JP2016180071A - White thermosetting epoxy resin composition for led reflector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a white thermosetting epoxy resin composition which is excellent in continuous moldability at the time of transfer molding, does not cause contamination on a lead frame, and does not hardly cause discoloration; and a semiconductor device in which a light-receiving element and other semiconductor elements are sealed with a cured product of the composition.SOLUTION: A white thermosetting epoxy resin composition contains (A) a prepolymer obtained by reaction of (A-1) a triazine derivative epoxy resin and (A-2) an acid anhydride, (B) a white pigment, (C) an inorganic filler, (D) a curing accelerator, (D) a release agent, and (F) a release aid. The release aid being the (F) component is a block copolymer obtained by addition reaction of an alkenyl group-containing epoxy compound and/or an alkenyl group of an alkenyl group-containing phenolic compound, and an SiH group of organopolysiloxane represented by an average composition formula (1). In formula (1), R is a substituted or unsubstituted monovalent hydrocarbon group; and a and b are positive numbers satisfying relationships of 0.001≤a≤1, 1≤b≤3 and 1.001≤a+b≤3.SELECTED DRAWING: None

Description

  The present invention is formed of a white thermosetting epoxy resin composition that is excellent in continuous formability during transfer molding, does not cause contamination on the lead frame, and does not easily cause discoloration, and the white thermosetting epoxy resin composition. The present invention relates to a semiconductor device including an optical semiconductor element case.

  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) is currently widely used as a light reflector material as one of materials for semiconductor and electronic equipment devices such as LEDs. A reflector material using PPA is excellent in that it has high strength and flexibility (Patent Document 1). However, in recent years, higher output and shorter wavelengths of optical semiconductor devices have progressed, and further improvement in long-term reliability has become more desirable. Under such circumstances, it is easy to use PPA around optical semiconductor elements. It is not suitable to use PPA for such applications because deterioration is severe, such as causing discoloration, causing a decrease in light output.

  Patent Document 2 describes an epoxy resin composition for sealing an optical semiconductor having a B-stage, which includes an epoxy resin, a curing agent, and a curing accelerator, and the above components are uniformly mixed at a molecular level. An optical semiconductor device having a cured product of a resin composition is described. Here, it is also described that bisphenol A type epoxy resin or bisphenol F type epoxy resin is mainly used as the epoxy resin, and triglycidyl isocyanate or the like can be used. However, the epoxy resin composition for encapsulating B-stage semiconductors described in Patent Document 2 has a problem that yellowing occurs particularly when left for a long time at a high temperature.

  Patent Document 3 describes an LED sealed with an alicyclic epoxy resin obtained by oxidizing a cyclic olefin. Patent Document 4 describes a light-emitting element sealing epoxy resin composition containing a triazine derivative epoxy resin and an acid anhydride curing agent. Patent Document 5 includes (A) a hydrogenated epoxy resin, a triazine ring-containing epoxy resin, and an epoxy resin containing an alicyclic epoxy resin obtained by epoxidizing an alicyclic olefin, and (B) acid anhydride curing. An epoxy resin composition for sealing a light emitting device containing an agent is described. However, the problem that the epoxy resin composition for sealing a light emitting element described in Patent Documents 3 to 5 is yellowed when left at high temperature for a long time has not been sufficiently solved.

  Patent Document 6 describes a substrate for mounting an optical semiconductor element that exhibits good light reflection characteristics even after a heat resistance test. As represented by Patent Document 6, a conventional white thermosetting epoxy resin composition used as a substrate material is released into a resin composition for the purpose of smooth release from a mold during substrate production. The agent is often added internally. However, a compound used as a release agent often includes a release agent because of its poor dispersibility in the base resin such as an epoxy resin and a curing agent constituting the thermosetting light reflecting resin composition. When a substrate is molded using a thermosetting resin composition, poor appearance is likely to occur due to a dispersion failure of a release agent, and further, continuous molding tends to be difficult. Therefore, it is desired to develop a white thermosetting epoxy resin composition that is excellent in various molding characteristics including releasability and can be continuously continuously formed.

  Patent Document 7 includes the following formulas (I) and (II):

(In Formula (I) and Formula (II), R ¹ is an alkylene group having 1 to 12 carbon atoms, and R ² and R ³ are each independently an alkyl group or aryl group having 1 to 10 carbon atoms. , An alkoxy group, a monovalent organic group having an epoxy group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, and a polyalkylene ether group having 3 to 500 carbon atoms)
A compound having a structural unit represented by the formula (III),

(In formula (III), l is an integer of 1 to 200, m ₁ + m ₂ is an integer of ₂ to 400, R ¹ is an alkylene group having 1 to 10 carbon atoms, and R ² and R ³ are , Each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkoxy group, a monovalent organic group having an epoxy group, a monovalent organic group having a carboxyl group having 1 to 10 carbon atoms, and the number of carbon atoms Selected from the group consisting of 3 to 500 polyalkylene ether groups, and R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms)
In combination with a trialkylene block copolymer represented by the above and a release agent, it is excellent in various properties such as optical properties and heat resistance required for a substrate for mounting an optical semiconductor element, and is released during transfer molding. An epoxy resin composition for light reflection that has excellent properties and can be continuously molded is disclosed. However, when a compound having an ester bond such as the above (I) is added, the ester bond portion is weak against heat and light, causing discoloration or poor reactivity with an epoxy resin or a curing agent. This is not preferable because there is a problem in that it becomes easy to bleed.

JP 2006-257314 A Japanese Patent No. 2656336 JP 2000-196151 A JP 2003-224305 A JP 2005-306952 A JP 2006-140207 A JP 2009-097005 A

  Therefore, the present invention provides a white thermosetting epoxy resin composition excellent in continuous formability during transfer molding, causing no contamination on the lead frame and hardly causing discoloration, and the white thermosetting epoxy resin composition. An object is to obtain a semiconductor device including the formed optical semiconductor element case.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a white thermosetting epoxy resin composition comprising a mixture of a triazine derivative epoxy resin and an acid anhydride or a prepolymer obtained by reacting them. In addition, it was found that the above-mentioned object can be achieved by blending a mold release aid, which is a block copolymer obtained by addition reaction of an SiH group of an organopolysiloxane and an alkenyl group of an alkenyl group-containing epoxy compound, The present invention has been completed.

  That is, this invention provides a semiconductor device provided with the optical semiconductor element case formed with the following white thermosetting epoxy resin composition and this white thermosetting epoxy resin composition.

<1>
(A) (A-1) A prepolymer obtained by reacting a triazine derivative epoxy resin with (A-2) an acid anhydride, and (A-2) based on the total number of acid anhydride groups in the component (A-1) a prepolymer in which the ratio of the total number of epoxy groups in the component is 0.6 to 2.0,
(B) a white pigment,
(C) inorganic filler,
(D) a curing accelerator,
(E) a release agent, and
(F) mold release aid,
A white thermosetting epoxy resin composition containing the component (F), wherein the release assistant of the component (F) is an alkenyl group-containing epoxy compound and / or an alkenyl group of the alkenyl group-containing phenol compound represented by the following average composition formula (1): A white thermosetting epoxy resin composition which is a block copolymer obtained by addition-reacting SiH groups of the organopolysiloxane shown.

(In Formula (1), R is a substituted or unsubstituted monovalent hydrocarbon group, and a and b satisfy 0.001 ≦ a ≦ 1, 1 ≦ b ≦ 3, and 1.001 ≦ a + b ≦ 3. (It is a positive number.)

<2>
Furthermore, the white thermosetting epoxy resin composition as described in <1> which contains antioxidant as (G) component.

<3>
(B) The white thermosetting epoxy resin composition according to <1> or <2>, wherein the average particle diameter of the white pigment is 1 μm or less.

<4>
(B) The white pigment is a titanium oxide whose surface is treated with alumina, and is further treated with at least one selected from the group consisting of silica, alumina, zirconia, polyol and siloxane <1> to <3 > The white thermosetting epoxy resin composition of any one of>.

<5>
The white thermosetting epoxy resin composition according to any one of <1> to <4>, wherein the triazine derivative epoxy resin as the component (A-1) is a 1,3,5-triazine derivative epoxy resin.

<6>
The white thermosetting epoxy resin composition according to any one of <1> to <5>, wherein the prepolymer of the component (A) contains a compound represented by the following general formula (2).

(In formula (2), R ¹ represents an acid anhydride residue, and m is a number from 0 to 200.)

<7>
An optical semiconductor device provided with the optical semiconductor element case formed with the white thermosetting epoxy resin composition of any one of <1>-<6>.

  The present invention can provide a white thermosetting epoxy resin composition that is excellent in continuous moldability during transfer molding, does not cause contamination on the lead frame, and hardly causes discoloration. In addition, the present invention can provide an optical semiconductor device with little deterioration over time by sealing an optical semiconductor element with a cured product of the composition of the present invention or having a light reflecting member made of the cured product. .

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

<White thermosetting epoxy resin composition>
(A) Prepolymer The component (A) is a prepolymer obtained by reacting (A-1) a triazine derivative epoxy resin and (A-2) an acid anhydride in advance. The cured product has a structure obtained by reacting (A-1) a triazine derivative epoxy resin and (A-2) an acid anhydride, thereby suppressing yellowing of the cured product when placed under high temperature. Can do.

In the preparation of the prepolymer, the ratio of the (A-1) triazine derivative epoxy resin and the (A-2) acid anhydride to be reacted is [total number of epoxy groups of the component (A-1) / (A-2 ) The total number of acid anhydride groups of the component] is 0.6 to 2.0, preferably 0.8 to 1.9, more preferably 1.0 to 1.8. Is the amount. 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. You may make reaction of (A-1) component and (A-2) component react in presence of (G) antioxidant mentioned later and / or (D) hardening accelerator mentioned later. (A-1) A solid product (that is, a prepolymer) obtained by reacting a triazine derivative epoxy resin with (A-2) an acid anhydride in the above ratio may be used as the component (A) of the present invention. preferable. At this time, the solid product 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. Incidentally, the average particle diameter 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.

  More specifically, the preparation of the prepolymer comprises the components (A-1) and (A-2), preferably at 60 to 120 ° C., more preferably at 70 to 110 ° C., and preferably for 4 to 20 hours. The reaction may be preferably performed for 6 to 15 hours. As described above, an antioxidant (G) described later may be added in advance to the mixture of the component (A-1) and the component (A-2). Or (A-1) component, (A-2) component, and (D) hardening accelerator mentioned later are 30-80 degreeC beforehand, Preferably it is 2 to 12 hours at 40-70 degreeC, Preferably it is 3-8. Let react for hours. 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.

(A-1) Triazine derivative epoxy resin (A-1) The triazine derivative epoxy resin is preferably a 1,3,5-triazine nucleus derivative epoxy resin. 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.

(A-2) Acid anhydride (A-2) The acid anhydride (A-1) acts as a curing agent for the epoxy resin. 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.

  When synthesizing the prepolymer, an epoxy resin other than the component (A-1) can be used in combination as long as it does not impair the effects of the present invention. Examples of the epoxy resin include 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 such as resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenylol ethane type epoxy resin, and Examples thereof include 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 epoxy resin preferably has a softening point of 50 to 100 ° C. from the viewpoint of ease of prepolymerization and improvement in handling properties.

  Examples of the prepolymer include compounds represented by the following general formula (2).

(In formula (2), R ¹ is a residue of an acid anhydride such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hydrogenated methyl nadic anhydride, etc. M is an integer from 0 to 200.)

  (A) It is preferable to contain 5.0-45.0 mass% of components in this invention composition, It is more preferable to contain 6.0-40.0 mass%, 7.0-35.0 More preferably, it is contained by mass%.

(B) White pigment The white thermosetting epoxy resin composition of the present invention contains a white pigment for applications such as a reflector (reflecting plate) of an optical semiconductor device. That is, the white pigment is blended in order to increase the whiteness of the cured product and increase the light reflectivity on the surface of the cured product. Examples of white pigments include titanium dioxide, rare earth oxides such as yttrium oxide, zinc sulfate, zinc oxide, and magnesium oxide. These may be used alone or in combination of two or more. The average particle diameter and shape of the white pigment are not particularly limited, and a conventionally known white pigment can be used. Usually, the average particle diameter of the white pigment is 0.05 to 5 μm, but is preferably 1 μm or less from the viewpoint of concealment. The average particle diameter is obtained as a mass average value D ₅₀ (or median diameter) in particle size distribution measurement by a laser light diffraction method.

  As the white pigment, titanium dioxide is preferably used from the viewpoint of whiteness. Further, as a method for producing titanium dioxide, those produced by any method such as sulfuric acid method and chlorine method can be used, but those obtained by chlorine method are preferred from the viewpoint of whiteness.

  The titanium dioxide is preferably one that has been surface-treated with alumina at least once in order to prevent aggregation of the titanium oxide particles themselves. Furthermore, in order to suppress the photocatalytic ability of titanium dioxide, and to improve compatibility and dispersibility with resins and inorganic fillers, surface treatment is further carried out with hydrous oxides such as Al, Si, Zr, polyols, organosilicon compounds, etc. You can also Examples of the organosilicon compound used here include various types. For example, polysiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, or copolymers thereof, hexamethylcyclotrisiloxane, heptamethylcyclotetrasiloxane, 1,3,5,7-tetra Cyclosiloxanes such as methylcyclotetrasiloxane, chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and other silanes having an epoxy functional group, 3-methacryloxypropyltri Toxisilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, Silanes having a methacrylic group or an acrylic group such as acryloxymethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, etc. Silanes having, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane, Silanes having an alkyl group such as tiltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, etc. Silane coupling agents exemplified by various silanes such as other silanes, one or more partial hydrolysates selected from the group consisting of these silanes, hexamethyldisiloxane, hexamethyldi Silazane and the like can be mentioned. Of these, polysiloxanes are preferable, and polydimethylsiloxane is more preferable.

  The method for treating the surface of the white pigment is not particularly limited. For example, the surface treatment with the organosilicon compound can be performed by a dry method in which a white pigment and an organosilicon compound are mixed. The surface treatment with alumina or silica can be performed by a wet method in which a layer is formed on the surface of the white pigment while neutralizing with sulfuric acid in an aqueous solution of sodium aluminate or sodium silicate.

  The blending amount of the white pigment is preferably 3 to 300 parts by mass, particularly preferably 5 to 250 parts by mass, with respect to 100 parts by mass of the component (A). If the amount is less than 3 parts by mass, sufficient whiteness may not be obtained. On the other hand, when the amount exceeds 300 parts by mass, not only the ratio of other components added for the purpose of improving the mechanical strength is decreased, but also the moldability may be significantly lowered. In addition, 1-50 mass% is preferable with respect to the whole white thermosetting epoxy resin composition (mass), and, as for the compounding quantity of this white pigment, the range of 3-40 mass% is especially preferable.

(C) Inorganic filler In the white thermosetting epoxy resin composition of the present invention, an inorganic filler other than the component (B) is further blended as the component (C). As such an inorganic filler, what is normally mix | blended with an epoxy resin composition can be used. Examples thereof include silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, antimony trioxide, glass fiber, potassium titanate, and the like. (White colorant) is excluded. The average particle size and shape of these inorganic fillers are not particularly limited, but the average particle size is usually 3 μm or more and 50 μm or less, particularly 5 μm or more and 45 μm or less. Alumina and silica can be used as a white pigment, but those having an average particle diameter of 1 μm or more are used as inorganic fillers, and those having an average particle diameter of less than 1 μm are used as the white pigment. 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.

  As the inorganic filler, silica-based inorganic fillers such as crushed silica and fused spherical silica are particularly preferably used, and this is not particularly limited, but in view of moldability and fluidity, fused spherical silica is preferably used. The average particle diameter is preferably 4 to 40 μm, and particularly preferably 7 to 35 μm. In order to obtain high fluidity, it is preferable to use a combination of a fine region of 0.1 to 3 μm, a medium particle size region of 4 to 8 μm, and a coarse region of 10 to 50 μm.

  Inorganic fillers other than the above component (B) are used for coupling such as a silane coupling agent and a titanate coupling agent in order to increase the bonding strength with the resin component of component (A) and the white pigment of component (B). You may use what was surface-treated beforehand with the agent. Examples of such a coupling agent include epoxy functions such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Functional alkoxysilanes such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercapto And mercapto-functional alkoxysilanes such as propyltrimethoxysilane. The amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited, but those that do not discolor the treated filler when left at 150 ° C. or higher are preferred.

  (C) As for the compounding quantity of the inorganic filler of a component, 50-850 mass parts is preferable with respect to 100 mass parts of (A) component, and 100-600 mass parts is especially preferable. If the amount is less than 50 parts by mass, sufficient strength may not be obtained. If the amount exceeds 850 parts by mass, unfilled defects due to thickening and flexibility are lost, resulting in defects such as peeling in the element. There is a case. In addition, 10-90 mass% of the whole composition (mass) is preferable, and the compounding quantity of the inorganic filler of this (C) component has the preferable range of 20-80 mass% especially.

(D) Curing accelerator The curing accelerator of component (D) is blended to cure the white thermosetting epoxy resin. As the type of curing accelerator, those known as curing accelerators for epoxy resin compositions can be used, and are not particularly limited. Tertiary amines, imidazoles, their organic carboxylates, organic carboxylate metal salts , Metal-organic chelate compounds, aromatic sulfonium salts, phosphorus-based curing catalysts such as organic phosphine compounds and phosphonium compounds, and one or more of these salts. Among these, imidazoles, phosphorus curing accelerators such as 2-ethyl-4-methylimidazole or methyltributylphosphonium dimethyl phosphate, and tertiary amine octylates are more preferable. A quaternary phosphonium bromide and an organic acid salt of amine can also be used in combination.

  0.05-5 mass% is preferable with respect to the sum total (mass) of (A) component, and, as for the compounding quantity of a hardening accelerator, 0.1-2 mass% is especially preferable. 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.

(E) Release agent A release agent is mix | blended with the white thermosetting epoxy resin composition of this invention as (E) component. (E) The mold release agent of a component is mix | blended in order to improve the mold release property at the time of shaping | 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 or carnauba wax with little discoloration over time, although having little color change, are preferred. These release agents may be used alone or in combination.

  The release agent which is the component (E) used in the white thermosetting epoxy resin composition according to the present invention is not particularly limited, but the compound used as a release aid which is the component (F). It is preferable to select in consideration of compatibility.

  The amount of release agent (E) added is 0.05 to 7.0% by mass, preferably 0.1 to 5.0% by mass, based on the total (mass) of component (A). When the addition amount is less than 0.05% by mass, sufficient releasability may not be obtained. When the addition amount exceeds 7.0% by mass, a squeeze out defect or poor adhesion may occur.

(F) Mold release aid The white thermosetting epoxy resin composition of the present invention contains a mold release aid as the component (F), which is an alkenyl group-containing epoxy compound and / or an alkenyl group-containing phenol compound. It is a block copolymer obtained by addition-reacting an SiH group of an organopolysiloxane represented by the following average composition formula (1) to an alkenyl group.

  Such a specific block copolymer plays a role of enhancing the releasability and reducing the contamination of the lead frame derived from the release agent by assisting the emulsification and dispersion of the release agent as the component (E). . The copolymer derived from the epoxy compound and the copolymer derived from the phenol compound may be used alone or in combination. Among them, it is preferable to use an addition copolymer of an alkenyl group-containing epoxy compound and an organopolysiloxane represented by the above formula (1) because the heat discoloration is more excellent. From the viewpoint of discoloration due to heat or light, the component (F) of the present invention is preferably a block copolymer that does not have a polyvalent functional group (for example, a methylene group, a carbonyl group, an imino group, etc.). .

  Here, R in Formula (1) is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups such as butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, decyl group, alkenyl group such as vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, phenyl group, xylyl group Group, aryl group such as tolyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, etc., and some or all of hydrogen atoms of these hydrocarbon groups are replaced by halogen atoms such as chlorine, fluorine, bromine, etc. And halogen-substituted monovalent hydrocarbon groups such as chloromethyl group, trifluoropropyl group, and bromoethyl group.

  In the formula (1), the ranges of a and b are positive numbers satisfying 0.001 ≦ a ≦ 1, 1 ≦ b ≦ 3, and 1.001 ≦ a + b ≦ 3, and the preferable range is 0.01 ≦ a ≦ 0.5, 1.5 ≦ b ≦ 2.5, 1.51 ≦ a + b ≦ 3.0, and the number of silicon atoms in one molecule of the organopolysiloxane of formula (1) is 2 to 1000, 10 The number is preferably 200, and the number of hydrogen atoms (SiH groups) directly bonded to silicon atoms is preferably 1 to 10 and 1 to 5. The organopolysiloxane content in the block copolymer is 5 to 50% by mass, preferably 10 to 20% by mass.

  The method for producing the copolymer of the present invention is already known (Japanese Patent Publication No. 63-60069, Japanese Patent Publication No. 63-60070, etc.), an alkenyl group of an alkenyl group-containing epoxy compound or an alkenyl group-containing phenol compound, It can be obtained by addition reaction with the SiH group of the organopolysiloxane represented by the above formula (1).

  More specifically, examples of the block copolymer include structures represented by the following formulas (3) and (4).

(In Formula (3), R ¹ is an organic group having a cyclic ether, and R ² is an addition of an organic group having a double bond and a polyorganosiloxane having a Si—H group capable of reacting with the double bond. (The reaction may be linear or branched.)

(In Formula (4), R ³ is an organic group having a double bond, and R ⁴ is an organic group having a double bond and a polyorganosiloxane having a Si—H group capable of reacting with the double bond. It is an addition-reaction product and may be linear or branched.)

  More specifically, examples of the block copolymer include structures represented by the following formulas (5) and (6).

(In Formula (5), R is the same as the above, n is an integer of 1 to 200, preferably 10 to 100, and s and t are integers of 1 to 100, preferably 1 to 20.)

(In Formula (6), R is the same as the above, n is an integer of 1 to 200, preferably 10 to 100, and s and t are integers of 1 to 100, preferably 1 to 20.)

  In the present invention, the content of organopolysiloxane in the mold release aid as component (F) is 5 to 50% by mass, preferably 10 to 20% by mass.

  As content when using the block copolymer which is (F) component, 0.01-5 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.03-3 mass parts. It is.

  In the present invention, the following components may be added as necessary.

(G) Antioxidant The white thermosetting epoxy resin composition of the present invention can contain an antioxidant as the component (G) for improving the initial reflectance and maintaining the reflectance over a long period of time. (G) As an antioxidant of a component, a phenol type, phosphorus type, and sulfur type antioxidant can be used, and the following are mentioned as a specific example of antioxidant.

  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 diphenyl alkyl phosphite, phenyl dialkyl phosphite, trilauryl phosphite, trioctadecyl phosphite, triphenyl phosphite, trisnonyl phenyl phosphite, distearyl pentaerythritol diphosphite, Tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, di (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite and tetrakis ( 2,4-di-tert-butylphenyl) -4,4′-biphenyl diphosphonate and the like.

  Examples of sulfur-based antioxidants include diuraryl thiopropionate, distearyl thiopropionate, dibenzyl disulfide, 4,4′-thiobis (6-tert-butyl-o-cresol), 4,4 ′. -Thiobis (6-tert-butyl-m-cresol) and the like.

  These antioxidants can be used alone or in combination of two or more. 0.01-10 mass% is preferable with respect to the sum total (mass) of (A) component, and, as for the compounding quantity of antioxidant, 0.03-8 mass% is especially preferable. If the blending amount is too small, sufficient heat resistance may not be obtained and discoloration may occur, and if it is too large, curing may be inhibited and sufficient curability and strength may not be obtained. The whiteness of the cured product of the white thermosetting epoxy resin composition may not be maintained due to discoloration of the component itself.

  You may mix | blend the following component with the composition of this invention further.

(H) Coupling agent The white thermosetting epoxy resin composition of the present invention includes a silane cup in order to increase the bonding strength between the resin and the inorganic filler or to improve the adhesion to the lead frame. Coupling agents such as a ring agent and a titanate coupling agent can be blended. 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. The amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited, but the resin discolors when left at 150 ° C. or more like an amine-based silane coupling agent. Is less preferred.

  Component (H) can be added in an amount of 0.1 to 8.0 mass%, preferably 0.5 to 6.0 mass%, based on the mass of component (A). If the content is less than 0.1% by mass, the effect of adhesion to the substrate is not sufficient, and if it exceeds 8.0% by mass, the viscosity is extremely lowered, which may cause voids.

Other Additives Various additives can be further blended into the white 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 silicone powder, silicone oil, thermoplastic resin, thermoplastic elastomer, and organic synthetic rubber can be added and blended within a range that does not impair the effects of the present invention.

  Although the manufacturing method of the white thermosetting epoxy composition of this invention is not specifically limited, For example, the following method is mentioned. An epoxy resin, a curing agent, a white pigment, an inorganic filler, a curing catalyst, and other additives are blended at a predetermined composition ratio, and mixed sufficiently uniformly by a mixer or the like, and then heated rolls, kneaders, extruders, etc. It can be melt-mixed, then cooled and solidified, and pulverized to an appropriate size to form a molding material for a white 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 not used for the preparation of the solid (reactant), the curing accelerator of component (D) and other additives as necessary are blended in a predetermined composition ratio, and after mixing this sufficiently uniformly with a mixer, etc., heat It can be melt-mixed with a roll, kneader, extruder, etc., then cooled and solidified, and pulverized to an appropriate size to form a molding material for the epoxy resin composition.

The most common molding method for 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 white thermosetting epoxy resin composition of the present invention can also be used for sealing a normal semiconductor sealing material and various on-vehicle modules. 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.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. 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 raw materials used in Examples and Comparative Examples are shown below.

(A) Prepolymer (A-1) Triazine derivative epoxy resin (A-1-1) Tris (2,3-epoxypropyl) isocyanurate (TEPIC-S: trade name, manufactured by Nissan Chemical Co., Ltd.)
(A-2) Acid anhydride (A-2-1) Methylhexahydrophthalic anhydride (Ricacid MH: trade name, manufactured by Shin Nippon Rika Co., Ltd.)

(B) White pigment (B-1) Alumina / silica / polyol treatment, titanium dioxide having an average particle size of 0.21 μm (CR-63: trade name manufactured by Ishihara Sangyo Co., Ltd.)

(C) Inorganic filler (C-1) Spherical fused silica having an average particle size of 10 μm (RS-8225 / 53C, trade name, manufactured by Tatsumori)

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

(E) Release agent (E-1) Montanic acid wax (LICOWAX E: trade name manufactured by Clearant Japan Co., Ltd.)
(E-2) Carnauba wax (TOWAX-131: trade name manufactured by Toa Kasei Co., Ltd.)

(F) Mold release aid (F-1) Block copolymer represented by the following formula (7) (manufactured)

  (F-2) Block copolymer represented by the following formula (8) (manufactured)

(F-3) Both-end epoxy silicone oil (KF-105: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
(F-4) Silicone oil (KF-96-1000: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

(G) Antioxidant (G-1) Phenol type antioxidant (AO-60: ADEKA Corporation product name)

(H) Coupling agent (H-1) 3-Mercaptopropyltrimethoxysilane (KBM-803: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

Examples 1-5 and Comparative Examples 1-5
(A-1) Epoxy resin and (A-2) acid anhydride were previously melt-mixed in a reaction kettle at 80 ° C. for 6 hours, cooled and solidified (softening point 50 ° C.), then average particle size 1 Crushed into a fine powder of 5 μm, blended with other components at a predetermined composition ratio, melted and mixed uniformly with two hot rolls, cooled and crushed to obtain a white thermosetting epoxy resin composition It was. The following properties were measured for these compositions. The results are shown in Table 1 (Examples) and Table 2 (Comparative Examples).

Spiral flow value A mold conforming to the EMMI standard was used 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.

Bending strength at room temperature, flexural modulus Using a mold conforming to JIS K 6911: 2006 standard, molding is performed 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. Post-curing at 1 ° C. for 1 hour. The post-cured test piece was measured for bending strength and bending elastic modulus at room temperature (25 ° C.).

Continuous moldability test and lead frame contamination confirmation Using a mold that can mold five frame packages with outer dimensions of 10 x 10 x 1 mm on a silver-plated lead frame and that can be released with an ejector pin, The continuous moldability of transfer molding of the resin composition prepared in each example and the contamination state on the lead frame were confirmed. The upper limit was set to 150 shots, and it was determined that continuous molding was possible when the molded product did not break, such as gate break or runner breakage, and did not stick to the mold. Regarding lead frame contamination, “○” indicates that no white haze occurs on the lead frame, and “x” indicates that white haze has occurred even once. The molding was performed 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.

Light reflectivity A disk-shaped cured product having a diameter of 50 mm and a thickness of 3 mm was prepared 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 manufactured by SDG Co., Ltd. The initial light reflectance at 450 nm was measured using X-rite 8200. Thereafter, secondary curing at 150 ° C. for 2 hours or 175 ° C. for 1 hour was performed, and an initial light reflectance at 450 nm was measured using X-lite 8200 manufactured by SDG Co., Ltd. in the same manner.

  As shown in Tables 1 and 2, when a predetermined block copolymer (for example, F-1, F-2) as the component (F) was used, continuous moldability was improved. The number of shots in continuous molding was 90 shots or less in the comparative example, but about 140 shots or more in the examples. In addition, the addition of component (F) has no problem with reactivity with epoxy resin or curing agent, no contamination of lead frame, and no influence on characteristics such as fluidity, mechanical strength, and light reflectance. Was confirmed. Furthermore, the component (F) used in the present invention is a block copolymer having no polyvalent functional group (for example, a methylene group, a carbonyl group, an imino group, etc.), and the block copolymer having a polyvalent functional group. It is difficult to cause discoloration due to heat or light that occurs when a polymer is used. From the above results, it was confirmed that the semiconductor device in which the LED reflector was sealed with the cured product having the composition was effective.

Claims (7)

(A) (A-1) A prepolymer obtained by reacting a triazine derivative epoxy resin with (A-2) an acid anhydride, and (A-2) based on the total number of acid anhydride groups in the component (A-1) a prepolymer in which the ratio of the total number of epoxy groups in the component is 0.6 to 2.0,
(B) a white pigment,
(C) inorganic filler,
(D) a curing accelerator,
(E) a release agent, and
(F) mold release aid,
A white thermosetting epoxy resin composition containing the component (F), wherein the release assistant of the component (F) is an alkenyl group-containing epoxy compound and / or an alkenyl group of the alkenyl group-containing phenol compound represented by the following average composition formula (1): A white thermosetting epoxy resin composition which is a block copolymer obtained by addition-reacting SiH groups of the organopolysiloxane shown.

(In Formula (1), R is a substituted or unsubstituted monovalent hydrocarbon group, and a and b satisfy 0.001 ≦ a ≦ 1, 1 ≦ b ≦ 3, and 1.001 ≦ a + b ≦ 3. (It is a positive number.)   Furthermore, the white thermosetting epoxy resin composition of Claim 1 which contains antioxidant as (G) component.   (B) The white thermosetting epoxy resin composition according to claim 1 or 2, wherein the white pigment has an average particle size of 1 µm or less.   (B) The white pigment is titanium oxide whose surface is treated with alumina, and further treated with at least one selected from the group consisting of silica, alumina, zirconia, polyol, and siloxane. The white thermosetting epoxy resin composition according to any one of the above.   The white thermosetting epoxy resin composition according to any one of claims 1 to 4, wherein the (A-1) component triazine derivative epoxy resin is a 1,3,5-triazine derivative epoxy resin. The white thermosetting epoxy resin composition according to any one of claims 1 to 5, wherein the prepolymer of the component (A) contains a compound represented by the following general formula (2).

(In formula (2), R ¹ represents an acid anhydride residue, and m is a number from 0 to 200.) An optical semiconductor device provided with the optical semiconductor element case formed with the white thermosetting epoxy resin composition of any one of Claims 1-6.