JP4766222B2 - Light emitting semiconductor coating protective material and light emitting semiconductor device - Google Patents

Description

  The present invention relates to a light emitting semiconductor coating protective material and a light emitting semiconductor device formed by coating a light emitting semiconductor element using the same.

  Although a light emitting semiconductor device such as a light emitting diode (LED) is used as a light emitting semiconductor device shown in FIG. 3, which is called a shell type in which an element is disposed on a lead electrode and the periphery thereof is covered with a transparent resin. In recent years, light-emitting semiconductor devices called “surface mount type” as shown in FIGS. 1 and 2 are becoming mainstream due to simplification of the mounting process.

  1-3, 1 is a glass fiber reinforced epoxy resin housing, 2 is a light emitting element, 3 and 4 are lead electrodes, 5 is a die bond material, 6 is a gold wire, and 7 is a covering protective material.

  As a resin composition for protecting a light-emitting semiconductor element such as a light-emitting diode (LED), the cured product is required to have transparency, and is generally an epoxy such as a bisphenol A type epoxy resin or an alicyclic epoxy resin. What is obtained using resin and an acid anhydride type hardening | curing agent is used (patent document 1: patent 3241338 gazette, patent document 2: Unexamined-Japanese-Patent No. 7-25987).

  However, even in such a transparent epoxy resin, the moisture absorption resistance of the resin is high, so the moisture resistance durability is low, particularly the light resistance to low-wavelength light is low, so the light resistance is low, or it is colored due to light deterioration. Had.

  Therefore, it consists of an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, a silicon compound containing at least two SiH groups in one molecule, and a hydrosilylation catalyst. Resin compositions for protecting the coating of optical semiconductor elements have also been proposed (see Patent Document 3: Japanese Patent Laid-Open No. 2002-327126, Patent Document 4: Japanese Patent Laid-Open No. 2002-338833).

  However, such an organic compound has a slow curing reaction, requires long-time curing, and has a large residual stress. Therefore, a metal having a thermoplastic resin having poor heat resistance or a hydrolyzable group having poor storage stability. The compound had to be used in combination. Therefore, what uses the high hardness silicone resin for protective coating is proposed (refer patent document 5: Unexamined-Japanese-Patent No. 2002-314139, patent document 6: Unexamined-Japanese-Patent No. 2002-314143).

  However, these high-hardness silicone resins still have poor adhesion, and in case-type light-emitting semiconductor devices in which light-emitting elements are arranged in a ceramic and / or plastic housing and the inside of the housing is filled with silicone resin, −40 ° C. In the thermal shock test at ˜120 ° C., there was a problem that the silicone resin was peeled off from the ceramic or plastic of the housing.

  Furthermore, since the refractive index of the optical crystal of various compound semiconductors such as SiC, GaAs, GaP, GaAsP, GaAlAs, InAlGaP, InGaN, and GaN used for the light emitting element is high, the refractive index of the coating protective resin is dimethyl silicone. When it is as low as a resin, there is a drawback in that the light emission efficiency decreases due to reflection at the interface between the coating resin and the optical crystal.

  For this reason, methods such as attaching an antireflection film have been proposed as means for increasing the light emission rate (see Patent Document 7: Japanese Patent Laid-Open No. 2001-246236, Patent Document 8: Japanese Patent Laid-Open No. 2001-217467). . However, the number of steps is increased to produce an antireflection film, resulting in an increase in cost.

Japanese Patent No. 3241338 JP 7-25987 A JP 2002-327126 A JP 2002-338833 A JP 2002-314139 A JP 2002-314143 A JP 2001-246236 A JP 2001-217467 A

  The present invention has been made in view of the above circumstances, and a light-emitting semiconductor coating protective material having a low internal stress, excellent adhesion, and excellent light transmission, and a light-emitting semiconductor coated with the same and having high light emission efficiency An object is to provide an apparatus.

  As a result of diligent studies to achieve the above object, the present inventor uses a phenyl group-containing organopolysiloxane having a vinyl group at the molecular chain terminal as a base polymer, and if necessary, a silicon atom-bonded alkoxy group-containing organosilicon compound It was found that the cured product of the addition reaction curable silicone resin composition had both low stress and transparency and good adhesiveness, and led to the present invention.

（式中、ｍ，ｎは１以上で、かつ一分子中のケイ素原子数を４〜３０とする整数である。）

を含有してなり、その硬化物の２５℃，５８９ｎｍ（ナトリウムのＤ線）での屈折率が１．４１〜１．５６であるとともにデュロメータ・タイプＡの硬度が５〜７５であることを特徴とする発光半導体被覆保護材。
［ＩＩ］硬化物の２５℃，５８９ｎｍでの屈折率が１．４３〜１．５５である［Ｉ］記載の発光半導体被覆保護材。
［ＩＩＩ］開口部を有する筐体内に配置された発光半導体を覆って筐体内に充填され、硬化される発光半導体被覆用である［Ｉ］又は［ＩＩ］記載の発光半導体被覆保護材。
［ＩＶ］発光半導体素子が、開口部を有するセラミック及び／又はプラスチック筐体内に配置された発光半導体装置で、その筐体内部が［Ｉ］又は［ＩＩ］記載の被覆保護材の硬化物で被覆保護された発光半導体装置。
［Ｖ］発光半導体素子が、開口部を有するセラミック及び／又はプラスチック筐体内のリード電極上に配置された発光半導体装置で、その筐体内部が［Ｉ］又は［ＩＩ］記載の被覆保護材の硬化物で被覆保護された発光半導体装置。 Accordingly, the present invention provides the following light emitting semiconductor coating protective material and light emitting semiconductor device.
[I] (A) The following average composition formula (1) having a vinyl group at the molecular chain terminal
R _a SiO _{(4-a) / 2} (1)
(In the formula, R represents a monovalent organic group, and at least 5 mol% to 80 mol% is a phenyl group. A is a number of 1.5 to 3.0.)
100 parts by mass of an organopolysiloxane represented by
(B) The following average composition formula (2) having hydrogen atoms directly bonded to at least two silicon atoms in one molecule
R ¹ _b H _c SiO _{{4- (b + c)} / 2} (2)
(Wherein R ¹ represents a monovalent organic group, b is 0.7 ≦ b ≦ 2.1, c is 0.001 ≦ c ≦ 1.0, and 0.8 ≦ b + c ≦ 3) (It is a positive number.)
An amount of 0.7 to 10 hydrogen atoms directly connected to silicon atoms in the component (B), with respect to one vinyl group in the component (A),
(C) Platinum group metal catalyst 1 to 1,000 ppm of the total mass of the component (A) and the component (B) as a platinum group metal,
(D) an organosilicon compound having silicon-bonded alkoxy group selected from an organosiloxane represented by the following formula from 0.5 to 10 parts by weight

(In the formula, m and n are integers of 1 or more and 4 to 30 silicon atoms in one molecule.)

The cured product has a refractive index of 1.41 to 1.56 at 25 ° C. and 589 nm (sodium D line) and a durometer type A hardness of 5 to 75. A light-emitting semiconductor coating protective material.
[II] The light emitting semiconductor coating protective material according to [I], wherein the cured product has a refractive index of 1.43 to 1.55 at 25 ° C. and 589 nm.
[III] The light-emitting semiconductor coating protective material according to [I] or [II], which covers the light-emitting semiconductor disposed in the housing having the opening and is filled into the housing and cured.
[IV] A light-emitting semiconductor device in which a light-emitting semiconductor element is disposed in a ceramic and / or plastic housing having an opening, and the inside of the housing is covered with a cured product of the coating protective material described in [I] or [II] Protected light emitting semiconductor device.
[V] A light emitting semiconductor device in which a light emitting semiconductor element is disposed on a lead electrode in a ceramic and / or plastic housing having an opening, and the inside of the housing is made of the covering protective material according to [I] or [II] A light-emitting semiconductor device coated and protected with a cured product.

  The light-emitting semiconductor device coated and protected with the light-emitting semiconductor coating protective material of the present invention has little discoloration due to a heat resistance test and has high light emission efficiency, so that it is possible to provide a light-emitting semiconductor device with long life and excellent energy saving. The benefits are tremendous.

The component (A) of the coating protective material (silicone resin composition) for coating and protecting the light emitting semiconductor of the present invention is a component that is a main component (base polymer) of the coating protective material of the present invention, and the catalyst of the component (C) Under the action, it is cured by crosslinking with component (B). This is represented by the following average composition formula (1) having vinyl groups bonded to silicon atoms at the molecular chain ends, particularly at each end.
R _a SiO _{(4-a) / 2} (1)
(In the formula, R represents a monovalent organic group, at least 5 mol% of which is a phenyl group. A is a number of 1.5 to 3.0.)
It is the organopolysiloxane shown by these.

  Here, examples of R include unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and specifically include methyl, ethyl, propyl, isopropyl, and butyl groups. Alkyl groups such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, Aralkyl groups such as benzyl, phenylethyl, and phenylpropyl, alkenyl such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl, and the like Hydrogen atoms partially or wholly substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc., such as chloromethyl Group, chloropropyl group, bromoethyl group, and a halogen-substituted alkyl group or cyanoethyl group such trifluoropropyl group.

  In this case, at least two of R are vinyl groups, and each has a vinyl group bonded to a silicon atom at the end of the molecular chain, particularly at each end. In addition to this, the side chain (that is, the monovalent organic group R bonded to the silicon atom in the middle of the molecular chain) may also have an alkenyl group such as a vinyl group. The content of the alkenyl group including the vinyl group is 0.01 to 20 mol%, particularly 0.1 to 10 mol% in the total organic group R. The elasticity, elongation, physical strength, etc. of the coating protective material after curing It is more preferable than this point.

Moreover, at least 5 mol% of R is a phenyl group. When the phenyl group is less than 5 mol%, the heat resistance of the cured coating protective material is deteriorated or the low-temperature characteristics are deteriorated, leading to a decrease in reliability by a thermal shock test. Therefore, at least 5 mol% needs to be a phenyl group. is there. Preferably 7 mol% or more, more preferably 10 mol% or more is a phenyl group. The upper limit is 80 mol% or less, particularly 60 mol% or less.

  Thus, a vinyl group always exists at the terminal of this component (that is, the silicon atom at the end of at least one molecular chain of component (A) has a vinyl group). There is a phenyl group, and it is particularly preferable that both a methyl group and a phenyl group exist. That is, the silicone resin composition of the present invention crosslinks at the terminal vinyl group of this organopolysiloxane, but the monovalent organic group other than the phenyl group and vinyl group is the above-mentioned one in which the methyl group has heat resistance and It is preferable in terms of cost.

a is a positive number of 1.5 to 3.0, and this component may be any of a chain, a branched chain, and a three-dimensional network, but usually the main chain is a diorganosiloxane unit (R ₂ It is preferably a basically linear diorganopolysiloxane consisting of repeating SiO _2/2 ) and having both molecular chain ends blocked with triorganosiloxy groups (R ₃ SiO _1/2 ). a is preferably a number of 1.8 to 2.2, more preferably a number of 1.95 to 2.05.

  The viscosity of the organopolysiloxane is preferably in the range of about 0.1 to 20 Pa · s, particularly about 0.5 to 10 Pa · s at 23 ° C. from the viewpoint of workability. If it is less than 0.1 Pa · s, it tends to flow, and thus molding burrs may increase, and if it exceeds 20 Pa · s, air bubbles mixed during mixing of necessary components may be difficult to escape.

（なお、上記各式において、

等の繰り返し単位の配列はランダムであり、また繰り返し単位の数の合計は上記粘度範囲を満足するように任意の自然数とすることができる。） Specific examples of the component (A) include those shown below.

(In the above equations,

The arrangement of repeating units such as these is random, and the total number of repeating units can be any natural number so as to satisfy the above viscosity range. )

Component (B) is an essential component for forming a cured product by crosslinking with component (A) in the presence of a catalyst of component (C) by an addition reaction, and preferably at least 2, preferably in one molecule. The following average composition formula (2) having 3 or more hydrogen atoms directly bonded to silicon atoms
R ¹ _b H _c SiO _{{4- (b + c)} / 2} (2)
(Wherein R ¹ represents a monovalent organic group, b is 0.7 ≦ b ≦ 2.1, c is 0.001 ≦ c ≦ 1.0, and 0.8 ≦ b + c ≦ 3) (It is a positive number.)
It is organohydrogen polysiloxane shown by these.

Examples of the organic group represented by R ¹ include an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and the same groups as R in the above formula (1) can be exemplified. What does not have an aliphatic unsaturated bond is good, and especially a methyl group and a phenyl group are more preferable.
b and c are positive numbers as described above, and preferably 0.9 ≦ b ≦ 2, 0.01 ≦ c ≦ 2, and 1 ≦ b + c ≦ 2.6.

Examples of the organohydrogenpolysiloxane include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends Trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy Blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer on both ends Body, (CH _{3) 2} HSiO copolymers consisting of _1/2 units and SiO _4/2 units, and, (CH _{3) 2} HSiO _1/2 units, and SiO _4/2 units (C ₆ H ₅₎ SiO _{3 A} copolymer composed of _{/ 2} units.

  The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms (or the degree of polymerization) in one molecule is 3 to 1. , Especially about 3 to 300 can be used. Moreover, it is preferable that the viscosity of this component is 0.1-5,000 mPa * s at 23 degreeC. If it is less than 0.1 mPa · s, it is likely to be volatilized at the time of heat curing, and if it exceeds 5,000 mPa · s, the coating workability may be lowered. In addition, silicon atoms directly bonded hydrogen atoms (SiH groups) in this component may be at least 2, preferably 3 or more in one molecule, but if it is too much, the cured product becomes too brittle. Preferably it is 50 or less, more preferably 30 or less.

  The blending ratio of this component is such that the amount of hydrogen atoms directly bonded to silicon atoms in this component is 0.7 to 10 for one vinyl group of component (A). If it is less than 0.7, the curing becomes sweet, and if it exceeds 10, the cured product becomes too brittle. Preferably it is 0.8-5 pieces.

  The platinum group metal catalyst of component (C) is for addition reaction of the vinyl group of component (A) and the silicon atom-bonded hydrogen atom of component (B), and the composition of the present invention by the action of this component. The object can be cured. These include particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, coordination compounds of chloroplatinic acid and vinylsiloxane, platinum black, etc. Examples include platinum-based catalysts, palladium catalysts, rhodium catalysts, and the like. As the usage-amount, it is 1-1000 ppm as a platinum group metal with respect to the total mass of (A) component and (B) component. If it is less than 1 ppm, the curing rate is slow, and if it exceeds 1,000 ppm, the workable time when all the components are mixed is shortened and it is uneconomical. Preferably it is 5-500 ppm.

Component (D) is a component for improving the adhesiveness of a cured product obtained by curing the silicone resin composition of the present invention, an organosilane having a silicon-bonded alkoxy group, a partially hydrolyzed condensate thereof, an organo Organic silicon compounds such as polysiloxane. Among such organosilicon compounds of component (D), as organosilane, the following general formula (3)
R ² _p Si (OR ³ ) _4-p (3)
The alkoxysilane shown by these is mentioned.

In this case, p is 0, 1 or 2, preferably 0 or 1, and R ² is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, etc. C1-C10 unsubstituted monovalent hydrocarbon groups such as alkyl groups, vinyl groups, allyl groups, propenyl groups, hexenyl groups, cyclohexenyl groups and other alkenyl groups, phenyl groups, tolyl groups, xylyl groups and other aryl groups , 3-glycidoxypropyl group, 3-methacryloxypropyl group, 3-aminopropyl group, N-2 (aminoethyl) -3-aminopropyl group, N-phenyl-3-aminopropyl group, etc. An epoxy-substituted alkyl group having 1 to 10 carbon atoms having a substituent such as an epoxy group, a (meth) acryloxy group, an amino group, or an N-substituted amino group, (meth) Kurirokishi substituted alkyl group, an amino-substituted alkyl group, (N-substituted amino) substituted monovalent hydrocarbon group, a substituted alkyl group, R ³ is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, tert -It is a C1-C4 alkyl group, such as a butyl group.

  Also, a partially hydrolyzed condensate of the alkoxysilane of the above formula (3) (that is, an organosiloxane oligomer derived from the alkoxysilane and having at least one, preferably two or more residual alkoxy groups in the molecule) is used. You can also

  Examples of the alkoxysilane of the formula (3) include tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Examples include alkoxysilane compounds such as vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane, and partial hydrolysis condensates thereof. Can be used.

  Furthermore, a silicon atom-bonded alkoxy group-containing siloxane compound (organosiloxane oligomer) having a linear or cyclic structure, usually having 4 to 30 silicon atoms, particularly about 4 to 20 silicon atoms, represented by the following formula can be used. .

（式中、ｍ，ｎは１以上で、かつ一分子中のケイ素原子数を４〜３０とする整数である。）

(In the formula, m and n are integers of 1 or more and 4 to 30 silicon atoms in one molecule .)

  Among such organosilicon compounds of component (D), the adhesiveness of the resulting cured product is particularly excellent. Therefore, as the organosilicon compound of component (D), a silicon atom-bonded alkoxy group in one molecule An organosilicon compound having a silicon atom-bonded alkenyl group or a silicon atom-bonded hydrogen atom (SiH group) is preferred.

  The blending amount of component (D) is preferably in the range of 0 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, especially 0.5 to 3 parts by weight with respect to 100 parts by weight of component (A). It is preferable to be within the range. This is because when the blending amount of the component (D) exceeds 10 parts by mass with respect to 100 parts by mass of the component (A), the obtained cured product becomes too hard, and the adhesiveness is lowered.

  In addition, when (D) component has a silicon atom bond alkenyl group or a silicon atom bond hydrogen atom (SiH group), the total SiH group amount with respect to the total alkenyl group amount X in the composition containing (A) and (B) components The ratio (molar ratio) Y / X of Y is preferably about 0.7 to 10 mol / mol, particularly about 0.8 to 5 mol / mol.

  The refractive index of the silicone resin obtained by curing the coating protective material (silicone resin composition) of the present invention is such that the light emitting element emits light when a MODEL 2010 PRISM COUPLER (made by Metricon) or a goniometer (made by MOLLERWEDEL) is used. It can be measured at the wavelength to be. However, since the refractive index at each wavelength of the silicone resin follows the Sellmeier equation, the refractive index at the wavelength used is calculated by measuring the refractive index at 589 nm (Cooper PR 1982 Refractive). index measurements of paraffin, a silicon elastomer, and an epoxy resin over the 500-1,500 nm spectral range Appl. Opt. 21 3413-15).

  Therefore, the refractive index of the silicone resin obtained by curing of the present invention can be managed by the refractive index at 589 nm (sodium D line). The refractive index at 25 ° C. and 589 nm of the silicone resin obtained by curing of the present invention is preferably 1.41-1.56. If the refractive index is less than 1.41, the light is reflected at the interface and the luminous efficiency is lowered. On the other hand, when the refractive index exceeds 1.56, the crystallinity of the silicone resin increases and birefringence increases, so that the light emission rate decreases. Preferably it is 1.43-1.55. The refractive index can be adjusted by the composition of the component (A) and the component (B), particularly the phenyl group content in the component (A) and the component (B).

Since the silicone resin of the present invention has a strong adhesive force, it does not cause peeling due to resin curing or IR reflow during mounting. The cured resin has low elasticity and usually has a hardness range of 75 or less in durometer type A, so it can absorb stress due to the difference in thermal expansion coefficient from the ceramic or plastic casing, so the low temperature side Cracks do not occur even when the thermal shock test at −40 ° C. and 120 ° C. on the high temperature side is performed for 1,000 cycles. The durometer type A hardness is usually 75 or less, preferably 5 to 75, more preferably 10 to 70, and still more preferably 20 to 65. The hardness is adjusted by adjusting the crosslink density of the composition evaluated by using the molar ratio (Y / X) of the amount of SiH groups to the amount of silicon-bonded alkenyl groups in the composition, and SiO that can be blended in the composition. methylpolysiloxane three dimensional network structure containing ₂ units (resin structure), vinyl methyl polysiloxane, amount of the organopolysiloxane such as methyl hydrogen polysiloxane, it may be performed by such amount, such as a reinforcing filler it can.

The silicone resin of the present invention can be easily produced by mixing and heating the four components (A), (B), (C) and (D). When these four components are mixed, curing proceeds even at room temperature. Therefore, it is preferable to add a trace amount of a reaction inhibitor such as an acetylene alcohol compound, a triazole, a nitrile compound, or a phosphorus compound in order to increase the workable time. In addition, a phosphor for changing the wavelength of the silicone resin of the present invention, a light scattering agent such as titanium oxide fine powder (TiO ₂ ), or the like can also be added.

  Furthermore, reinforcing fillers such as fumed silica and precipitated silica, flame retardants, organic solvents and the like may be added without departing from the object of the present invention.

  In addition, it is preferable that the coating protective material of this invention is a liquid, and the viscosity of 23 degreeC is 10-1,000,000 mPa * s, Especially about 100-1,000,000 mPa * s is preferable.

  The coating protective material of the present invention is used for coating protection of a light emitting semiconductor. In this case, examples of the light emitting semiconductor include a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array. The mode of covering and protecting the light emitting semiconductor is not particularly limited, but as shown in FIGS. 1 and 2, the casing is filled with a covering protective material covering the light emitting semiconductor disposed in the housing having an opening. Then, a method such as curing it can be adopted.

  In addition, the curing conditions of the coating protective material of the present invention are arbitrary depending on the working conditions from 72 hours to 200 ° C. for 3 minutes at room temperature (25 ° C.). It is possible to select appropriately from the balance.

で表される末端ビニルジメチルジフェニルポリシロキサン（粘度３Ｐａ・ｓ）１００部、下記式（ＩＩ）

で表されるメチルハイドロジェンポリシロキサン（粘度１５ｍＰａ・ｓ）２．５部、塩化白金酸２−エチルヘキシルアルコール変性溶液（Ｐｔ濃度２ｗｔ％）０．０３部、エチニルシクロヘキシルアルコール０．０５部、３−グリシドキシプロピルトリメトキシシラン７部及び平均粒径９μｍの球状アルミナ微粉末４００部を均一混合してシリコーンダイボンド材を調製した。 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. In addition, in the following example, a part shows a mass part. Moreover, a viscosity is a value of 23 degreeC. First, the evaluation method of the coating protective material of an Example and a comparative example is shown.
[Evaluation methods]
Preparation of silicone die bond material

100 parts of terminal vinyldimethyldiphenylpolysiloxane (viscosity 3 Pa · s) represented by the following formula (II)

Methyl hydrogen polysiloxane (viscosity 15 mPa · s) 2.5 parts, chloroplatinic acid 2-ethylhexyl alcohol modified solution (Pt concentration 2 wt%) 0.03 parts, ethynyl cyclohexyl alcohol 0.05 parts, 3- A silicone die bond material was prepared by uniformly mixing 7 parts of glycidoxypropyltrimethoxysilane and 400 parts of spherical alumina fine powder having an average particle size of 9 μm.

Method for Manufacturing Light-Emitting Semiconductor Device A light-emitting semiconductor device as shown in FIG. 1 was manufactured using an LED chip having a light-emitting layer made of InGaN and having a main light emission peak of 470 nm as a light-emitting element. The light emitting element 2 was fixed to a glass fiber reinforced epoxy resin casing 1 having a pair of lead electrodes 3 and 4 by using a silicone die bond material 5 and heated at 180 ° C. for 10 minutes. After the light emitting element 2 and the lead electrodes 3 and 4 were connected by the gold wire 6, the covering protective material 7 was potted and cured at 180 ° C. for 1 hour to produce a light emitting semiconductor device.
Method of Measuring Luminance of Light-Emitting Semiconductor Device A constant current was passed through the light-emitting semiconductor device manufactured by the above-described protection method, and the luminance was measured by obtaining the output current value of the light receiving element 5 seconds after the current application as the luminance (the light emission of Example 1). It was obtained by a comparative value where the luminance of the semiconductor device was 1.00).
Method of measuring deterioration of current-carrying luminance of light-emitting semiconductor device at high temperature Further, after the semiconductor device was energized for 20 hours at 150 ° C. for 1,000 hours, it was returned to room temperature, and a constant current was passed through the light-emitting semiconductor device The output current value of the light receiving element 5 seconds after the application was obtained and compared with the output current value before energization at high temperature, and the luminance deterioration during heating deterioration was obtained (the initial luminance of the light emitting semiconductor device of Example 1 was determined). It was determined with a comparative value of 1.00).
Thermal Shock Resistance Test Method The manufactured light-emitting semiconductor device was subjected to 1,000 cycles of thermal shock tests at a low temperature side of −40 ° C. and a high temperature side of 120 ° C., and the number of appearance cracks was observed.

で表される末端ビニルジメチルジフェニルポリシロキサン（粘度３Ｐａ・ｓ）１００部、下記式（ＩＩ）

で表されるメチルハイドロジェンポリシロキサン（粘度１５ｍＰａ・ｓ）２．５部、塩化白金酸２−エチルヘキシルアルコール変性溶液（Ｐｔ濃度２ｗｔ％）０．０３部、エチニルシクロヘキシルアルコール０．０５部及び下記式（ＩＩＩ）

で表されるアルコキシ基含有シリコーン化合物２部を均一混合して、シリコーン被覆保護材を調製した。
このシリコーン被覆保護材硬化物の硬さはデュロメータ・タイプＡで３３、２５℃，５８９ｎｍでの屈折率は１．４８であった。この樹脂を用いて発光半導体装置を作製した。 [Example 1]
Formula (I)

100 parts of terminal vinyldimethyldiphenylpolysiloxane (viscosity 3 Pa · s) represented by the following formula (II)

Methyl hydrogen polysiloxane (viscosity 15 mPa · s) 2.5 parts, chloroplatinic acid 2-ethylhexyl alcohol modified solution (Pt concentration 2 wt%) 0.03 parts, ethynyl cyclohexyl alcohol 0.05 parts and the following formula (III)

A silicone coating protective material was prepared by uniformly mixing 2 parts of an alkoxy group-containing silicone compound represented by the formula:
The cured silicone-coated protective material had a durometer type A hardness of 33, a refractive index of 1.48 at 25 ° C. and 589 nm. A light emitting semiconductor device was manufactured using this resin.

で表される末端ビニルジメチルジフェニルポリシロキサン（粘度５Ｐａ・ｓ）１００部、下記式（Ｖ）

で表されるメチルハイドロジェンポリシロキサン（粘度９０ｍＰａ・ｓ）７．０部、塩化白金酸２−エチルヘキシルアルコール変性溶液（Ｐｔ濃度２ｗｔ％）０．０３部、エチニルシクロヘキシルアルコール０．０５部及び３−メタクリロキシプロピルトリメトキシシラン３部を均一混合して、シリコーン被覆保護材を調製した。
このシリコーン被覆保護材硬化物の硬さはデュロメータ・タイプＡで２４、２５℃，５８９ｎｍでの屈折率は１．４５であった。この樹脂を用いて発光半導体装置を作製した。 [ Reference Example 1 ]
Formula (IV) below

100 parts of terminal vinyldimethyldiphenylpolysiloxane (viscosity 5 Pa · s) represented by the following formula (V)

7.0 parts of methyl hydrogen polysiloxane (viscosity 90 mPa · s), 0.03 part of chloroplatinic acid 2-ethylhexyl alcohol modified solution (Pt concentration 2 wt%), 0.05 part of ethynylcyclohexyl alcohol and 3-part A silicone coating protective material was prepared by uniformly mixing 3 parts of methacryloxypropyltrimethoxysilane.
The cured silicone-coated protective material had a durometer type A hardness of 24, 25 ° C., and a refractive index of 1.45 at 589 nm. A light emitting semiconductor device was manufactured using this resin.

で表される末端ビニルジメチルジフェニルポリシロキサン（粘度２Ｐａ・ｓ）１００部、下記式（ＶＩＩ）

で表されるフェニルメチルハイドロジェンポリシロキサン（粘度３０ｍＰａ・ｓ）４．１部、塩化白金酸２−エチルヘキシルアルコール変性溶液（Ｐｔ濃度２ｗｔ％）０．０３部、エチニルシクロヘキシルアルコール０．０５部及び下記式（ＶＩＩＩ）

で表されるアルコキシ基含有シリコーン化合物２部を均一混合して、シリコーン被覆保護材を調製した。
このシリコーン被覆保護材硬化物の硬さはデュロメータ・タイプＡで６２、２５℃，５８９ｎｍでの屈折率は１．５３であった。この樹脂を用いて発光半導体装置を作製した。 [Example 2 ]
The following formula (VI)

Terminal vinyldimethyldiphenylpolysiloxane (viscosity 2 Pa · s) represented by the following formula (VII)

Phenylmethylhydrogenpolysiloxane (viscosity 30 mPa · s) 4.1 parts, chloroplatinic acid 2-ethylhexyl alcohol modified solution (Pt concentration 2 wt%) 0.03 parts, ethynylcyclohexyl alcohol 0.05 parts and the following Formula (VIII)

A silicone coating protective material was prepared by uniformly mixing 2 parts of an alkoxy group-containing silicone compound represented by the formula:
The cured silicone-coated protective material had a durometer type A hardness of 62, a refractive index of 1.53 at 25 ° C. and 589 nm. A light emitting semiconductor device was manufactured using this resin.

[Comparative Example 1]
100 parts of bisphenol A type epoxy resin (EP827, manufactured by Yuka Shell Epoxy Co., Ltd.) and 20 parts of polydimethylsiloxane having two amino groups with a molecular weight of 1,680 are blended in an organic solvent (xylene) and heat-treated at 150 ° C. Then, a modified bisphenol A type epoxy resin was produced by volatilizing and removing the organic solvent. 120 parts of this modified bisphenol A type epoxy resin, 100 parts of 4-methylhexahydrophthalic anhydride, and 0.4 parts of 2-ethyl-4-methylimidazole were blended and mixed uniformly to prepare an epoxy coating protective material.
The cured epoxy-coated protective material had a durometer type A hardness of 92, a refractive index of 1.56 at 25 ° C. and 589 nm. A light emitting semiconductor device was manufactured using this resin.

で表される末端ビニルジメチルポリシロキサン（粘度３Ｐａ・ｓ）１００部、下記式（ＩＩ）

で表されるメチルハイドロジェンポリシロキサン（粘度１５ｍＰａ・ｓ）２．０部、塩化白金酸２−エチルヘキシルアルコール変性溶液（Ｐｔ濃度２ｗｔ％）０．０３部及びエチニルシクロヘキシルアルコール０．０５部を均一混合して、シリコーン被覆保護材を調製した。
このシリコーン被覆保護材硬化物の硬さはデュロメータ・タイプＡで５８、２５℃，５８９ｎｍでの屈折率は１．４０であった。この樹脂を用いて発光半導体装置を作製した。 [Comparative Example 2]
Formula (IX) below

100 parts of a terminal vinyldimethylpolysiloxane (viscosity 3 Pa · s) represented by the following formula (II)

A homogeneous mixture of 2.0 parts of methylhydrogenpolysiloxane (viscosity 15 mPa · s), 0.03 part of chloroplatinic acid 2-ethylhexyl alcohol modified solution (Pt concentration 2 wt%) and 0.05 part of ethynylcyclohexyl alcohol Thus, a silicone coating protective material was prepared.
The cured silicone-coated protective material had a durometer type A hardness of 58, a refractive index at 25 ° C. and 589 nm of 1.40. A light emitting semiconductor device was manufactured using this resin.

で表される末端ビニルジメチルポリシロキサン（粘度３Ｐａ・ｓ）５０部、下記式（ＩＩ）

で表されるメチルハイドロジェンポリシロキサン（粘度１５ｍＰａ・ｓ）４．０部、塩化白金酸２−エチルヘキシルアルコール変性溶液（Ｐｔ濃度２ｗｔ％）０．０３部及びエチニルシクロヘキシルアルコール０．０５部を均一混合して、シリコーン被覆保護材を調製した。
このシリコーン被覆保護材硬化物の硬さはデュロメータ・タイプＡで８０、２５℃，５８９ｎｍでの屈折率は１．４１であった。この樹脂を用いて発光半導体装置を作製した。 [Comparative Example 3]
Resin-structured vinylmethylpolysiloxane 50 composed of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi (CH ₃ ) ₂ SiO _0.5 units (Vi represents a vinyl group). Part, the following formula (IX)

50 parts of a terminal vinyldimethylpolysiloxane (viscosity 3 Pa · s) represented by the following formula (II)

A homogeneous mixture of 4.0 parts of methylhydrogenpolysiloxane (viscosity 15 mPa · s), 0.03 part of chloroplatinic acid 2-ethylhexyl alcohol modified solution (Pt concentration 2 wt%) and 0.05 part of ethynylcyclohexyl alcohol Thus, a silicone coating protective material was prepared.
The cured silicone-coated protective material had a durometer type A hardness of 80, a refractive index of 1.41 at 25 ° C. and 589 nm. A light emitting semiconductor device was manufactured using this resin.

＊実施例１の発光半導体装置の初期の輝度を１．００とした比較値で表す。
Table 1 shows the evaluation results of the coating protective materials of the above Examples and Comparative Examples.

* Represented by a comparative value where the initial luminance of the light emitting semiconductor device of Example 1 is 1.00.

It is sectional drawing of the light emitting diode which shows an example (thing by which the light emitting element was die-bonded on the insulating housing | casing) of a surface mount type semiconductor light-emitting device. It is sectional drawing of the light emitting diode which shows the other example (The thing by which the light emitting element was die-bonded on the lead electrode inserted in the housing | casing). It is sectional drawing of the light emitting diode which shows a shell-type semiconductor light-emitting device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Case 2 Light emitting element 3, 4 Lead electrode 5 Die-bonding material 6 Gold wire 7 Covering protective material

Claims (5)

(A) The following average composition formula (1) having a vinyl group at the molecular chain terminal
R _a SiO _{(4-a) / 2} (1)
(In the formula, R represents a monovalent organic group, and at least 5 mol% to 80 mol% is a phenyl group. A is a number of 1.5 to 3.0.)
100 parts by mass of an organopolysiloxane represented by
(B) The following average composition formula (2) having hydrogen atoms directly bonded to at least two silicon atoms in one molecule
R ¹ _b H _c SiO _{{4- (b + c)} / 2} (2)
(Wherein R ¹ represents a monovalent organic group, b is 0.7 ≦ b ≦ 2.1, c is 0.001 ≦ c ≦ 1.0, and 0.8 ≦ b + c ≦ 3) (It is a positive number.)
An amount of 0.7 to 10 hydrogen atoms directly connected to silicon atoms in the component (B), with respect to one vinyl group in the component (A),
(C) Platinum group metal catalyst 1 to 1,000 ppm of the total mass of the component (A) and the component (B) as a platinum group metal,
(D) an organosilicon compound having silicon-bonded alkoxy group selected from an organosiloxane represented by the following formula from 0.5 to 10 parts by weight

(In the formula, m and n are integers of 1 or more and 4 to 30 silicon atoms in one molecule.)

The cured product has a refractive index of 1.41 to 1.56 at 25 ° C. and 589 nm (sodium D line) and a durometer type A hardness of 5 to 75. A light-emitting semiconductor coating protective material.   The light emitting semiconductor coating protective material according to claim 1, wherein the cured product has a refractive index of 1.43 to 1.55 at 25 ° C. and 589 nm.   The light-emitting semiconductor coating protective material according to claim 1 or 2, wherein the light-emitting semiconductor coating protective material is for covering a light-emitting semiconductor disposed in a housing having an opening and filling and curing the housing.   3. A light emitting semiconductor device, wherein the light emitting semiconductor element is disposed in a ceramic and / or plastic housing having an opening, and the inside of the housing is covered and protected with a cured product of the covering protective material according to claim 1 or 2. apparatus.   3. A light emitting semiconductor device in which a light emitting semiconductor element is disposed on a lead electrode in a ceramic and / or plastic housing having an opening, and the inside of the housing is covered and protected with a cured product of the covering protective material according to claim 1 or 2. Light emitting semiconductor device.

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