ) -5- (2-methyl-epoxypropyl) isocyanurate, tris (2-methyl-propenyl) isocyanurate.

  When the curable silicone resin composition of the present invention contains the isocyanurate compound, the content (blending amount) of the isocyanurate compound in the curable silicone resin composition of the present invention is not particularly limited. 0.01-10 weight% is preferable with respect to a resin composition (100 weight%), More preferably, it is 0.05-5 weight%, More preferably, it is 0.1-3 weight%. When the content of the isocyanurate compound is 0.01% by weight or more, the sulfur barrier property of the cured product and the adhesion to the adherend tend to be further improved. On the other hand, by setting the content of the isocyanurate compound to 10% by weight or less, there is a tendency that a curable silicone resin composition that is uniform and has superior curability is easily obtained.

[Silane coupling agent]
The curable silicone resin composition of the present invention may contain a silane coupling agent. When the curable silicone resin composition of the present invention contains a silane coupling agent, the adhesion of the cured product to the adherend tends to be improved.

  As the silane coupling agent, a known or conventional silane coupling agent can be used, and is not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silane coupling agents such as trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-triethoxysilyl-N- (1,3-dimethyl Ru-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (β-aminoethyl) -Amino group-containing silane coupling agent such as γ-aminopropylmethyldiethoxysilane; tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxy Ethoxysilane), phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) actyl B propyl methyl dimethoxy silane, .gamma. (meth) acryloxy propyl methyl diethoxy silane, mercapto propylene trimethoxysilane, and mercapto propylene triethoxysilane and the like. Among these, an epoxy group-containing silane coupling agent (particularly 3-glycidoxypropyltrimethoxysilane) is preferable. In addition, a silane coupling agent can be used individually by 1 type or in combination of 2 or more types.

  When the curable silicone resin composition of the present invention contains a silane coupling agent, the content (blending amount) of the silane coupling agent in the curable silicone resin composition of the present invention is not particularly limited. 0.01-15 weight% is preferable with respect to a resin composition (100 weight%), More preferably, it is 0.1-10 weight%, More preferably, it is 0.5-5 weight%. By setting the content of the silane coupling agent to 0.01% by weight or more, the adhesion to the adherend is improved. In particular, when the isocyanurate compound is used in a compatible state, the curing is more sufficiently performed. Prone. On the other hand, by setting the content of the silane coupling agent to 15% by weight or less, curing is difficult to be insufficient, and the gas barrier property and thermal shock resistance of the cured product are easily improved.

[Hydrosilylation reaction inhibitor]
The curable silicone resin composition of the present invention may contain a hydrosilylation reaction inhibitor in order to adjust the speed of the curing reaction (hydrosilylation reaction). As the hydrosilylation reaction inhibitor, known or conventional hydrosilylation reaction inhibitors can be used, and are not particularly limited. For example, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyne Alkyne alcohols such as 3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol; enynes such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne Compounds: thiazole, benzothiazole, benzotriazole and the like. The said hydrosilylation reaction inhibitor can also be used individually by 1 type, and can also be used in combination of 2 or more type. The content (blending amount) of the hydrosilylation reaction inhibitor varies depending on the crosslinking conditions and the like of the curable silicone resin composition, but as a content relative to the curable silicone resin composition (100% by weight), it is practically 0. It is preferably within the range of 00001 to 5% by weight.

[Cyclic siloxane]
The curable silicone resin composition of the present invention includes, for example, two siloxane compounds other than the above-described polysiloxane ((A) component, (B) component, (E) component, and other polysiloxane) in the molecule. The cyclic siloxane which has the above aliphatic carbon-carbon double bonds (especially alkenyl group) may be included. Moreover, the curable silicone resin composition of this invention may contain the cyclic siloxane which has a 2 or more hydrosilyl group in a molecule | numerator as said siloxane compound. Each of the above cyclic siloxanes can be used alone or in combination of two or more. When the curable silicone resin composition of the present invention contains a cyclic siloxane, the content (blending amount) of the cyclic siloxane in the curable silicone resin composition of the present invention is not particularly limited, but the curable silicone resin composition 0.01 to 30% by weight is preferable with respect to (100% by weight), more preferably 0.1 to 20% by weight, and still more preferably 0.5 to 10% by weight.

[solvent]
The curable silicone resin composition of the present invention may contain a solvent. Examples of the solvent include known or commonly used organic solvents and water, and are not particularly limited. Examples thereof include toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate, and the like. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type. Moreover, the content is not specifically limited, It can select suitably.

[Phosphor]
The curable silicone resin composition of the present invention may contain a phosphor. As the phosphor, a known or commonly used phosphor (for example, a phosphor known in the field of optical semiconductor devices) can be used, and is not particularly limited. For example, the function of converting blue light into white light is sealed. In the case where it is desired to give to the stopping material, the general formula A ₃ B ₅ O ₁₂ : M [wherein A is selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm. B represents one or more elements selected from the group consisting of Al, Ga, and In, and M represents a group consisting of Ce, Pr, Eu, Cr, Nd, and Er. YAG phosphor fine particles (for example, Y ₃ Al ₅ O ₁₂ : Ce phosphor fine particles, (Y, Gd, Tb) ₃ (Al, Ga) ₅ O _12: Ce phosphor particles, etc.); based phosphor particles (e.g., (Sr, Ca Ba) ₂ SiO _4: Eu, etc.), and the like. Note that the phosphor may have been subjected to a well-known and conventional surface treatment. Moreover, the fluorescent substance can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  When the curable silicone resin composition of the present invention contains a phosphor, the content (blending amount) of the phosphor in the curable silicone resin composition of the present invention is not particularly limited, but the curable silicone resin composition ( 100% by weight) is preferably 0.01 to 20% by weight, more preferably 0.5 to 10% by weight. By containing the phosphor in the above range, the wavelength conversion function of light by the sealing material can be sufficiently exerted in the optical semiconductor device, and the viscosity of the curable silicone resin composition does not become too high and is cured. There exists a tendency for workability | operativity at the time of product preparation (especially sealing work) to improve more.

[Other ingredients]
The curable silicone resin composition of the present invention may contain components other than those described above (sometimes referred to as “other components”). Examples of other components include, but are not limited to, silica filler, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and the like. Inorganic fillers, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; fine organic resin powders such as silicone resins, epoxy resins, fluororesins; silver, copper, etc. Fillers such as conductive metal powders, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants) Etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents other than silane coupling agents, lubricants, waxes, acceptable Agent, mold release agent, impact resistance improver, hue improver, fluidity improver, colorant (dye, pigment, etc.), surface conditioner (for example, various polyether-modified silicones, polyester-modified silicones, phenyl-modified silicones, Compounds such as alkyl-modified silicones), dispersants, antifoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, and other functional additives (for example, zinc such as zinc salts of carboxylic acids) Compound and the like, and well-known and commonly used additives. These other components can be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, content (blending amount) of another component is not specifically limited, It can select suitably.

  Although the curable silicone resin composition of the present invention is not particularly limited, the composition (formulation) is such that the alkenyl group is 0.2 to 4 mol per 1 mol of the hydrosilyl group present in the curable silicone resin composition. Composition), more preferably 0.5 to 1.5 mol, and still more preferably 0.8 to 1.2 mol. By controlling the ratio between the hydrosilyl group and the alkenyl group within the above range, the thermal shock resistance and gas barrier property of the cured product tend to be further improved.

  The total amount (total content) of the (A) component, the (B) component, the (E) component, and other polysiloxanes contained in the curable silicone resin composition of the present invention is not particularly limited, but is a curable silicone resin. 70% by weight or more (for example, 70% by weight or more and less than 100% by weight) is preferable with respect to the composition (100% by weight), more preferably 80% by weight or more (for example, 80 to 99% by weight), and still more preferably It is 90% by weight or more (for example, 90 to 99% by weight). By setting the total amount to 70% by weight or more, the heat resistance of the cured product is improved, and there is a tendency that an increase in hardness, a decrease in weight, and a decrease in transparency are less likely to occur.

  Although the total amount (total content) of (B) component, (E) component, and other polysiloxane contained in the curable silicone resin composition of the present invention is not particularly limited, the curable silicone resin composition (100 weight) %) Is preferably 40 to 90% by weight, more preferably 50 to 85% by weight, and still more preferably 60 to 80% by weight. By setting the total amount to 40% by weight or more, durability and transparency of the cured product tend to be further improved. On the other hand, when the total amount is 90% by weight or less, the curability tends to be further improved.

  The content (blending amount) of component (A) in the curable silicone resin composition of the present invention is not particularly limited, but the total amount (total content) of component (B), component (E), and other polysiloxanes. The amount is preferably 1 to 200 parts by weight with respect to 100 parts by weight. By controlling the content of the component (A) within the above range, the curability of the curable silicone resin composition is further improved, and a cured product tends to be formed efficiently.

  When the curable resin composition of the present invention contains the component (E), the total amount (total content) of the component (B), the component (E), and other polysiloxanes contained in the curable silicone resin composition of the present invention The ratio of the component (E) to the amount (100 wt%) is not particularly limited, but is preferably 10 wt% or more (for example, 10 wt% or more and less than 100 wt%), more preferably 15 wt% or more (for example, 15 wt%). -90 wt%), more preferably 20 wt% or more (for example, 20-80 wt%). By setting the above ratio to 10% by weight or more, gas barrier properties are further improved, tackiness is reduced, and yellowing tends to be suppressed.

  Although the curable silicone resin composition of this invention is not specifically limited, For example, it can prepare by stirring and mixing each said component at room temperature (or heating as needed). In addition, the curable silicone resin composition of the present invention can be used as a one-component composition in which all components are mixed in advance as they are, for example, 2 prepared separately. It can also be used as a multi-component (for example, two-component) composition in which the above components are mixed at a predetermined ratio before use.

  Although the curable silicone resin composition of this invention is not specifically limited, It is preferable that it is a liquid at normal temperature (about 25 degreeC). More specifically, the curable silicone resin composition of the present invention has a viscosity at 25 ° C. of preferably 300 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1000 to 8000 mPa · s. -S. There exists a tendency for the heat resistance of hardened | cured material to improve more because the said viscosity is 300 mPa * s or more. On the other hand, when the viscosity is 20,000 mPa · s or less, it is easy to prepare a curable silicone resin composition, the productivity and handleability are further improved, and air bubbles hardly remain in the cured product. Therefore, the productivity and quality of the cured product (especially the sealing material) tend to be further improved. The viscosity of the curable silicone resin composition was determined using a viscometer (trade name “MCR302”, manufactured by Anton Paar Co., Ltd.) with a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25. It is measured under the condition of ° C.

<Hardened product>
By curing the curable silicone resin composition of the present invention (particularly, curing by hydrosilylation reaction), a cured product (sometimes referred to as “cured product of the present invention”) is obtained. The conditions for curing are not particularly limited and can be appropriately selected from conventionally known conditions. For example, the temperature (curing temperature) is 25 to 180 ° C. (more preferably 60 to 150) from the viewpoint of the reaction rate. C.), and the time (curing time) is preferably 5 to 720 minutes. The cured product of the present invention has high heat resistance peculiar to polysiloxane materials, and is hard to cause increase in hardness, decrease in weight, and decrease in transparency, as well as thermal shock resistance, adhesion to an adherend. In addition, when it contains the isocyanurate compound, a cured product having a particularly excellent sulfur barrier property can be obtained.

  Although the hardness (D hardness) of the hardened | cured material of this invention is not specifically limited, 20-80 are preferable, More preferably, it is 25-75, More preferably, it is 30-70. When the D hardness is 20 or more, the gas barrier property tends to be excellent. When the D hardness is 80 or less, the thermal shock resistance and the adhesion to an adherend tend to be excellent. In addition, it is preferable that the hardness (D hardness) of the hardened | cured material after storing hardened | cured material at 200 degreeC for 100 hours is also in the said range.

  The difference in hardness (D hardness) before and after storing the cured product at 200 ° C. for 300 hours is not particularly limited, but is preferably 30 or less, more preferably 25 or less, and still more preferably 23 or less. When the difference in hardness is 30 or less, flexibility is maintained even when exposed to a severe environment such as high temperature for a long time, and the cured product is used as a sealing material for LED packages. If so, cracks tend not to occur. In addition, the occurrence of peeling between the sealing material and the electrode or LED package also tends to be reduced.

  The weight reduction rate before and after storing the cured product at 200 ° C. for 300 hours is not particularly limited, but is preferably 5.0% or less, more preferably 4.5% or less, and still more preferably 4.0% or less. When the weight reduction rate is 5.0% or less, flexibility is maintained even when exposed to a severe environment such as high temperature for a long time, and the cured product is sealed in an LED package. When used as a material, cracks tend not to occur. In addition, the light extraction efficiency tends to be maintained high.

  The transmittance (thickness direction) of light having a wavelength of 450 nm of the cured product (thickness 3 mm) of the present invention is not particularly limited, but is preferably 75% or more, more preferably 80% or more, and still more preferably 85% or more. When the transmittance is 75% or more, the cured product is more excellent in transparency. In addition, the light extraction efficiency tends to be maintained high.

  The transmittance (thickness direction) of the light having a wavelength of 450 nm after the cured product of the present invention (thickness 3 mm) is stored at 200 ° C. for 300 hours is not particularly limited, but is preferably 70% or more, more preferably. Is 75% or more, more preferably 80% or more. When the transmittance is 70% or more, the transparency of the cured product is even better even when exposed to a harsh environment such as high temperature for a long time. In addition, the light extraction efficiency tends to be maintained high.

  The transmittance maintenance ratio before and after storing the cured product at 200 ° C. for 300 hours is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. When the transmittance maintenance ratio is 80% or more, transparency is further improved even when exposed to a harsh environment such as a high temperature for a long time. In addition, the light extraction efficiency tends to be maintained high.

<Sealant, optical semiconductor device>
The curable silicone resin composition of the present invention is particularly a resin composition for sealing an optical semiconductor element (LED element) in an optical semiconductor device (resin composition for optical semiconductor sealing) (“encapsulant of the present invention”). May be preferably used. The encapsulant (cured product) obtained by curing the encapsulant of the present invention has high heat resistance unique to polysiloxane materials, resulting in increased hardness, decreased weight, and decreased transparency. In addition to being difficult, it has excellent thermal shock resistance, adhesion to an adherend, and gas barrier properties. For this reason, the sealing agent of this invention can be preferably used especially as a sealing agent etc. of a high-intensity, short wavelength optical semiconductor element. By sealing the optical semiconductor element using the sealing agent of the present invention, an optical semiconductor device (sometimes referred to as “optical semiconductor device of the present invention”) can be obtained. That is, the optical semiconductor device of the present invention includes at least an optical semiconductor element and a sealing material that seals the optical semiconductor element, and the sealing material includes the curable silicone resin composition of the present invention (the sealing of the present invention). It is an optical semiconductor device which is a cured product (cured product of the present invention). The sealing of the optical semiconductor element can be carried out 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 mold, and is cured by heating under predetermined conditions. Can be implemented. The curing temperature and the curing time are not particularly limited, and can be appropriately set within the same range as when the cured product is prepared. An example of the optical semiconductor device of the present invention is shown in FIG. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring (electrode), 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).

<Composition for forming lens for optical semiconductor, optical semiconductor device>
Further, the curable silicone resin composition of the present invention is a composition for forming a lens (lens for an optical semiconductor) provided in an optical semiconductor device (a composition for forming an optical semiconductor lens) (“the lens of the present invention. It may also be preferably used as a “forming composition”. The lens obtained by curing the composition for forming a lens of the present invention has high heat resistance, and it is difficult to cause increase in hardness, decrease in weight, and decrease in transparency. Excellent adhesion to the adherend and gas barrier properties. By using the lens forming composition of the present invention, an optical semiconductor device (also referred to as “optical semiconductor device of the present invention”) may be obtained. That is, the optical semiconductor device of the present invention includes at least an optical semiconductor element and a lens, and the lens is a cured product of the curable silicone resin composition of the present invention (lens forming composition of the present invention) (cured of the present invention). An optical semiconductor device. The production of a lens for an optical semiconductor using the lens forming composition of the present invention can be carried out by a known or conventional method, and is not particularly limited. For example, the lens forming composition of the present invention is applied to a predetermined mold. It can be carried out by a method of injecting into the heat and curing under a predetermined condition, a method of applying with a dispenser or the like and a heat curing under a predetermined condition. The curing temperature and the curing time are not particularly limited, and can be appropriately set within the same range as when the cured product is prepared. The aspect in which the optical semiconductor device of the present invention includes the lens is not particularly limited. For example, when the optical semiconductor device of the present invention has a sealing material, the optical semiconductor device is disposed on a part or all of the surface of the sealing material. The aspect which sealed the optical semiconductor element of the said optical semiconductor device (namely, the aspect which the hardened | cured material of this invention serves as a sealing material and a lens) etc. may be sufficient. More specifically, for example, embodiments disclosed in International Publication No. 2012/147342, Japanese Patent Application Laid-Open No. 2012-188627, Japanese Patent Application Laid-Open No. 2011-233605, and the like.

  The optical semiconductor device of the present invention includes an optical semiconductor element, a sealing material that seals the optical semiconductor element, and a lens, and the sealing material includes the curable silicone resin composition of the present invention (the sealing of the present invention). And a cured product of the curable silicone resin composition of the present invention (lens-forming composition of the present invention) (cured product of the present invention). It may be an optical semiconductor device.

  The curable silicone resin composition of the present invention is not limited to the above-described encapsulant application (encapsulant application for optical semiconductor elements) and lens formation application (lens formation application in an optical semiconductor device). For example, an optical semiconductor device Semiconductor device sealants, functional coating agents, heat-resistant plastic lenses, transparent equipment, adhesives (heat-resistant transparent adhesives, etc.), electrical insulating materials (insulating films, etc.), laminates, coatings, inks, Paint, sealant, resist, composite material, transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, stereolithography, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, etc. It can be preferably used for optical-related and semiconductor-related applications.

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

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the unit of the mixture ratio of each component shown in Table 1 is a weight part.

The description of each component described in Table 1 is shown below.
(A agent)
ETERLED GS5145A: Trade name “ETERLED GS5145A” [silicone resin containing component (E)], manufactured by Changko Material Industries, about 24 mol% of aryl group (phenyl group), and hydrosilylation catalyst [component (C)].
Octopor R: 2-ethylhexanoic acid rare earth [including rare earths such as cerium, lanthanum, neodymium and praseodymium. As a solvent, 2-ethylhexanoic acid: 8% by weight, mineral spirit 68% included], manufactured by Hope Pharmaceutical Co., Ltd. cerium octylate (III): cerium 2-ethylhexanoate (III) (active ingredient: 49% by weight, 2-ethylhexanoic acid solution), manufactured by Wako Pure Chemical Industries, Ltd., cerium acetate (III): cerium acetate (III), manufactured by Daiichi Elemental Chemical Co., Ltd. acetylacetone cerium (III) dihydrate: acetylacetone cerium (III) Dihydrate, manufactured by Kishida Chemical Co., Ltd. Cerium nitrate (III) hexahydrate: Cerium nitrate (III) hexahydrate, manufactured by Kishida Chemical Co., Ltd. (agent B)
ETERLED GS5145B: Trade name “ETERLED GS5145B” [including silicone resin, component (A) and component (B)], manufactured by Changxing Materials Industry

Example 1
[Production of curable silicone resin composition]
First, as shown in Table 1, 20 parts by weight of a trade name “ETERLED GS5145A” and 0.033 parts by weight of Octope R were mixed and stirred at 40 ° C. for 2 hours to prepare an agent A.
Next, 80 parts by weight of the product name “ETERLED GS5145B” is mixed as the B agent to the A agent obtained above, and a self-revolving stirrer (trade name “Awatori Nertaro”, manufactured by Shinky Corporation, A curable silicone resin composition was produced by kneading using a model No .: ARE-310) with stirring for 5 minutes and defoaming for 2 minutes.

[Manufacture of optical semiconductor devices]
The curable silicone resin composition obtained above is injected into the LED package (InGaN element, 3.5 mm × 2.8 mm) of the embodiment shown in FIG. 1, and then at 60 ° C. for 1 hour and subsequently at 80 ° C. for 1 hour. Furthermore, the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the said curable silicone resin composition was manufactured by heating at 150 degreeC for 4 hours.

Examples 2 to 10, Comparative Example 1
A curable silicone resin composition and an optical semiconductor device were produced in the same manner as in Example 1 except that the composition of the curable silicone resin composition was changed as shown in Table 1.

(Evaluation)
The following evaluation was performed about the curable silicone resin composition and optical semiconductor device which were obtained above. The evaluation results are shown in Table 1.

[Rare earth metal atom content (ppm)]
The content of rare earth metal atoms relative to the curable silicone resin compositions (100% by weight) obtained in Examples 2 to 10 and Comparative Example 1 was determined using the ICP-MS. Measured by quantitative analysis.
Device: Product name “Agilent 7500cs” (manufactured by Yokogawa Analytical Systems)
A sample diluted with a solvent was used as a test solution for ICP-MS measurement. The standard solution for the calibration curve was used by adding a solution obtained by appropriately diluting the standard solution for atomic absorption of each element to the above test solution.

[hardness]
The molds were filled with the curable silicone resin compositions obtained in Examples and Comparative Examples, and heated at 60 ° C. for 1 hour, subsequently at 80 ° C. for 1 hour, and further at 150 ° C. for 4 hours, so that the thickness was 3 mm. A cured product was obtained. The D hardness of the obtained cured product was measured using a type D durometer (trade name “GS-702G”, manufactured by Tecrock Co., Ltd.) (referred to as “initial hardness”). The results are shown in the column of “Initial hardness” in Table 1.
Further, the D hardness of the cured product after the cured product obtained above was heated in an oven set at 200 ° C. for 300 hours was measured in the same manner as the initial hardness (after “200 ° C. heat resistance test (300 hr)”. Hardness ”).
Then, an increase in hardness from “initial hardness” to “hardness after 200 ° C. heat resistance test (300 hr)” was calculated as “hardness increase value after 200 ° C. heat resistance test (300 hr)”.
And "the hardness increase value after a 200 degreeC heat test (300 hr)" was evaluated on the following references | standards. The results are shown in the column of “Hardness increase value after 200 ° C. heat resistance test (300 hr)” in Table 1.
A (very good): hardness increase value is 25 or less B (good): hardness increase value is greater than 25 and 30 or less C (poor): hardness increase value is greater than 30

[Weight reduction rate]
The molds were filled with the curable silicone resin compositions obtained in Examples and Comparative Examples, and heated at 60 ° C. for 1 hour, subsequently at 80 ° C. for 1 hour, and further at 150 ° C. for 4 hours, so that the thickness was 3 mm. A cured product was obtained. The weight of the obtained cured product was measured (referred to as “initial weight”). Next, the weight of the cured product after heating the cured product obtained above in an oven set at 200 ° C. for 300 hours was measured (referred to as “weight after 200 ° C. heat resistance test (300 hr)”). And the "weight reduction rate after a 200 degreeC heat test (300 hr)" was computed by the following formula.
[Weight reduction rate after 200 ° C. heat resistance test (300 hr)] (%) = {[initial weight] − [Weight reduction rate after 200 ° C. heat resistance test (300 hr)]} / [initial weight] × 100
And "the weight reduction rate after a 200 degreeC heat test (300 hr)" was evaluated on the following references | standards. The results are shown in the column of “weight reduction rate after 200 ° C. heat resistance test (300 hr)” in Table 1.
A (very good): Weight reduction rate is 3.8% or less B (good): Weight reduction rate is larger than 3.8% and 4.0% or less C (can be used): Weight reduction rate Is greater than 4.0% and less than or equal to 4.5% D (defective): Weight reduction rate is greater than 4.5%

[Transmissivity]
The molds were filled with the curable silicone resin compositions obtained in Examples and Comparative Examples, and heated at 60 ° C. for 1 hour, subsequently at 80 ° C. for 1 hour, and further at 150 ° C. for 4 hours, so that the thickness was 3 mm. A cured product was obtained. The transmittance (thickness direction) of light having a wavelength of 450 nm of the obtained cured product was measured using a spectrophotometer (trade name “UV-2400”, manufactured by Shimadzu Corporation) (“initial transmittance”) To do). The results are shown in the column of “Initial transmittance” in Table 1.
Further, the transmittance of the cured product obtained by heating the cured product obtained above in an oven set at 200 ° C. for 300 hours was measured in the same manner as the initial transmittance (“200 ° C. heat resistance test (300 hr)”). Later transmittance "). And "the transmittance | permeability maintenance factor after a 200 degreeC heat test (300hr)" was computed by the following formula.
[Transmittance maintenance rate after 200 ° C. heat test (300 hr)] (%) = [Transmittance after 200 ° C. heat test (300 hr)] / [Initial transmittance] × 100
And "the transmittance | permeability maintenance factor after a 200 degreeC heat test (300hr)" was evaluated on the following references | standards. The results are shown in the column of “Transmittance maintenance rate after 200 ° C. heat resistance test (300 hr)” in Table 1.
A (very good): transmittance maintenance rate is 90% or more B (good): transmittance maintenance rate is 85% or more and less than 90% C (can be used): transmittance maintenance rate is 80% or more Less than 85% D (defect): Transmittance maintenance rate is less than 80%

[Comprehensive evaluation]
About the curable silicone resin compositions obtained in Examples and Comparative Examples, the hardness increase value after the 200 ° C. heat resistance test (300 hr), the weight reduction rate after the 200 ° C. heat resistance test (300 hr), and the 200 ° C. heat resistance test (300 hr) Based on the evaluation results of the following three items of transmittance maintenance rate, comprehensive evaluation was performed according to the following criteria.
A: Effective in two or more items compared to Comparative Example 1 B: Effective in one item compared to Comparative Example 1 C: No effect compared to Comparative Example 1

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

Claims (9)

A curable silicone resin composition comprising the following component (A), component (B), component (C), and component (D).
(A): a polyorganosiloxane having one or more hydrosilyl groups in the molecule and no aliphatic unsaturated group (B): a branched polyorganosiloxane having one or more alkenyl groups in the molecule (C): Hydrosilylation catalyst containing platinum group metal (D): Rare earth metal compound   2. The curable silicone resin composition according to claim 1, wherein the rare earth metal atom content is 0.1 to 500 ppm with respect to 100 wt% of the curable silicone resin composition. The curable silicone resin composition of Claim 1 or 2 containing the following (E) component.
(E): polyorganosiloxysilalkylene having two or more alkenyl groups and one or more aryl groups in the molecule   Furthermore, the curable silicone resin composition of any one of Claims 1-3 containing fluorescent substance.   Hardened | cured material obtained by hardening the curable silicone resin composition of any one of Claims 1-4.   It is a resin composition for optical semiconductor sealing, The curable silicone resin composition of any one of Claims 1-4.   It is a resin composition for formation of the lens for optical semiconductors, The curable silicone resin composition of any one of Claims 1-4.   An optical semiconductor device comprising: an optical semiconductor element; and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the curable silicone resin composition according to claim 6. .   An optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable silicone resin composition according to claim 7.

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