JP6540620B2 - Thermosetting silicone resin composition and optical semiconductor device using the molded article - Google Patents

Description

  The present invention relates to a thermosetting silicone resin composition and an optical semiconductor device having a molded body obtained by curing the composition.

  BACKGROUND ART Optical semiconductor devices such as LEDs (Light Emitting Diodes) are used as various indicators and light sources such as street displays, automobile lamps, and home lighting. Above all, white LEDs are rapidly developing products applied in various fields, with the keywords of carbon dioxide reduction and energy saving.

  Polyphthalamide resin (PPA) has been widely used as a light reflector material as one of the materials for semiconductor and electronic devices such as LEDs, but epoxy resin is representative because of its poor heat discoloration resistance and light discoloration resistance of PPA. The use of thermosetting resins is becoming central.

  Patent documents 1 and 2 disclose white thermosetting epoxy resin compositions using triazine derivative epoxy resin, and patent document 3 describes white thermosetting epoxy resin compositions using alicyclic epoxy compound. There is. The white thermosetting epoxy resin compositions described in these are all using an epoxy resin and an acid anhydride which do not have an aromatic group, and are used because they have certain heat resistance and light resistance. In the current situation where applications for lighting and automotive applications are increasing, those having higher reliability in terms of heat resistance and light resistance have become necessary.

  Patent Documents 4 and 5 disclose a white thermosetting silicone resin composition using organopolysiloxane as a material excellent in heat resistance and light resistance. Although these are very excellent materials from the viewpoint of reliability, they have poor toughness due to the chemical characteristics of the silicone resin, and have a very large value of thermal expansion coefficient from room temperature to high temperature. Therefore, the balance between the formability and the warping property was not sufficiently satisfied.

JP, 2006-140207, A JP, 2008-189827, A Unexamined-Japanese-Patent No. 2013-100410 Unexamined-Japanese-Patent No. 2009-221393 JP, 2015-229749, A

  Accordingly, an object of the present invention is to provide a thermosetting silicone resin composition which gives a cured product having excellent warping characteristics by being excellent in toughness, in particular flexibility, and reduced in elasticity, and an optical semiconductor device using the same. Intended to be provided.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to solve the said subject, the present inventors discovered that the following thermosetting silicone resin composition was a thermosetting silicone resin which can achieve the said objective, and completed this invention .
That is, the present invention provides the following thermosetting silicone resin composition and a semiconductor device using the same.

<1>
A thermosetting silicone resin composition comprising the following components (A), (B), (C), (D) and (E). However, the mass part of each component is a mass part with respect to a total of 100 mass parts of (A) and (B) component.
(A) Condensation-resin-like resinous organopolysiloxane solid at 25 ° C .: 70 to 98 parts by mass (B) having a linear diorganopolysiloxane residue represented by the following general formula (2), and having one molecule Organopolysiloxane having at least one cyclohexyl group or phenyl group in: 2 to 30 parts by mass
(Wherein, R ² is each independently a monovalent hydrocarbon group selected from a hydroxyl group, an alkyl group of 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a vinyl group and an allyl group, and m is 5 to 50) Indicates an integer of
(C) Acrylic modified silicone resin powder: 1 to 30 parts by mass (D) Inorganic filler: 300 to 1,200 parts by mass (E) Organometallic condensation catalyst: 0.01 to 10 parts by mass

<2>
Furthermore, the thermosetting silicone resin composition as described in <1> which contains 3-300 mass parts of white pigments as (F) component.

<3>
Condensation reaction type resinous organopolysiloxane resin solid at room temperature of component (A) Resinous organopolysiloxane resin has the following average composition formula (1)
(CH ₃ ) _a Si (OR ¹ ) _b (OH) _c O _{(4-abc) / 2} (1)
(Wherein, R ¹ represents the same or different organic group having 1 to 4 carbon atoms, and a, b and c each satisfy 0.8 ≦ a ≦ 1.5, 0 ≦ b ≦ 0.3, 0. 001 ≦ c ≦ 0.5 and 0.801 ≦ a + b + c <2)
The thermosetting silicone resin composition as described in <1> or <2> which is a resin-like organopolysiloxane whose weight average molecular weight of polystyrene conversion represented by these is 1,000-20,000.

<4>
The (C) component acrylic modified silicone resin powder is an organopolysiloxane represented by the following formula (3), an acrylic acid ester monomer and / or a methacrylic acid ester monomer, and a functional copolymerizable therewith A thermosetting silicone resin composition according to any one of <1> to <3>, which is obtained by emulsion graft polymerization of a mixture with a group-containing monomer.
Wherein R ³ is the same or different substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y is the same or different substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms Alkyl group, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or hydroxyl group, and Z is the same or different group represented by Y or-[O-Si (Y) ₂ ] _f -Y And at least two of Y and Z are hydroxyl groups, d, e and f are a number of 0 ≦ d ≦ 1,000, a positive number of 100 ≦ e ≦ 10,000, 1 ≦ f ≦ 1,000 Is a positive number of

<5>
The case for optical semiconductor elements formed with the thermosetting silicone resin composition of any one of <1> to <4>.

<6>
The optical semiconductor device provided with the case for optical semiconductor elements as described in <5>.

<7>
The photocoupler sealed by the thermosetting silicone resin composition of any one of <1> to <4>.

<8>
The optical semiconductor device which has a photocoupler as described in <7>.

  The thermosetting silicone resin composition of the present invention gives a cured product not only excellent in toughness, particularly flexibility, but also excellent in warpage characteristics. Therefore, it is useful as a thermosetting silicone resin composition for optical semiconductor devices.

  Hereinafter, the present invention will be described in more detail.

<(A) condensation reaction resin-like organopolysiloxane solid at 25 ° C.>
The organopolysiloxane of the component (A) forms a crosslinked structure together with the linear organopolysiloxane of the component (B) in the presence of an organometallic condensation catalyst of the component (E) described later.

As the organopolysiloxane of component (A), for example, the following average composition formula (1)
(CH ₃ ) _a Si (OR ¹ ) _b (OH) _c O _{(4-abc) / 2} (1)
(In the above formula (1), R ¹ is the same or different organic group having 1 to 4 carbon atoms. A, b and c are 0.8 ≦ a ≦ 1.5, 0 ≦ b ≦ 0. 3, 0.001 ≦ c ≦ 0.5 and 0.801 ≦ a + b + c <2)
Resin-like (i.e., branched or three-dimensional network structure) organogel having a weight average molecular weight of 1,000 to 20,000 in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran or the like as a developing solvent Polysiloxane is mentioned.

  The composition containing an organopolysiloxane having a methyl group content of less than 0.8 in the above average composition formula (1) is not preferable because the cured product is too hard and the crack resistance is poor. On the other hand, when a exceeds 1.5, the resinous organopolysiloxane obtained is not likely to be solidified, which is not preferable. The content of the methyl group in the component (A) is preferably 0.8 ≦ a ≦ 1.2, more preferably 0.9 ≦ a ≦ 1.1.

  In the above average composition formula (1), when b indicating the content of the alkoxy group exceeds 0.3, the molecular weight of the resinous organopolysiloxane to be obtained tends to be small, and the crack resistance often decreases. The content of the alkoxy group in the component (A) is preferably 0.001 ≦ b ≦ 0.2, and more preferably 0.01 ≦ b ≦ 0.1.

In the above average composition formula (1), when c indicating the content of hydroxyl groups bonded to Si atoms exceeds 0.5, the resulting resinous organopolysiloxane exhibits high hardness due to the condensation reaction during heat curing. On the other hand, it is not preferable because the cured product is poor in crack resistance. On the other hand, when c is less than 0.001, the resinous organopolysiloxane obtained tends to have a high melting point, which may cause problems in workability, which is not preferable. The content of the hydroxyl group bonded to the Si atom in the component (A) is preferably 0.01 ≦ c ≦ 0.3, and more preferably 0.05 ≦ c ≦ 0.2. In order to control the value of c to 0.001 ≦ c ≦ 0.5, it is preferable to set the complete condensation ratio of the alkoxy group of the raw material to 86 to 96%. When the complete condensation ratio is less than 86%, the value of c exceeds 0.5 and the melting point is lowered, and when it exceeds 96%, the value of c tends to be less than 0.001 and the melting point tends to be too high. Absent.
Here, the complete condensation ratio indicates the ratio of the number of moles in which all the alkoxy groups contained in one molecule are subjected to the condensation reaction with respect to the total number of moles of the raw material.

  From the above, in the above average composition formula (1), the range of a + b + c is preferably 0.9 ≦ a + b + c ≦ 1.8, and more preferably 1.0 ≦ a + b + c ≦ 1.5.

In the above average composition formula (1), R ¹ is an organic group having 1 to 4 carbon atoms, and examples thereof include alkyl groups such as a methyl group, an ethyl group, and an isopropyl group, and obtaining of raw materials is easy Preferably a methyl group or an isopropyl group.

The resinous organopolysiloxane of component (A) preferably has a weight average molecular weight of 1,000 to 20,000, particularly preferably 1,500 to 10,000, and more preferably 2, based on polystyrene standard determined by GPC measurement. It is 000-8,000. When the molecular weight is less than 1,000, the resinous organopolysiloxane obtained is difficult to solidify, and when the molecular weight exceeds 20,000, the resulting composition has too high a viscosity to reduce fluidity. Formability may deteriorate.
In addition, the weight average molecular weight referred to in the present invention refers to a weight average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) measured under the following conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min
Detector: RI
Column: TSK-GEL H type (made by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 5 μL

The component (A) represented by the above average composition formula (1) generally has Q units (SiO _4/2 ), T units (CH ₃ SiO _3/2 ), D units ((CH ₃ ) ₂ SiO _2/2 And M units ((CH ₃ ) ₃ SiO _1/2 ) in combination. When component (A) is expressed in this manner, the ratio of the number of T units to the total number of all siloxane units is preferably 70% or more (less than 70 to 100%), and preferably 75% or more ( It is more preferable that it is 75-100%, and it is especially preferable that it is 80% or more (less than 80-100%). If the ratio of the number of T units contained is less than 70%, the overall balance such as hardness, adhesion and appearance of the resulting cured product may be lost. The remainder may be M, D or Q units, and the ratio of the total of these units to all siloxane units is 30% or less (0 to 30%), particularly more than 0% and 30% or less. Preferably it is less than 100%.

The component (A) represented by the above average composition formula (1) can be obtained as a hydrolysis condensate of an organosilane represented by the following general formula (4).
(CH ₃ ) _n SiX _4-n (4)
(Wherein X represents a halogen atom such as chlorine or an alkoxy group having 1 to 4 carbon atoms, and n is 0, 1 or 2). In this case, X is a solid at 25 ° C. From the viewpoint of obtaining an organopolysiloxane of the above, a chlorine atom or a methoxy group is preferable.

  Examples of the silane compound represented by the above formula (4) include organotrichlorosilanes such as methyltrichlorosilane; organotrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane; disilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane Organodialkoxysilanes; tetrachlorosilanes; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, etc. may be mentioned.

  The hydrolysis and condensation of the above-mentioned silane compound having a hydrolyzable group may be carried out by a usual method, but it is preferable to carry out in the presence of a catalyst. As the catalyst, either an acid catalyst or an alkali catalyst can be used. For example, an acid catalyst is preferably an organic acid catalyst such as acetic acid, or an inorganic acid catalyst such as hydrochloric acid or sulfuric acid. An alkali catalyst is preferably an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, tetramethylammonium hydroxide or the like. Organic alkaline catalysts are preferred. As a specific example, when using a silane containing a chloro group as a hydrolyzable group, a hydrolytic condensate having a target appropriate molecular weight can be obtained by using hydrogen chloride gas and hydrochloric acid generated by water addition as a catalyst. You can get it.

  The amount of water used in the hydrolysis and condensation is generally 0 with respect to 1 mole of the total amount of hydrolyzable groups (eg, chloro group) in the above-described hydrolyzable group-containing silane compound. It is 0.9 to 1.6 moles, preferably 1.0 to 1.3 moles. When the addition amount satisfies the range of 0.9 to 1.6 mol, the composition described later is excellent in workability, and the cured product tends to be excellent in toughness.

  The silane compound having a hydrolyzable group is preferably used after being hydrolyzed in an organic solvent such as alcohols, ketones, esters, cellosolves, and aromatic compounds. Specifically, for example, alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol, and 2-butanol, or aromatic compounds such as toluene and xylene are preferable, and the curability of the composition obtained and Isopropyl alcohol, toluene, or a combination of isopropyl alcohol and toluene is more preferable in that the toughness of the cured product is excellent.

  The reaction temperature for hydrolysis and condensation is preferably 10 to 120 ° C., more preferably 20 to 80 ° C. When the reaction temperature falls within the above range, it is difficult to gel and a solid hydrolytic condensate usable for the next step can be obtained.

  The organopolysiloxane (A) is preferably blended in an amount of 7 to 20% by mass, particularly 8 to 19% by mass, and further preferably 8.5 to 17% by mass, in the thermosetting silicone resin composition of the present invention. It is preferable to do.

<(B) Organopolysiloxane>
The thermosetting silicone resin composition of the present invention has a linear diorganopolysiloxane residue represented by the following formula (2) as a component (B) for stress relaxation and improvement of crack resistance, Organopolysiloxanes are used which are characterized in that they have at least one, preferably two or more, cyclohexyl or phenyl groups in the molecule.

In the above formula (2), R ^2, each independently, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a group selected from a vinyl group and allyl group. R ² is preferably a methyl group or a phenyl group. m is an integer of 5 to 50, preferably 8 to 40, more preferably 10 to 35. If m is less than 5, the resulting cured product is likely to be less resistant to cracking, and a device containing the cured product may be warped. On the other hand, when m exceeds 50, the mechanical strength of the resulting cured product tends to be insufficient.

The component (B) is, in addition to the D unit (R ² ₂ SiO _2/2 ) represented by the above formula (2), a D unit (R ₂ SiO _2/2 ) not falling under the above formula (2), and M It may comprise units (R ₃ SiO _1/2 ) and / or T units (RSiO _3/2 ). The ratio of D units: M units: T units is 90 to 24: 75 to 9: 50 to 1, especially 70 to 28: 70 to 20: 10 2 (provided that the total of these units is 100) It is preferable from the cured product characteristics. Here, R represents a hydroxyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, a vinyl group or an allyl group. In addition to these, the component (B) may contain Q units (SiO _4/2 ). The organopolysiloxane (B) is a D unit (R ² ₂ SiO _2/2 ) of the formula (2), a D unit (R ₂ SiO _2/2 ) not corresponding to the formula (2), an M unit (R ₃ At least one cyclohexyl group or phenyl group is contained in one molecule in SiO _1/2 ) and / or T unit (RSiO _3/2 ).

Preferably 30% or more (e.g. 30 to 90%), particularly 50% or more (e.g. 50 to 80%) of D units (R ² ₂ SiO _2/2 ) present in the organopolysiloxane of component (B) It is preferable that) is a continuous D unit (R ² ₂ SiO _2/2 ) represented by the general formula (2) in the molecule. Moreover, it is preferable that the polystyrene conversion weight average molecular weight by the gel permeation chromatography (GPC) of (B) component is 3,000-100,000, More preferably, it is 10,000-100,000. When the molecular weight is in this range, the component (B) is solid or semisolid, which is preferable from the workability and curability of the composition obtained.

  The component (B) can be synthesized by combining the compounds serving as the raw materials of the above-mentioned units into the required molar ratio in the produced polymer, for example, by performing hydrolysis and condensation in the presence of an acid .

As the raw material of D units forming the linear diorganopolysiloxane residue of formula _{^{(2) (R 2 2 SiO}} 2/2),

(Here, m is an integer from 3 to 48 (average value), n is an integer from 0 to 48 (average value), and m + n is 3 to 48 (average value, and each repeating unit is block or random And the like) can be exemplified.

As raw materials of T unit (RSiO _3/2 ), trichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane and cyclohexyltrichlorosilane, and trimethoxysilane corresponding to these trichlorosilanes. And alkoxysilanes can be exemplified.

As the raw material of D units such as not corresponding to the M unit, the formula _{(2), Me 2 PhSiCl,} Me 2 ViSiCl, Ph 2 MeSiCl, Ph 2 ViSiCl, Me 2 SiCl 2, MeEtSiCl 2, ViMeSiCl 2, Ph 2 Mono or dichlorosilanes such as SiCl ₂ and PhMeSiCl ₂ and mono or dialkoxysilanes such as mono or dimethoxysilanes corresponding to each of these chlorosilanes can be exemplified. Here, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, and Vi is a vinyl group.

  The component (B) can be obtained by combining the compounds as the raw materials at a predetermined molar ratio, and reacting them, for example, as follows. Phenylmethyldichlorosilane, phenyltrichlorosilane, Si-terminated double-ended chlorodimethyl silicone oil, and toluene are added and mixed, mixed silane is dropped into water and cohydrolyzed at 30 to 50 ° C. for 1 hour. Then, after aging at 50 ° C. for 1 hour, water is added and washed, then azeotropic dehydration, polymerization using ammonia or the like as a catalyst at 25 to 40 ° C., filtration, and vacuum stripping are performed.

The organopolysiloxane of component (B) has 0.5 to 10% of silanol units (siloxane units having silanol groups) based on all siloxane units, and preferably contains about 1 to 5%. As the silanol unit, for example, R (HO) SiO _2/2 units, R (HO) ₂ SiO _1/2 units include R ₂ (HO) SiO _1/2 units (wherein, R represents a hydroxyl The aforementioned groups other than groups). Since the organopolysiloxane contains a silanol group, it undergoes a condensation reaction with the resinous polyorganosiloxane of the component (A) containing a hydroxyl group represented by the above formula (1).

  The blending amount of the component (B) is preferably such that the ratio of the component (A) to the component (B) is in the range of 98: 2 to 70:30, more preferably 95 with respect to a total of 100 parts by mass with the component (A). The amount is in the range of 5 to 80:20. When the blending amount of the component (B) is too small, the effect of improving the continuous formability of the composition obtained is small, and it becomes difficult to achieve low warpage and crack resistance in the obtained cured product. On the other hand, when the compounding quantity of (B) component is large, the viscosity of the composition obtained will be easy to rise and it may interfere with shaping | molding.

<(C) Acrylic modified silicone resin powder>
The addition of the acrylic modified silicone resin powder which is the component (C) not only improves the toughness, in particular the flexibility, of the silicone resin composition of the present invention by adding it, but also reduces the elasticity of the cured product to improve the warpage characteristics. Let

  The acrylic modified silicone resin powder which is the component (C) can be copolymerized with a polyorganosiloxane represented by the following general formula (3), an acrylic acid ester monomer and / or a methacrylic acid ester monomer It is obtained by emulsion graft polymerization with a mixture with a functional group-containing monomer.

Wherein R ³ is the same or different substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y is the same or different substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms Alkyl group, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or hydroxyl group, and Z is the same or different group represented by Y or-[O-Si (Y) ₂ ] _f -Y And at least two of Y and Z are hydroxyl groups, d, e and f are a number of 0 ≦ d ≦ 1,000, a positive number of 100 ≦ e ≦ 10,000, 1 ≦ f ≦ 1,000 Is a positive number of

In the general formula (3), the alkyl group having 1 to 20 carbon atoms represented by R ³ may be linear or branched, or may be cyclic. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, A cyclohexyl group, a cycloheptyl group, etc. are mentioned. These alkyl groups may be substituted by a halogen atom, an acryloxy group, a methacryloxy group, a carboxy group, an alkoxy group, an alkenyloxy group, an amino group, an alkyl, an alkoxy or a (meth) acryloxy substituted amino group.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^3, a phenyl group, a tolyl group, a naphthyl group.
R ³ is preferably a methyl group.

Examples of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by Y in the general formula (3) include the same groups as the alkyl group and the aryl group exemplified for R ^3. .
Examples of the alkoxy group having 1 to 20 carbon atoms represented by Y include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a tetradecyloxy group. Be

In the general formula (3), d, e and f are a number of 0 ≦ d ≦ 1,000, a positive number of 100 ≦ e ≦ 10,000, and a positive number of 1 ≦ f ≦ 1,000, but d is Preferably it is a number of 0-200. When d is larger than 1,000, the strength of the obtained film becomes insufficient. e is preferably a positive number of 1,000 to 5,000. When e is less than 100, the flexibility of the film is poor, and when it is greater than 10,000, it becomes difficult to become powder-like solid. f is preferably a positive number of 1 to 200.
In addition, the polyorganosiloxane represented by the general formula (3) has at least two, preferably 2 to 4 hydroxyl groups in one molecule from the viewpoint of crosslinkability, and the hydroxyl groups are at both molecular chain terminals. It is preferable to have.

  As acrylic acid ester monomer or methacrylic acid ester monomer, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, etc. Can be mentioned.

  As a functional group-containing monomer copolymerizable with an acrylic acid ester monomer and / or a methacrylic acid ester monomer, unsaturated bonds containing a carboxyl group, an amide group, a hydroxyl group, a vinyl group, an allyl group, etc. Monomers and the like can be mentioned.

  In the acrylic modified silicone resin powder which is the component (C), the acrylic acid ester monomer and / or the methacrylic acid ester monomer is 10 to 10 parts by mass of the polyorganosiloxane represented by the above general formula (3). It is obtained by mixing 100 parts by mass and 0.01 to 20 parts by mass of a functional group-containing monomer copolymerizable therewith and subjecting it to emulsion graft polymerization. The conditions in the emulsion graft polymerization are not particularly limited, and a known radical initiator generally used for an acrylic polymer can be used as an initiator used at the time of polymerization. Moreover, an emulsifying agent can also use a well-known anionic surfactant and nonionic surfactant.

The (C) component acrylic-modified silicone resin powder is granulated and powdered by the methods listed below. That is, spray drying, air flow drying and the like can be mentioned, but in view of productivity, a spray dryer is preferable. It is preferable to hot-dry powdering, and it is preferable to process at 80-150 degreeC. The smaller the average particle diameter of the obtained powder particles, the better, and the particle diameter is preferably 50 μm or less. More preferably, it is 1 to 40 μm. The average particle diameter of the polymer is a value determined as a mass average value D ₅₀ (or median diameter) in particle size distribution measurement by laser diffraction method.

  Moreover, as acrylic modified silicone resin powder which is (C) component, commercial items, such as Charyne R-170S and Charyne R-200 (above, Nisshin Chemical Industry Co., Ltd. product), can be used, for example.

  The acrylic modified silicone resin powder of the component (C) is 1 to 30 parts by mass, preferably 2 to 20 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). If it is less than 1 part by mass, the desired effect can not be obtained sufficiently. On the other hand, when the content is more than 30 parts by mass, the heat resistance may decrease or the flowability may decrease.

<(D) Inorganic filler>
The inorganic filler of component (D) is blended to increase the strength of the cured product of the silicone resin composition of the present invention. As an inorganic filler of (D) ingredient, what is usually blended with a silicone resin composition and an epoxy resin composition can be used. For example, silicas such as spherical silica, fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, glass fiber, glass particles, antimony trioxide and the like can be mentioned, but component (F) described later White pigment (white colorant) is removed.

The average particle size and shape of the inorganic filler of the component (D) are not particularly limited, but the average particle size is usually 3 to 40 μm. As the component (D), spherical silica having an average particle diameter of 0.5 to 40 μm is suitably used. The average particle diameter is a value determined as a mass average value D ₅₀ (or median diameter) in particle size distribution measurement by laser diffraction method.

  In addition, from the viewpoint of high fluidity of the composition to be obtained, inorganic fillers of a plurality of particle size ranges may be combined, and in such a case, fine particles of 0.1 to 3 μm, medium particles of 3 to 7 μm It is preferred to use spherical silica in the size range and in the coarse range of 10-40 μm in combination. It is preferable to use spherical silica having a larger average particle size for further fluidization.

  The filling amount of the inorganic filler as the component (D) is preferably 300 to 1,200 parts by mass, and particularly preferably 600 to 1,000 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). If the amount is less than 300 parts by mass, sufficient strength may not be obtained, and if the amount exceeds 1,200 parts by mass, defects such as peeling in the element occur because unfilling defects due to thickening and flexibility are lost. It may occur. In addition, it is preferable to contain this inorganic filler in 10-90 mass% of the whole composition, especially 20-80 mass%.

<(E) Organometallic condensation catalyst>
The organometallic condensation catalyst of the component (E) is a condensation catalyst for use in curing the resinous organopolysiloxane which is the component (A) and the organopolysiloxane of the component (B), and the stability of the component (A) It is selected in consideration of the hardness of the film, non-yellowing, curability and the like. When an organic compound such as a base such as imidazole is used as a curing catalyst, the cured product is easily colored.
For example, organic acid zinc, organic aluminum compounds, organic titanium compounds and the like are suitably used as the organometallic condensation catalyst, and specifically, zinc benzoate, zinc octylate, zinc p-tert-butylbenzoate, zinc laurate , Zinc stearate, aluminum triisopropoxide, aluminum acetylacetonate, ethyl acetoacetate aluminum di (normal butyrate), aluminum n-butoxydiethylacetoacetate, tetrabutyl titanate, tetraisopropyl titanate, tin octoate And cobalt naphthenate, tin naphthenate and the like. Among them, zinc benzoate is preferably used.

  The addition amount of the organic metal condensation catalyst is preferably 0.01 to 10 parts by mass, particularly preferably 100 parts by mass of the total of the resinous organopolysiloxane of the component (A) and the organopolysiloxane of the component (B). Is 0.1 to 1.6 parts by mass. When the amount is in such a range, the curability is good and stable.

In the present invention, in addition to the above components, the following optional components can be blended.
<(F) White pigment>
The white pigment of the component (F) can be blended to enhance the whiteness required for applications such as the reflector (reflector) of the optical semiconductor device of the thermosetting silicone resin composition of the present invention. For example, as the white pigment, titanium dioxide, rare earth oxides represented by yttrium oxide, zinc sulfate, zinc oxide, magnesium oxide and the like can be mentioned, and these can be used alone or in combination of several kinds.

Among these, as the white pigment of the component (F), it is preferable to use titanium dioxide in order to further enhance the whiteness. The unit cell of this titanium dioxide may be rutile type, anatase type or brookite type, and any of them can be used, but it is preferable to use rutile type from the viewpoint of whiteness and photocatalytic ability of titanium dioxide. Further, the average particle size and shape of titanium dioxide are not limited, but the average particle size is preferably 0.05 to 5.0 μm, and more preferably 1.0 μm or less, and more preferably 0.30 μm or less. The above-mentioned titanium dioxide can be surface-treated in advance with a hydrous oxide such as aluminum or silicon, an organic substance such as polyol, an organic polysiloxane or the like in order to enhance the compatibility with the resin component and the inorganic filler and the dispersibility. The average particle size is one calculated as a weight average value D ₅₀ of the particle size distribution measurement (or median diameter) by a laser diffraction method.

  Moreover, although the manufacturing method of titanium dioxide may be any methods, such as a sulfuric acid method and a chlorine method, the method of a chlorine method is preferable from a viewpoint of whiteness.

  The amount of the white pigment blended is preferably 3 to 300 parts by mass, and more preferably 5 to 250 parts by mass, with respect to 100 parts by mass of the total of the components (A) and (B). When the content of the white pigment is less than 3 parts by mass, sufficient whiteness may not be obtained, and when it exceeds 300 parts by mass, the proportion of other components to be added for the purpose of mechanical strength improvement decreases. The sex may decrease significantly. The white pigment is preferably contained in an amount of 1 to 50% by mass with respect to the entire thermosetting silicone resin composition requiring high whiteness such as a reflective material for optical semiconductor devices, and more preferably It is in the range of 3 to 40% by mass.

<(G) mold release agent>
The mold release agent as the component (G) can be blended with the thermosetting silicone resin composition of the present invention in order to enhance the mold release property at the time of molding. It is preferable to add (G) component so that 0.2-5.0 mass% may be contained with respect to the whole composition. The release agent may, for example, be a natural wax, an acid wax, a polyethylene wax, or a synthetic wax typified by a fatty acid wax, among which calcium stearate having a melting point of 120 to 140 ° C. is desirable.

<(H) Coupling agent>
The coupling agent of the component (H) strengthens the bond strength between the resin and the inorganic filler, and improves the adhesive strength to the plated metal substrate, so the thermosetting silicone resin composition of the present invention Can be formulated into Examples of the coupling agent of the component (H) include a silane coupling agent and a titanate coupling agent.

  Specifically, for example, epoxy functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. It is preferable to use a mercapto functional alkoxysilane such as γ-mercaptopropyltrimethoxysilane from the viewpoint that the resin is not discolored even when left at high temperature.

  The blending amount of the component (H) is preferably 0.1 to 8.0 parts by mass, particularly preferably 0.5 to 6.0 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). . If it is less than 0.1 part by mass, the adhesion effect to the substrate may not be sufficient, and if it exceeds 8.0 parts by mass, the viscosity may be extremely reduced to cause voids. .

<Other additives>
Various additives can be further added to the thermosetting silicone resin composition of the present invention as required. For example, in order to improve the properties of the resin, additives such as other organopolysiloxanes, silicone oils, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, or light stabilizers are added within the range not to impair the effects of the present invention. It can be blended.

<Method of producing composition>
The method for producing the composition of the present invention includes (A) component organopolysiloxane, (B) component organopolysiloxane, (C) component acrylic modified silicone resin powder, (D) component inorganic filler and (E) And the like. The organic metal condensation catalyst of the component) is blended at a predetermined composition ratio, and this is sufficiently uniformly mixed by a mixer or the like. If necessary, in addition to the above components, the white pigment of the (F) component and other additives may be blended at a predetermined blending ratio. Thereafter, the mixture is melt-blended by a heat roll, a kneader, an extruder or the like, then cooled and solidified, and crushed to a suitable size to obtain a molding material of a silicone resin composition. The cured product of the silicone resin composition of the present invention preferably has a linear expansion coefficient of 30 ppm / K or less, preferably 25 ppm / K or less at 50 ° C. to 100 ° C.

  Further, as described above, from the viewpoint of dispersibility, it is preferable to melt and mix the organopolysiloxane which is the component (A) and the organopolysiloxane which is the component (B) in a kneader or a flask in advance.

The most common molding method of the thermosetting silicone resin composition includes a transfer molding method and a compression molding method. In the transfer molding method, using a transfer molding machine, molding pressure is 5 to 20 N / mm ² , molding temperature is 120 to 190 ° C., molding time is 30 to 500 seconds, and molding temperature is 150 to 185 ° C., and molding time is 30 to 180 seconds. Is preferred. In the compression molding method, it is preferable to use a compression molding machine at a molding temperature of 120 to 190 ° C. and a molding time of 60 to 600 seconds, and particularly a molding temperature of 130 to 160 ° C. and a molding time of 120 to 300 seconds. Furthermore, post curing may be performed at 150 to 200 ° C. for 2 to 20 hours in any molding method.

  EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Each component used by the Example and the comparative example is shown below. In the following, the weight average molecular weight is measured under the following measurement conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min
Detector: RI
Column: TSK-GEL H type (made by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 5 μL

<(A) Synthesis of resinous organopolysiloxane>
Synthesis Example 1
100 parts by mass of methyltrichlorosilane and 200 parts by mass of toluene were placed in a 1 L flask, and a mixed solution of 8 parts by mass of water and 60 parts by mass of isopropyl alcohol was added dropwise under ice cooling. The internal temperature was dropped over 5 hours while maintaining the range of -5 to 0 ° C, and then heated and stirred at reflux temperature for 20 minutes. Then, it was cooled to room temperature, and 12 parts by mass of water was added dropwise over 30 minutes at a temperature of 30 ° C. or less, and stirred for 20 minutes. Furthermore, after 25 mass parts of water was dripped, it stirred at 40-45 degreeC for 60 minutes. Thereafter, 200 parts by mass of water was added to separate the organic layer. The organic layer is washed until neutrality and then subjected to azeotropic dehydration, filtration and vacuum stripping to obtain a colorless transparent solid (melting point 76 ° C., weight average molecular weight 3) represented by the following average formula (A-1) , 060) 36.0 parts by mass of a thermosetting organopolysiloxane (A-1) was obtained.
(CH ₃ ) _1.0 Si (OC ₃ H ₇ ) _0.07 (OH) _0.10 O _1.4 (A-1)

<(B) Synthesis of organopolysiloxane>
Synthesis Example 2
100 g (4.4 mol%) of phenylmethyldichlorosilane, 2,100 g (83.2 mol%) of phenyltrichlorosilane, 2,400 g (12.4 mol%) of dimethylpolysiloxane oil having 21 Si both-end chloroblocked ) And 3,000 g of toluene were mixed, and the above silane mixed in 11,000 g of water was dropped and cohydrolyzed at 30 to 50 ° C. for 1 hour. Then, after aging for 1 hour at 30 ° C., water was added and washed, then azeotropic dehydration, filtration, and vacuum stripping were performed to obtain a colorless and transparent product (organosiloxane (B-1)). The siloxane (B-1) had a melt viscosity of 5 Pa · s at 150 ° C. using an ICI cone plate, and had a weight average molecular weight of 50,000.
[(Me ₂ SiO) ₂₁ ] _0.124 (PhMeSiO) _0.044 (PhSiO _1.5 ) _0.832 (B-1)

<(C-1) Acrylic modified silicone resin powder>
(C-1-1) Acrylic modified silicone resin powder (Chaline R-170S: trade name of Nisshin Chemical Industry Co., Ltd .; average particle diameter 30 μm)
(C-1-2) Acrylic modified silicone resin powder (Charine R-200: trade name of Nisshin Chemical Industry Co., Ltd .; average particle diameter: 2.0 μm)
<(C-2) Sample for Comparative Example>
(C-2-1) Silicone composite powder (KMP-600: trade name of Shin-Etsu Chemical Co., Ltd .; average particle diameter 5 μm)
(C-2-2) Silicone resin powder (KMP-590: trade name of Shin-Etsu Chemical Co., Ltd .; average particle diameter: 2.0 μm)
(C-2-3) Acrylic powder (W-5500: trade name of Mitsubishi Rayon Co., Ltd .; average particle diameter 60 μm)

<(D) Inorganic filler>
(D-1) Fused spherical silica (CS-6103 53C2, trade name of Ryumori Co., Ltd., average particle diameter 10 μm)

<(E) Organometallic condensation catalyst>
(E-1) Zinc benzoate (manufactured by Wako Pure Chemical Industries, Ltd.)

<(F) White pigment>
(F-1) Titanium dioxide rutile type (PC-3, trade name of Ishihara Sangyo Co., Ltd.)

<(G) mold release agent>
(G-1) Hardened castor oil (Kaow Wax 85P, trade name of Kao Corporation)

<(H) Silane coupling agent>
(H-1) 3-mercaptopropyltrimethoxysilane (KBM-803, trade name of Shin-Etsu Chemical Co., Ltd.)

[Examples 1 to 4, Comparative Examples 1 to 7]
The composition (parts by mass) shown in Tables 1 and 2 was manufactured by a two-heat roller, cooled and pulverized to obtain a thermosetting silicone resin composition. The following properties were measured for these compositions. The results are shown in Tables 1 and 2.

<Spiral flow value>
Using a mold conforming to the EMMI standard, the spiral flow value of the molding of the thermosetting silicone resin composition was measured under the conditions of a molding temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , and a molding time of 120 seconds. It was measured.

<Shrinkage percentage, flexural strength, flexural modulus, deflection (25 ° C)>
The thermosetting silicone resin composition is molded under the conditions of a molding temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds using a mold according to JIS K 6911: 2006 standard, 180 Post cured at 4 ° C for 4 hours. The length of the post-cured molded product was measured with an electric micrometer at room temperature (25 ° C.) to calculate the shrinkage factor. Subsequently, flexural strength, flexural modulus and deflection were measured at room temperature (25 ° C.) of the test piece.

Thermal expansion coefficient
The thermosetting silicone resin composition is molded under the conditions of a molding temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , and a molding time of 120 seconds using a mold according to the EMMI standard, and the molding for 4 hours at 180 ° C. It was post cured. The thermal expansion coefficient of the test piece of the post-cured molded body was measured in the range of 50 ° C. to 100 ° C. by TMA (TMA 8310, manufactured by RIGAKU Co., Ltd.).

<Light reflectance (initial light reflectance, long-term heat resistance test)>
Under the conditions of molding temperature 175 ° C, molding pressure 6.9 N / mm ² , molding time 120 seconds, a disc-shaped cured product of 50 mm in diameter and 3 mm in thickness is formed, and then secondary curing at 180 ° C. for 4 hours is performed. The initial light reflectance at 450 nm was measured using X-rite 8200 manufactured by S.D.G. Further, heat treatment was carried out at 200 ° C. for 96 hours, and the light reflectance at 450 nm was similarly measured using X-rite 8200 manufactured by S & D Co., Ltd.

As shown in Table 1, in the molded article of the resin composition of the present invention, the amount of deflection increased and the toughness increased by the addition of the acrylic modified silicone resin powder. Moreover, it became low elasticity and the contraction rate was falling. It was also found that the heat resistance was not adversely affected. Therefore, it has been confirmed that the molded article of the resin composition of the present invention is excellent in toughness and effective for the improvement of the warpage characteristics. Therefore, it has been confirmed that the composition of the present invention is useful as a material for optical semiconductor devices.

Claims (7)

A thermosetting silicone resin composition comprising the following components (A), (B), (C), (D) and (E). However, the mass part of each component is a mass part with respect to a total of 100 mass parts of (A) and (B) component.
(A) A resinous organopolysiloxane having a polystyrene equivalent weight average molecular weight of 1,000 to 20,000 represented by the following average composition formula (1), which is a solid condensation reaction resinous organopoly at 25 ° C. Siloxane: 70 to 98 parts by mass

(CH ₃ ) _a Si (OR ¹ ) _b (OH) _c O _{(4-abc) / 2} (1)
(Wherein, R ¹ represents the same or different organic group having 1 to 4 carbon atoms, and a, b and c represent 0.8 ≦ a ≦ 1.5, 0 ≦ b ≦ 0.3, 0.001 C ≦ 0.5 and 0.801 ≦ a + b + c <2)

(B) Organopolysiloxane having a linear diorganopolysiloxane residue represented by the following general formula (2) and having at least one cyclohexyl group or phenyl group in one molecule: 2 to 30 parts by mass
(Wherein, R ² is each independently a monovalent hydrocarbon group selected from a hydroxyl group, an alkyl group of 1 to 3 carbon atoms, a cyclohexyl group, a phenyl group, a vinyl group and an allyl group, and m is 5 to 50) Indicates an integer of
(C) Acrylic modified silicone resin powder: 1 to 30 parts by mass (D) (F) Inorganic filler excluding white pigment : 300 to 1,200 parts by mass (E) Organometallic condensation catalyst: 0.01 to 10 parts Department   The thermosetting silicone resin composition according to claim 1, further comprising 3 to 300 parts by mass of a white pigment as component (F). An organopolysiloxane represented by the following formula (3), an acrylic acid ester monomer and / or a methacrylic acid ester monomer, and a functional group copolymerizable therewith: (C) component acrylic modified silicone resin powder The thermosetting silicone resin composition according to claim 1 or 2 , which is obtained by emulsion graft polymerization of a mixture with a monomer containing.
Wherein R ³ is the same or different substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y is the same or different substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms Alkyl group, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or hydroxyl group, and Z is the same or different group represented by Y or-[O-Si (Y) ₂ ] _f -Y And at least two of Y and Z are hydroxyl groups, d, e and f are a number of 0 ≦ d ≦ 1,000, a positive number of 100 ≦ e ≦ 10,000, 1 ≦ f ≦ 1,000 Is a positive number of The case for optical semiconductor elements formed with the thermosetting silicone resin composition of any one of Claims 1-3 . The optical semiconductor device provided with the case for optical semiconductor elements of Claim 4 . A photocoupler sealed with the thermosetting silicone resin composition according to any one of claims 1 to 3 . An optical semiconductor device comprising the photocoupler according to claim 6 .