JP2013159776A - Silicon-containing curable white resin composition, cured product thereof, and optical semiconductor package and reflecting material using the cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicon-containing curable white resin composition which is excellent in heat resistance, light resistance, cracking resistance and various mechanical and physical properties such as warpage and is useful as an optical semiconductor material or the like and to provide a cured product obtained by curing the silicon-containing curable white resin composition, and an optical semiconductor package and a reflecting material which are obtained by using the cured product.SOLUTION: A silicon-containing curable white resin composition contains: a polymer containing specific silicon; a prepolymer containing two or more Si-H groups in one molecule thereof; a linear siloxane compound containing two or more carbon-carbon double bonds, each of which has reactivity with the Si-H group or a Si-CH, in one molecule thereof; an organic peroxide; a metallic catalyst; and a filler or white pigment having specific particle size.

Description

  The present invention relates to a silicon-containing curable white resin composition, a white resin cured product obtained by curing the silicon-containing curable white resin composition, an optical semiconductor package and a reflective material using the cured product, and in particular, has an optical reflectance of 70 at an ultraviolet region wavelength of 405 nm. The present invention relates to a white resin cured product having a high luminance performance of at least%, an optical semiconductor package and a reflective material using the cured product.

  In recent years, LEDs (light-emitting diodes) have been used for displays, destination display boards, in-vehicle lighting, signal lights, video cameras, etc. due to advantages such as high energy efficiency and long life, and as light sources to replace fluorescent lamps, incandescent lamps, etc. The demand is expanding. These are usually equipped with an LED device in which LED elements are mounted on a circuit pattern on a substrate with a conductive adhesive, solder, or the like and necessary connections are made by wire bonding. A reflector (reflecting material) for increasing the light utilization rate is provided, and the LED element located in the reflector is sealed with a translucent resin such as an epoxy resin or a silicone resin.

  The white LED is generally a combination of a plurality of LEDs such as red (R: 630 nm), green (G: 525 nm), blue (B: 470 nm), etc. It is known that a fluorescent substance such as a green or blue pigment is blended to use the wavelength conversion action. In the latter case, the ultraviolet light emitting LED is used as a light source. The molded body of the resin composition which mix | blended white pigment particles, such as a metal oxide, may be used for the reflector of these white LED. Since LED elements generate heat during light emission, in such a type of LED lighting device, the temperature rise during light emission of the LED elements becomes a factor that degrades the reflector, leading to a decrease in brightness, a shortened life of the LED elements, and the like. It becomes. Therefore, it is desired to develop a reflector material having high light reflectance and excellent heat resistance, light resistance, crack resistance, warpage, and the like. In recent years, light in the ultraviolet region (420 nm or less) is emitted. Since LEDs have come to be used, what has a high light reflectance even in such a wavelength region is required.

  The following Patent Documents 1 to 3 disclose high light reflectance silicone resin compositions in which titanium oxide is added as a white pigment to a silicone resin as a reflector material. These silicone resin compositions are visible light. Although it has a very high light reflectance in the region, since titanium oxide absorbs UV light with a wavelength of 420 nm or less well, it hardly reflects light in the UV region with a wavelength of 420 nm or less, and these silicone resin compositions are The mechanical properties such as heat resistance, light resistance, crack resistance and warpage were not fully satisfactory.

JP 2010-263165 A JP 2010-274540 A International Publication No. WO2009 / 069741

  Accordingly, an object of the present invention is to provide a silicon-containing curable white resin composition having excellent mechanical properties such as heat resistance, light resistance, crack resistance and warpage, and useful for optical semiconductor materials and the like, and curing the same. It is to provide a cured product and an optical semiconductor package and a reflective material using the cured product.

  As a result of intensive studies to solve the above problems, the present inventor has completed the present invention with a composition comprising a silicone resin having a specific silicon-containing compound structure and a filler or white pigment.

That is, the present invention
As the component (A), one or more types of the organosilane (a) represented by the following general formula (1-1), 5 to 50 mol%, the organosilane (b) represented by the following general formula (1-2) One or more types of 0 to 50 mol%, one or more types of organosilane (c) represented by the following general formula (1-3) 0 to 40 mol%, an organosilane (d) represented by the following general formula (1-4) 1) or more and 0 to 50 mol% of the organosilane (e) represented by the following general formula (1-5) and 0 to 40 mol% of the organosilane (b), the organosilane (c), 100 parts by mass of a silicon-containing polymer obtained by hydrolyzing and condensing an organosilane mixture having a sum of 5 to 60 mol% and having a weight average molecular weight of 300 to 100,000,
(B) As a component, 1 or more types chosen from the cyclic siloxane compound ((alpha)) represented by the following general formula (2), the following general formula (3-1), the following formula (3-2), or the following general formula ( 3-3) Prepolymer 0 to 200 parts by mass containing two or more Si—H groups in one molecule, obtained by hydrosilylation reaction of one or more selected from the compound (β) represented by 3-3) ,
As component (C), 0.1 to 30 parts by mass of a linear siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si-H group or Si-CH ₃ in one molecule;
As component (D), organic peroxide 0.0001 to 10 parts by mass and metal catalyst 0 to 1.0 parts by mass,
(E) As a component, 0-1500 mass parts of fillers or white pigments having an average particle size of 3 μm or more and 150 μm or less,
(F) A silicon-containing curable white resin composition characterized by containing 10 to 1500 parts by mass of a filler or white pigment (excluding titanium oxide) having an average particle size of 0.05 μm or more and less than 3 μm as a component. It is to provide.

（式中、Ｒ¹は炭素原子数２〜６のアルケニル基を表し、Ｒ²は水素原子又は炭素原子数１〜６のアルキル基を表し、Ｒ³及びＲ⁴は、それぞれ独立に、水素原子又は炭素原子数１〜６のアルキル基、炭素原子数２〜６のアルケニル基又は炭素原子数１〜６のアルキル基で置換されていてもよいフェニル基を表し、Ｒ²、Ｒ³及びＲ⁴のうちの少なくとも１つはメチル基であり、Ｒ⁵は炭素原子数１〜６のアルキル基で置換されていてもよいフェニル基を表し、Ｒ⁶は炭素原子数２〜１０のエポキシ基を表し、Ｘは水酸基、炭素原子数１〜６のアルコキシ基又はハロゲン原子を表す。）

(In the formula, R ¹ represents an alkenyl group having 2 to 6 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ are each independently a hydrogen atom. Or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and R ² , R ³ and R ⁴ At least one of them is a methyl group, R ⁵ represents a phenyl group which may be substituted with an alkyl group having 1 to ⁶ carbon atoms, and R ⁶ represents an epoxy group having 2 to 10 carbon atoms. , X represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.)

（式中、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ独立に、炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルキル基で置換されていてもよいフェニル基を表し、ｆ個のＲ⁷は同一であっても異なっていてもよく、ｇ個のＲ⁸、ｇ個のＲ⁹もそれぞれ同一であっても異なっていてもよい。ｆは２〜１０の数を表し、ｇは０〜８の数を表し、ｆ＋ｇ≧２である。）

(In the formula, R ⁷ , R ⁸ and R ⁹ each independently represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; R ⁷ may be the same or different, and g R ⁸ and g R ⁹ may be the same or different, and f represents a number of 2 to 10, g represents a number from 0 to 8, and f + g ≧ 2.

（式中、Ｒ¹⁰は炭素原子数２〜１０のアルケニル基を表し、Ｒ¹¹及びＲ¹²は、それぞれ独立に、炭素原子数１〜１０のアルキル基、炭素原子数２〜１０のアルケニル基又は炭素原子数２〜１０のエポキシ基を表し、ｎは１又は２を表す。）

(Wherein R ¹⁰ represents an alkenyl group having 2 to 10 carbon atoms, and R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or Represents an epoxy group having 2 to 10 carbon atoms, and n represents 1 or 2.)

Moreover, this invention provides the said silicon containing curable white resin composition whose content of the said (B) component with respect to 100 mass parts of said (A) component is 10-200 mass parts.
The present invention also provides the silicon-containing curable white resin composition, wherein the component (C) is a linear siloxane compound represented by the following general formula (4).

（式中、Ｒ¹³及びＲ³²は、それぞれ独立に、炭素原子数２〜６のアルケニル基、炭素原子数１〜６のアルキル基、炭素原子数２〜１０のエポキシ基又はトリメチルシリル基を表し、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ²¹、Ｒ²⁵、Ｒ²⁹、Ｒ³⁰及びＲ³¹は、それぞれ独立に、水素原子又は炭素原子数１〜６のアルキル基を表し、Ｒ¹⁸、Ｒ¹⁹及びＲ²⁰は、フェニル基を表し、Ｒ²²、Ｒ²³及びＲ²⁴は、それぞれ独立に、炭素原子数２〜６のアルケニル基を表し、Ｒ²⁶、Ｒ²⁷及びＲ²⁸は、それぞれ独立に、炭素原子数２〜１０のエポキシ基を表し、Ｒ¹³及びＲ³²が炭素原子数１〜６のアルキル基である時、ｖ≧１又はｖ＋ｗ≧２であり、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ²¹、Ｒ²⁵、Ｒ²⁹、Ｒ³⁰及びＲ³¹のうち少なくとも一つが水素原子である時、ｖ≧１又はｗ≧１であり、ｐ個のＲ¹⁶及びＲ¹⁷はそれぞれ同一であっても異なっていてもよく、ｒ個のＲ²¹、ｖ個のＲ²²びＲ²³、ｗ個のＲ²⁴びＲ²⁵、ｘ個のＲ²⁶びＲ²⁷、ｙ個のＲ²⁸びＲ²⁹もそれぞれ同一であっても異なっていてもよい。ｐ、ｑ、ｒ、ｖ、ｗ、ｘ及びｙは、それぞれ独立に、０〜３０００の数を表し、ｐ＋ｑ＋ｒ＋ｖ＋ｗ＋ｘ＋ｙ≧１である。）

(Wherein R ¹³ and R ³² each independently represents an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an epoxy group having 2 to 10 carbon atoms, or a trimethylsilyl group, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²¹ , R ²⁵ , R ²⁹ , R ³⁰ and R ³¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁸ , R ¹⁹ and R ²⁰ each represent a phenyl group, R ²² , R ²³ and R ²⁴ each independently represent an alkenyl group having 2 to 6 carbon atoms, and R ²⁶ , R ²⁷ and R ²⁸ each independently represent Represents an epoxy group having 2 to 10 carbon atoms, and when R ¹³ and R ³² are alkyl groups having 1 to 6 carbon atoms, v ≧ 1 or v + w ≧ 2, and R ¹⁴ , R ¹⁵ , R ^16, when at least one of ^{R 17, R 21, R 25} , R 29, R 30 and R ³¹ are hydrogen atoms, v ≧ Or a w ≧ 1, p pieces are of R ¹⁶ and R ¹⁷ may be the each be the same or different, r pieces of R ^21, v number of R ²² beauty R ^23, w pieces of R ²⁴ Beauty R ²⁵ , x R ^{26 and} R ²⁷ , and y R ^{28 and} R ²⁹ may be the same or different, and p, q, r, v, w, x and y are each independently Represents a number from 0 to 3000, and p + q + r + v + w + x + y ≧ 1.)

The present invention also provides the silicon-containing curable white resin composition, wherein the component (F) is alumina.
The present invention also provides a cured product obtained by curing the silicon-containing curable white resin composition.
Further, the present invention is an optical semiconductor package provided with a reflector, the reflector is made of the cured product, has a light reflectance at a wavelength of 460 nm of 80% or more, and a light reflectance at a wavelength of 405 nm. It is 70% or more, and further provides an optical semiconductor package characterized in that the light reflectance at a wavelength of 405 nm after heat treatment at 300 ° C. for 10 minutes is 60% or more.

  According to the present invention, mold molding such as transfer molding and injection molding is possible, and the cured product has high light reflectance and excellent physical properties such as heat resistance, light resistance, crack resistance and warpage. A silicon-containing curable white resin composition useful for semiconductor materials such as a reflector material for LEDs can be provided.

  Hereinafter, the silicon-containing curable white resin composition of the present invention, a cured product obtained by curing the same, an optical semiconductor package and a reflective material using the cured product will be described in detail.

<(A) component>
First, the silicon-containing polymer as the component (A) will be described.

  The weight average molecular weight of the silicon-containing polymer as the component (A) is in the range of 300 to 100,000, preferably in the range of 800 to 50,000, in terms of polystyrene. Here, when the weight average molecular weight of the silicon-containing polymer is less than 300, desirable physical properties cannot be obtained (decrease in thermal weight loss temperature), and when it exceeds 100,000, it does not melt at the processing temperature in transfer molding or melts. However, it is not preferred because the viscosity of the resin is low, the flowability of the resin is low, and the moldability is lowered.

The silicon-containing polymer of the component (A) is represented by one or more types of the organosilane (a) represented by the general formula (1-1), 5 to 50 mol%, and the general formula (1-2). One or more types of organosilane (b) 0 to 50 mol%, one or more types of organosilane (c) represented by the above general formula (1-3) 0 to 40 mol%, represented by the above general formula (1-4) 1 to 1 to 50 mol% of the organosilane (d) and 1 to 40 mol% of the organosilane (e) represented by the general formula (1-5), It can be obtained by hydrolyzing and condensing an organosilane mixture having a sum of 5 to 60 mol% with the organosilane (c). In the organosilane mixture, the organosilane (a) is preferably 10 to 40 mol% from the viewpoint of controlling the crosslinking density during curing. Organosilanes (b) and (c) may not contain any one component as long as the sum of organosilane (b) and organosilane (c) is 5 to 60 mol%, The organosilane (b) is preferably 20 to 40 mol% from the viewpoint of controlling the crosslinking density at the time of curing, and the organosilane (c) is preferably 10 to 25 from the viewpoint of imparting flexibility to the resin. It is preferable that it is mol%. Although organosilane (d) may not contain, it is preferable that it is 5-45 mol% from the point of control of resin melting temperature. Although organosilane (e) may not contain, it is preferable that it is 5-25 mol% from the point of the adhesive provision to a dissimilar material.
Moreover, it is preferable that the sum of organosilane (b) and organosilane (c) is 25-55 mol% from the point of control of the crosslinking density at the time of hardening. The organosilane contained in the organosilane mixture is composed of only five components of organosilanes (a), (b), (c), (d) and (e) from the viewpoint of controlling the molecular weight of the silicon-containing polymer. Preferably there is.

The silicon-containing polymer as component (A) is derived from organosilanes (a), (b), (c), (d) and (e), respectively (R ¹ SiO _3/2 ), (R ² SiO _3/2 ), (R ³ R ⁴ SiO), (R ⁵ SiO _3/2 ) and (R ⁶ SiO _3/2 ), 5 types of structural units are randomly connected in 2D and 3D. Each terminal is an OH group or X. X is a group derived from organosilane (a), (b), (c), (d) or (e). The (R ¹ SiO _3/2 ) includes (R ¹ SiX′O _2/2 ), and the (R ² SiO _3/2 ) includes (R ² SiX′O _2/2 ). (R ⁵ SiO _3/2 ) includes (R ⁵ SiX′O _2/2 ), and (R ⁶ SiO _3/2 ) includes (R ⁶ SiX′O _2/2 ). Shall be. X ′ is the same as X contained in each of the organosilanes (a), (b), (d) and (e), or represents an OH group.

In the general formula (1-1), examples of the alkenyl group having 2 to 6 carbon atoms represented by R ¹ include a vinyl group, a 2-propenyl group, and a 3-butenyl group. R ^l is preferably a vinyl group from the viewpoint of reactivity. In the general formula (1-2), the alkyl group having 1 to 6 carbon atoms represented by R ² may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, and a propyl group. Group, isopropyl group, butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, cyclohexyl group and the like. R ² is preferably a methyl group from the viewpoint of reactivity.

In the general formula (1-3), R ³ and an alkyl group having 1 to 6 carbon atoms represented by R ^4, and R ³ and optionally carbon atoms be substituted phenyl group represented by R ⁴ Examples of the alkyl group of 1 to 6 include the same groups as those described above for R ² . Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ³ and R ⁴ include the same groups as those represented by R ¹ above. R ³ and R ⁴ are preferably a methyl group or an unsubstituted phenyl group, and particularly preferably a methyl group, from the viewpoint of industrial availability. In the above general formula (1-4), the alkyl group having 1 to 6 carbon atoms which may substitute the phenyl group represented by R ⁵ is the same as those exemplified as those represented by R ^2. Can be mentioned. R ⁵ is preferably an unsubstituted phenyl group from the viewpoint of industrial availability.

In the above general formula (1-5), the epoxy group having 2 to 10 carbon atoms represented by R ⁶ is a substituent having a three-membered cyclic ether, such as an epoxyethyl group, glycidyl group, 2 , 3-epoxybutyl group, 3,4-epoxybutyl group, epoxyethylphenyl group, 4-epoxyethylphenylethyl group, 3,4-epoxycyclohexyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2 , 3-epoxynorbornylethyl group and the like. R ⁶ is preferably a glycidyl group, a 3,4-epoxycyclohexyl group, or a 2- (3,4-epoxycyclohexyl) ethyl group from the viewpoint of imparting adhesion to different materials.

  In the general formulas (1-1) to (1-5), examples of the alkoxy group having 1 to 6 carbon atoms represented by X include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom represented by the formula include a chlorine atom, a bromine atom, and an iodine atom. X is preferably a methoxy group or an ethoxy group from the viewpoint of reactivity. In addition, each X in the general formulas (1-1) to (1-5) may be the same as or different from each other.

  When X is an alkoxy having 1 to 6 carbon atoms (alkoxysilane) as the five components, the hydrolysis / condensation reaction of alkoxysilane may be performed by a so-called sol-gel reaction. Examples of the reaction include a method of performing a hydrolysis / condensation reaction with a catalyst such as an acid or a base in the absence of a solvent or in a solvent. The solvent used here is not particularly limited. Specifically, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene and the like can be used. 1 type of these can be used, and 2 or more types can also be mixed and used.

  The hydrolysis / condensation reaction of the alkoxysilane proceeds when the alkoxysilane generates silanol groups (Si—OH) by hydrolysis with water, and the generated silanol groups or silanol groups and alkoxy groups condense. In order to advance this reaction, it is preferable to add an appropriate amount of water. Water may be added to the solvent, or the catalyst may be added after dissolving in water. The hydrolysis / condensation reaction proceeds even with moisture in the air or a trace amount of moisture contained in the solvent.

  The catalyst such as acid or base used in the hydrolysis / condensation reaction is not particularly limited as long as it promotes the hydrolysis / condensation reaction. Specifically, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and the like are used. Organic acids such as acetic acid, oxalic acid, p-toluenesulfonic acid and monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; trimethylamine, triethylamine, monoethanolamine, diethanolamine and the like Amine compounds; titanium esters such as tetraisopropyl titanate and tetrabutyl titanate; tin carboxylates such as dibutyltin laurate and tin octylate; boron compounds such as trifluoroboron; iron, cobalt, manganese, zinc and the like Metal carboxylates such as metal chlorides, naphthenates or octylates ; Include aluminum compounds such as aluminum tris acetyl acetate are also using these one can also be used in combination of two or more.

  A preferred example of the hydrolysis / condensation reaction of the alkoxysilane is a method in which a base catalyst is added and a polycondensation reaction is performed under basic conditions (pH 7 or more). In addition, hydrolysis and dehydration polycondensation can be performed under the acidic condition (pH 7 or less) by adding an acid catalyst.

  In addition, when performing the said hydrolysis and condensation reaction, it is preferable to stir a reaction system, and reaction can be accelerated | stimulated by heating at 40-150 degreeC.

The order of the hydrolysis / condensation reaction is not particularly limited. For example, an alkoxysilane (R ¹ SiX ₃ ) having an alkenyl group and another alkoxysilane (R ² SiX ₃ , R ³ R ⁴ SiX ₂ , R ⁵ SiX _3). , R ⁶ SiX ₃ ) may be mixed to carry out hydrolysis / condensation reaction. After hydrolysis / condensation reaction is performed to some extent with one kind of these alkoxysilanes alone, Hydrolysis / condensation reaction may be further performed by adding silane.

  As the above five components, those in which X is a hydroxyl group and those in which X is an alkoxy group may be used in combination. In this case, those in which X is a hydroxyl group can be used without hydrolysis.

  Even when halogenosilane such as chlorosilane (where X in the above five components is a halogen atom) is used, the hydrolysis / condensation reaction may be carried out in the same manner as in the case of alkoxysilane.

  In order to obtain the produced silicon-containing polymer from the reaction system in which the hydrolysis / condensation reaction is completed, the reaction solvent, water, and catalyst may be removed. For example, after solvent extraction by adding a solvent such as toluene, The extraction solvent may be distilled off under reduced pressure under a nitrogen stream.

  The component (A) may be used as the component (A) after being modified. The modification applied to the silicon-containing polymer is not particularly limited, and various modifications that can be performed to make the silicone resin a reactive silicone resin are possible. More specifically, amino modification, epoxy modification, Carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification and the like can be carried out by conventional methods.

  In the silicon-containing polymer of the component (A), the proportion of the phenyl group with respect to the proportion in the total organic components (components excluding silicon) is preferably 50% by mass or less, more preferably 30% by mass or less. It is preferable that it is 10-0 mass%. If the proportion of the phenyl group is large, the melting point of the silicon-containing polymer becomes high and it is difficult to melt at the molding temperature, making it difficult to increase the molecular weight of the cured product (polymer) during molding, Since the light reflectance when used as a reflective material tends to decrease, it is preferable that the ratio of the phenyl group is small. If the ratio of the phenyl group is 10% by mass or less, the light reflection in the ultraviolet region near the wavelength of 405 nm Since the rate becomes higher, a more suitable reflective material can be obtained.

  In addition, as said (A) component, the above 1 type (s) or 2 or more types can be used.

<(B) component>
Next, the prepolymer which is the component (B) will be described.
The prepolymer of the component (B) has an effect of improving adhesion to metals, resins, and the like, and includes one or more selected from the above (α) component and one or more selected from the (β) component. It is obtained by hydrosilylation reaction and contains two or more Si-H groups in one molecule. The silicon-containing curable white resin composition of the present invention contains 0 to 200 parts by mass of the prepolymer of the component (B) with respect to 100 parts by mass of the component (A). (B) Although it does not need to contain a component, it is preferable to contain 10-200 mass parts from a viewpoint of said adhesive improvement effect, and it is still more preferable to contain 20-135 mass parts.

The component (α) is a cyclic siloxane compound represented by the general formula (2) and containing two or more Si—H groups in one molecule. R ^7, R ⁸ and alkyl group having 1 to 6 carbon atoms represented by R ^9, and R ^7, R ⁸ and R ⁹ represented phenyl group to be C 1 -C 6 also substitutions Examples of the alkyl group include the same groups as those described above for R ² . R ⁷ is preferably a methyl group from the viewpoint of industrial availability, and R ⁸ and R ⁹ are preferably a methyl group or a phenyl group from the viewpoint of industrial availability. f is preferably 4 to 6 from the viewpoint of ease of production, and g is preferably 0 to 1 from the viewpoint of the crosslinking density of the curing reaction. When the general formula (2) includes both a methyl group and a phenyl group, the ratio of the methyl group to the phenyl group is 4: 1 to 1: 4 in terms of molecular weight control in the entire substituents R ^{7 to} R ^9. Preferably there is.

  Specific examples of the component (α) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9. , 11-hexamethylcyclohexasiloxane and the like, and 1,3,5,7-tetramethylcyclotetrasiloxane is preferred from the viewpoint of industrial availability and the appropriate number of Si-H functional groups. The component (α) may be used alone or in combination of two or more.

  The component (β) is a compound represented by the general formula (3-1), the formula (3-2), or the general formula (3-3).

The compound represented by the general formula (3-1) as the component (β) indicates divinylbenzene when n is 1, and may be any of o-divinylbenzene, m-divinylbenzene or p-divinylbenzene. When n is 2, it represents trivinylbenzene, and any of 1,2,3-trivinylbenzene, 1,2,4-trivinylbenzene, and 1,3,5-trivinylbenzene may be used. The compound represented by the general formula (3-1) may be one in which a functional group other than a vinyl group (for example, an alkyl group such as a methyl group) is bonded to a benzene ring, or a mixture thereof. In the compound represented by the general formula (3-3) as the component (β), the alkenyl group having 2 to 10 carbon atoms represented by R ¹⁰ , R ¹¹ and R ¹² may be the above general formula (1). -1) are the same as those represented by R ^1. Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹¹ and R ¹² include the above general formula (1- 2) In addition to those represented as R ² in 2), heptyl group, octyl group, nonyl group, decyl group, ethylhexyl group and the like can be mentioned, and the number of carbon atoms represented by R ¹¹ and R ¹² is 2 to 10 The epoxy group is an organic group containing an epoxy group, and examples thereof include the same groups as those represented by R ⁶ in the general formula (1-5). As the (β) component, divinylbenzene and trivinylcyclohexane are preferable from the viewpoint of industrial availability. The (β) component may be used alone or in combination of two or more.

  The prepolymer of the component (B) can be obtained by subjecting the component (α) and the component (β) to a hydrosilylation reaction. The blending ratio of the (α) component and the (β) component is not particularly limited as long as two or more Si—H groups are contained in one molecule of the prepolymer of the (B) component. Preferably, from the viewpoint of the viscosity of the prepolymer, a carbon-carbon double bond having reactivity between the number (X) of Si-H groups in the component (α) and the Si-H groups in the component (β). The ratio with respect to the number (Y) is X: Y = 10: 1 to 2: 1, more preferably X: Y = 4: 1 to 2: 1.

  The concentration of the Si-H group contained in the prepolymer of the component (B) is preferably 0.0001 mmol / g to 100 mmol / g, more preferably 0.01 mmol / g to 20 mmol, from the viewpoint of curability and storage stability. / G is preferred.

  The prepolymer of the component (B) preferably has a weight average molecular weight of 500 to 500,000, and more preferably 1000 to 300,000 from the viewpoint of heat resistance and handling properties. The measurement of the weight average molecular weight of the present prepolymer may use GPC, and may be obtained by polystyrene conversion.

  The hydrosilylation reaction between the (α) component and the (β) component may be performed using a platinum catalyst. The platinum-based catalyst may be a known catalyst containing one or more metals of platinum, palladium, and rhodium that promote the hydrosilylation reaction. Platinum-based catalysts used as catalysts for these hydrosilylation reactions include platinum-carbonyl vinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-cyclovinylmethylsiloxane complexes, platinum-octylaldehyde complexes, etc. In addition to the catalyst, compounds containing palladium, rhodium, etc., which are also platinum-based metals, may be used instead of platinum, and one or more of these may be used in combination. In particular, those containing platinum are preferable from the viewpoint of curability, and specifically, platinum-divinyltetramethyldisiloxane complex (Karsttedt catalyst) and platinum-carbonylvinylmethyl complex (Ossko catalyst) are preferable. In addition, a so-called Wilkinson catalyst containing the above platinum-based metal such as chlorotristriphenylphosphine rhodium (I) is also included in the platinum-based catalyst in the present invention. The amount of the platinum-based catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass of the total amount of the component (α) and the component (β) from the viewpoint of reactivity. The hydrosilylation reaction conditions for the (α) component and the (β) component are not particularly limited, and may be carried out under the conventionally known conditions using the above catalyst, but from the point of curing speed, it is carried out at room temperature to 130 ° C. Preferably, a conventionally known solvent such as toluene, xylene, hexane, MIBK (methyl isobutyl ketone), cyclopentanone, or PGMEA (propylene glycol monomethyl ether acetate) may be used during the reaction. The catalyst may be removed after the hydrosilylation reaction between the (α) component and the (β) component, or may be used as it is in the silicon-containing curable white resin composition without being removed.

  The prepolymer of the component (B) is represented by the component (α) which is a cyclic siloxane compound and the general formula (3-1), the formula (3-2) or the general formula (3-3). This is a prepolymer obtained by subjecting the (β) component, which is a compound, to a hydrosilylation reaction, and in the present invention, the (α) component constituting the (B) component is cyclic, and the (α) component is ( A major feature is that the prepolymer reacted with the component β) is used as a blending component of the curable composition. In the silicon-containing curable white resin composition of the present invention, since the component (α) constituting the component (B) has a cyclic structure, the curing shrinkage is small, and therefore a cured product having excellent adhesion can be obtained. Furthermore, since the silicon content can be increased while the viscosity is low, a curable composition having excellent heat resistance and adhesion can be obtained.

<(C) component>
Next, the component (C) will be described.
The component (C) is a linear siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si—H groups or Si—CH ₃ in one molecule. The linear siloxane compound may be a random copolymer or a block copolymer. The number of carbon-carbon double bonds having reactivity with the Si—H group or Si—CH ₃ is preferably 2 to 10, and more preferably 2 to 6 in view of the crosslinking density of the cured product. Further, examples of the carbon-carbon double bond having reactivity with the Si-H group or Si-CH ₃ include alkenyl groups such as vinyl group, 2-propenyl group, and 3-butenyl group. From this point, a vinyl group (Si—CH═CH ₂ group) bonded to a silicon atom is preferable. Moreover, as a (C) component especially preferable from the point of the physical property of hardened | cured material, the linear siloxane compound represented by the said General formula (4) is mentioned.

In the general formula (4), the alkenyl group having 2 to 6 carbon atoms represented by R ¹³ and R ³² , R ²² , R ²³ , and R ²⁴ is exemplified as represented by R ¹ . The thing similar to a thing is mentioned. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹³ and R ³² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²¹ , R ²⁵ , R ²⁹ , R ³⁰ and R ³¹ include The thing similar to what was mentioned as what is represented by R < ² > is mentioned. Examples of the epoxy group having 2 to 10 carbon atoms represented by R ¹³ and R ³² , R ²⁶ , R ²⁷ and R ²⁸ are the same as those exemplified above for R ^6. .

In the above general formula (4), R ¹³ and R ³² are preferably vinyl groups or 2-propenyl groups from the viewpoint of reactivity, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²¹ , R ²⁵ , R ²⁹ , R ³⁰ and R ³¹ are preferably a methyl group or an ethyl group from the viewpoint of industrial availability, and R ²² , R ²³ and R ²⁴ are a vinyl group or a 2-propenyl group from the viewpoint of industrial availability. Is preferred. Specific examples of the preferred component (C) include linear siloxane compounds represented by the following general formulas (5) to (14). Among these, from the viewpoint of reactivity and resin strength increase, the general formula ( The linear siloxane compounds represented by 6), (8), (9) and (14) are particularly preferred.

（式中、ｐ、ｑ及びｒは、上記一般式（４）と同義である。）

(In the formula, p, q and r have the same meaning as in the general formula (4).)

（式中、ｒ及びｑは、上記一般式（４）と同義である。）

(In the formula, r and q have the same meaning as in the general formula (4)).

（式中、ｐは、上記一般式（４）と同義である。）

(In the formula, p has the same meaning as in the general formula (4)).

（式中、ｐ及びｑは、上記一般式（４）と同義である。）

(In the formula, p and q have the same meaning as in the general formula (4)).

（式中、ｐ及びｗは、上記一般式（４）と同義である。）

(In the formula, p and w are as defined in the general formula (4).)

（式中、ｐ、ｒ及びｗは、上記一般式（４）と同義である。）

(In the formula, p, r and w have the same meanings as in the general formula (4)).

（式中、ｐ、ｒ及びｗは、上記一般式（４）と同義である。）

(In the formula, p, r and w have the same meanings as in the general formula (4)).

（式中、ｐ、ｒ及びｗは、上記一般式（４）と同義である。）

(In the formula, p, r and w have the same meanings as in the general formula (4)).

（式中、ｐは、上記一般式（４）と同義である。）

(In the formula, p has the same meaning as in the general formula (4)).

The component (C) is a linear siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si—H group or Si—CH ₃ group in one molecule. Adhesiveness improves because a component is a linear siloxane compound. The silicon-containing curable white resin composition of the present invention contains 0.1 to 30 parts by mass of the linear siloxane compound of the component (C) with respect to 100 parts by mass of the component (A). From the viewpoint of the effect of improving adhesion, it is preferable to contain 0.1 to 25 parts by mass, and more preferably 3 to 20 parts by mass.

In the silicon-containing curable white resin composition of the present invention, the component (A) is preferably 5 to 90% by mass, particularly preferably 5 to 80% by mass, and the sum of the component (B) and the component (C) is 0.05 to 50%. % By mass is preferable, and 5 to 40% by mass is more preferable. The content of the component (B) and the component (C) is the ratio of the carbon-carbon double bond having reactivity with the Si—H group and the Si—H group or the Si—CH ₃ group and the Si—CH ₃ group. May be determined appropriately in consideration of the ratio of carbon-carbon double bonds having reactivity with the Si-H group contained in the component (B) and the reactivity with the Si-H group contained in the component (C). The equivalent ratio (the former / the latter) of the carbon-carbon double bond having the above is preferably 0.1 to 10, particularly preferably 1.0 to 5.0, and the Si—CH ₃ group contained in the component (B) The equivalent ratio (the former / the latter) of the carbon-carbon double bond having reactivity with the Si—CH ₃ group contained in the component (C) is preferably 0.1 to 10, and 1.0 to 5.0. Particularly preferred.

<(D) component>
Next, the organic peroxide which is the component (D) which is a curing accelerator will be described. The component (D) activates the methyl group (Si—CH ₃ group) bonded to the silicon atom in the component (A), and further bonds to the silicon atom in the component (B) and / or the component (C). If methyl groups are present, they are also activated to cause a polymerization reaction between these Si—CH ₃ groups and the alkenyl group in component (A) and further the carbon-carbon double bond in component (C). Acts as a catalyst. The organic peroxide as the component (D) is not particularly limited, and those generally used when curing the silicone rubber composition can be used. For example, benzoyl peroxide, o-methylbenzoyl par Oxide, p-methylbenzoyl peroxide, o-monochlorobenzoyl peroxide, p-monochlorobenzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide, 2,4-dicumylbenzoyl peroxide, di-t-butylbenzoyl Peroxide, t-butylbenzoate, t-butylcumylbenzoyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, 1,1-bis ( t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5- Methyl-2,5-di (t-butylperoxy) hexane, 1,6-bis (t-butylperoxycarboxy) hexane, dichromyl peroxide, dimyristyl peroxycarbonate, t-butylperoxy 2 -Ethyl hexyl carbonate, dicyclo dodecyl peroxy dicarbonate, the compound represented by the following general formula (15) or (15 '), etc. are mentioned. Among these, benzoyl peroxide compounds are preferable from the viewpoint of reactivity and workability, and in particular, benzoyl peroxide, 2,4-dicumylbenzoyl peroxide, 3,6,9-triethyl-3,6,9. -Trimethyl-1,4,7-triperoxonan, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferred.

（式中、Ｒ及びＲ’は、それぞれ独立に、炭素原子数３〜１０の炭化水素基である。）

(In the formula, R and R ′ are each independently a hydrocarbon group having 3 to 10 carbon atoms.)

  Examples of the hydrocarbon group having 3 to 10 carbon atoms represented by R in the general formulas (15) and (15 ′) and R ′ in the general formula (15 ′) include propyl, isopropyl, butyl, Dibutyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, cyclohexylmethyl, 2-cyclohexylethyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl Alkyl groups such as nonyl, isononyl, decyl, vinyl, 1-methylethenyl, 2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, alkenyl groups such as 1-phenylpropen-3-yl, Phenyl, 2-methylphenyl, 3-methyl Phenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,4- Alkylaryl groups such as dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-ditertiarybutylphenyl, benzyl, 2- Arylalkyl groups such as phenylpropan-2-yl, styryl, cinnamyl, etc., which are interrupted by an ether bond or a thioether bond, such as 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxy Ethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl , 3-methoxybutyl, 2-phenoxyethyl, 3-phenoxypropyl, 2-methylthioethyl, 2-phenylthioethyl, and these groups include an alkoxy group, an alkenyl group, a nitro group, a cyano group, and a halogen atom. Etc. may be substituted.

  In the silicon-containing curable white resin composition of the present invention, the content of the organic peroxide as the component (D) is 0.0001 to 100 parts by mass of the silicon-containing polymer as the component (A). It is 10 mass parts, and it is preferable that it is 0.01-5 mass parts.

Next, the metal catalyst that is the component (D) will be described. As the metal catalyst that is the component (D), the platinum-based catalyst that can be used in the hydrosilylation reaction of the component (α) and the component (β) when the prepolymer that is the component (B) is obtained. A catalyst can be used. As the platinum-based catalyst, a platinum-based catalyst contained in a prepolymer obtained in the hydrosilylation reaction of the (α) component and the (β) component as the component (B) may be used. The metal catalyst is a component _{(D), Al (acac) 3, Al} (O-i-Pr) 3, Al (ClO 4) 3, Ti (O-i-Pr) 4, Ti (O -I-Bu) ₄ , Bu ₂ Sn (acac) ₂ , Bu ₂ Sn (C ₇ H ₁₅ COO) ₂ , Al-based, Ti-based, and Sn-based metal catalysts can also be used. Among these, platinum-based catalysts and Al-based catalysts are preferable from the viewpoint of reactivity and colorability, and in particular, platinum-carbonylvinylmethyl complex (Ossko catalyst), platinum-divinyltetradimethyldisiloxane complex (Karstedt complex), Al (Acac) ₃ is preferred.

The metal catalyst as the component (D) has the effect of promoting the hydrosilylation reaction and the effect of dehydrating and condensing silanol groups. The silicon-containing curable white resin composition of the present invention contains 0 to 1.0 part by mass of the metal catalyst as the component (D) with respect to 100 parts by mass of the silicon-containing polymer as the component (A). However, from the viewpoint of the above effect, it is preferable to contain 1 × 10 ^{−4 to} 0.5 part by mass, and 1 × 10 ^{−3 to} 0.2 More preferably, it is contained in parts by mass.

  In the silicon-containing curable white resin composition of the present invention, the content of the component (D) is 5% by mass or less in total from the organic peroxide and the metal catalyst in terms of curability and storage stability. Is preferable, and 0.0001-3.0 mass% is more preferable. When the content is less than 0.0001% by mass, the effect of sufficiently promoting the reaction of the silicon-containing curable white resin composition cannot be obtained, and even when the content is more than 5% by mass, the obtained effect does not change. .

<(E) component>
Next, the filler or white pigment having an average particle size of 3 μm or more and 150 μm or less as the component (E) will be described.
When a filler or a white pigment is contained, the obtained cured product can be colored in a desired color, and the hardness of the obtained cured product can be increased. Examples of the filler or white pigment include inorganic and organic fillers and white pigments, and the average particle diameter is 3 μm or more and 150 μm or less, preferably 4 to 80 μm, and is not particularly limited. The average particle size can be determined as a mass average value D ₅₀ in the particle size distribution measurement by laser diffraction method (or median diameter).

  Examples of the inorganic filler or white pigment include silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, and silica gel; alumina, iron oxide, titanium oxide, magnesium oxide, zircon oxide, Metal oxides such as zinc oxide, magnesium oxide, beryllium oxide and antimony trioxide; ceramics such as silicon nitride, aluminum nitride, boron nitride and silicon carbide; minerals such as mica and montmorillonite; metals such as aluminum hydroxide and magnesium hydroxide Hydroxides or those modified by organic modification treatment; metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, barium carbonate or the like modified by organic modification treatment; metal borate , Pigments such as carbon black; carbon fiber, Rafaito, whiskers, kaolin, talc, glass fibers, glass beads, glass microspheres, silica glass, layered clay mineral, clay, silicon carbide, quartz, aluminum, zinc, and the like. Examples of the organic filler include acrylic beads, polymer fine particles, transparent resin beads, wood powder, pulp, and cotton chips.

  Of these, silicas, metal oxides, metal carbonates which may be modified, and pigments are preferable from the viewpoint of moldability and strength of the resin of the present invention, and silica and metal oxides (alumina, titanium oxide, magnesium oxide) are particularly preferable. Zircon oxide, zinc oxide, magnesium oxide, beryllium oxide) are more preferable, and these may be added singly or in combination of two or more. The particle shape of the filler or white pigment is preferably spherical from the viewpoint of resin fluidity and filling properties. For example, spherical fillers such as fused spherical silica and spherical alumina, or spherical white pigments can be suitably used. Incidentally, it is preferable not to use a titanium oxide inorganic filler or a white pigment when the reflection of the ultraviolet region is necessary because the light reflectance in the ultraviolet region of the cured resin is lowered.

  Moreover, when the average particle diameter of the said (E) component exceeds 150 micrometers, since compatibility with a resin composition is inferior, it is unpreferable. Moreover, in order to obtain high fluidization, it is desirable to use a combination of a medium particle size region of 3 to 10 μm and a coarse region of 10 to 150 μm.

  In the silicon-containing curable white resin composition of the present invention, the content of the component (E) is 0 to 1500 parts by mass in total with respect to 100 parts by mass of the silicon-containing polymer as the component (A). The component (E) may not be contained, but is preferably 100 to 1400 parts by mass, and more preferably 300 to 1350 parts by mass from the viewpoint of compatibility with the resin and high fluidization.

<(F) component>
Next, the filler or white pigment having an average particle size of 0.05 μm or more and less than 3 μm, which is the component (F), will be described.
The component (F) is not particularly limited as long as the average particle size is 0.05 or more and less than 3 μm. For example, among the materials mentioned for the inorganic filler, the average particle size other than titanium oxide is 0.05 μm. Those having a thickness of less than 3 μm can be used. Among these, metal oxides such as zircon oxide, zinc sulfide, alumina, zinc oxide, magnesium oxide, and beryllium oxide are preferable from the viewpoint of light reflectance in the ultraviolet region, and alumina is particularly preferable. These may be added singly or in combination of two or more. (F) The average particle diameter of a component is 0.05 micrometer or more and less than 3 micrometers, Preferably it is 0.08-2 micrometers, More preferably, it is 0.1-1.0 micrometer. If the average particle size is less than 0.05 μm, not only does the resin composition tend to thicken, but it is not preferable from the viewpoint of availability and cost, and those having an average particle size of 3 μm or more are UV rays of the cured resin. The light reflectance in the region tends to be inferior, which is not preferable. Furthermore, it is preferable not to use a titanium oxide-based white pigment when the reflection in the ultraviolet region is necessary because the light reflectance in the ultraviolet region of the cured resin is extremely lowered.

  In the silicon-containing curable white resin composition of the present invention, the content of the component (F) is 10 to 1500 parts by mass in total with respect to 100 parts by mass of the silicon-containing polymer as the component (A). 50 to 1400 parts by mass, and 100 to 1350 parts by mass are more preferable. If the amount is less than 10 parts by mass, the effect of improving the light reflectance is small, and if it exceeds 1500 parts by mass, the resin tends to thicken, which is not preferable.

  The inorganic filler and white pigment of the above component (E) or component (F) are blended in advance with a surface treatment with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to improve the adhesion to the metal. Also good.

  Examples of such a coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Alkyl functional alkoxysilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane Epoxy-functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) Aminofunctional alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane , Titanium alkoxides such as titanium tetraisopropoxide and titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), zirco Tetra acetyl acetonate, zirconium chelates such as zirconium tributoxy monoacetylacetonate, zirconium acylates such as zirconium tributoxy monostearate, it is preferable to use an isocyanate silanes such as methyl triisocyanate silane. The amount of coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

A cyclic siloxane compound can be further added to the silicon-containing curable white resin composition of the present invention to improve the close contact property. As the cyclic siloxane compound, a cyclic siloxane compound containing two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule can be used. It may be a polymer or a block copolymer. The number of carbon-carbon double bonds having reactivity with the Si-H group is preferably 2 to 10, and more preferably 2 to 6 from the viewpoint of the crosslinking density of the cured product. In addition, examples of the carbon-carbon double bond having reactivity with the Si-H group include alkenyl groups such as a vinyl group. From the viewpoint of reactivity, a vinyl group bonded to a silicon atom (Si-CH ═CH ₂ group). Moreover, the cyclic siloxane compound especially preferable from the point of the physical property of hardened | cured material includes the cyclic siloxane compound represented by the following general formula (16).

（式中、Ｒ³³、Ｒ³⁴及びＲ³⁵は、それぞれ独立に、炭素原子数１〜６のアルキル基又は炭素原子数１〜６のアルキル基で置換されていてもよいフェニル基を表し、ｓ個のＲ³³は同一であっても異なっていてもよく、ｔ個のＲ³⁴、ｔ個のＲ³⁵もそれぞれ同一であっても異なっていてもよい。ｓは２〜１０の数を表し、ｔは０〜８の数を表し、ｓ＋ｔ≧２である。）

(In the formula, each of R ³³ , R ³⁴ and R ³⁵ independently represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; R ³³ may be the same or different, and t R ³⁴ and t R ³⁵ may be the same or different, and s represents a number of 2 to 10, t represents a number from 0 to 8, and s + t ≧ 2.

In the general formula ^{(16), R 33, R} 34 and the alkyl group having 1 to 6 carbon atoms represented by R ^35, and substituted with a phenyl group represented by R ^33, R ³⁴ and R ³⁵ Examples of the preferable alkyl group having 1 to 6 carbon atoms include the same groups as those described above for R ² .

In the general formula (16), R ³³ , R ³⁴ and R ³⁵ are preferably a methyl group or a phenyl group from the viewpoint of industrial availability. s is preferably 2 to 4 from the viewpoint of crosslinking density, and t is preferably 1 to 3 from the viewpoint of viscosity. Specific examples of preferable cyclic siloxane compounds include cyclic siloxane compounds represented by the following formulas (17) to (19).

  In the silicon-containing curable white resin composition of the present invention, a compound having a cyanuric acid structure can be further added as an adhesion aid to improve close adhesion. Examples of the compound having a cyanuric acid structure include isocyanuric acid, triallyl cyanuric acid, 1,3,5-triglycidyl isocyanuric acid, tris (2-hydroxyethyl) isocyanuric acid, and tris (2,3-dihydroxypropyl). Isocyanuric acid, tris (2,3-epoxypropyl) isocyanuric acid, described in Japanese Patent No. 2768426, Japanese Patent Laid-Open No. 3-261769, Japanese Patent Laid-Open No. 4-139221, Japanese Patent Laid-Open No. 4-139174, Japanese Patent Laid-Open No. 10-333330, etc. Can be used. In addition, these compounds may be subjected to various modification treatments such as silicone modification, ethylene oxide modification, propylene oxide modification and the like by conventional methods. When using a compound having a cyanuric acid structure, the content of the compound in the silicon-containing curable white resin composition of the present invention is preferably 0.0001 to 10% by mass, and 0.01 to 1.0% by mass. Is more preferable.

  The silicon-containing curable white resin composition of the present invention may further contain a free radical scavenger as an optional component. The free radical scavenger in this case may be any antioxidant substance such as an antioxidant or a stabilizer, such as triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl). ) Propionate], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-paracresol (DBPC) and the like. The content of the free radical scavenger in the silicon-containing curable white resin composition of the present invention is 0.1 to 50% by mass from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling. Preferably, 1-30 mass% is more preferable.

  The silicon-containing curable white resin composition of the present invention may further contain a coupling agent as an optional component. When a coupling agent is blended, the adhesiveness can be improved. As the coupling agent, in addition to those listed as those that can be used for the surface treatment of the inorganic filler, compounds represented by the following formula (20) can be used. Among these, epoxy functional alkoxysilanes can be used. It is preferable to use a silane coupling agent such as amino-functional alkoxysilane or mercapto-functional alkoxysilane, and in particular, γ-glycidoxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Phenyl-γ-aminoethyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane are preferred. 0.1-0.5 mass% is preferable and, as for content of the coupling agent in the silicon-containing curable white resin composition of this invention, 0.2-0.3 mass% is more preferable.

  In addition, the silicon-containing curable white resin composition of the present invention includes other components other than the above-mentioned adhesion assistant, free radical scavenger, and coupling agent, as long as the target performance of the present invention is not impaired. Various known resins, mold release agents, additives and the like can be blended. The amount of optional components other than the adhesion assistant, free radical scavenger and coupling agent is not particularly limited, but in order not to impair the effects of the present invention, the silicon-containing curability of the present invention. In the white resin composition, the total content is preferably 5% by mass or less. In the present invention, various organic functional groups are further bonded to any one or more of (A) component, (B) component, (C) component, (D) component, (E) component and (F) component. And further functions can be added. In addition, a highly functional composite material in which the silicon-containing curable white resin composition of the present invention or a cured product thereof is used as a matrix and other useful compounds are dispersed therein can also be produced.

  Examples of various resins that can be arbitrarily blended include polybutadiene resin and modified products thereof, modified products of acrylonitrile copolymer, polyether resins such as polystyrene resin, polyethylene resin, fluororesin, polyimide resin, polyethylene glycol, polyphenylene ether, and polypropylene glycol. Resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, melamine resins, polyamide resins, polyphenylene sulfide resins and the like can be mentioned. Examples of additives that can be optionally blended include brighteners, waxes, UV absorbers, antistatic agents, antioxidants, deterioration inhibitors, modifiers, silane coupling agents, defoaming agents, dyes, maleimide compounds, Examples include cyanate ester compounds, silicone gels, and silicone oils.

  As release agents, carnauba wax, fatty acid ester, glyceric acid ester, stearic acid, montanic acid, behenic acid and its metal salt, alkali metal compound, organic titanium, organic zirconia, organic tin compound, imidazole compound, carboxyl group-containing polyolefin , Polyethylene-polyoxyethylene resins, carnauba and the like can be used.

  Since the silicon-containing curable white resin composition of the present invention is solid at room temperature (25 ° C.), it has excellent handling properties. The silicon-containing curable white resin composition of the present invention may be in the form of powder, granule or tablet, and may be used after dissolved in a solvent. The silicon-containing curable white resin composition of the present invention preferably has a melting point of 50 ° C. or higher and 150 ° C. or lower, and more preferably 50 ° C. or higher and 120 ° C. or lower. The silicon-containing curable white resin composition of the present invention is preferably melted at 50 ° C. to 150 ° C. and then cured by heat. Moreover, the hardened | cured material which consists of a silicon-containing curable white resin composition of this invention is excellent in especially heat resistance and adhesiveness. As for the heat resistance, specifically, a cured product having a temperature causing a weight loss of 5% by mass of the cured product is preferably 400 ° C. or higher, more preferably 500 ° C. or higher. Moreover, the hardened | cured material with few generation | occurrence | production of a crack is suitably obtained from the silicon containing curable white resin composition of this invention.

The silicon-containing curable white resin composition of the present invention has an Si—CH ₃ group and a carbon-carbon two component contained in any of the components (A) to (C) due to the effect of the organic peroxide of the component (D). The curing reaction by the polycondensation reaction of a heavy bond (for example, Si—CH═CH ₂ group) proceeds promptly. Furthermore, since the silicon-containing curable white resin composition of the present invention is uniform and transparent, it has good light transmittance such as ultraviolet rays, and can be photocured by adding a photoreactive catalyst. Of course, a photoreactive monomer or resin may be further blended, and any one or more of each component in the silicon-containing curable white resin composition may have a photoreactive group. Furthermore, the silicon-containing curable white resin composition of the present invention has weather resistance, hardness, contamination resistance, flame resistance, moisture resistance, gas barrier properties, flexibility, elongation and strength, electrical insulation, low dielectric constant. A material excellent in mechanical properties such as efficiency, optical properties, electrical properties and the like can be obtained.

Next, the cured product of the present invention will be described.
The silicon-containing curable white resin composition of the present invention can be cured by heating and can be a cured product. This curing reaction may be any method such as a method of mixing the components of the silicon-containing curable white resin composition of the present invention immediately before use, a method of mixing all in advance and curing by heating when performing a curing reaction, etc. You may carry out by the method. The heating temperature in the case of curing is preferably equal to or higher than the temperature at which the resin melts, that is, 35 to 350 ° C, and more preferably 50 to 250 ° C. The curing time is preferably 2 to 60 minutes, more preferably 2 to 10 minutes. Further, after curing, it can be annealed or molded. The annealing time varies depending on the temperature, but it is preferably about 5 to 60 minutes at 150 ° C. By performing a curing reaction under these curing reaction conditions, a cured product having performances excellent in heat resistance, durability, adhesion and the like can be obtained from the silicon-containing curable white resin composition of the present invention. As the molding method, known methods such as transfer molding, compression molding, and cast molding can be used, and transfer molding is preferable from the viewpoint of workability and dimensional stability.

Transfer molding is preferably performed using a transfer molding machine at a molding pressure of 5 to 20 N / mm ² and a molding temperature of 120 to 190 ° C. for 30 to 500 seconds, particularly 150 to 185 ° C. for 30 to 180 seconds. The compression molding method is preferably performed using a compression molding machine at a molding temperature of 120 to 190 ° C. for 30 to 600 seconds, particularly 130 to 160 ° C. for 120 to 300 seconds. In any molding method, it can be cured at 150 to 185 ° C. for 2 to 20 hours.

  When the silicon-containing curable white resin composition of the present invention is cured, film forming methods such as spin casting, potting, dipping, etc. can be appropriately applied.

  The silicon-containing curable white resin composition of the present invention can be used as a curable composition excellent in various physical properties such as light reflectance, heat resistance, light resistance, crack resistance and warpage. . Applications include sealing materials such as display materials, optical materials, recording materials, printed circuit boards, semiconductors, and solar cells in the field of electrical and electronic materials; electrical and electronic equipment and components such as lighting, displays, indicators, and mobile phone backlights. Various reflective materials such as LED light reflector materials such as emergency lights and display devices such as video cameras, etc .; high voltage insulation materials, insulation / vibration / waterproof / moisture protection It can be used as various intended materials, and can be suitably used as a reflective material, particularly as a reflector material for LEDs. Prototype mold for plastic parts, coating material, interlayer insulation film, prepreg, insulation packing, heat shrink rubber tube, O-ring, sealant / protective material for display device, optical waveguide, optical fiber protective material, optical lens, Adhesives for optical equipment, high heat resistant adhesives, elastic adhesives, adhesives, die bonding agents, high heat dissipation materials, high heat resistant sealing materials, solar cell / fuel cell members, solid electrolytes for batteries, insulation coating materials, Photosensitive drums for copying machines, gas separation membranes, concrete protective materials in the civil engineering / building materials field, linings, soil injection agents, sealing agents, cold storage materials, glass coatings, foams, medical tubes, medical sealing materials, sterilization equipment Suitable for sealing materials, contact lenses, oxygen-enriched films, films, gaskets, casting materials, and rust-proof / waterproof sealants for meshed glass It is possible to.

Next, the optical semiconductor package of the present invention will be described.
In the optical semiconductor package of the present invention, a reflector (reflecting material) for increasing the light utilization factor of the light emitting element is provided around the light emitting element, and the silicon-containing white curable resin composition of the present invention is used as the reflector. It is characterized by using the cured product.
The cured product used as a reflector has a light reflectance at a wavelength of 460 nm of 80% or more, a light reflectance at a wavelength of 405 nm of 70% or more, and a wavelength of 405 nm after heat treatment at 300 ° C. for 10 minutes. The light reflectance at 60 is 60% or more, and particularly has a high light reflectance for light in the ultraviolet region (420 nm or less).
The light reflectance in this case is obtained from the light reflectance by an integrating sphere.
There are no particular limitations on the type of light-emitting element that can be used, but by using a light-emitting element having a wavelength of 420 nm or less, preferably 350 nm to 420 nm, the high color rendering index Ra is 85 or more. It is possible to obtain an opto-semiconductor package.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on mass.

  Synthesis Examples 1 to 3 are synthesis examples of the silicon-containing polymer that is the component (A), Synthesis Examples 4 and 5 are synthesis examples of the prepolymer that is the component (B), and Synthesis Examples 6 to 8 are , (C) is a synthesis example of a linear siloxane compound component, Examples 1, 2 and Comparative Examples 1-3 are preparation and evaluation examples of the present invention and comparative silicon-containing curable white resin composition is there.

[Synthesis Example 1] Component (A): Synthesis of silicon-containing polymer A-1 To a 2000 ml four-necked flask equipped with a condenser and a stirrer, 0.5 mol of vinyltrimethoxysilane as component (a), (b) Add 0.5 mol of methyltrimethoxysilane as a component, 0.25 mol of dimethyldimethoxysilane as a component (c), 1.0 mol of phenyltrimethoxysilane as a component (d), and 650 g of toluene. 31.4 g of an aqueous sodium oxide solution was added dropwise over 30 minutes, and a dehydration polymerization reaction was performed at 60 to 65 ° C. for 3 hours. After cooling to room temperature, 600 g of toluene and 1500 g of ion-exchanged water are added, the oil layer is extracted, washed with water until neutrality, the solvent is removed, and the silicon-containing polymer A-1 as component (A) is obtained. 232.6 g was obtained (white powder). When the weight average molecular weight (Mw) of the silicon-containing polymer A-1 was analyzed by GPC under the following conditions, it was Mw = 15000 (polystyrene conversion).
(GPC measurement conditions)
Column: supermilipore HZ-M
Developing solvent: Tetrahydrofuran

[Synthesis Example 2] Component (A): Synthesis of silicon-containing polymer A-2 To a 1000 ml four-necked flask equipped with a condenser and a stirrer, 0.139 mol of vinyltrimethoxysilane as component (a), (b) Add 0.278 mol of methyltriethoxysilane as component, 0.056 mol of dimethyldimethoxysilane and 0.034 mol of diphenylsilanediol as component (c), 0.05 mol of phenyltrimethoxysilane as component (d), and 280 g of methyl ethyl ketone, and stir. Then, 30 g of 0.1% oxalic acid aqueous solution was added and stirred at room temperature for 1 hour. While stirring, 40 g of a 0.1% aqueous sodium hydroxide solution was added dropwise, and a dehydration polymerization reaction was carried out for 10 hours under reflux conditions. After cooling to room temperature, 50 g of ion-exchanged water was added, the oil layer was extracted, washed with water until neutral, and then the solvent was removed to obtain 52 g of silicon-containing polymer A-2 as component (A). (White powder). When analyzed by GPC under the same conditions as in Synthesis Example 1, the weight-average molecular weight of the silicon-containing polymer A-2 was Mw = 20000 (in terms of polystyrene).

[Synthesis Example 3] Component (A): Synthesis of silicon-containing polymer A-3 To a 1000 ml four-necked flask equipped with a condenser and a stirrer, 0.139 mol of vinyltrimethoxysilane as component (a), (b) 0.34 mol of methyltriethoxysilane was added as a component, 0.056 mol of dimethyldimethoxysilane and 280 g of methyl ethyl ketone were added as component (c), and 30 g of a 0.1% oxalic acid aqueous solution was added with stirring, and stirred at room temperature for 1 hour. While stirring, 40 g of a 0.1% aqueous sodium hydroxide solution was added dropwise, and a dehydration polymerization reaction was carried out for 10 hours under reflux conditions. After cooling to room temperature, 50 g of ion-exchanged water was added, the oil layer was extracted, washed with water until neutral, and then the solvent was removed to obtain 52 g of silicon-containing polymer A-3 as component (A). (White powder). When analyzed by GPC under the same conditions as in Synthesis Example 1, the weight-average molecular weight of the silicon-containing polymer A-3 was Mw = 10000 (in terms of polystyrene).

[Synthesis Example 4] Component (B): Synthesis of Prepolymer B-1 1,3,5,7-tetramethylcyclotetrasiloxane 100 parts, divinylbenzene 100 parts, toluene 60 parts and platinum-carbonylvinylmethyl complex (Ossko) Catalyst) 0.0005 part was added and refluxed for 5 hours with stirring. The solvent was distilled off from the reaction solution under reduced pressure at 70 ° C. to obtain a prepolymer B-1 as component (B). When analyzed by GPC under the same conditions as in Synthesis Example 1, the weight average molecular weight of the prepolymer B-1 is Mw = 140,000 (polystyrene conversion), and the content of the hydrosilyl group (Si—H group) is It was 5.3 mmol / g from ¹ H-NMR.

[Synthesis Example 5] Component (B): Synthesis of Prepolymer B-2 100 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 25 parts of trivinylcyclohexane, 80 parts of toluene and platinum-divinyltetramethyldisiloxane 0.001 part of the complex (Karstedt catalyst) was added and refluxed for 5 hours with stirring. The solvent was distilled off from the reaction solution at 70 ° C. under reduced pressure to obtain a prepolymer B-2 as component (B). When analyzed by GPC under the same conditions as in Synthesis Example 1, the weight average molecular weight of the prepolymer B-2 is Mw = 50,000 (polystyrene conversion), and the content of the hydrosilyl group (Si—H group) is It was 3.2 mmol / g from ¹ H-NMR.

[Synthesis Example 6] Component (C): Synthesis of Linear Siloxane Compound C-1 30 parts of dichlorodiphenylsilane was dissolved in 450 parts of methyl isobutyl ketone, and 60 parts of dimethylvinylchlorosilane was added dropwise. After dropping, the mixture was reacted at room temperature for 2 hours, and the solvent was removed to obtain a linear siloxane compound C-1 as the component (C) represented by the above formula (6).

[Synthesis Example 7] Component (C): Synthesis of linear siloxane compound C-2 100 parts of dichlorodimethylsilane was dropped into a mixture composed of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of a 48% aqueous sodium hydroxide solution. And polymerized at 105 ° C. for 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then this toluene solution was dehydrated, 20 parts of pyridine was added, 20 parts of dimethylvinylchlorosilane was further added, and the mixture was stirred at 70 ° C. for 30 minutes. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Next, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C. to obtain a linear siloxane compound C-2 as the component (C) represented by the above formula (8). As a result of analysis by GPC under the following conditions, the weight average molecular weight of the linear siloxane compound C-2 was Mw = 20,000 (polystyrene conversion). All subsequent GPCs were performed under these conditions.
(GPC measurement conditions)
Column: Tosoh Corporation TSK-GEL MULTIPORE HXL M, 7.8 mm X 300 mm
Developing solvent: Tetrahydrofuran

[Synthesis Example 8] Component (C): Synthesis of Linear Siloxane Compound C-3 100 parts of the linear siloxane compound C-2 obtained in Synthesis Example 7 was dissolved in 200 parts of toluene, and 1,4-bis (dimethyl Silyl) 20 parts of benzene and 0.001 part of platinum-carbonylvinylmethyl complex (Ossko catalyst) were added and reacted at 70 ° C. for 2 hours, and then 3-vinyl-7-oxabicyclo [4,1,0] heptane. 20 parts were added and stirred at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C., and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C., and the linear siloxane compound C as component (C) represented by the above formula (14) -3 was obtained. As a result of analysis by GPC, the weight average molecular weight of the linear siloxane compound C-3 is Mw = 30,000 (polystyrene conversion), and the epoxy equivalent (per number of epoxy groups) determined by potentiometric titration based on JIS standard K7236. The molecular weight was 3000 g / mmol.

[Example 1 and Comparative Example 1] Preparation and Evaluation of Silicon-containing Curable White Resin Composition (A) Silicon-containing polymer, (B) prepolymer, (C) linear siloxane compound having the composition shown in Table 1 below. (D) An organic peroxide and / or a metal catalyst, (E) a filler or white pigment having an average particle size of 3 μm or more and 150 μm or less, (F) a filler or white pigment having an average particle size of 0.05 μm or more and less than 3 μm A silicon-containing curable white resin composition was obtained. The obtained silicon-containing curable white resin composition was tested for mechanical properties such as light reflectance, heat resistance, light resistance, crack generation, and bending strength by the methods shown below. The test results are shown in [Table 1] and [Table 2] below.

<Test method>
1. Light reflectance: light reflectance at a wavelength of 405 nm immediately after molding 180 ° C., molding time 300 seconds, after baking 180 ° C., 1 hour, a cured product having a diameter of 50 mm × thickness 1 mm is molded, and at a wavelength of 405 nm immediately after molding. The light reflectance was measured using an ultraviolet-visible spectrophotometer V570 manufactured by JASCO.
2. Heat resistance: light reflectivity at a wavelength of 405 nm after heat treatment The cured product immediately after the above molding was heated in an oven at 300 ° C. for 5 minutes, and the light reflectivity at a wavelength of 405 nm was measured using an ultraviolet-visible spectrophotometer V570 manufactured by JASCO Corporation. Measured using.
3. A cured product having a diameter of 50 mm and a thickness of 1 mm was molded under conditions of light resistance of 180 ° C., molding time of 300 seconds, after baking at 180 ° C. for 1 hour, and UV irradiation was performed on the cured product immediately after molding and the cured product with a high-pressure mercury lamp. The light reflectance at a wavelength of 405 nm after the time was measured was measured using an ultraviolet-visible spectrophotometer V570 manufactured by JASCO Corporation.
4). Crack generation 180 ° C., molding time 300 seconds, after baking 180 ° C., 1 hour, a cured product having a diameter of 50 mm × thickness 1 mm was molded, and the cured product was allowed to stand at 180 ° C. for 100 hours. Observed at.
5. Mechanical properties (1) Bending strength A cured product of length 80mm x width 10mm x thickness 1mm was molded under conditions of 180 ° C, molding time 300 seconds, after baking 180 ° C, 1 hour, bending strength according to JIS K7171 (2) A linear expansion coefficient of 180 ° C., molding time of 300 seconds, after baking at 180 ° C. for 1 hour, a cured product having a diameter of 5 mm × thickness of 5 mm was molded, and 40 ° C. by thermomechanical analysis (TMA). The average value of the linear expansion coefficient from 1 to 300 ° C. was measured.
(3) Warpage amount 180 ° C., molding time 300 seconds, after baking 180 ° C., 1 hour on a copper plate (0.2 mm), a cured product having a length of 50 mm × width 50 mm × thickness 1 mm is formed. The attached resin cured product was placed on a surface plate, and the size of the gap between the surface plate and the end of the cured material was measured to obtain the amount of warpage.

[Example 2]
About the silicon-containing curable white resin composition having the same composition as that of Example 1, the light reflectance at a wavelength of 460 nm was measured by the following method.
(Evaluation method): Light reflectivity at a wavelength of 460 nm immediately after molding A cured product having a diameter of 50 mm and a thickness of 1 mm was molded under the conditions of 180 ° C., molding time of 300 seconds, after baking at 180 ° C. for 1 hour, and at a wavelength of 460 nm immediately after molding. The light reflectance was measured using an ultraviolet-visible spectrophotometer V570 manufactured by JASCO. The results are shown in [Table 3] below.

  From the results of the above [Table 1] to [Table 3], the cured product of the silicon-containing curable white resin composition of the present invention has a high light reflectance of 80% or more at a wavelength of 460 nm which is a visible light region, and The light reflectance immediately after molding at a wavelength of 405 nm in the ultraviolet region is 70% or more, and the light reflectance after heat treatment at 300 ° C. is 60% or more. Compared to the light reflectance of Comparative Examples 1 to 3. It shows a high value. Further, the cured product of the silicon-containing curable white resin composition of the present invention is clearly excellent in mechanical properties such as heat resistance, light resistance, and crack resistance, and the silicon-containing curable white resin composition of the present invention. The cured product is useful as a reflector such as a reflector for an optical semiconductor package.

Claims (6)

As the component (A), one or more types of the organosilane (a) represented by the following general formula (1-1), 5 to 50 mol%, the organosilane (b) represented by the following general formula (1-2) One or more types of 0 to 50 mol%, one or more types of organosilane (c) represented by the following general formula (1-3) 0 to 40 mol%, an organosilane (d) represented by the following general formula (1-4) 1) or more and 0 to 50 mol% of the organosilane (e) represented by the following general formula (1-5) and 0 to 40 mol% of the organosilane (b), the organosilane (c), 100 parts by mass of a silicon-containing polymer obtained by hydrolyzing and condensing an organosilane mixture having a sum of 5 to 60 mol% and having a weight average molecular weight of 300 to 100,000,
(B) As a component, 1 or more types chosen from the cyclic siloxane compound ((alpha)) represented by the following general formula (2), the following general formula (3-1), the following formula (3-2), or the following general formula ( 3-3) Prepolymer 0 to 200 parts by mass obtained by hydrosilylation reaction of at least one selected from compounds (β) represented by 3-3) and containing two or more Si—H groups in one molecule; ,
As component (C), 0.1 to 30 parts by mass of a linear siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si-H group or Si-CH ₃ group in one molecule; ,
As component (D), organic peroxide 0.0001 to 10 parts by mass and metal catalyst 0 to 1.0 parts by mass,
(E) As a component, 0-1500 mass parts of fillers or white pigments having an average particle size of 3 μm or more and 150 μm or less,
A silicon-containing curable white resin composition containing 10 to 1500 parts by mass of a filler or white pigment (excluding titanium oxide) having an average particle size of 0.05 or more and less than 3 μm as the component (F).

(In the formula, R ¹ represents an alkenyl group having 2 to 6 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ are each independently a hydrogen atom. Or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and R ² , R ³ and R ⁴ At least one of them is a methyl group, R ⁵ represents a phenyl group which may be substituted with an alkyl group having 1 to ⁶ carbon atoms, and R ⁶ represents an epoxy group having 2 to 10 carbon atoms. , X represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.)

(In the formula, R ⁷ , R ⁸ and R ⁹ each independently represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; R ⁷ may be the same or different, and g R ⁸ and g R ⁹ may be the same or different, and f represents a number of 2 to 10, g represents a number from 0 to 8, and f + g ≧ 2.

(Wherein R ¹⁰ represents an alkenyl group having 2 to 10 carbon atoms, and R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or Represents an epoxy group having 2 to 10 carbon atoms, and n represents 1 or 2.)   The silicon-containing curable white resin composition according to claim 1, wherein the content of the component (B) is 10 to 200 parts by mass with respect to 100 parts by mass of the component (A). The silicon-containing curable white resin composition according to claim 1 or 2, wherein the component (C) is a linear siloxane compound represented by the following general formula (4).

(Wherein R ¹³ and R ³² each independently represents an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an epoxy group having 2 to 10 carbon atoms, or a trimethylsilyl group, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²¹ , R ²⁵ , R ²⁹ , R ³⁰ and R ³¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁸ , R ¹⁹ and R ²⁰ each represent a phenyl group, R ²² , R ²³ and R ²⁴ each independently represent an alkenyl group having 2 to 6 carbon atoms, and R ²⁶ , R ²⁷ and R ²⁸ each independently represent Represents an epoxy group having 2 to 10 carbon atoms, and when R ¹³ and R ³² are alkyl groups having 1 to 6 carbon atoms, v ≧ 1 or v + w ≧ 2, and R ¹⁴ , R ¹⁵ , R ^16, when at least one of ^{R 17, R 21, R 25} , R 29, R 30 and R ³¹ are hydrogen atoms, v ≧ Or a w ≧ 1, p pieces are of R ¹⁶ and R ¹⁷ may be the each be the same or different, r pieces of R ^21, v number of R ²² beauty R ^23, w pieces of R ²⁴ Beauty R ²⁵ , x R ^{26 and} R ²⁷ , and y R ^{28 and} R ²⁹ may be the same or different, and p, q, r, v, w, x and y are each independently Represents a number from 0 to 3000, and p + q + r + v + w + x + y ≧ 1.)   The silicon-containing curable white resin composition according to any one of claims 1 to 3, wherein the component (F) is alumina.   Hardened | cured material formed by hardening the silicon-containing curable white resin composition of any one of Claims 1-4.
An optical semiconductor package provided with a reflector, the reflector comprising the cured product according to claim 5, having a light reflectance at a wavelength of 460 nm of 80% or more and a light reflectance at a wavelength of 405 nm of 70. An optical semiconductor package characterized in that the light reflectance at a wavelength of 405 nm after heat treatment at 300 ° C. for 10 minutes is 60% or more.