JP2018039956A - Thermosetting epoxy resin composition and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting epoxy resin composition that gives a cured product having excellent heat resistance, having excellent flexibility, and also having reduced elasticity for improved warpage properties, and an optical semiconductor device prepared therewith.SOLUTION: A thermosetting silicone resin composition contains the following (A), (B), (C), (D) and (E) components, where, parts by mass of each component are relative to the total parts by mass of the (A) and (B) components, 100 pts.mass: (A) epoxy resin, (B) curing agent, (C) curing accelerator of 0.01-5.0 pts.mass, (D) acryl modified silicone resin powder of 1-30 pts.mass, and (E) an inorganic filler of 300-1,200 pts.mass.SELECTED DRAWING: None

Description

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

  Optical semiconductor elements such as LEDs (Light Emitting Diodes) are used as various indicators and light sources such as street displays, automobile lamps, and residential lighting. Above all, white LEDs are rapidly developing products that are 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 equipment such as LEDs. Epoxy resin is representative of PPA's poor heat discoloration and light discoloration resistance. The use of thermosetting resins is increasing.

  Patent Documents 1 and 2 describe a white thermosetting epoxy resin composition using a triazine derivative epoxy resin, and Patent Document 3 describes a white thermosetting epoxy resin composition using an alicyclic epoxy compound. Yes. The white thermosetting epoxy resin compositions described in these are all made of epoxy resins and acid anhydrides that do not have aromaticity, and are used because they have certain heat resistance and light resistance. However, in the present situation where lighting applications and in-vehicle applications are increasing, those having higher reliability in terms of heat resistance and light resistance have become necessary.

  Patent Document 4 shows that a white thermosetting epoxy resin composition using a triazine derivative epoxy resin can have a higher heat resistance and light resistance by containing a specific antioxidant. However, even now, satisfactory reliability cannot be obtained.

JP 2006-140207 A JP 2008-189827 A JP 2013-100410 A JP, 2015-101614, A

  Accordingly, an object of the present invention is not only excellent heat resistance but also excellent flexibility and low elasticity, and thus a warp property is improved, and a thermosetting epoxy resin composition that gives a cured product having excellent reliability. And providing an optical semiconductor device using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that the following thermosetting silicone resin composition is a thermosetting silicone resin that can achieve the above object, and completed the present invention. .
That is, this invention provides the following thermosetting epoxy resin composition and an optical 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 100 mass parts in total of (A) and (B) component.
(A) Epoxy resin (B) Curing agent (C) Curing accelerator: 0.01 to 5.0 parts by mass (D) Acrylic-modified silicone resin powder: 1 to 30 parts by mass (E) Inorganic filler: 300 to 1 200 parts by mass

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

<3>
Furthermore, the thermosetting epoxy resin composition as described in <1> or <2> which contains 0.1-15.0 mass parts of antioxidant as (G) component.

<4>
The (A) component epoxy resin is a triazine derivative epoxy resin, the (B) component curing agent is a non-aromatic acid anhydride having no carbon-carbon double bond, and the (B) component acid anhydride. The thermosetting epoxy resin composition according to any one of <1> to <3>, wherein the ratio of the total number of epoxy groups in component (A) to the total number of groups is 0.6 to 2.0. .

<5>
The thermosetting epoxy according to any one of <1> to <4>, wherein the component (A) and the component (B) are prepolymers of the component (A) and the component (B). Resin composition.

<6>
(D) Component acrylic modified silicone resin powder is from (d-1) to (d-3) below
The thermosetting epoxy resin composition according to any one of <1> to <5>, which is an emulsion graft polymer of a mixture of the above.
(D-1) The following formula (1)

(In the formula, R ¹ represents the same or different substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, and X represents the same or different substituted or unsubstituted carbon number 1. Represents an alkyl group having ˜20, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, and Y is the same as represented by X or — [O—Si (X) ₂ ] _c —X. Or at least two of X and Y are hydroxyl groups, a, b and c are a number of 0 ≦ a ≦ 1,000, a positive number of 100 ≦ b ≦ 10,000, 1 ≦ (It is a positive number satisfying c ≦ 1,000.)
(D-2) Acrylic acid ester monomer and / or methacrylic acid ester monomer (d-3) Functionality copolymerizable with the above (d-1) and (d-2) Monomers containing groups

<7>
The case for optical semiconductor elements which consists of a thermosetting epoxy resin composition of any one of <1> to <6>.
<8>
An optical semiconductor device comprising the optical semiconductor element case according to <7>.
<9>
A semiconductor device, wherein the sealing layer is a cured product of the thermosetting epoxy resin composition according to any one of <1> to <6>.

  The thermosetting epoxy resin composition of the present invention not only has excellent heat resistance, but also provides a cured product having excellent flexibility and improved warping properties by making it low elastic. Therefore, it is useful as a thermosetting epoxy resin composition for optical semiconductor devices.

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

<(A) Epoxy resin>
The epoxy resin as component (A) is preferably a triazine derivative epoxy resin from the viewpoint of excellent heat resistance and light resistance. As the triazine derivative epoxy resin, 1,3,5-triazine nucleus derivative epoxy resin is preferable. The epoxy resin having an isocyanurate ring is excellent in light resistance and electrical insulation, and preferably has a divalent, more preferably a trivalent epoxy group with respect to one isocyanurate ring. Specific examples include tris (2,3-epoxypropyl) isocyanurate, tris (α-methylglycidyl) isocyanurate, and tris (α-methylglycidyl) isocyanurate.

  The triazine derivative epoxy resin used in the present invention preferably has a softening point of 40 to 125 ° C. In addition, the said triazine derivative epoxy resin used by this invention does not include what hydrogenated the triazine ring.

  As the component (A), epoxy resins other than those described above can be used, but it is mainly preferable to use the above epoxy resins. As other epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol type epoxy resin, and 4,4′-biphenol Type epoxy resin, biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenylol ethane type epoxy resin And an epoxy resin obtained by hydrogenating an aromatic ring of a phenol dicyclopentadiene novolac type epoxy resin, and an alicyclic epoxy resin. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin with hydrogenated aromatic ring, alicyclic epoxy resin, and silicone-modified epoxy resin are preferable from the viewpoint of heat resistance and ultraviolet resistance. The said epoxy resin has a softening point of 50-100 degreeC from the point of the ease of prepolymerization mentioned later and the improvement of handling property.

<(B) Curing agent>
(B) As a hardening | curing agent which is a component, a phenol hardening | curing agent, an amine hardening | curing agent, and an acid anhydride hardening | curing agent are mentioned. Here, like the component (A), it is preferable to use an acid anhydride curing agent from the viewpoint of heat resistance. The acid anhydride is preferably non-aromatic and has no carbon-carbon double bond in order to impart light resistance to the cured product. For example, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hydrogenated methylnadic acid anhydride and the like can be mentioned. Of these, hexahydrophthalic anhydride and / or methylhexahydrophthalic anhydride are preferred. An acid anhydride may be used individually by 1 type, and may use 2 or more types together.

<Prepolymer>
The resin composition is preferably used as a prepolymer by reacting (A) an epoxy resin and (B) an acid anhydride as a curing agent in advance for the purpose of improving the handling property of the resin composition during production. The structure obtained by pre-reacting (A) epoxy resin and (B) acid anhydride which is a curing agent can suppress yellowing of the cured product when placed under high temperature. Because.

In the preparation of the prepolymer, the ratio of (A) epoxy resin to be reacted and (B) acid anhydride as a curing agent is [total number of epoxy groups of (A) component / acid anhydride of (B) component] The total number of groups] is 0.6 to 2.0, preferably 0.8 to 1.9, and more preferably 1.0 to 1.8. If the blending ratio is less than the above lower limit of 0.6, unreacted acid anhydride remains in the cured product, which may deteriorate the moisture resistance of the resulting cured product. On the other hand, if the upper limit value is more than 2.0, poor curing may occur and reliability may be lowered. The reaction between the component (A) and the component (B) may be caused to react in the presence of an antioxidant (G) described later and / or a curing accelerator (C) described later. It is preferable to use the solid product (that is, prepolymer) obtained by reacting (A) an epoxy resin and (B) a curing agent in a fine powder state by pulverization or the like. The average particle size of the fine powder is preferably in the range of 5 μm to 3 mm. Incidentally, the average particle size refers to those calculated as a mass average value D ₅₀ of the particle size distribution measurement _(or median diameter) by a laser diffraction method.

In more detail, the preparation of the prepolymer comprises the components (A) and (B), preferably at 60 to 120 ° C., more preferably at 70 to 110 ° C., preferably 4 to 20 hours, more preferably 6 to What is necessary is just to make it react for 15 hours. As described above, the antioxidant (G) described later may be added in advance to the mixture of the component (A) and the component (B). Alternatively, the component (A), the component (B), and the later-described (C) curing accelerator are reacted in advance at 30 to 80 ° C., preferably 40 to 70 ° C. for 2 to 12 hours, preferably 3 to 8 hours. Also good. At this time, (G) antioxidant may be added to the mixture in advance. The above reaction yields a solid product that is a prepolymer. The softening point of the solid product is 40-100 ° C, preferably 45-70 ° C. If the softening point is less than 40 ° C., it does not become a solid, and if it exceeds 100 ° C., the fluidity required for molding as a composition may be too low. As described above, the solid product is preferably pulverized by pulverization or the like before blending with the composition of the present invention.
In order to mix the prepolymer with the composition of the present invention, it is preferably used in a fine powder state by pulverization or the like. The average particle diameter of the fine powder is preferably in the range of 5 μm to 3 mm, particularly preferably in the range of 20 μm to 2 mm. If it exists in this range, since it becomes easy to disperse | distribute the (C) and / or (G) component added to a small amount to a composition uniformly in a composition, it is preferable. Incidentally, the average particle size is one calculated as a cumulative weight average value D _{50 (or} median diameter) in particle size distribution measurement by laser diffraction method.

  The component (A) and the component (B) or these prepolymers are preferably blended in the composition of the present invention in an amount of 10 to 45% by mass, particularly 12 to 40% by mass, and further 15 to 35% by mass. It is preferable.

<(C) Curing accelerator>
(C) The hardening accelerator of a component is mix | blended as an essential component in order to accelerate | stimulate hardening of a thermosetting epoxy resin. Although it does not specifically limit as a hardening accelerator, A well-known thing can be used as a curing catalyst of an epoxy resin composition, Tertiary amines, imidazoles, those organic carboxylates, organic carboxylic acid metal salt, metal- One type or two or more types of phosphorus-based curing catalysts such as organic chelate compounds, aromatic sulfonium salts, organic phosphine compounds, and phosphonium compounds, and salts thereof can be used. Among these, imidazoles, phosphorus-based curing catalysts such as 2-ethyl-4-methylimidazole or methyltributylphosphonium dimethyl phosphate, and tertiary amine octylates are more preferable. Further, the combined use of a quaternary phosphonium bromide and an organic acid salt of amine is also preferably used.

The blending amount of the curing accelerator is preferably 0.01 to 5 parts by mass, particularly 0.1 to 2 parts by mass with respect to 100 parts by mass of the sum of the components (A) and (B). If it is out of the above range, the balance of heat resistance and moisture resistance of the cured product of the epoxy resin composition may be deteriorated, or curing at the time of molding may be very slow or fast.
(C) The hardening accelerator of a component may be mixed with the prepolymer which consists of (A) component and (B) component.

<(D) Acrylic-modified silicone resin powder>
Addition of the (D) component acrylic-modified silicone resin powder not only improves the heat resistance and flexibility of the epoxy resin composition of the present invention, but also lowers the elasticity of the cured product to improve the warp characteristics. .

  As the acrylic modified silicone resin powder as component (D), polyorganosiloxane (d-1) represented by the following general formula (1), an acrylate monomer and / or a methacrylic acid ester monomer (d -2) and an emulsion graft polymer of a functional group-containing monomer (d-3) copolymerizable therewith.

(In the formula, R ¹ represents the same or different substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, and X represents the same or different substituted or unsubstituted carbon number 1. Represents an alkyl group having ˜20, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, and Y is the same as represented by X or — [O—Si (X) ₂ ] _c —X. Or at least two of X and Y are hydroxyl groups, a, b and c are a number of 0 ≦ a ≦ 1,000, a positive number of 100 ≦ b ≦ 10,000, 1 ≦ (It is a positive number satisfying c ≦ 1,000.)

In the general formula (1), the alkyl group having 1 to 20 carbon atoms represented by R ¹ may be linear, branched, or 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, Examples include a cyclohexyl group and a cycloheptyl group. These alkyl groups may be substituted with a halogen atom, acryloxy group, methacryloxy group, carboxy group, alkoxy group, alkenyloxy group, amino group, alkyl, alkoxy or (meth) acryloxy-substituted amino group.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include a phenyl group, a tolyl group, and a naphthyl group.
R ¹ is preferably a methyl group.

In the general formula (1), examples of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by X include the same groups as the alkyl group and aryl group exemplified in R ^1. .
Examples of the alkoxy group having 1 to 20 carbon atoms represented by X include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group and the like. It is done.

In the general formula (1), a, b and c are numbers of 0 ≦ a ≦ 1,000, positive numbers of 100 ≦ b ≦ 10,000, and positive numbers of 1 ≦ c ≦ 1,000. Preferably it is the number of 0-200. If a is greater than 1,000, the strength of the resulting film will be insufficient. b is preferably a positive number of 1,000 to 5,000. When b is less than 100, the flexibility of the film is poor, and when it is more than 10,000, it is difficult to form a solid like powder. c is preferably a positive number of 1 to 200.
In addition, the polyorganosiloxane represented by the general formula (1) has at least 2, preferably 2 to 4 hydroxyl groups in one molecule from the viewpoint of crosslinkability, and the hydroxyl groups are present at both ends of the molecular chain. What has is preferable.

  Examples of acrylic acid ester monomers or methacrylic acid ester monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, etc. Is mentioned.

  As a functional group-containing monomer copolymerizable with an acrylate monomer and / or a methacrylic acid ester monomer, an unsaturated bond containing a carboxyl group, an amide group, a hydroxyl group, a vinyl group, an allyl group, etc. And the like.

  The acrylic-modified silicone resin powder as component (D) is 10 to 10 parts by weight of the acrylate monomer and / or methacrylic acid ester monomer with respect to 100 parts by mass of the polyorganosiloxane represented by the general formula (1). What is obtained by mixing 0.01 to 20 parts by mass of 100 parts by mass and 0.01 to 20 parts by mass of a functional group-containing monomer copolymerizable therewith is preferable. The conditions in the emulsion graft polymerization are not particularly limited, and as the initiator used at the time of polymerization, a known radical initiator usually used for an acrylic polymer can be used. As the emulsifier, a known anionic surfactant or nonionic surfactant can be used.

The acrylic modified silicone resin powder (D) is granulated and powdered by the following method. That is, spray drying drying, airflow drying, and the like can be mentioned, but a spray dryer is preferable in view of productivity. The pulverization is preferably performed by hot drying, and is preferably processed at 80 to 150 ° C. The average particle size of the obtained powder particles is preferably as small as possible, and is preferably 50 μm or less. More preferably, it is 1-40 micrometers. The average particle size 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 (D) component, commercial items, such as Charine R-170S and Charine R-200 (above, Nissin Chemical Industry Co., Ltd. product), can also be used, for example.

  The (D) component acrylic-modified silicone resin powder is 1 to 30 parts by mass, preferably 2 to 20 parts by mass, with respect to 100 parts by mass in total of the (A) component and the (B) component. When the amount is less than 1 part by mass, the effect of the present invention cannot be obtained. On the other hand, when there is more content than 30 mass parts, there exists a possibility that fluidity | liquidity may fall.

<(E) Inorganic filler>
(E) The inorganic filler of a component is mix | blended in order to raise the intensity | strength of the hardened | cured material of the epoxy resin composition of this invention. (E) As an inorganic filler of a component, what is normally mix | blended with an epoxy resin composition or a silicone 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. White pigments (white colorants) are excluded.

(E) Although the average particle diameter and shape of the inorganic filler of a component are not specifically limited, A thing with an average particle diameter of 0.5-40 micrometers is preferable. As the component (E), spherical silica having an average particle size of 0.5 to 40 μm is preferably 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 increasing the fluidity of the resulting composition, inorganic fillers having a plurality of particle size ranges may be combined. In such a case, a fine region of 0.1 to 3 μm, a medium particle of 3 to 7 μm It is preferable to use a combination of spherical silica having a diameter region and a coarse region of 10 to 40 μm. For further high fluidization, it is preferable to use spherical silica having a larger average particle diameter.

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

In the present invention, the following optional components can be blended in addition to the above components.
<(F) White pigment>
The white pigment of component (F) is a component of the component (E) described above in order to increase the whiteness necessary for the thermosetting epoxy resin composition of the present invention for uses such as a reflector (reflector) of an optical semiconductor device. Can be blended separately. Examples of white pigments include titanium dioxide, rare earth oxides typified by yttrium oxide, zinc sulfate, zinc oxide, magnesium oxide, and the like, 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 increase the whiteness. The unit cell of titanium dioxide includes a rutile type, an anatase type, and a brookite type, and any of them can be used, but it is preferable to use a rutile type from the viewpoint of the whiteness and photocatalytic ability of titanium dioxide. Moreover, although the average particle diameter and shape of titanium dioxide are not limited, the average particle diameter is preferably 0.05 to 5.0 μm, of which 1.0 μm or less is preferable and 0.30 μm or less is more preferable. In order to enhance the compatibility and dispersibility with the resin component and the inorganic filler, the titanium dioxide can be surface-treated in advance with a hydrous oxide such as aluminum or silicon, an organic substance such as polyol, or an organic polysiloxane. 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.

  The titanium dioxide production method may be any method such as a sulfuric acid method or a chlorine method, but the chlorine method is preferred from the viewpoint of whiteness.

  The blending amount of the white pigment is preferably from 3 to 300 parts by weight, particularly preferably from 5 to 250 parts by weight, based on 100 parts by weight of the sum of the components (A) and (B). When the blending amount 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, not only the ratio of other components added for the purpose of improving the mechanical strength is reduced, but also molding. May be significantly reduced. In addition, it is preferable to contain 1-50 mass% of this white pigment with respect to the whole thermosetting epoxy resin composition which requires high whiteness like the reflector for optical semiconductor devices, More preferably It is the range of 3-40 mass%.

(G) Antioxidant The thermosetting epoxy resin composition of this invention can mix | blend (G) antioxidant for the initial stage reflectance improvement and long-term reflectance maintenance. (G) As an antioxidant of a component, a phenol type, phosphorus type, and sulfur type antioxidant can be used, Specifically, the following antioxidants are mentioned.

  Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [ 5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Phosphorus antioxidants include triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tri (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, triphenyl phosphite , Distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, di (2,4-di-tert-butylphenyl) pentaerythritol diphosphite , Tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenyl diphosphonate and the like.

  Examples of the sulfur-based antioxidant include dilauryl thiopropionate, distearyl dithiopropionate, and dibenzyl disulfide.

These antioxidants can be used alone or in combination of two or more. It is preferable that the compounding quantity of antioxidant shall be 0.01-15 mass parts with respect to the sum total of (A) and (B) component, especially 0.03-10 mass parts. If the amount is too small, the effect as an antioxidant cannot be obtained, sufficient heat resistance cannot be obtained, and discoloration may occur, and if it is too large, curing inhibition will occur and sufficient curability and strength will be obtained. May not be possible.
In addition, you may mix the antioxidant of (G) component with the prepolymer which consists of (A) component and (B) component.

<(H) Release agent>
A mold release agent can be mix | blended with the thermosetting epoxy resin composition of this invention. The mold release agent of component (H) is blended in order to improve the mold release property at the time of molding.

  Mold release agents include natural waxes such as carnauba wax, synthetic waxes such as acid wax, polyethylene wax, and fatty acid ester. Generally, yellowing easily occurs under high temperature conditions or under light irradiation. In many cases, glycerin derivatives and fatty acid esters with little discoloration and carnauba wax with little color change with time but less color change are preferable.

  Component (H) is blended in an amount of 0.05 to 7.0 mass%, particularly 0.1 to 5.0 mass%, based on the sum of components (A) and (B). If the blending amount is less than 0.05% by mass, sufficient releasability may not be obtained, and if it exceeds 7.0% by mass, a squeeze out defect or poor adhesion may occur.

<(I) Coupling agent>
In the thermosetting epoxy resin composition of the present invention, a coupling agent such as a silane coupling agent or a titanate coupling agent can be blended in order to increase the bond strength between the resin and the inorganic filler.
Examples of such a coupling agent include epoxy functions such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Mercapto-functional alkoxysilanes such as functional alkoxysilane and γ-mercaptopropyltrimethoxysilane. It is not preferable that the thermal resin discolors when left at 150 ° C. or higher, such as an amine-based silane coupling agent. The blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited, and may be performed according to a conventional method.

  The blending amount of the component (I) is preferably 0.1 to 8.0% by mass, particularly 0.5 to 6.0% by mass with respect to the sum of the components (A) and (B). It is preferable. If it is less than 0.1% by mass, the adhesion effect to the substrate may not be sufficient, and if it exceeds 8.0% by mass, the viscosity may be extremely lowered, which may cause voids. .

<Other additives>
Various additives can be further blended in the thermosetting epoxy resin composition of the present invention as necessary. For example, for the purpose of improving the properties of the resin, additives such as organopolysiloxane, silicone oil, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, or light stabilizer are added and blended within a range that does not impair the effects of the present invention. be able to.

<Method for producing composition>
Although the manufacturing method of the thermosetting epoxy composition of this invention is not specifically limited, For example, the following method is mentioned. Epoxy resin, curing agent, curing accelerator, acrylic-modified silicone resin powder, inorganic filler, white pigment, antioxidant, and other additives were blended at a predetermined composition ratio, and this was mixed sufficiently uniformly with a mixer or the like. Thereafter, a melt mixing process using a hot roll, a kneader, an extruder or the like is performed, followed by cooling and solidification, and pulverization to an appropriate size to obtain a molding material for the thermosetting epoxy resin composition. At this time, the epoxy resin and the curing agent are preferably used after being prepolymerized as a solid product from the viewpoint of handling. When solid (reactant) is not used for preparation (production) of epoxy composition, (A) component, (B) component, (C) component, (D) component and (E) component and other components as required Additives are blended at a predetermined composition ratio and mixed sufficiently with a mixer, etc., then melt mixed with a hot roll, kneader, extruder, etc., then cooled and solidified, and pulverized to an appropriate size. Thus, a molding material for the epoxy resin composition can be obtained.

When the thermosetting epoxy composition of the present invention is used as a reflector, the most common molding method of the reflector includes a transfer molding method and a compression molding method. In the transfer molding method, using a transfer molding machine, a molding pressure of 5 to 20 N / mm ² , a molding temperature of 120 to 190 ° C. and a molding time of 30 to 500 seconds, preferably a molding temperature of 150 to 185 ° C. and a molding time of 30 to 180 seconds. Do. In the compression molding method, a compression molding machine is used, and the molding temperature is 120 to 190 ° C., the molding time is 30 to 600 seconds, preferably the molding temperature is 130 to 160 ° C. and the molding time is 120 to 300 seconds. Further, in any molding method, post-curing may be performed at 150 to 185 ° C. for 0.5 to 20 hours.

  The thermosetting epoxy resin composition of the present invention can also be used for sealing a normal semiconductor sealing material, various on-vehicle modules, and the like. In that case, carbon black or the like is used as a colorant. Any carbon black may be used as long as it is commercially available, but a high-purity one that does not contain a large amount of alkali metal or halogen is preferred.

The components used in Examples and Comparative Examples are shown below. Here, 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.
<(A) Triazine derivative epoxy resin>
(A-1): Tris (2,3-epoxypropyl) isocyanurate (TEPIC-s: trade name, manufactured by Nissan Chemical Co., Ltd.)

<(B) Acid anhydride>
(B-1): Methylhexahydrophthalic anhydride (Ricacid MH: trade name, manufactured by Shin Nippon Rika Co., Ltd.)

<(C) Curing accelerator>
(C-1) 1-benzyl-2-phenylimidazole (1B2PZ: trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.)

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

<(E) Inorganic filler>
(E-1) Fused spherical silica (CS-6103 53C2, trade name, manufactured by Tatsumori Co., Ltd., average particle size 10 μm)

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

<(G) Antioxidant>
(G-1) Phosphite-based antioxidant (PEP-36A: trade name, manufactured by ADEKA Corporation)

<(H) Release agent>
(H-1) Carnauba wax (TOWAX-131: trade name manufactured by Toa Kasei Co., Ltd.)

<(I) Coupling agent>
(I-1) Silane coupling agent: 3-mercaptopropyltrimethoxysilane (KBM-803: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Examples 1 to 5, Comparative Examples 1 to 4]
The composition (parts by mass) shown in Table 1 was produced with a hot two roll, cooled and pulverized to obtain a thermosetting epoxy resin composition. The following properties were measured for these compositions. The results are shown in Table 1. In Examples 1 to 4 and Comparative Examples 1 to 4, the components (A) and (B) are prepolymers obtained by pre-melting and mixing with a gate mixer at 80 ° C. for 8 hours in the ratio shown in Table 1. In Example 5, the component (A) and the component (B) were added separately without using a prepolymer.

<Spiral flow value>
Using a mold conforming to the EMMI standard, the spiral flow value of the molded article of the thermosetting epoxy resin composition was determined under the conditions of a molding temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , and a molding time of 90 seconds. It was measured.

<Shrinkage rate, bending strength, flexural modulus, deflection amount (25 ° C.)>
Using the mold according to JIS K 6911: 2006 standard, the thermosetting epoxy resin composition was 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 90 seconds, and 150 Post-cured for 2 hours at ° C. The length of the post-cured molded body was measured with an electric micrometer at room temperature (25 ° C.), and the shrinkage was calculated. Subsequently, the test piece was measured for bending strength, bending elastic modulus, and amount of deflection at room temperature (25 ° C.).

<Glass transition temperature, thermal expansion coefficient>
The thermosetting silicone resin composition was molded using a mold conforming to the EMMI standard at a molding temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , and a molding time of 90 seconds, and at 180 ° C. for 4 hours. Post cure. The glass transition temperature and the thermal expansion coefficient of the test piece of the post-cured molded product were measured with TMA (manufactured by TMA8310 Rigaku Corporation).

<Light reflectivity (initial light reflectivity, long-term heat resistance test)>
A disk-shaped cured product having a diameter of 50 mm and a thickness of 3 mm was prepared under conditions of a molding temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , and a molding time of 90 seconds, and then secondary curing at 150 ° C. for 2 hours was performed. The initial light reflectance at 450 nm was measured using X-lite 8200 manufactured by SDG Co., Ltd. Further, heat treatment was performed at 180 ° C. for 168 hours, and the light reflectance at 450 nm was measured using X-lite 8200 manufactured by SDG Co., Ltd. in the same manner.

  As shown in Table 1, in the molded product of the resin composition of the present invention, the amount of deflection was increased and the toughness was increased by adding the acrylic-modified silicone resin powder. Further, the elasticity was lowered and the shrinkage rate was reduced. Moreover, it turned out that heat resistance improves. Therefore, it was confirmed that the molded body of the resin composition of the present invention has improved heat resistance, excellent toughness, and is effective in improving warpage characteristics. Therefore, it was confirmed that the composition of the present invention was useful as an optical semiconductor device material.

Claims (9)

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 100 mass parts in total of (A) and (B) component.
(A) Epoxy resin (B) Curing agent (C) Curing accelerator: 0.01 to 5.0 parts by mass (D) Acrylic-modified silicone resin powder: 1 to 30 parts by mass (E) Inorganic filler: 300 to 1 200 parts by mass   Furthermore, the thermosetting silicone resin composition of Claim 1 which contains 3-300 mass parts of white pigments as (F) component.   Furthermore, 0.1-15.0 mass parts of antioxidant is contained as (G) component, The thermosetting epoxy resin composition of Claim 1 or 2.   The (A) component epoxy resin is a triazine derivative epoxy resin, the (B) component curing agent is a non-aromatic acid anhydride having no carbon-carbon double bond, and the (B) component acid anhydride. The thermosetting epoxy resin composition according to any one of claims 1 to 3, wherein a ratio of the total number of epoxy groups in the component (A) to the total number of groups is 0.6 to 2.0.   The thermosetting epoxy resin composition according to any one of claims 1 to 4, wherein the component (A) and the component (B) are prepolymers of the component (A) and the component (B). object. The component (D) acrylic-modified silicone resin powder comprises the following (d-1) to (d-3)
The thermosetting epoxy resin composition according to any one of claims 1 to 5, wherein the thermosetting epoxy resin composition is an emulsion graft polymer.
(D-1) The following formula (1)

(In the formula, R ¹ represents the same or different substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, and X represents the same or different substituted or unsubstituted carbon number 1. Represents an alkyl group having ˜20, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, and Y is the same as represented by X or — [O—Si (X) ₂ ] _c —X. Or at least two of X and Y are hydroxyl groups, a, b and c are a number of 0 ≦ a ≦ 1,000, a positive number of 100 ≦ b ≦ 10,000, 1 ≦ (It is a positive number satisfying c ≦ 1,000.)
(D-2) Acrylic acid ester monomer and / or methacrylic acid ester monomer (d-3) Functionality copolymerizable with the above (d-1) and (d-2) Monomers containing groups   The case for optical semiconductor elements which consists of a thermosetting epoxy resin composition of any one of Claims 1-6.   An optical semiconductor device comprising the optical semiconductor element case according to claim 7.   A semiconductor device, wherein the sealing layer is a cured product of the thermosetting epoxy resin composition according to claim 1.