JP2005158762A - Shell type light emitting semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shell type light emitting semiconductor device which is excellent in thermal shock resistance, has good surface dust nonadhesion, and further, in a lead coming-off tension test, and can prevent generation of crack and lead coming-off. <P>SOLUTION: The shell type light emitting semiconductor device is constituted in such a manner that the light emitting element is sealed with (A)vinylgroup content ORGANO polysiloxane, (B) ORGANO hydrogen polysilane having hydrogen atom combined with two or more silicon atoms in one molecule, and (C)transparent curing object of hardenability silicon resin composite which uses platinum group metal system catalyst as inevitable component. A lead portion is sealed with cured object of epoxy-silicone hybrid resin composite which consists of epoxy resin and aluminum based catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  In the present invention, the light extraction portion is sealed with a silicone light emitting semiconductor coating protective material having no dust adhesion on the surface of the cured product, low elasticity and excellent crack resistance, and the lead portion is an epoxy made of silicone and epoxy resin. -It is related with the bullet-type light-emitting semiconductor device sealed with the hardened | cured material of the silicone hybrid resin composition.

  As a light emitting semiconductor device such as a light emitting diode (LED), a light emitting semiconductor device as shown in FIG. 1 is used which is called a shell type in which elements are arranged on lead electrodes and the periphery thereof is covered with a transparent resin. When this type of light-emitting semiconductor device is sealed with a low-elasticity silicone resin, the silicone resin is soft and weak, so there are problems such as pulling out the lead or breaking the silicone. It is not used in any type of semiconductor device.

  In FIG. 1, 1 is a light emitting element, 2 is a die bond material, 3 and 4 are lead electrodes, and 5 is a gold wire, which are sealed with 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, in order to improve the crack resistance, such a silicone-based cured product generally has a drawback that tack remains on the surface of the cured product, and dust easily adheres and impairs light transmission. 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 lack strength, and no light-emitting semiconductor element that can withstand practical use has been manufactured.

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

  The present invention has been made in view of the above circumstances, and seals the light extraction portion with a silicone light emitting semiconductor coating protective material that has no surface tackiness, excellent adhesion, and excellent impact resistance and light transmission. It is another object of the present invention to provide a shell type light emitting semiconductor device in which a lead portion is sealed with a cured product of an epoxy / silicone hybrid resin composition comprising a silicone compound and an epoxy resin.

As a result of intensive studies to achieve the above object, the present inventor,
(A) vinyl group-containing organopolysiloxane,
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule;
(C) A light-emitting element portion is sealed with a transparent cured product of a curable silicone resin composition containing a platinum group metal catalyst as an essential component, and the lead portion contains a silanol group and / or an alkoxyl group-containing silicone compound and epoxy resin By sealing with a cured product of an epoxy / silicone hybrid resin composition comprising an aluminum catalyst, it is possible to manufacture a shell-type light emitting semiconductor device in which lead omission and cracks, which have been problems in the past, are greatly improved. It has been found that there is. Among these, as the curable silicone resin composition, an organopolysiloxane represented by the following general formula (1) and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C., an SiO ₂ unit, and R ³ _n R Resin-structured organopolysiloxane composed of ⁴ _p SiO _0.5 units and R ³ _q R ⁴ _r SiO _0.5 units (in the above formula, R ³ is a vinyl group or an allyl group, and R ⁴ does not contain an aliphatic unsaturated bond) A monovalent hydrocarbon group, n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, and q + r = 3). Cured product of addition reaction curable silicone rubber composition obtained by using in combination has no surface tack, has low elasticity and transparency, has good adhesion, and is used effectively as a protective material for light emitting semiconductor coatings. And the present invention It came to an eggplant.

Therefore, the present invention
(A) vinyl group-containing organopolysiloxane,
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule;
(C) A silicone compound or epoxy resin in which a light emitting element portion is sealed with a transparent cured product of a curable silicone resin composition containing a platinum group metal catalyst as an essential component, and a lead portion contains a silanol group and / or an alkoxyl group And a bullet-type light emitting semiconductor device sealed with a cured product of an epoxy-silicone hybrid resin composition comprising an aluminum catalyst.

In this case, the bullet-type light emitting semiconductor device preferably has the following configuration.
(A ′) an organopolysiloxane represented by the following general formula (1) and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C.,

(Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² is an unsubstituted or substituted monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond. , K, m is 0 or a positive integer, and k + m is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)
(D) Organopolysiloxane having a resin structure composed of SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units and R ³ _q R ⁴ _r SiO _0.5 units (wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, q + r = 3),
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule;
(C) platinum group metal catalyst,
(E) The following general formula (3)

(Wherein R ⁶ represents the following formula (4)

Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4), and R ⁷ is a hydrogen atom or having 1 to 6 carbon atoms. A monovalent hydrocarbon group, s is an integer of 1-6. )
The component (D) is an amount of 20 to 70% by mass with respect to the total amount of the components (A) and (D). An epoxy silicone comprising a silicone compound containing a silanol group and / or an alkoxyl group, an epoxy resin and a curing catalyst, wherein the light emitting element portion is sealed with a transparent cured product of a silicone light emitting semiconductor coating protective material blended in A bullet-type light emitting semiconductor device sealed with a cured product of a hybrid resin composition.

  The bullet-type light emitting semiconductor device of the present invention is excellent in thermal shock resistance, has good surface dust non-adhesiveness, and has improved crack generation and lead omission in a lead tensile test.

  The components (A) and (D) of the coating protective material (silicone resin composition) for coating and protecting the light emitting semiconductor of the present invention are components that become the main component (base polymer) of the coating protective material of the present invention, and (C ) It is cured by crosslinking with the component (B) under the catalytic action of the component.

(A) Organopolysiloxane The vinyl group-containing organopolysiloxane (A) has at least one vinyl group bonded to a silicon atom at each end represented by the following general formula (1), and is 25 ° C. It is preferably a basically linear organopolysiloxane having a viscosity of 10 to 1,000,000 mPa · s, particularly 100 to 100,000 mPa · s. The linear organopolysiloxane may contain a small amount of a branched structure (trifunctional siloxane unit) in the molecular chain. The viscosity is a value measured with a rotational viscometer (BM type) (hereinafter the same).

(Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² is an unsubstituted or substituted monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond. , K, m is 0 or a positive integer, and k + m is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)

Here, the monovalent hydrocarbon group for R ¹ is preferably a group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Group, alkyl group such as tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group , Aralkyl groups such as phenylethyl group and phenylpropyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group, and hydrogen atoms of these groups Are substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, etc., such as a chloromethyl group, Roropuropiru group, bromoethyl group, and a halogen-substituted alkyl group or cyanoethyl group such trifluoropropyl group.

Further, the monovalent hydrocarbon group for R ² is preferably one having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and the same examples as the specific examples for R ¹ described above can be exemplified, but an alkenyl group is not included.
k and m are generally 0 or a positive integer satisfying 5 ≦ k + m ≦ 10,000, preferably 10 ≦ k + m ≦ 2,000, and 0 <k / (k + m) ≦ 0.2. A satisfying integer.

Specific examples of the component (A) include the following.

(In the above formula, t is an integer of 8 to 2,000.)

(In the above formula, k and m are as described above.)

(D) Resin-structured organopolysiloxane The resin-structured (that is, three-dimensional network) organopolysiloxane that can be a constituent of the composition of the present invention comprises SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units, and R ³ _q R ⁴ _r Resin-structured organopolysiloxane composed of _0.5 units of SiO (wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond) , N is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, and q + r = 3.
Examples of the monovalent hydrocarbon group for R ⁴ include those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, similar to the above R ² .

Here, when the SiO ₂ unit is a unit, the R ³ _n R ⁴ _p SiO _0.5 unit is b unit, and the R ³ _q R ⁴ _r SiO _0.5 unit is c unit,
(B + c) /a=0.3-3, especially 0.7-1
c / a = 0.01 to 1, especially 0.07 to 0.15
In addition, the organopolysiloxane of component (D) has a weight average molecular weight of 500 to 100,000, particularly 1,000 to 10,000, as determined by a polystyrene conversion measurement method by GPC (gel permeation chromatography). Those within the range are preferred.

  In addition to the a unit, b unit, and c unit, the organopolysiloxane having a resin structure as the component (D) is further difunctional siloxane unit or trifunctional siloxane unit (that is, organosilsesquioxane). (Unit) may be contained in a small amount within a range not impairing the object of the present invention.

  Such an organopolysiloxane having a resin structure can be easily synthesized by combining the compounds serving as the unit sources so as to have the above molar ratio, and performing cohydrolysis in the presence of an acid, for example.

  Here, examples of the a unit source include sodium silicate, alkyl silicate, polyalkyl silicate, silicon tetrachloride and the like.

Moreover, as a b unit source, the following can be illustrated.

Further, examples of the c unit source include the following.

  The organopolysiloxane having a resin structure as the component (D) is blended in order to improve the physical strength and the tackiness of the surface of the cured product. As described above, the component (A) It is preferable to mix | blend in the quantity of 20-70 mass% per total amount of this, More preferably, 30-60 mass% is mix | blended. When the blending amount of component (D) is too small, the above effect cannot be achieved sufficiently, and when it is too large, there are disadvantages such as the viscosity of the composition being remarkably increased and cracks being easily generated in the cured product.

(B) Organohydrogenpolysiloxane The (B) component organohydrogenpolysiloxane acts as a crosslinking agent, and the SiH group in the component and the vinyl groups in the (A) and (D) components are added. A cured product is formed by reaction. The organohydrogenpolysiloxane may be any one as long as it has two or more hydrogen atoms (that is, SiH groups) bonded to a silicon atom in one molecule. In particular, the following average composition formula (2)
H _a (R ⁵ ) _b SiO _{(4-ab) / 2} (2)
Wherein R ⁵ is the same or different unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and a and b are 0.001 ≦ a <2, 0.7 ≦ b ≦ 2 and 0.8 ≦ a + b ≦ 3.)
And one having at least 2, preferably 3 or more hydrogen atoms (SiH groups) bonded to a silicon atom in one molecule.

Here, R ⁵ in the above formula (2) is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 7 carbon atoms, which does not contain an aliphatic unsaturated bond. It is preferable that there are, for example, lower alkyl groups such as a methyl group, aryl groups such as a phenyl group, and those exemplified for the substituent R ² in the above general formula (1). A and b are numbers satisfying 0.001 ≦ a <2, 0.7 ≦ b ≦ 2, and 0.8 ≦ a + b ≦ 3, preferably 0.05 ≦ a ≦ 1, 0.8 ≦ b ≦ 2 and 1 ≦ a + b ≦ 2.7. The position of the hydrogen atom bonded to the silicon atom is not particularly limited, and may be at the end of the molecule or in the middle.

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 copolymer comprising a _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 Examples include copolymers composed of _{/ 2} units.

Moreover, a compound as shown by the following structure can also be used.

  The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is 3 to 1. , Especially about 3 to 300 can be used.

Such organohydrogenpolysiloxanes are usually R ⁵ SiHCl ₂ , (R ⁵ ) ₃ SiCl, (R ⁵ ) ₂ SiCl ₂ , (R ⁵ ) ₂ SiHCl (R ⁵ is as described above). Such chlorosilanes can be hydrolyzed or siloxanes obtained by hydrolysis can be equilibrated.

  In addition, the compounding amount of the organohydrogenpolysiloxane is the effective curing amount of the above components (A) and (D), and in particular, the SiH group is an alkenyl group (for example, vinyl) in the components (A) and (D). It is preferable to use at a molar ratio of 0.1 to 4.0, particularly preferably 1.0 to 3.0, and more preferably 1.2 to 2.8 per the total amount of (base). If it is less than 0.1, the curing reaction does not proceed and it is difficult to obtain a cured silicone rubber. If it exceeds 4.0, a large amount of unreacted SiH groups remain in the cured product, so that the rubber physical properties are deteriorated over time. May cause a change.

(C) Platinum group metal-based catalyst This catalyst component is blended in order to cause the addition curing reaction of the composition of the present invention, and there are platinum-based, palladium-based and rhodium-based ones. From the viewpoint of platinum, platinum-based materials such as platinum, platinum black and chloroplatinic acid, for example, H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ Examples include mH ₂ O, PtO ₂ .mH ₂ O (m is a positive integer), and complexes thereof with hydrocarbons such as olefins, alcohols, or vinyl group-containing organopolysiloxanes. These can be used alone or in combination of two or more. The compounding amount of these catalyst components may be a so-called catalyst amount, and is usually 0.1 to 1, in terms of platinum group metal (mass) with respect to the total amount of the components (A), (B) and (D). 000 ppm, preferably in the range of 0.5 to 200 ppm.

(E) Adhesion aid The coating protective material of the present invention has an organosilicon compound such as organosilane or organopolysiloxane having a silicon atom-bonded alkoxy group in order to improve the adhesion of a cured product obtained by curing the coating protective material. You may add and mix | blend adhesive adjuvants, such as such as an arbitrary component as needed. Examples of such organosilicon compounds include tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and vinyl. Alkoxysilane compounds such as trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and hydrogen atoms bonded to silicon atoms in one molecule ( SiH group), alkenyl groups bonded to silicon atom (e.g., Si-CH = CH ₂ groups), such as trialkoxysilyl groups alkoxysilyl group (e.g., such as trimethoxysilyl group), an epoxy group (eg Glycidoxypropyl group, 3,4-epoxycyclohexylethyl group) containing at least 2, preferably 2 or 3 functional groups, usually having 4 to 30 silicon atoms, particularly about 4 to 20 And a siloxane compound (organosiloxane oligomer) having a linear or cyclic structure.

In this case, an organooxysilyl-modified isocyanurate compound represented by the following general formula (3) and / or a hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) is preferably used as an adhesion assistant.
(Wherein R ⁶ represents the following formula (4)
Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4), and R ⁷ is a hydrogen atom or having 1 to 6 carbon atoms. A monovalent hydrocarbon group, s is an integer of 1-6, especially 1-4. )

In this case, the monovalent hydrocarbon group containing an aliphatic unsaturated bond of R ⁶ includes vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclohexenyl group. And alkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms. Examples of the monovalent hydrocarbon group for R ⁷ include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, hexyl groups, cyclohexyl groups, and other alkyl groups, vinyl A monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms such as an alkenyl group and an aryl group such as a phenyl group, which are the same as those exemplified as R ⁶ such as a group, an allyl group, a propenyl group and an isopropenyl group And preferably an alkyl group.

(E) As an adhesion assistant of a component, the compound shown by a following formula is illustrated.
(In the formula, m and n are each a positive integer satisfying m + n of 2 to 50, preferably 4 to 20.)

  Among such organosilicon compounds, compounds having particularly excellent adhesion of the resulting cured product include organic compounds having silicon-bonded alkoxy groups and alkenyl groups or silicon-bonded hydrogen atoms (SiH groups) in one molecule. A silicon compound is preferred.

  In the present invention, the blending amount of the above-mentioned (E) component (arbitrary component) adhesion assistant is usually 10 parts by mass or less (that is, 0) with respect to 100 parts by mass in total of the (A) component and the (D) component. 10 parts by mass), preferably 0.01-5 parts by mass, more preferably about 0.1-1 part by mass. When the blending amount of the component (E) is too small, the adhesion to the substrate may be inferior, and when it is too large, the hardness of the cured product may be lowered or the surface tackiness of the cured product may be adversely affected.

  In addition, since the coating protective material obtained by blending the adhesion assistant in this way has a strong adhesive force, it does not cause peeling due to resin curing or IR reflow during mounting. Further, the cured product is durometer type A, has a hardness of 70 or more, has no adhesion of dust to the surface of the cured product, and has a low elastic property, so it depends on a difference in thermal expansion coefficient from a ceramic or plastic casing. Since stress can be absorbed, cracks do not occur even when 1,000 cycles of the thermal shock test at −40 ° C. on the low temperature side and 120 ° C. on the high temperature side are performed.

The silicone resin of the present invention can be easily produced by mixing and heating the components (A), (B), (C) and preferably the component (D). When these 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, a light scattering agent such as fine titanium oxide powder (TiO ₂ ), or the like can be added to the silicone resin of the present invention.

  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 25 degreeC is 10-1,000,000 mPa * s, Especially about 100-1,000,000 mPa * s is preferable.

Next, the epoxy / silicone hybrid resin composition for protecting and sealing the lead portion is composed of the following materials.
(F) a silicone compound having at least one silicon atom-bonded hydroxyl group (silanol group) and / or silicon atom-bonded alkoxy group per molecule;
(G) a compound (epoxy resin) containing an average of one or more epoxy groups per molecule,
(H) A composition containing a catalytic amount of an aluminum compound as an essential component.

  In this case, the silicone compound having at least one silicon atom-bonded hydroxyl group (silanol group) and / or silicon atom-bonded alkoxy group per molecule of the component (F) is a single monomer or polymer, or a mixture thereof. It may be. Examples of these silicone compounds include silane, a silicone compound having a SiOSi unit (that is, organo (poly) siloxane), silcarban (that is, silalkylene unit such as silethylene), silcarban and siloxane unit, silphenylene and silphenylene. A silicone resin having a siloxane unit is used.

Typical examples of this type of silicone monomer include (CH ₃ ) ₃ SiOH, C ₆ H ₅ (CH ₃ ) ₂ SiOH, (C ₆ H ₅ ) ₂ Si (OH) ₂ , C ₆ H ₅ (CH ₃ ) (CH ₃ O) SiOH and the like.

As the silicone polymer, those having the following siloxy units are preferably used. For example, (CH ₃ ) ₂ (OH) SiO _1/2 , (CH ₃ ) ₂ SiO, CH ₃ (C ₆ H ₅ ) (OH) SiO _1/2 , CH ₃ SiO _3/2 , (C ₆ H ₅ ) (CH ₃ O) (CH ₃ ) SiO _1/2 , (C ₆ H ₅ ) (OH) SiO, (CH ₃ ) (CH ₃ O) (OH) SiO _{1/2 and the} like.

  It is sufficient that the silicon atom-bonded hydroxyl group or the silicon atom-bonded alkoxy group is 0.01 to 10% by mass of the silicone compound.

  On the other hand, as the epoxy resin (G), any compound having an average of one or more epoxy groups per molecule can be used. Among them, bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins and their hydrogenated novolak type epoxy resins. , Alicyclic epoxy resin, cyclopentadiene type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, epoxy resin hydrogenated with these phenyl groups, biphenyl type epoxy resin, hydrogenated biphenyl type epoxy resin, polyfunctional type epoxy Examples thereof include a resin and an epoxy resin represented by the following structure. Among these, hydrogenated epoxy resins and alicyclic epoxy resins are preferably used in order to prevent deterioration and coloring due to light.

  The epoxy resin in the epoxy / silicone hybrid resin composition is preferably 5 to 70% by mass, and the silicone compound is preferably 30 to 95% by mass. Particularly preferably, the epoxy resin is 10 to 50% by mass, and the silicone compound is 50 to 90% by mass. If the epoxy resin exceeds 70% by mass, there is a risk of discoloration due to the temperature at the time of LED emission or ultraviolet rays. On the other hand, if it is less than 5% by mass, the strength of the cured product of the hybrid resin composition is insufficient, and there is a risk of lead removal and cracks. The above-mentioned defect can be prevented if the sealing thickness of the epoxy / silicone hybrid resin composition is about 0.5 to 5 mm.

  An aluminum-based catalyst is used as a curing catalyst (H) for reacting the epoxy resin with the silicone compound. Typical examples of these catalysts are aluminum trihydroxide, or aluminum alcoholates such as aluminum triethoxide, aluminum triisopropoxide, alkoxyaryl aluminate, aluminum triacetate, aluminum tribenzoate, aluminum tristearate, aluminum Aluminum acylates such as hydroxy distearate and aluminum hydroxy diacetate, salts of aluminum acylates and alkoxides, silicon atom-bonded hydroxyl groups, reaction products of silicon atom-bonded alkoxy groups with aluminum alkoxides and aluminum acylates, and aluminosyloxy compounds And organoaluminum compounds selected from aluminum chelates. As the amount of the catalyst, 0.05 to 5 parts by mass is sufficient per 100 parts by mass of the total amount of the epoxy resin and the silicone compound.

  In addition, by using the epoxy / silicone hybrid resin composition used in the present invention, a strong bond is formed at the interface with the transparent silicone sealing resin, improving moisture resistance reliability and reliability in temperature cycle, etc. To do.

  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. However, as a method for manufacturing a shell-type light emitting device, a lead frame having a light emitting semiconductor element mounted on a plastic mold or the like is inserted, and a transparent silicone resin composition is poured. After curing or semi-curing, the target light-emitting semiconductor device can be easily manufactured by pouring an epoxy-silicone hybrid resin composition and curing by heating.

  FIG. 1 shows this. In FIG. 1, reference numeral 1 denotes a light emitting element. The light emitting element 1 is fixed to a lead electrode 3 by a die bonding material 2 and is connected to lead electrodes 3 and 4 by a gold wire 5. ing. The light emitting element 1 is sealed with a cured product 6 of a silicone resin composition (silicone coating protective material), and the lead portion (the lower part of the lead electrodes 3 and 4) is made of an epoxy / silicone hybrid resin composition. It is sealed with a cured product 7.

  The curing condition of the silicone resin coating protective material of the present invention can be appropriately selected from the balance between productivity and heat resistance of the light emitting device and the case, but the curing condition of the silicone resin composition is from room temperature to 200 ° C. It can be arbitrarily selected according to the working conditions. Further, the curing condition of the epoxy / silicone hybrid resin composition for sealing the lead portion is 100 to 200 ° C., preferably 120 to 170 ° C., whereby the light emitting semiconductor device can be easily manufactured.

  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. Further, Me represents a methyl group, and Vi represents a vinyl group. In addition, a part shows a mass part by the following example.

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

A terminal vinyldimethylsiloxy group-capped dimethylsiloxane / diphenylsiloxane copolymer (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% by mass) 0.03 parts, ethynylcyclohexyl 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.

[Silicone sealing resin composition A]
Following formula

And 50 parts by weight of polysiloxane (VF) represented by the following formula: Resin-structure vinylmethyl consisting of 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₃ SiO _0.5 units 50 parts of siloxane (VMQ), following formula

8 parts of an organohydrogenpolysiloxane represented by

5 parts of an organohydrogenpolysiloxane represented by

A silicone sealing resin composition A was prepared by adding 0.3 part of an adhesion assistant represented by the above and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid and stirring well. The cured product cured at 160 ° C. for 30 minutes (hereinafter the same) was colorless and transparent.

[Silicone sealing resin composition B]
The following formula as VF

A silicone sealing resin composition B was prepared with the same composition as the composition A except that was used. The cured product was colorless and transparent.

[Silicone sealing resin composition C]
70 parts of polysiloxane (VF) used in Example 1, 50 mol% of SiO ₂ units as VMQ resin, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₂ MeSiO _0.5 units Resin structure vinyl methylsiloxane (VMQ) 30 parts, following formula

A silicone encapsulating resin composition C was prepared in the same manner as the composition A except that 10 parts of the organohydrogenpolysiloxane represented by the formula (1) was used. The cured product was colorless and transparent.

[Silicone sealing resin composition D]
Following formula

50 parts by weight of polysiloxane represented by the following formula: 50 parts by weight of SiO ₂ units, 50 parts by weight of (CH ₃ ) ₃ SiO _0.5 units and 50 parts by weight of vinyl methylsiloxane (VMQ) having a resin structure consisting of 10 mol% of Vi ₃ SiO _0.5 units, Following formula

3 parts of an organohydrogenpolysiloxane represented by

5 parts of an organohydrogenpolysiloxane represented by

A silicone sealing resin composition D was prepared by adding 0.2 part of an adhesion aid represented by the formula (II) and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid and stirring well. The cured product was colorless and transparent.

[Epoxy / silicone hybrid resin composition A]
100 parts of transparent bisphenol A type epoxy resin (EP828: manufactured by Japan Epoxy Co., Ltd.) as an epoxy resin, phenylmethyl silicone resin (CH ₃ SiO _3/2 unit, C ₆ H ₅ SiO _3/2 unit and C ₆ H ₅ 100 parts of (CH ₃ ) containing SiO units and 5% by mass of hydroxyl group) and 2 parts of γ-glycidoxypropyltrimethoxysilane (KBM403: manufactured by Shin-Etsu Chemical Co., Ltd.) are heated and mixed at 100 ° C. As a result, a liquid composition was produced. To this, 1.5 parts of aluminum benzoate was added and mixed at room temperature to obtain a transparent curable epoxy / silicone hybrid resin composition A. The cured product was colorless and transparent.

[Epoxy / silicone hybrid resin composition B]
100 parts of transparent hydrogenated bisphenol A type epoxy resin (YX8000: manufactured by Japan Epoxy Co., Ltd.) as an epoxy resin, phenylmethyl silicone resin (CH ₃ SiO _3/2 unit, C ₆ H ₅ SiO _3/2 unit and C ₆ 100 parts of H ₅ (CH ₃ ) SiO unit and 5% by mass of hydroxyl group) and 2 parts of γ-glycidoxypropyltrimethoxysilane (KBM403: manufactured by Shin-Etsu Chemical Co., Ltd.) were heated to 100 ° C. A liquid composition was prepared by mixing while mixing. To this, 1.5 parts of aluminum benzoate was added and mixed at room temperature to obtain a transparent curable epoxy / silicone hybrid resin composition B. The cured product was colorless and transparent.
[Epoxy resin composition C]
100 parts of transparent bisphenol F type epoxy resin (EP828: manufactured by Japan Epoxy Co., Ltd.) as an epoxy resin, 100 parts of methyltetrahydrophthalic anhydride (MH700: manufactured by Shin Nippon Rika Co., Ltd.) as an acid anhydride, γ-glycid A liquid composition was prepared by mixing 2 parts of xylpropyltrimethoxysilane (KBM403: manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 parts of 2-phenylimidazole as a curing catalyst at room temperature. The cured product was colorless and transparent.

[Example 1]
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 1 was fixed by heating at 180 ° C. for 10 minutes using the silicone die bond material 2 as the lead electrode 3. After the light emitting element 1 and the lead electrodes 3 and 4 are connected by the gold wire 5, the lead frame on which the light emitting element is mounted is installed in the cylindrical case 8 as shown in FIG. As shown in b), the silicone resin composition A was potted from the top to a predetermined height and cured at 150 ° C. for 30 minutes. Thereafter, as shown in FIG. 2C, the epoxy / silicone hybrid resin composition A was further potted and cured at 180 ° C. for 1 hour to produce a semiconductor element.
This light-emitting semiconductor device was subjected to 1,000 cycles of the thermal shock test on the low temperature side −40 ° C. and the high temperature side 120 ° C. by the following method to observe the number of appearance cracks and peeling between the silicone resin and the epoxy / silicone hybrid resin interface. As a result, no defect occurred. Further, no dust adhered to the surface of the semiconductor device. Further, as a result of strongly pulling the external lead terminal in the direction shown in FIG. 1, no cracks or lead omission occurred in the sealing material.

Thermal shock resistance test method The manufactured light-emitting semiconductor device (n = 10) 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 appearance cracks and a mixture of silicone resin and epoxy / silicone The number of peeling at the resin interface was observed.
Surface dust adhesion The light-emitting semiconductor device produced was sprinkled with fine powder silica and adhered to the surface, and then air was blown to confirm whether the fine powder silica adhered to the surface of the semiconductor device could be removed.
Lead Tensile Test It was confirmed whether a crack or lead omission occurred in the sealing portion by pulling the lead of the light emitting semiconductor device produced by hand strongly in the direction shown in FIG.

[Examples 2 to 5]
Using the silicone sealing resin composition and the epoxy / silicone hybrid resin composition shown in Table 1 below, a light emitting semiconductor device was produced under the same conditions as in Example 1, and various special products were evaluated.

[Comparative Example 1]
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 1 was fixed by heating at 180 ° C. for 10 minutes using the silicone die bond material 2 as the lead electrode 3. After the light emitting element 1 and the lead electrodes 3 and 4 are connected by the gold wire 5, the lead frame on which the light emitting element is mounted is installed in the cylindrical case 8 as shown in FIG. As shown in b), the silicone resin composition A was potted from the top to a predetermined height and cured at 150 ° C. for 30 minutes. Thereafter, as shown in FIG. 2C, the epoxy / silicone hybrid resin composition A was further potted and cured at 180 ° C. for 1 hour to produce a semiconductor element.
As a result of performing 1,000 cycles of the thermal shock test on the low temperature side −40 ° C. and the high temperature side 120 ° C. for this light emitting semiconductor device, and observing the number of appearance cracks and peeling of the silicone resin / epoxy / silicone hybrid resin interface, No defects occurred. Further, no dust adhered to the surface of the semiconductor device. Further, as a result of the external lead terminal being pulled strongly in the direction shown in FIG. 1, cracks occurred in the cured silicone resin, and lead removal occurred.

[Comparative Example 2]
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 1 was fixed by heating at 180 ° C. for 10 minutes using the silicone die bond material 2 as the lead electrode 3. After the light emitting element 1 and the lead electrodes 3 and 4 are connected by the gold wire 5, the lead frame on which the light emitting element is mounted is installed in the cylindrical case 8 as shown in FIG. As shown in b), the silicone resin composition A was potted from the top to a predetermined height and cured at 150 ° C. for 30 minutes. Thereafter, as shown in FIG. 2C, the epoxy / silicone hybrid resin composition A was further potted and cured at 180 ° C. for 1 hour to produce a semiconductor element.
As a result of performing 1,000 cycles of the thermal shock test on the low temperature side −40 ° C. and the high temperature side 120 ° C. for this light emitting semiconductor device, and observing the number of appearance cracks and peeling of the silicone resin / epoxy / silicone hybrid resin interface, Although no cracks occurred, 100% peeling occurred at the interface between the cured silicone and the cured epoxy / silicone resin composition. Further, no dust adhered to the surface of the semiconductor device. Further, as a result of strongly pulling the external lead terminal in the direction shown in FIG. 1, no cracks or lead omission occurred in the sealing material.

It is sectional drawing of the light emitting diode which shows a shell-type semiconductor light-emitting device. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing explaining the sealing method of the light emitting element in an Example, (a) is the state which installed the lead in a case, (b) is the state which injected and hardened the silicone resin composition, (c) is epoxy * The state which injected and hardened the silicone hybrid resin composition is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light emitting element 2 Die-bonding material 3, 4 Lead electrode 5 Gold wire 6 Hardened | cured material of a silicone coating protective material 7 Hardened | cured material of an epoxy silicone mixed resin composition

Claims (2)

(A) vinyl group-containing organopolysiloxane,
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule;
(C) A silicone compound or epoxy resin in which a light emitting element portion is sealed with a transparent cured product of a curable silicone resin composition containing a platinum group metal catalyst as an essential component, and a lead portion contains a silanol group and / or an alkoxyl group And a bullet-type light emitting semiconductor device sealed with a cured product of an epoxy / silicone hybrid resin composition comprising an aluminum catalyst. (A ′) an organopolysiloxane represented by the following general formula (1) and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C.,

(Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R ² is an unsubstituted or substituted monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond. , K, m is 0 or a positive integer, and k + m is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)
(D) Organopolysiloxane having a resin structure composed of SiO ₂ units, R ³ _n R ⁴ _p SiO _0.5 units and R ³ _q R ⁴ _r SiO _0.5 units (wherein R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, q + r = 3),
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule;
(C) platinum group metal catalyst,
(E) The following general formula (3)

(Wherein R ⁶ represents the following formula (4)

Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4), and R ⁷ is a hydrogen atom or having 1 to 6 carbon atoms. A monovalent hydrocarbon group, s is an integer of 1-6. )
The component (D) is an amount of 20 to 70% by mass with respect to the total amount of the components (A) and (D). The light-emitting element part is sealed with a transparent cured product of the light-emitting semiconductor coating protective material blended in the above, and the lead part is an epoxy-silicone hybrid comprising a silicone compound containing a silanol group and / or an alkoxyl group, an epoxy resin and a curing catalyst. A bullet-type light emitting semiconductor device sealed with a cured product of a resin composition.