JP2016186061A - Polysiloxane composition, cured product obtained by curing the composition and semiconductor device using the cured product as sealing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a polysiloxane composition capable of suppressing formation of metal nanoparticles (fine particles) formed by a metal member constituting a semiconductor device and suppressing coloration by metal nanoparticles even when stored at high temperature and high humidity; a cured product obtained by curing the composition; and a semiconductor device using the cured product as a sealing agent.SOLUTION: There is provided a curable resin composition which comprises (A) an organic acid having at least two or more polar groups in the molecule, (B) a polysiloxane composition and (C) a hydrosilylation catalyst. There is provided a curable resin composition in which the carbon number constituting the organic acid (A) is 20 or less and one or more, preferably two or more polar groups are a carboxyl group. There is provided a curable resin composition in which the polysiloxane composition (B) is a compound having an alkenyl group and a compound having a hydrosilyl group.SELECTED DRAWING: None

Description

  The present invention relates to a polysiloxane composition capable of suppressing migration of a metal member by adding an organic acid having at least two polar groups in the molecule, a cured product obtained by curing the composition, and the The present invention relates to a semiconductor device using as a sealant.

  The polysiloxane composition is excellent in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, coloring, non-adhesiveness, and non-corrosion It is used in various industries. For example, in semiconductor device encapsulant applications, many attempts have been made to use polysiloxane-based compositions in place of conventional materials having an epoxy group as the output of devices increases. As described above, the required characteristics required for the encapsulant are increased, and at the same time, there is an increasing demand for each characteristic in an optical semiconductor device such as a light emitting diode (hereinafter abbreviated as “LED”). In particular, discoloration due to migration or the like causes a decrease in luminance, which is an important issue from the viewpoint of increasing the luminance of LEDs.

  As a factor that promotes migration, a material constituting a semiconductor device, for example, a trace amount of ionic components or alkali substances contained in a package resin or a sealing resin is inferred. In Patent Document 1, an ion trapping agent such as hydrotalcite is used. It is disclosed that migration is suppressed by trapping a small amount of ionic components or alkali substances by adding a small amount of ion.

  However, in Patent Document 1, an ion trap agent to be added may be precipitated during curing, and the initial luminance may be lowered by covering the light emitting element.

JP 2003-092379 A

When a polysiloxane composition is used as a sealant for semiconductor devices, the silver plating on the lead frame appears to be colored (discolored) when stored under high temperature and high humidity even when no electric field is applied. discovered. When this phenomenon was examined in detail, the surface of the lead frame was not discolored, and there were fine particles in the encapsulant that clearly differ from the dendrites of migration that occur when an electric field is applied. It was discovered that this is the cause. Accordingly, an object of the present invention is to suppress the generation of the fine particles and suppress the coloring, a cured product obtained by curing the composition, and a semiconductor using the same as a sealing agent. An object is to provide an apparatus.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have suppressed the occurrence of fine particles by adding an organic acid having at least two polar groups in the molecule, thereby suppressing coloring. Invented a polysiloxane composition that can be made.
The gist of the present invention is as follows.
1). (A) an organic acid having at least two polar groups in the molecule;
(B) a polysiloxane composition,
(C) a hydrosilylation catalyst,
A curable resin composition comprising:
2). The curable resin composition according to 1), wherein at least one of the polar groups contained in the organic acid (A) is a carboxy group.
3). The curable resin composition according to 2), wherein at least two of the polar groups contained in the organic acid (A) are carboxy groups.
4). Curable resin composition as described in 3) whose carbon number which comprises the said organic acid (A) is 20 or less.
5). The curable resin composition according to any one of 1) to 4), wherein the polysiloxane composition (B) is a compound having an alkenyl group and a compound having a hydrosilyl group.
6). 6. The polyhedral polysiloxane modified body (B-1) containing a hydrosilyl group is contained in the resin component that constitutes the polysiloxane composition (B), according to any one of 1) to 5). Curable resin composition.
7). The curable resin according to any one of 1) to 6), wherein the polysiloxane composition (B) comprises the following (B-1), (B-2), and (B-3): Composition.
(B-1) Polyhedral modified polysiloxane containing a hydrosilyl group (B-2) Isocyanuric acid derivative containing a hydrosilyl group (B-3) Compound 8 having two or more alkenyl groups). The component (B-1) is a polyhedral polysiloxane compound (a) having an alkenyl group and an organosilicon compound (c) having one alkenyl group in one molecule and / or 1 alkenyl group in one molecule. It is an organically modified polyhedral polysiloxane modified product (B-1 ′) obtained by hydrosilylation reaction of a cyclic olefin compound (d) having one compound with a compound (b) having a hydrosilyl group. Curable composition as described in 6) and 7).
9). The component (a) has the following general formula
[AR ¹ ₂ SiO—SiO _3/2 ] a [R ² ₃ SiO—SiO _3/2 ] b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group 8), characterized in that it is an alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by a group connected to an aryl group or another polyhedral skeleton polysiloxane) Curable resin composition.
10). The curable resin composition according to 8) and 9), wherein the component (b) is a cyclic siloxane containing a hydrosilyl group and / or a linear siloxane.
11). The curable composition according to any one of 1) to 5), wherein the polysiloxane composition (B) is phenyl silicone.
12). The curable composition according to any one of 1) to 5), wherein the polysiloxane composition (B) is methyl silicone.
13). A cured product obtained by curing the curable resin composition according to any one of 1) to 12).
14). A semiconductor device obtained by sealing and curing the curable resin composition of 1) to 12).
15). 14. The semiconductor device according to 14), which is an optical semiconductor device in which silver is plated on the surface of the lead frame.

A polysiloxane composition capable of suppressing the generation of fine particles even when no electric field is applied and suppressing coloring, a cured product obtained by curing the composition, and a semiconductor using the polysiloxane composition as a sealant Providing equipment.

It is a schematic sectional drawing of the surface mount type light emitting diode (LED) which is an example of the optical semiconductor device of this invention.

Hereinafter, the present invention will be described in detail.
<(A) Organic acid having at least two polar groups in the molecule>
In the present invention, (A) the polar group of the organic acid having at least two polar groups in the molecule may be a group having a polarity composed of carbon atom, hydrogen atom, nitrogen atom, oxygen atom and sulfur atom. There is no particular limitation. Examples of polar groups are hydroxy, amino, hydroxyamino, cyano, epoxy, acetyl, carboxy, thiol, vinyl, allyl, phenyl, naphthyl, and the following general formula (1) Is a functional group represented

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ³ may be different or the same.)

Furthermore, from the viewpoint of compatibility with the polysiloxane composition, a hydroxyl group, amino group, acetyl group, carboxy group, thiol group, vinyl group, allyl group, phenyl group, naphthyl group, and a functional group represented by the following general formula desirable.

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ³ may be different or the same.)
One or more of these polar groups may be present in one molecule.

  The organic acids shown here are not only those having a carboxy group or a sulfo group in the molecule, but also compounds containing weakly acidic functional groups exemplified by hydroxy groups and thiol groups as organic acids. Among the compounds having the functional group shown, compounds having at least one or more of the polar groups in the molecule may be mentioned. Examples of organic acids having at least two polar groups in the molecule include α-hydroxy acid, β-hydroxy acid, γ-hydroxy acid, lactic acid, 3-hydroxypropanoic acid, glyceric acid, 2-hydroxy Butyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, acrylic acid, methacrylic acid, crotonic acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinaleic acid, linoleic acid, linolenic acid, arachidonic acid, cerebonic acid, quinic acid , Shikimic acid, caffeic acid, cinnamic acid, chlorogenic acid, ferulic acid, salicylic acid, acetylsalicylic acid, 4-hydroxymethylbenzoic acid, 2-hydroxymethylbenzoic acid, 4-hydroxy-3-methoxybenzoic acid, 2,3- Dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, , 6-Dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, orthothelic acid, 3,4,5-trihydroxybenzoic acid, 2,4,6 -Trihydroxybenzoic acid, 3,4,5-trimethoxybenzoic acid, 4-hydroxy-3,5-dimethoxybenzoic acid, mandelic acid, benzylic acid, atrolactic acid, phloretic acid, melitroic acid, coumaric acid, umbelic acid, sinapine Monocarboxylic acids having one carboxyl group and aromatic ring in the molecule such as acid, pyruvic acid and toluic acid, and one or more polar groups such as hydroxyl group and acyl group, alanine, arginine, asparagine, cysteine (sulfur, Amino), glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine (thi ), Phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, hydroxylysine, cidroxyproline, thyroxine, sarcosine, ornithine, citrulline, and so on. Monocarboxylic acids represented by amino acids having, oxalacetic acid, 2-hydroxymalonic acid, 2-hydroxybutanedioic acid, 2-methyl-2-hydroxymalonic acid, fumaric acid, maleic acid, tartaric acid, malonic acid, adipic acid, Molecules such as 2-methyl-2-hydroxybutanoic acid, itaconic acid, citraconic acid, mesaconic acid, succinic acid, succinic acid, gluconic acid, oxalic acid and other dicarboxylic acids having two carboxyl groups in the molecule, aspartic acid, glutamic acid, cystine, etc. With two carboxyl groups Dicarboxylic acids represented by amino acids having one or more amino groups, citric acid, isocitric acid, cis-aconitic acid, trans-aconitic acid, trimellitic acid, 1,2,3-propanetricarboxylic acid, 1,2,4 -Tricarboxylic acids having three carboxyl groups in the molecule such as butanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,3,5-hexanetricarboxylic acid, 2,34-butanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid , 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid, ethylenediaminetetraacetic acid, desmosine Tetracarboxylic acids having a carboxyl group, dodecyl benzene sulfonic acid, aryl sulfonic acids such as p- toluenesulfonic acid.

  Among these organic acids, oxalacetic acid, 2-hydroxymalonic acid, 2-hydroxybutanedioic acid, 2-methyl-2-hydroxymalonic acid, fumaric acid, malein from the viewpoint of easy coordination to metal Acid, tartaric acid, malonic acid, 2-methyl-2-hydroxybutanoic acid, itaconic acid, citraconic acid, mesaconic acid, succinic acid, oxalic acid, aspartic acid, glutamic acid, cystine, citric acid, isocitric acid, cis-aconitic acid, trans-aconitic acid, trimellitic acid, 1,2,3-propanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2 Tricarboxylic acids having three carboxyl groups in the molecule, such as 1,3,5-hexanetricarboxylic acid, Butanetetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′ 4,4'-diphenyl ether tetracarboxylic acid, ethylenediaminetetraacetic acid, desmosine and other tetracarboxylic acids having four carboxyl groups in the molecule are preferred.

  Further, from the viewpoint of availability, 2-hydroxybutanoic acid, fumaric acid, maleic acid, tartaric acid, malonic acid, itaconic acid, aspartic acid, glutamic acid, citric acid, aconitic acid, trimellitic acid, 1,2,3-propane Tricarboxylic acid and ethylenediaminetetraacetic acid are preferred.

  One or more selected from the group consisting of these compounds can be added. Moreover, as an addition method, it may be added as it is, or may be added after diluted in an organic solvent. Examples of organic solvents that can be used include organic solvents such as methanol, ethanol, propyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, dimethyl ether, diethyl ether, hexane, toluene, and xylene. These solvents can be used alone or in combination of two or more. You may combine.

  There is no restriction | limiting in particular in the usage-amount of the organic acid in this invention, Although arbitrary amounts can be used, if it dares to illustrate, when the polysiloxane composition is made into 100 weight%, (B) polysiloxane composition Preferably it is 0.0000001-10 weight% in a thing, More preferably, it is 0.000001-1 weight%. If the amount of organic acid added is small, the effect of suppressing the generation of fine particles (metal nanoparticles: silver nanoparticles in this case) that are generated even when no electric field is applied may be insufficient, and coloring may occur. If the amount of the acid added is large, the polysiloxane composition may be decomposed to deteriorate the resin performance.

  The cause of the generation of fine particles in the optical semiconductor device (in the encapsulant) is not clear even when no electric field is applied, but the fine particles are detected by a scanning transmission electron microscope-energy dispersive X-ray spectrometer. When observed, it was found that the size was about 10 to 200 nm and that the particles were silver nanoparticles.

For this reason, the study was conducted assuming that metal nanoparticles were generated (synthesized) in the optical semiconductor device.
One method for synthesizing metal nanoparticles is a chemical reduction method. This is a method in which a metal compound is reacted with a reducing agent in a reaction mixture containing a metal compound, a reducing agent, a stabilizer, and a solvent to form metal nanoparticles having stabilizer molecules on the surface. It was assumed that such a reaction occurred in the optical semiconductor device. The presumed mechanism that metal nanoparticles (Mn) are generated in the optical semiconductor device is as follows.

Oxides MO and metal salts M ⁺ P ⁻ are formed on the metal surface due to the usage environment of the optical semiconductor device and trace components contained in the raw materials used.
M (metal) → MO (metal oxide) or M ⁺ P ⁻ (metal salt)
These metal oxides MO and metal salts M ⁺ P ⁻ are subjected to a reduction reaction by hydrosilyl groups contained in the polysiloxane composition to form metal nanoparticles Mn.
MO (metal oxide) or M ⁺ P ⁻ (metal salt) → Mn (metal nanoparticles)
The metal nanoparticles (Mn) are stabilized by the structure L that is easily coordinated to the metal in the polysiloxane composition, so that they diffuse into the polysiloxane resin near the silver-plated lead frame, and coloring (according to plasmon absorption) Inferred). The structure L that stabilizes the metal nanoparticles is a component that is easily coordinated to a metal, and is a cyclic structure formed from only carbon atoms such as benzene, naphthalene, and anthracene contained in polysiloxane, cyanuric acid, and isocyanuric acid. , Triazine, pyridine, pyrazine, imidazoline, thiazine, oxazole, thiophene, thiazole, indole, isoindole, benzimidazole, quinoline, isoquinoline, quinoxaline, acridine, xanthene, carbazole, etc. A structure is assumed.
Mn (metal nanoparticles) → MnL (stabilized metal nanoparticles)
That is, it was estimated that the hydrosilyl group contained in the polysiloxane composition is a factor that generates metal nanoparticles, and that it is the structure that stabilizes the metal nanoparticles in the polysiloxane composition that promotes it.

Next, an estimation mechanism for suppressing the metal nanoparticles Mn generated from the metal member constituting the semiconductor device by the organic acid (component (A)) having at least two polar groups in the molecule will be described.
The metal oxide MO and the metal salt M ⁺ P ⁻ form a complex before undergoing a reduction reaction by a hydrosilyl group, and the complex is stabilized, whereby the reduction reaction to Mn (metal nanoparticle) by the hydrosilyl group. It was speculated that the generation of metal nanoparticles could be suppressed if the above could be suppressed. Based on the reasoning, the component (A) (the following formula Q) was selected.
MO (metal oxide) or M ⁺ P ⁻ (metal salt) → M ⁺ Q ⁻ (acid coordination complex)
Further, it is assumed that this estimation mechanism can suppress the formation of metal nanoparticles generated regardless of the influence of the electric field generated from the semiconductor device.
That is, component (A) can be rephrased as an organic acid that can be coordinated before MO (metal oxide) or metal salt M ⁺ P ⁻ undergoes a reduction reaction with a hydrosilyl group.

<Polysiloxane composition (B)>
The polysiloxane composition (B) in the present invention may be any resin that can cure a compound having an alkenyl group and a compound having a hydrosilyl group by a hydrosilylation reaction using a hydrosilylation catalyst described later. The structure may be any as long as it has a linear, branched, cyclic and three-dimensional crosslinked structure.

Although it does not specifically limit as an example of a linear (B) component, General formula (2)
R ⁴ R ⁵ SiO ₂ (2)
(In the formula, R ⁴ is an alkenyl group or a hydrosilyl group, and R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group and a hydrosilyl group, which may be the same or different.) And a compound having two or more alkenyl groups and / or hydrosilyl groups per molecule at the terminal or side chain.

  Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups and hydrosilyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. An aryl group such as a group, or the same selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc. Alternatively, a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which is different or unsubstituted, can be exemplified.

  Although it does not specifically limit as an example of cyclic | annular (B) component, It has the cyclic structure represented by following General formula (3) as a main structure, and has 2 or more alkenyl groups and / or hydrosilyl groups per molecule. Compounds.

(In the formula, R ⁴ is an alkenyl group or a hydrosilyl group, and R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group and a hydrosilyl group, which may be the same or different.)
Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups and hydrosilyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. An aryl group such as a group, or the same selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc. Alternatively, a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which is different or unsubstituted, can be exemplified.

Although it does not specifically limit as an example of (B) component which has a three-dimensional crosslinked structure, following General formula (4)
SiO _4/2 (4)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by the following general formulas (5) and (6).
R ⁴ R ⁵ ₂ SiO _1/2 (5)
R ⁵ ₃ SiO _1/2 (6)
(In the formula, R ⁴ is an alkenyl group or a hydrosilyl group, and R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group and a hydrosilyl group, which may be the same or different.) The terminal of the main structure is the following general formula (7), which is blocked with a monofunctional structural unit represented by
R ⁴ R ⁵ ₂ SiO _1/2 (7)
And having at least two blocked structures.

  Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups and hydrosilyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. An aryl group such as a group, or the same selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc. Alternatively, a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which is different or unsubstituted, can be exemplified.

  Although the polysiloxane composition in this invention is not specifically limited, For example, the polysiloxane composition containing the polyhedral polysiloxane modified body (B-1) containing phenyl silicone, methyl silicone, and a hydrosilyl group etc. are mentioned. Among them, from the viewpoint that the resin composition has a structure L that stabilizes the metal nanoparticles (fine particles) described above, and the coloration due to the formation of metal nanoparticles is likely to occur, and the effect of adding the component (A) is high. A polysiloxane composition comprising phenylsilicone, an isocyanuric acid derivative (B-2) containing a component (B-1) and a hydrosilyl group, and a compound (B-3) having two or more alkenyl groups is preferred.

  The siloxane unit of phenyl silicone always includes a phenyl siloxane unit, and examples thereof include methyl phenyl siloxane and diphenyl siloxane. Examples of methylsilicone include polysiloxane compounds that do not have phenylsiloxane units and have dimethylsiloxane units as the main component.

  Specific examples of phenyl silicone include OE-6630 manufactured by Toray Dow Corning, and specific examples of methyl silicone include JCR-6140 manufactured by Toray Dow Corning. Details of (B-1), (B-2), and (B-3) are shown below.

<Modified polyhedral polysiloxane containing hydrosilyl groups (B-1)>
The polyhedral polysiloxane modified body (B-1) containing a hydrosilyl group in the present invention is not particularly limited as long as it is a polyhedral polysiloxane compound containing a hydrosilyl group in the molecular skeleton. For example, it contains an alkenyl group. The polyhedral polysiloxane compound can be obtained by modifying a compound having a hydrosilyl group capable of hydrosilylation reaction. The modified polyhedral polysiloxane obtained in the present invention is preferably in a liquid state at a temperature of 20 ° C. from the viewpoints of handling properties and moldability.

The preferable polyhedral polysiloxane modified body (B-1) in the present invention will be specifically described. A preferred polyhedral polysiloxane-modified product in the present invention is characterized in that [XR ⁶ ₂ SiO—SiO _3/2 ] is an essential unit as a siloxane unit having a reactive functional group, and, if necessary, An arbitrary siloxane unit [R ⁷ ₃ SiO—SiO _3/2 ] as a physical property adjusting unit is contained as a structural unit, and the following general formula (8),
[XR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ ₃ SiO—SiO _3/2 ] _b (8)
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; X is the following general formula (9)

Or the following general formula (10)

R ⁶ is an alkyl group or an aryl group; R ⁷ is a group linked to an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or another polyhedral polysiloxane) A polyhedral polysiloxane modified body composed of siloxane units is exemplified. Here, a is an average of 1 or more, preferably 2 or more, and b is 0 or an integer of 1 or more. a + b is an integer of 6 to 24, preferably an integer of 6 to 12.
(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, it may be the same or different, provided that at least one of Y or Z is an alkenyl group or a hydrogen atom; R is an alkyl group or an aryl group; 9) or the structure of formula (10) may be different, or the structure of formula (9) or formula (10) may be mixed)
Hereinafter, a siloxane unit having a reactive functional group
[XR ⁶ ₂ SiO—SiO _3/2 ]
Will be described in detail.

  The siloxane unit having a functional group capable of reacting, for example, causes a crosslinking reaction with a curing agent by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later, or in the presence of a thermal curing initiator or a photocuring initiator. It is a unit that plays a role of crosslinking and curing.

  The modified polyhedral polysiloxane containing a hydrosilyl group of the present invention has a structure of the formula (9) or the formula (10) as the group X having a reactive functional group, and contains at least one hydrosilyl group. Although it will not specifically limit if it is a modified body, it is preferable that m is an integer of 1-7, and it is preferable that n is an integer of 2-4.

As R ⁶ in the siloxane unit having a reactive functional group, a substituent having substantially no reactivity, specifically, for example, an alkyl group or an aryl group can be used.

  The siloxane unit having a functional group capable of reacting in the present invention preferably contains, on average, two or more siloxane units constituting the polyhedral skeleton. That is, a in general formula (8) is preferably 2 or more. When there are few siloxane units containing the reactive functional group to contain, sclerosis | hardenability will become inadequate and there exists a possibility that the intensity | strength of the hardened | cured material obtained may fall.

Then any siloxane unit
^{_{[R 7 3 SiO-SiO 3/2}} ]
Will be described.
This siloxane unit is a unit for adjusting the physical properties of the modified polyhedral polysiloxane and the resulting cured product in the present invention. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

As R ⁷ in the present siloxane unit, an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group connected to another polyhedral polysiloxane can be preferably used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. May be replaced. Specific examples of the alkyl group partially substituted with a substituent having substantially no reactivity include, for example, a polysiloxanylalkyl group. Leveling properties and film properties, and a curing agent described later and Compatibility with a curing initiator can be imparted, and the properties of the compound can be made liquid.
The modified polyhedral polysiloxane (B-1) in the present invention is preferably an organic modified polyhedral polysiloxane (B-1) ′ described later from the viewpoint of gas barrier properties.

<Organic modified polyhedral polysiloxane modified (B-1) '>
The modified organic polyhedral polysiloxane (B-1) ′ according to the present invention includes a polyhedral polysiloxane compound (a) having an alkenyl group and an alkenyl group in one molecule in the presence of a hydrosilylation catalyst described later. It can be obtained by hydrosilylation reaction of the organosilicon compound (c) having 1 and / or the cyclic olefin compound (d) having 1 alkenyl group in one molecule with the compound (b) having a hydrosilyl group. The method for obtaining the organically modified polyhedral polysiloxane modified body (B-1) ′ of the present invention is not particularly limited and can be variously set, but after reacting the component (a) and the component (b) in advance, (C) and / or (d) component may be reacted, or (c) and / or (d) component and (b) component are reacted in advance, and then (a) component is reacted. The component (a) and the component (c) and / or the component (d) may be allowed to coexist and react with the component (b). After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound that does not contain the component (a) in which only the component (c) and / or the component (d) and the component (b) are reacted, the component (a) and the component (b) are reacted, A method of reacting the components (c) and / or (d) after distilling off the unreacted component (b) is preferred.
Part of the alkenyl group of the component (a) used in the reaction may remain in the organically modified polyhedral polysiloxane modified product (B-1) ′ thus obtained.

Although there is no restriction | limiting in particular as an addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of the organic modification polyhedral polysiloxane modified body (B-1) ', (a) component used for reaction, and (c) and / or (d It is good to use in the range of 10 ^{< -1} > ^-10 < ^-10 > mol with respect to 1 mol of alkenyl groups of a component. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The organically modified polyhedral polysiloxane modified body (B-1) ′ thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further introduces a hydrosilyl group into the molecule. Therefore, it can be reacted with a compound having various alkenyl groups. Specifically, a cured product can be obtained by reacting with a compound (B-3) having two or more alkenyl groups in one molecule described later.

In addition, the organically modified polyhedral polysiloxane modified body (B-1) ′ in the present invention can be liquefied at a temperature of 20 ° C. The organically modified polyhedral polysiloxane modified (B-1) ′ is preferably in a liquid form because it is excellent in handling properties.
The organically modified polyhedral polysiloxane modified body (B-1) ′ in the present invention is represented by the general formula (11).
[XR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ ₃ SiO—SiO _3/2 ] _b (11)
[A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ⁶ is an alkyl group or an aryl group; R ⁷ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure of the following general formula (12) or general formula (13), and when there are a plurality of X, the general formula (12 ) Or the structure of the general formula (13) may be different, or the structure of the general formula (12) or the general formula (13) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Which may be the same or different. Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain, which may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (14).
^{_{- [CH 2] l -R 8}} (14)
(L is an integer of 0 or more; R ⁸ is a group containing an organosilicon compound or a residue of the component (d) after hydrosilylation); R is an alkyl group or an aryl group}]
It is a polyhedral polysiloxane compound composed of siloxane units represented by the formula:

The polyhedral polysiloxane modified body (B-1) ′ thus obtained is modified by controlling the amount of components (a) to (d) added, the reaction sequence, the reaction time, the reaction temperature, and the like. It is possible to control the viscosity of the modified polyhedral polysiloxane (B-1) ′. It is also possible to adjust the viscosity of the polysiloxane composition (B) by controlling the viscosity of the modified polyhedral polysiloxane (B-1) ′. The viscosity of the modified polyhedral polysiloxane (B-1) ′ is not particularly limited, but when the modified polyhedral polysiloxane (B-1) ′ is liquid at a temperature of 20 ° C., the viscosity at 20 ° C. The pressure is preferably 0.01 Pa · s to 500 Pa · s, more preferably 1 Pa · s to 300 Pa · s. If the modified polyhedral polysiloxane (B-1) ′ has a too low viscosity, the polysiloxane composition described later has a low viscosity, and additives such as phosphors may settle without being dispersed. If the viscosity is too high, the handling property may be deteriorated.
In addition, the organically modified polyhedral polysiloxane modified body (B-1) ′ has at least three hydrosilyl groups in the molecule from the viewpoint of the strength and hardness of the resulting cured product, and further, heat resistance and light resistance. It preferably has a group.

<Polyhedral polysiloxane compound (a) having an alkenyl group>
The polyhedral polysiloxane compound (a) having an alkenyl group in the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. Specifically, for example, the following general formula (15)
[R ⁹ SiO _3/2 ] _x [R ¹⁰ SiO _3/2 ] _y (15)
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁹ is an alkenyl group or a group having an alkenyl group; R ¹⁰ is any organic group, or An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by a group linked to other polyhedral skeleton polysiloxanes can be suitably used. Furthermore, the following general formula (16)
[AR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ ₃ SiO—SiO _3/2 ] _b (16)
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ⁶ is an alkyl group or an aryl group; R ⁷ is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of siloxane units represented by the formula:

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ⁶ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ⁶ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.
R ⁷ is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ⁷ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

  a is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more, from the handleability of the compound and the physical properties of the resulting cured product. Further, b is not particularly limited as long as it is 0 or an integer of 1 or more.

The sum of a and b (= a + b) is an integer from 6 to 24, but from the viewpoint of the stability of the compound and the stability of the resulting cured product, it should be 6 to 12, and more preferably 6 to 10. preferable.
The method for synthesizing the component (a) is not particularly limited, and the component can be synthesized using a known method. As a synthesis method, for example, a silane of R ¹¹ SiX ^a ₃ (wherein R ¹¹ represents R ⁶ or R ⁷ described above, and X ^a represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by the hydrolysis condensation reaction of the compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolysis and condensation reaction of R ¹¹ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds, and the polyhedron Methods for synthesizing structural polysiloxanes are also known.

  In addition, for example, there is a method of hydrolytic condensation of tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide. In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polyhedral polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded through a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

<Compound (b) having hydrosilyl group>
The compound (b) having a hydrosilyl group used in the present invention is not particularly limited as long as it has one or more hydrosilyl groups in the molecule, but the obtained polyhedral polysiloxane modified product has transparency, heat resistance, From the viewpoint of light resistance, it is preferably a siloxane compound having a hydrosilyl group, and more preferably a cyclic siloxane having a hydrosilyl group or a linear polysiloxane. In particular, from the viewpoint of gas barrier properties, a cyclic siloxane is preferable.

  The linear polysiloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked at the end with dimethylhydrogensilyl groups, polyblocked at the ends with dimethylhydrogensilyl groups Examples thereof include diphenylsiloxane and polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group.

  In particular, as a linear polysiloxane having a hydrosilyl group, a polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group from the viewpoints of reactivity during modification, heat resistance of the resulting cured product, light resistance, etc. Furthermore, polydimethylsiloxane having a molecular end blocked with a dimethylhydrogensilyl group can be suitably used. Specific examples thereof include tetramethyldisiloxane and hexamethyltrisiloxane.

Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1. , 3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Specific examples of the cyclic siloxane in the present invention include, for example, 1,3,5,7-tetrahydro, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the resulting cured product. Gen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.
These compounds (b), which have a hydrosilyl group, may be used alone or in combination of two or more.

<Organic silicon compound (c) having one alkenyl group in one molecule>
In the present invention, the organosilicon compound (c) having one alkenyl group per molecule reacts with the hydrosilyl group of the compound (b) having a hydrosilyl group. By using the component (c), the elastic modulus of the obtained cured product can be reduced, and the thermal shock resistance can be improved.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.
The component (c) in the present invention is not particularly limited as long as it is an organosilicon compound having one alkenyl group in one molecule, but it is a gas barrier that at least one aryl group is contained in one molecule. From the viewpoint of heat resistance and refractive index, it is more preferable that the aryl group is directly bonded to the silicon atom from the viewpoint of heat resistance and light resistance.

The component (c) in the present invention is preferably silane or polysiloxane from the viewpoints of heat resistance and light resistance. When the component (c) is a silane having one alkenyl group in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane And ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane, and the like. Among these, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane are also preferable from the viewpoint of gas barrier properties and refractive index. Triphenylvinylsilane is a preferred example.
In addition, when the component (c) is a polysiloxane, examples include a linear polysiloxane having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and a cyclic siloxane having one alkenyl group. .

  When the component (c) is a linear polysiloxane having one alkenyl group, specifically, for example, polydimethylsiloxane, dimethylvinyl each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Polymethylphenylsiloxane blocked with a silyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group respectively, and terminated with a dimethylvinylsilyl group and a trimethylsilyl group A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit, each of which is blocked one by one, a dimethylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Copolymers, copolymers of terminal and methylphenylsiloxane units and diphenylsiloxane units are blocked one by one, respectively dimethylvinylsilyl group and trimethylsilyl group and the like.

In the case of a polysiloxane having one alkenyl group at the molecular end, specifically, for example, polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit, SiO _{3 /} Examples include at least one siloxane unit selected from the group consisting of ₂ units, SiO units, and SiO _1/2 units, and polysiloxane composed of one dimethylvinylsiloxane unit.
When the component (c) is a cyclic siloxane having one alkenyl group, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl -3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1 -Vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane and the like are exemplified.
These (c) component organosilicon compounds having one alkenyl group per molecule may be used alone or in combination of two or more.

<Cyclic olefin compound (d) having one alkenyl group in one molecule>
(D) component in this invention should just be a cyclic olefin compound which has one carbon-carbon double bond in 1 molecule, and this carbon-carbon double bond is any of a vinylene group, a vinylidene group, and an alkenyl group. It may be. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.
In addition, the component (d) in the present invention preferably has an average molecular weight of 1000 or less from the viewpoint of reactivity with the component (b). Examples of such cyclic olefin compounds include aliphatic cyclic olefin compounds and substituted aliphatic cyclic olefin compounds.

  Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptene, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, and methylenecyclohexane. It is done.

  Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, z2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, 7-allylnorbornane, 2-methylene norbornane, 7-methylene norbornane, camphene, vinyl norcamphene, 6-methyl-5-vinyl-bicyclo [2,2,1] -heptane, 3-methyl-2-methylene-bicyclo [2,2,1 ] -Heptane, α-pinene, β-pinene, 6,6-dimethyl-bicyclo [3,1,1] -2-heptaene, 2-vinyladamantane, 2-methyleneadamantane and the like.

Among these, cyclohexene, vinylcyclohexane, norbornene, camphene, and pinene are preferable examples from the viewpoint of availability.
These cyclic olefin compounds (d) having one alkenyl group in one molecule may be used alone or in combination of two or more.

  The amount of the cyclic olefin compound (d) having one alkenyl group in one molecule is such that the number of alkenyl groups in the component (d) is 0 per hydrosilyl group of the compound (b) having a hydrosilyl group described later. It is preferable to use so that it may become 0.01-0.5 piece. When the addition amount is small, the thermal shock resistance of the resulting cured product may be lowered, and when the addition amount is large, a curing failure may occur in the resulting cured product.

<Isocyanuric acid derivative containing hydrosilyl group (B-2)>
Next, the isocyanuric acid derivative (B-2) containing a hydrosilyl group used in the present invention will be described.
The component (B-2) of the present invention is obtained by subjecting an organic compound (f) having an alkenyl group and an isocyanuric ring skeleton to a compound (b) having a hydrosilyl group in the presence of a hydrosilylation catalyst described later. It is done. A method for obtaining a compound having both an isocyanuric ring skeleton and a siloxane skeleton and a SiH group in one molecule is not particularly limited. As an example, after reacting the component (f) with a large excess of the component (b) For example, volatile unreacted components can be distilled off under reduced pressure and heating conditions.
In the component (B-2) thus obtained, a part of the alkenyl group of the component (f) used in the reaction may remain.

  The amount of component (b) added is preferably 2 to 20 hydrosilyl groups, more preferably 2.5 to 15 with respect to one alkenyl group of component (f). 10 to 10 is even more preferable. When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handling property of the modified organopolysiloxane may be inferior, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

Although there is no restriction | limiting in particular as addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of an organopolysiloxane modified body, It uses in the range of 10 ^{< -1} > ^-10-10 mol with respect to 1 mol of alkenyl groups of (f) component used for reaction. It is good. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.
The isocyanuric acid derivative (B-2) containing a hydrosilyl group in the present invention is preferably an isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group described later from the viewpoint of gas barrier properties. .

<Isocyanuric acid derivative containing organically modified hydrosilyl group (B-2) '>
In the present invention, an isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group includes an organic compound (f) having an alkenyl group and an isocyanuric ring skeleton in the presence of a hydrosilylation catalyst described later, and an alkenyl group. It can be obtained by subjecting a compound (g) contained in one molecule to a hydrosilylation reaction with a compound (b) having a hydrosilyl group.

The method for obtaining the isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group of the present invention is not particularly limited and can be variously set, but the (f) component and the (b) component are reacted in advance. Thereafter, the component (g) may be reacted, or (g
The component (f) may be reacted with the component (f) after reacting the component (b) with the component (b), or may be reacted with the component (b) in the presence of the component (f) and the component (g). After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound containing only the component (f) and the component (b) and not including the component (g), the component (g) and the component (b) are reacted to form an unreacted (g) A method in which the component (f) is reacted after the component is distilled off is preferred.
In the isocyanuric acid derivative containing the organically modified hydrosilyl group thus obtained, a part of the alkenyl group of the component (f) used in the reaction may remain.

Although there is no restriction | limiting in particular as addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of the isocyanuric acid derivative (B-2) 'containing the organically modified hydrosilyl group, (f) component used for reaction and (g) component alkenyl It is good to use in the range of 10 ^{< -1} > ^-10 < ^-10 > mol with respect to 1 mol of group. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group thus obtained can ensure compatibility with various compounds, particularly siloxane-based compounds and isocyanuric acid derivatives. Since a hydrosilyl group is introduced into the compound, it can be reacted with a compound having various alkenyl groups. Specifically, a cured product can be obtained by reacting with a compound (B-3) having two or more alkenyl groups in one molecule described later.

  The isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group thus obtained has the following contents: (f) and (g), (b) component addition amount, reaction sequence, reaction time, reaction By controlling the temperature and the like, the viscosity of the isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group can be controlled. It is also possible to adjust the viscosity of the polysiloxane composition (B) by controlling the viscosity of the isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group. The viscosity of the isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group is not particularly limited, but the isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group has a temperature of 20 ° C. In the case of liquid, the viscosity at 20 ° C. is preferably 0.01 Pa · s to 500 Pa · s, more preferably 1 Pa · s to 300 Pa · s. If the viscosity of the isocyanuric acid derivative (B-2) ′ containing an organically modified hydrosilyl group is too low, the viscosity of the polysiloxane composition described below will be low, and additives such as phosphors may settle without dispersing. There is. If the viscosity is too high, the handling property may be deteriorated.

  Further, at least three isocyanuric acid derivatives (B-2) ′ containing an organically modified hydrosilyl group are present in the molecule from the viewpoint of the strength and hardness of the resulting cured product, and further, heat resistance and light resistance. It preferably has a hydrosilyl group.

<Organic compound (f) having alkenyl group and isocyanuric ring skeleton>
The organic compound (f) having an alkenyl group and an isocyanuric ring skeleton of the present invention is not particularly limited as long as it is an organic compound having an alkenyl group and an isocyanuric ring skeleton, but the transparency, heat resistance, and light resistance of the polysiloxane composition are not limited. From the viewpoint of properties, an organic compound represented by the following general formula (17) is preferable.

(Wherein R ¹² represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ¹² may be different or the same.)
(F) Component skeleton may have a functional group other than an alkenyl group and an isocyanuric ring skeleton, but (B-2) component (B-1) component and (B) which are reactants obtained. -3) From the viewpoint of compatibility with the component, it is preferably a functional group having a low polarity including a linear aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, From the viewpoint of light resistance, a methyl group is particularly preferable.

  The component (f) is represented by the above general formula (17), for example, from the viewpoint of adhesion to the substrate when the curable composition is cured with the substrate, and 1 alkenyl group is contained in one molecule. It is preferably an isocyanuric acid derivative containing at least one, and from the viewpoint of a balance between heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl isocyanurate, Monoallyl dimethyl isocyanurate and monoallyl diglycidyl isocyanurate are more preferable, and triallyl isocyanurate, diallyl monomethyl isocyanurate, and diallyl monoglycidyl isocyanurate are more preferable. These may be used alone or in combination of two or more.

<Compound (g) containing one alkenyl group in one molecule>
The component (g) is not particularly limited as long as it is a compound containing one alkenyl group in one molecule, but the component (g) is a siloxane such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer. It is preferable not to include a unit (Si—O—Si) but to include only C, H, N, O, S, and halogen as constituent elements.

  The compound (g) can be classified into a polymer compound and a monomer compound.

  Examples of the polymer compound include polysiloxane, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde ( Phenol resin type) and polyimide type compounds can be used.

  Examples of monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as straight-chain and alicyclics: heterocyclic compounds, and silicon-based compounds. Examples thereof include compounds and mixtures thereof.

  The alkenyl group of the component (g) is not particularly limited, and examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group. From the viewpoint of heat resistance and light resistance, a vinyl group and an allyl group are exemplified. Groups are preferred.

  Specific examples of the component (g) include ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1- Undecene, linearene manufactured by Idemitsu Petrochemical Co., Ltd., 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1-pentene Chain aliphatic hydrocarbon compounds such as cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, allylcyclohexyl, cyclic aliphatic such as camphene, carene, α-pinene, β-pinene, etc. Hydrocarbon compounds, styrene, α-methylstyrene, indene, phenylacetylene, 4-ethynyl Aromatic hydrocarbon compounds such as ruene, allylbenzene, 4-phenyl-1-butene, allyl ethers such as alkyl allyl ether, allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl Aliphatic compounds such as -1,3-dioxolan-2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene, allylanisole, o-allylphenol, monoallyldibenzylisocyanate Examples thereof include substituted isocyanurates such as nurate and monoallyldiglycidyl isocyanurate, and silicon compounds such as vinyltrimethylsilane, vinyltrimethoxysilane, vinyldimethylphenylsilane, vinylmethyldiphenylsilane, and vinyltriphenylsilane. Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.

  The structure may be linear or branched, and the molecular weight is not particularly limited, and various types can be used. The molecular weight distribution is not particularly limited, but in terms that the viscosity of the reaction product tends to be low, the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and preferably 1.5 or less. Further preferred.

  In the case where the glass transition temperature of the component (g) is present, there is no particular limitation on this, and various materials are used. However, the glass point transfer temperature is 100 ° C. or less in that the obtained cured product tends to be tough. It is preferably 50 ° C. or lower, more preferably 0 ° C. or lower. Examples of preferred resins include polybutyl acrylate resins. Conversely, the glass transition temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, in that the heat resistance of the cured product obtained is increased. Most preferably, it is 170 ° C. or higher. The glass transition temperature can be determined as a temperature at which tan δ exhibits a maximum in the dynamic viscoelasticity measurement.

  The component (g) is preferably an aliphatic hydrocarbon compound in that the light resistance of the resulting cured product is increased. In this case, the preferable lower limit of the carbon number is 2, and the preferable upper limit of the carbon number is 10.

  The component (g) is preferably an aromatic hydrocarbon compound in that the heat resistance of the resulting cured product is increased. In this case, the preferable lower limit of the carbon number is 7, and the preferable upper limit of the carbon number is 10.

  (G) As a component, you may have another reactive group. Examples of the reactive group in this case include an epoxy group, an amino group, a radically polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, an alkoxysilyl group, a vinyloxyl group, and an acid anhydride group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high. Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyl vinyl ether, allyl methacrylate, allyloxyethyl methacrylate, allyl acrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, 4-vinylcyclohexene-1-oxide and the like. It is done.

  The molecular weight of the component (g) is preferably 500 or less, more preferably 300 or less, from the viewpoint that the viscosity is easy to handle.

  As the above component (g), a single component may be used, or a plurality of components may be used in combination.

<Compound (B-3) having two or more alkenyl groups>
The compound (B-3) used in the present invention is not particularly limited as long as it is a compound having two or more alkenyl groups in one molecule.

  The amount of the compound (B-3) added can be variously set, but the hydrosilyl group contained in the compounds (B-1) and (B-2) is 0.3 to 0.3 per alkenyl group of the compound (B-3). It is desirable to add five, preferably 0.5-3. When the proportion of alkenyl groups is small, appearance defects due to foaming or the like are likely to occur, and when the proportion of alkenyl groups is large, physical properties after curing may be adversely affected.

  Here, examples of the compound (B-3) include polysiloxane (B-3a) having two or more alkenyl groups in one molecule, and an organic compound (B-3b) described later. It is not limited to. In addition, you may use together the (B-3a) component and the (B-3b) component.

<Polysiloxane (B-3a) having two or more alkenyl groups in one molecule>
The number of siloxane units of the polysiloxane (B-3a) having two or more alkenyl groups in one molecule that can be contained in the curable composition of the present invention is not particularly limited, but preferably two or more, and more preferably. Is 2-10. When the number of siloxane units in one molecule is small, the composition tends to volatilize, and desired physical properties may not be obtained after curing. Moreover, when there are many siloxane units, the gas barrier property of the obtained hardened | cured material may fall.

  The polysiloxane having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. In addition, in the polysiloxane having two or more alkenyl groups in one molecule having an aryl group, the aryl group is preferably bonded directly to the Si atom from the viewpoint of heat resistance and light resistance. In addition, the aryl group may be present at either the side chain or the end of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited. For example, the aryl group-containing polysiloxane has a straight chain, branched chain, or partially branched chain. In addition to the chain shape, it may have a cyclic structure.

  Examples of such aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, and 4-ethylphenyl. Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethyl Examples include phenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group and the like. . Among these, a phenyl group is a preferred example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

  The polysiloxane having two or more alkenyl groups in one molecule in the present invention is a linear polysiloxane having two or more alkenyl groups from the viewpoint of heat resistance and light resistance, and two or more alkenyl groups at the molecular ends. Preferred examples include polysiloxanes having a cyclic structure and cyclic siloxanes having two or more alkenyl groups.

  Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, methylphenylsiloxane unit, copolymer of methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane blocked with dimethylvinylsilyl group, endblocked with dimethylvinylsilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular terminals include polysiloxanes whose ends are blocked with the dimethylvinylsilyl group exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-tri Nyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11 -Hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.
These polysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

<Organic compound (B-3b)>
The organic compound (B-3b) that may be contained in the curable composition of the present invention is an organic compound represented by the following general formula (18), and has two or more alkenyl groups in one molecule. If it is an organic compound, there will be no limitation in particular.

(Wherein R ¹³ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ¹³ may be different or the same.)
Since the component (B-3b) contains two or more alkenyl groups on average in one molecule, the strength, gas barrier property, heat resistance, light resistance and the like of the resulting cured product are excellent. Further, from the viewpoint of gas barrier properties, the number average molecular weight is preferably less than 900.

  Further, the skeleton of the component (B-3b) may have a functional group other than an alkenyl group, but from the viewpoint of compatibility with the polyhedral polysiloxane, a methyl group, an ethyl group, a propyl group, etc. A functional group having a low polarity such as a linear aliphatic hydrocarbon group is preferred, and a methyl group is particularly preferred from the viewpoint of heat resistance and light resistance.

  The component (B-3b) is represented by the above general formula (19), for example, from the viewpoint of adhesion to the substrate when the composition is cured with the substrate, and 2 alkenyl groups in one molecule. It is preferably an isocyanuric acid derivative containing at least one, and from the viewpoint of balance between heat resistance and light resistance, it is more preferable to use triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, and particularly resistance to thermal shock resistance From this viewpoint, diallyl monomethyl isocyanurate is more preferable. These may be used alone or in combination of two or more.

<Hydrosilylation catalyst (C)>
As the hydrosilylation catalyst that can be used in the present invention, a known hydrosilylation catalyst can be usually selected, and there is no particular limitation.

Specifically, a platinum-olefin complex, chloroplatinic acid, platinum alone, a carrier (alumina, silica, carbon black, polymer, etc.) supported by solid platinum; a platinum-vinylsiloxane complex, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, eg Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m are integers) represented), Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al Country Patent No. 3220972 No. platinum Arcola described in the specification - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Curable composition>
The polysiloxane composition used in the optical semiconductor device of the present invention can be obtained by mixing a curing retarder, an inorganic filler, a phosphor, or the like, if necessary.
The viscosity of the curable composition used in the present invention is not particularly limited, but it is preferably 0.1 Pa · s to 300 Pa · s, more preferably 0.5 Pa · s to 200 Pa · s at a temperature of 23 ° C. It is. If the viscosity of the curable composition is low, the phosphor may settle and the chromaticity deviation between individuals increases, and if the viscosity is high, the handling property of the curable composition may deteriorate.

When adding temperature when hardening a curable composition, Preferably it is 30-400 degreeC, More preferably, it is 50-250 degreeC. When the curing temperature is high, the resulting cured product tends to have poor appearance, and when it is low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.
The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst to be used and the amount of reactive groups, and other combinations of the curable composition. Preferably, a cured product can be obtained by performing for 10 minutes to 8 hours.

  In order to improve the storage stability of the curable composition used in the present invention or to adjust the hydrosilylation reactivity during the curing process, a curing retarder may be used. As the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds, organosulfur compounds, Nitrogen-containing compounds, tin compounds, organic peroxides and the like can be mentioned. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and N, N-dibutyl. -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, per 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

  An adhesiveness imparting agent can be added to the curable composition used in the optical semiconductor device of the present invention as necessary.

  The adhesion-imparting agent is used for the purpose of improving the adhesion between the polysiloxane composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect. A coupling agent can be exemplified as a preferred example.

  The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.

  The addition amount of the silane coupling agent is preferably 0.05 to 30 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the curable composition. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, in order to raise the effect of an adhesive provision agent, a well-known adhesive promoter can also be used. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

  An inorganic filler can be added to the curable composition used in the optical semiconductor device of the present invention as necessary. By using an inorganic filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, flame retardancy, fire resistance, gas barrier properties, etc. of the molded product obtained Various physical properties can be improved.

  The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples thereof include ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, and silver powder. These may be used alone or in combination of two or more.

  The inorganic filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. More preferably. Similarly, the BET specific surface area, although not particularly limited, from the viewpoint of gas barrier properties, it is preferably ^70m 2 / g or more, more preferably 100 m ² / g or more, further 200 meters ² / It is especially preferable that it is g or more.

  Although the addition amount of an inorganic filler is not specifically limited, It is 1-1000 weight part with respect to 100 weight part of curable compositions, More preferably, it is 3-500 weight part, More preferably, it is 5-300 weight part. . When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

  The means for mixing the inorganic filler is not particularly limited. Specifically, for example, a two-roll or three-roll, a planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer, or the like, Examples thereof include a melt kneader such as a plast mill. The mixing of the inorganic filler may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.

  The curable composition used for the optical semiconductor device of the present invention contains a phosphor and forms a phosphor layer. The phosphor absorbs light emitted from the light-emitting element and generates light of different wavelengths. The phosphor used in the optical semiconductor device of the present invention is not particularly limited and is generally known inorganic fluorescence. And an organic phosphor can be used, and any one can be selected in order to obtain the emission color required by the optical semiconductor device of the present invention. Specifically, for example, YAG phosphors, TAG phosphors, orthosilicate alkaline earth phosphors, α-sialon phosphors, β-sialon phosphors, cousin phosphors, nitrides and oxynitride phosphors However, it is not limited to these. These phosphors can be used alone or in combination of two or more in any ratio and combination.

  The amount of the phosphor used in the present invention is not particularly limited, and any amount can be used to obtain the luminescent color required by the optical semiconductor device. Is preferably 0.1% by weight or more, more preferably 1% by weight or more, further preferably 2% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably 35% by weight or less. It is. If the amount of phosphor used is small, wavelength conversion by the phosphor may be insufficient, and the target emission color may not be obtained. If the amount of phosphor used is large, the handleability of the composition may be reduced. There is a possibility that the utilization efficiency of the phosphor may be lowered due to the optical interference action.

  The method of mixing the phosphor with the curable composition is not particularly limited as long as the phosphor can be uniformly mixed without damaging the crystal structure of the phosphor. For example, a mixer, a high-speed disper, A conventionally known method such as a homogenizer, 3 rolls, 2 rolls, a kneader, or a bead mill can be used. Of these, planetary agitation mixers, 3 rolls, 2 rolls, etc., which generate less heat during mixing and those with less metal wear particles from the mixer are preferred. This is preferable because it can be mixed with little defoaming. These mixing methods may be performed alone or in combination of two or more.

  In addition, the curable composition used in the optical semiconductor device of the present invention may include various additives such as a colorant and a heat resistance improver, a reaction control agent, a release agent, or a dispersant for a filler as necessary. It can be optionally added. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

The curable composition used in the optical semiconductor device of the present invention is a mixture of the above components uniformly using a kneader such as a roll, a Banbury mixer, a kneader, or using a planetary stirring deaerator. You may heat-process.
The polysiloxane composition of the present invention can be used as a molded article.

As a molding method, any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding can be used.
Specific uses of the molded product obtained in the present invention include, for example, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, color filters, polarizers. Examples of the peripheral material of the liquid crystal display device such as a protective film and a film for liquid crystal such as a passivation film are exemplified. It is also used in PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, color filters, passivation films, and LED display devices. LED element mold material, front glass protective film, front glass substitute material, adhesive, color filter, passivation film, substrate material for plasma addressed liquid crystal display, light guide plate, prism sheet, deflector plate, retardation plate, field of view Corner correction film, adhesive, color filter, polarizer protective film, passivation film, front glass protective film, front glass substitute material, color filter, adhesive, passivation film, and field emission in organic EL displays Various film substrate in Isupurei (FED), front glass protective films, front glass substitute material, adhesive, a color filter, a passivation film is exemplified.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives. More specifically, optical pickup members such as next-generation DVDs, such as pickup lenses, collimator lenses, objective lenses, sensor lenses, protective films, element sealants, sensor sealants, gratings, adhesives, prisms And a wave plate, a correction plate, a splitter, a hologram, a mirror, and the like.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, die-bonding agents, adhesives, and chip coating agents. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include an interlayer insulating film, a passivation film, an LSI, and a resist material for microlithography for an LSI material.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, corrosion-resistant coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior products, drive engines, brake oil tanks, and automobile protection Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, and glass substitutes. Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.

  In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

<Semiconductor device>
The semiconductor device of the present invention is not particularly limited, but for example, the structure shown in FIG. FIG. 1 is a schematic cross-sectional view of an optical semiconductor device.
The optical semiconductor element 1 in FIG. 1 of the present invention is not particularly limited, and those widely used as LEDs of optical semiconductor devices can be used. For example, a phosphor is excited by emitted light to emit visible light, and examples thereof include a visible light emitting type LED and an ultraviolet light emitting type LED. In the optical semiconductor element 1 of the present invention, a plurality of the same or different types of LEDs may be mounted per optical semiconductor device.

  The reflector 2 in FIG. 1 of the present invention may be used as necessary, and is intended to efficiently reflect the optical semiconductor device from the optical semiconductor element 1. As the material, thermoplastic resin, thermosetting resin, glass epoxy, ceramics, and the like can be used, but are not particularly limited.

  The cured product 3 of the polysiloxane composition in FIG. 1 of the present invention efficiently penetrates the optical semiconductor device from the optical semiconductor element 1 to the outside, and protects the optical semiconductor element and wires from external force and dust. It has the effect of preventing the corrosive gas from entering the apparatus.

  The lead 4 in FIG. 1 of the present invention is for ensuring conductivity when mounting the LED and enhancing the reflection efficiency of the LED. In particular, since the reflectance in the visible light region is high, a metal surface with silver plating is often used, but the present invention is not limited to silver plating.

  The wire 5 in FIG. 1 of the present invention electrically connects the optical semiconductor element 1 and the lead 4 and is not particularly limited as long as the material is conductive, but gold, gold alloy, copper, etc. Is mentioned. Further, instead of using the wire 5, an electrical connection may be made using a conductive adhesive or eutectic solder.

  The phosphor 6 in FIG. 1 of the present invention absorbs light emitted from the optical semiconductor element 1 and emits different wavelengths. Although there is no restriction | limiting in particular in the composition of the fluorescent substance to be used, The fluorescent substance which emits visible light of 400 nm-800 nm is generally used. Further, there is no restriction on whether the phosphor is settled or floats in the cured product 3.

  The optical semiconductor device of the present invention can be used for various known applications. Specifically, for example, backlights such as light receiving and emitting device liquid crystal display devices, illumination, sensor light sources, instrument light sources for vehicles, signal lights, indicator lights, display devices, light sources of planar light emitters, displays, decorations, various lights, etc. Can be mentioned.

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

(SiH value)
A mixed solution of 0.200 g of modified polyhedral polysiloxane (B-1) containing hydrosilyl groups, 0.200 g of dibromoethane, and 1.000 g of deuterated chloroform was prepared. The SiH value of the modified polyhedral polysiloxane was determined by measuring the obtained solution using 400 MHz NMR manufactured by Varian Technologies Japan Limited. The following calculation formula (1)
SiH value (mol / kg) = [integral value of peak attributed to SiH group of polyhedral polysiloxane modified product] / [integral value of peak attributed to methyl group of dibromoethane] × 4 × [in the mixture Dibromoethane weight] / [Molecular weight of dibromoethane] / [Modified polyhedral polysiloxane weight in mixture] (1)
It was calculated by using.
The SiH value of the isocyanuric acid derivative containing a hydrosilyl group was also calculated by the same method as described above.

(Production Example 1)
To 1803 g of a 48% choline aqueous solution (trimethyl-2-hydroxyethylammonium hydroxide aqueous solution), 1459 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1400 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While vigorously stirring a solution of 1149 g of dimethylvinylchlorosilane, 830 g of trimethylsilyl chloride and 1400 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid is washed by stirring vigorously in methanol and filtered to obtain tetrakis (polysiloxane compound containing 16 Si atoms and an alkenyl group having 4 vinyl groups). 760 g of vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1175.8) was obtained as a white solid.

(Production Example 2)
33.0 g of the polysiloxane compound having an alkenyl group obtained in Production Example 1 was dissolved in 123.0 g of toluene, 31.5 g of vinyldiphenylmethylsilane, a xylene solution of a platinum vinylsiloxane complex (platinum containing 3 wt% as platinum). 1.46 μL of vinyl siloxane complex, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 24.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 24.6 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 2.8 μl of ethynylcyclohexanol and 0.65 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 80.8 g (SiH valence of 1) of the liquid polysiloxane modified (B1). 0.8 mol / kg).

(Production Example 3)
Into a 1 L three-necked flask, 300 g of toluene and 100 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added, the gas phase portion was replaced with nitrogen, and then heated and stirred at 50 ° C. A mixed solution of 95 g of allyl glycidyl ether, 95 g of toluene and 0.017 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. After completion of the dropping, the temperature was raised to 60 ° C. for 120 minutes, and ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more. After dropwise addition of 7 g of triallyl isocyanurate and 7 g of toluene, the jacket temperature was raised to 105 ° C., and 28 g of triallyl isocyanurate, 28 g of toluene and a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) 014 g of the mixed solution was added dropwise over 30 minutes. The reaction rate of the allyl group by ¹ H-NMR 9 hours after the completion of dropping was 90%. The reaction was terminated by cooling. There was no unreacted 1,3,5,7-tetramethylcyclotetrasiloxane. By-products of toluene and allyl glycidyl ether (internally transferred products of allylic glycidyl ether (cis isomer and trans isomer)) were distilled off under reduced pressure to a total of 5,000 ppm or less, and isocyanuric acid derivatives containing liquid hydrosilyl groups ( 211 g (SiH valence 2.8 mol / kg) of B2) was obtained.

(Formulation example 1)
To 8.4 g of the modified polysiloxane (B1) obtained in Production Example 2, 3.3 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, diallylmonomethyl isocyanate Add 1.3 g of nurate, 2.1 μL of platinum vinylsiloxane complex in xylene solution (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X), 2.0 μl of ethynylcyclohexanol A single solution was prepared by stirring and mixing uniformly.

(Formulation example 2)
To 5.3 g of the polysiloxane modified product (B1) obtained in Production Example 2, 2.5 g of the polysiloxane modified product (B2) obtained in Production Example 3, 1,5-divinyl-3,3-diphenyl-1 , 1,5,5-tetramethyltrisiloxane 0.9 g, diallyl monomethyl isocyanurate 1.3 g, platinum vinylsiloxane complex xylene solution 2.5 μL, ethynylcyclohexanol 4.3 μl, and stirred and mixed uniformly. It was created.

(Formulation example 3)
2.00 g of A agent and 8.00 g of B agent of OE6630A / B manufactured by Toray Dow Corning Co., which is phenyl silicone, were uniformly stirred and mixed to prepare one liquid.

Example 1
A solution obtained by adding 63.5 uL of a 1% acetone solution of aconitic acid to one solution prepared in Formulation Example 1 was stirred for 3 minutes using Awatori Nertaro AR-250 manufactured by Thinky Co., defoaming 3 minutes, stirring 3 A polysiloxane composition was prepared by performing the steps in order.

Three reflectors made by Enomoto (product number: TOP LED 1-IN-1) mounted with 12 mil × 13 mil square blue LED chips (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelites, Inc. were prepared, and the curable composition was Within 15 minutes from the above stirring and defoaming, the Saneitech dispenser 1500 series, the Saneitech 3cc barrel-piston set (product number: SH09CP-B), the Saneitech chip (product number: SH23-B) Within 30 minutes after the injection, the temperature was raised in a convection oven at 80 ° C. for 120 minutes, 100 ° C. for 60 minutes, and 150 ° C. for 300 minutes in order. Using the total luminous flux measuring device (integrating sphere: Φ300 mm) manufactured by Otsuka Electronics Co., Ltd., the obtained optical semiconductor device was made to emit light by being energized under the conditions of a temperature of 25 ° C. and a current of 20 mA, and the total luminous flux after curing was measured. Three average values were calculated. These optical semiconductor devices were subjected to a storage test for 2000 hours under an environment tester (LH21-13M) manufactured by Nagano Science Co., Ltd. under conditions of 85 ° C. and 85% RH, and the total luminous flux after the test was obtained using the total luminous flux measurement device. Measurement was performed to calculate the average value of the three, and the total luminous flux retention before and after the test was calculated from the following calculation formula.
Total luminous flux retention (%)
= (Average value of total luminous flux after test) / (Average value of total luminous flux after curing) × 100
Further, by visually observing the metal surface of the optical semiconductor device after the test, the degree of coloring was classified into three stages: ◯, Δ, and X. ◯ indicates no change before and after the test, Δ indicates slightly colored after the test, and × indicates colored after the test.

  (Example 2) 63.5 uL of a 1% acetone solution of citric acid was added to Formulation Example 1, and a polysiloxane composition and an optical semiconductor device were produced in the same procedure. Using the apparatus described in Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Example 3) 63.5 uL of a 1% acetone solution of aconitic acid was added to Formulation Example 2, and a polysiloxane composition and an optical semiconductor device were produced in the same procedure. Using the apparatus described in Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Example 4) 63.5 uL of 1% acetone solution of citric acid was added to Formulation Example 2, and a polysiloxane composition and an optical semiconductor device were produced in the same procedure. Using the apparatus described in Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Example 5) 63.5 uL of 1% acetone solution of citric acid was added to Formulation Example 3, and a polysiloxane composition and an optical semiconductor device were produced in the same procedure. Using the apparatus described in Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Comparative Example 1) Using the apparatus described in Example 1 for the optical semiconductor device of Formulation Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Comparative Example 2) 63.5 uL of a 1% acetone solution of acetic acid was added to Formulation Example 1, and a polysiloxane composition and an optical semiconductor device were produced in the same procedure. Using the apparatus described in Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Comparative Example 3) The total light flux retention before and after the test was calculated using the optical semiconductor device of Formulation Example 2 using the apparatus described in Example 1. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Comparative Example 4) 63.5 uL of a 1% acetone solution of acetic acid was added to Formulation Example 2, and a polysiloxane composition and an optical semiconductor device were produced in the same procedure. Using the apparatus described in Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

  (Comparative Example 5) Using the apparatus described in Example 1 for the optical semiconductor device of Formulation Example 3, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.

(Comparative Example 6) 63.5 uL of a 1% acetone solution of acetic acid was added to Formulation Example 3, and a polysiloxane composition and an optical semiconductor device were produced in the same procedure. Using the apparatus described in Example 1, the total luminous flux retention before and after the test was calculated. The degree of coloring was evaluated by visual observation of the metal surface of the optical semiconductor device after the test.
Table 1 summarizes the composition of the examples and comparative examples, the type and amount of acid added, the total luminous flux retention of the optical semiconductor device, and the degree of coloring of the metal surface.

  As shown in Table 1, in the optical semiconductor device using the curable composition of the present invention, the metal nanoparticles (fine particles) were compared with the comparative example from the total luminous flux retention rate after the test and the visual color observation. It can be seen that coloring due to the formation of) is suppressed. Moreover, it turns out that this inhibitory effect is not exhibited by addition of monocarboxylic acid.

1 LED chip 2 reflector 3 cured product of polysiloxane composition 4 lead 5 bonding wire 6 phosphor

Claims (15)

(A) an organic acid having at least two polar groups in the molecule;
(B) a polysiloxane composition,
(C) a hydrosilylation catalyst,
A curable resin composition comprising: The curable resin composition according to claim 1, wherein at least one of polar groups contained in the organic acid (A) is a carboxy group. The curable resin composition according to claim 2, wherein at least two of the polar groups contained in the organic acid (A) are carboxy groups. The curable resin composition according to claim 3, wherein the organic acid (A) has 20 or less carbon atoms. The curable resin composition according to any one of claims 1 to 4, wherein the polysiloxane composition (B) is a compound having an alkenyl group and a compound having a hydrosilyl group. 6. The polyhedral polysiloxane modified body (B-1) containing a hydrosilyl group is contained in the resin component constituting the polysiloxane composition (B), according to any one of claims 1 to 5. Curable resin composition. The said polysiloxane composition (B) consists of following (B-1), (B-2), (B-3), The curable resin of any one of Claims 1-6 characterized by the above-mentioned. Composition.
(B-1) Polyhedral modified polysiloxane containing hydrosilyl group (B-2) Isocyanuric acid derivative containing hydrosilyl group (B-3) Compound having two or more alkenyl groups The component (B-1) is a polyhedral polysiloxane compound (a) having an alkenyl group and an organosilicon compound (c) having one alkenyl group in one molecule and / or 1 alkenyl group in one molecule. It is an organically modified polyhedral polysiloxane modified product (B-1 ′) obtained by hydrosilylation reaction of a cyclic olefin compound (d) having one compound with a compound (b) having a hydrosilyl group. The curable composition according to claim 6 and 7. The component (a) has the following general formula
[AR ¹ ₂ SiO—SiO _3/2 ] a [R ² ₃ SiO—SiO _3/2 ] b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group 9. An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by an aryl group or a group linked to another polyhedral skeleton polysiloxane), The curable resin composition described. The curable resin composition according to claim 8 or 9, wherein the component (b) is a cyclic siloxane containing a hydrosilyl group and / or a linear siloxane. The curable composition according to claim 1, wherein the polysiloxane composition (B) is phenyl silicone. The curable composition according to claim 1, wherein the polysiloxane composition (B) is methyl silicone. Hardened | cured material obtained by hardening | curing the curable resin composition of any one of Claims 1-12. A semiconductor device obtained by sealing and curing the curable resin composition according to claim 1. 15. The semiconductor device according to claim 14, which is an optical semiconductor device in which silver is plated on the surface of the lead frame.