JP4636242B2 - Optical semiconductor element sealing material and optical semiconductor element - Google Patents

Description

The present invention relates to a sealing material ( sealing resin composition ) for an optical semiconductor element, and more particularly to a silicone-based addition-curable resin composition for sealing an optical semiconductor element, particularly a light-emitting diode (LED) sealing. The present invention relates to a stopping resin composition.
The present invention also relates to an optical semiconductor element and an LED sealed with a cured product of this resin composition.

As a resin composition for protecting a coating of an optical 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, when such a silicone-based cured product is to be improved in crack resistance, generally, tack remains on the surface of the cured product, and there is a defect that dust easily adheres and impairs light transmission.
Therefore, what uses the silicone resin which raised hardness 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, in these silicone resins, the adhesiveness is still poor, and in a case type light emitting semiconductor device in which a light emitting element is arranged in a ceramic and / or plastic housing and the inside of the housing is filled with silicone resin, −40 ° C. to 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.

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, high transparency high hardness, high thermal shock resistance, also, an optical element encapsulating material that does not corrode the substrate (circuit) used in the semiconductor component It is an object of the present invention to provide ( addition-curable silicone resin composition for sealing ) and an optical semiconductor element sealed using the composition, particularly an LED.

  As a result of intensive studies to achieve the above object, the present inventor has obtained an optical semiconductor device excellent in reliability by not containing silanol in an addition-curable silicone resin composition for sealing an optical semiconductor device. It has been found that, in this case, the corrosion of the optical semiconductor component can be effectively prevented by further reducing the total chloro content to 30 ppm or less.

から選ばれる１種又は２種以上の一分子中に珪素原子に結合した水素原子を２個以上有するオルガノハイドロジェンポリシロキサンを（Ａ）成分のアルケニル基一個当り珪素原子結合水素原子を０．７５〜２．０個与えるに十分な量、
（Ｃ）触媒量の白金系触媒
を必須成分とし、（Ａ）成分及び（Ｂ）成分のオルガノポリシロキサンがシラノールを含有しないことを特徴とする光半導体素子封止材を提供する。 Therefore, the present invention
(A) The following average composition formula (1)
(R ¹ SiO _3/2 ) _a (R ² R ³ SiO) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (SiO _4/2 ) _d (1)
(Wherein R ^{1 to} R ⁶ each represent the same or different monovalent hydrocarbon group, 1 to 50 mol% of the total monovalent hydrocarbon group is an alkenyl group, and a, b, c and d are It is a positive number indicating the molar ratio of each siloxane unit, a / (a + b + c + d) = 0.40-0.95, b / (a + b + c + d) = 0.05-0.60, c / (a + b + c + d) = 0-0 .05, d / (a + b + c + d) = 0 to 0.10, a + b + c + d = 1.0.)
(A) 30 to 100% by mass of the total component (A) , and
The following general formula (2)
^{R 7 R 8 R 9 SiO- (} R 10 R 11 SiO) e - (R 12 R 13 SiO) f -SiR 7 R 8 R 9 (2)
(Wherein R ⁷ represents a non-covalent double bond group-containing monovalent hydrocarbon group, R ^{8 to} R ¹³ each represent the same or different monovalent hydrocarbon group, of which R ¹² and / or R ¹³ represents an aromatic monovalent hydrocarbon group, an integer of 0 ≦ e + f ≦ 500, and an integer of 0 ≦ e ≦ 500 and 0 ≦ f ≦ 250.
0 to 70% by mass of the whole component (A)
Organosilicon compound having two or more alkenyl groups in one molecule consisting of,
(B) The following formula

An organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one or two or more molecules selected from 0.75 to 0.75 silicon atom-bonded hydrogen atoms per alkenyl group of component (A) Enough to give ~ 2.0 ,
(C) Provided is an optical semiconductor element sealing material characterized in that a catalytic amount of a platinum-based catalyst is an essential component, and the organopolysiloxanes of the components ( A) and (B) do not contain silanol.

  In this case, it is preferable that the total chloro content in the composition excluding the component (C) is 30 ppm or less.

  Furthermore, the present invention provides an optical semiconductor element sealed with a cured product of the resin composition for sealing an optical semiconductor element, and an LED sealed with a cured product of the resin composition for sealing an optical semiconductor element. provide.

  The resin composition for encapsulating an optical semiconductor element of the present invention is highly transparent, has high hardness, has no corrosiveness to metals, and is excellent in storage stability of a resin. And is particularly effective for LED packages.

In the resin composition for encapsulating an optical semiconductor element of the present invention, the organosilicon compound having two or more non-covalent double bond groups in one molecule as the component (A) includes organosilane, organosiloxane, Organosylalkylene, organosylarylene and the like can be mentioned. Particularly, as the organosiloxane, those represented by the following average composition formula (1) or the following general formula (2) described later can be preferably used.
(R ¹ SiO _3/2 ) _a (R ² R ³ SiO) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (SiO _4/2 ) _d (1)
(In the formula, R ^{1 to} R ⁶ each represent the same or different monovalent hydrocarbon group, and 1 to 50 mol%, preferably 2 to 40 mol%, more preferably 5 to 5 mol% of the total monovalent hydrocarbon group. 30 mol% is a non-covalent double bond-containing group, a, b, c and d are positive numbers indicating the molar ratio of each siloxane unit, and a / (a + b + c + d) = 0.40-0.95. , Preferably 0.50 to 0.90, b / (a + b + c + d) = 0.05 to 0.60, preferably 0.10 to 0.50, c / (a + b + c + d) = 0 to 0.05, preferably 0 -0.03, d / (a + b + c + d) = 0-0.10, preferably 0-0.05, a + b + c + d = 1.0.

In this case, R ^{1 to} R ⁶ preferably have 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms.
Specifically, in R ^{1 to} R ⁶ , the non-covalent double bond-containing group is typically an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, or a butenyl group. And an alkyl group substituted with an acryloxy group or a methacryloxy group (for example, a (meth) acryloxypropyl group). In addition, at least one of R ^{1 to} R ⁶ is preferably the same or different aromatic monovalent hydrocarbon group from the viewpoint of controlling the refractive index in optical semiconductor applications. Typical examples include aryl groups such as tolyl group and aralkyl groups such as benzyl group. Other typical monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, isopropyl, isobutyl, tert-butyl, and cyclohexyl groups. It is done. In addition, one or two or more hydrogen atoms of these groups may be substituted with a halogen atom such as a fluorine atom.

The organopolysiloxane represented by the above average composition formula (1) is usually the following organoxysilane (3) to (6) or chlorosilane (7) to (10) corresponding to the siloxane unit of the average composition formula as a raw material. In a predetermined reaction molar ratio, that is, organoxysilanes represented by the following formulas (3) to (6) are 0.40 to 0.95, 0.05 to 0.60, 0 to 0.05, 0 to 0, respectively. .10 or a chlorosilane represented by the following formulas (7) to (10): 0.40 to 0.95, 0.05 to 0.60, 0 to 0.05, 0 to These silanes are obtained by hydrolysis under acidic conditions using a molar ratio of 0.10. In the present invention, silanol groups remaining in the hydrolyzate, particularly silanol groups and chloro Minutes or less than a certain level (The silanol group is completely removed at the mass% level, and the chloro content is reduced to 30 ppm or less with respect to the total of the component (A) and the component (B) described later). It is important that the decomposition products are further condensed (equilibrated) under alkaline conditions to remove or reduce these silanol groups, especially silanol groups and chloro. The conventional mere hydrolysis product containing a chloro component and / or silanol group in excess of a predetermined amount, which has not been subjected to the condensation (equilibration) treatment under the alkaline condition, cannot exhibit the purpose and action of the present application. .
R ¹ Si (OR ¹⁴ ) ₃ (3)
R ² R ³ Si (OR ¹⁴ ) ₂ (4)
R ⁴ R ⁵ R ⁶ SiOR ¹⁴ (5)
Si (OR ¹⁴ ) ₄ (6)
R ¹ SiCl ₃ (7)
R ² R ³ SiCl ₂ (8)
R ⁴ R ⁵ R ⁶ SiCl (9)
SiCl ₄ (10)
(In the formula, R ^{1 to} R ⁶ are as described above. R ¹⁴ preferably represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, particularly an alkyl group.)

  The hydrolysis / condensation method will be further described. Acid hydrolysis does not require the addition of a separate acid catalyst when chlorosilane is used as a reaction raw material, but when alkoxysilane is used as a raw material, hydrochloric acid, sulfuric acid, Although the reaction may be performed at a low temperature using an acid catalyst such as oxalic acid, the reaction can usually be carried out for several tens of minutes to about one day in a temperature range from about 0 ° C. to about 100 ° C. Thereafter, operations such as neutralization and water washing are performed to perform alkali condensation (equilibration). Alkaline condensation is carried out for about 1 hour to several days in a temperature range of about 80 to 200 ° C., although alkali metal salts such as potassium and sodium, ammonia and ammonium salts are mainly used as catalysts, and depending on the solvent. it can.

  In addition, it is preferable that the polystyrene conversion weight average molecular weight by GPC (gel permeation chromatography analysis) of the organopolysiloxane of the above formula (1) is 500 to 1,000,000, particularly 1,000 to 300,000.

  The organopolysiloxane represented by the above formula (1) is contained in the component (A) in an amount of 30 to 100% by mass, preferably 35 to 95% by mass, and more preferably 40 to 95% by mass.

On the other hand, the organopolysiloxane represented by the following general formula (2) that can be used as a part of the component (A) is as follows.
^{R 7 R 8 R 9 SiO- (} R 10 R 11 SiO) e - (R 12 R 13 SiO) f -SiR 7 R 8 R 9 (2)
(In the formula, R ⁷ represents a monovalent hydrocarbon group containing a non-covalent double bond group, and R ^{8 to} R ¹³ each represents the same or different monovalent hydrocarbon group, of which R ^{10 to} R ¹³ Preferably represents a monovalent hydrocarbon group excluding an aliphatic unsaturated bond, and R ¹² and / or R ¹³ represents an aromatic monovalent hydrocarbon group, and 0 ≦ e + f ≦ 500, preferably 10 ≦ e + f ≦ 500, 0 ≦ e ≦ 500, preferably 10 ≦ e ≦ 500, 0 ≦ f ≦ 250, preferably 0 ≦ f ≦ 150.
In this case, R ⁷ has an aliphatic unsaturated bond represented by an alkenyl group having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and R ^{8 to} R ¹³ have 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms. Those within the range are preferred, and examples thereof include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. Among them, R ^{10 to} R ¹³ are preferably an alkyl group excluding an aliphatic unsaturated bond such as an alkenyl group. , Aryl group, aralkyl group and the like. R ¹² and / or R ¹³ is preferably an aromatic monovalent hydrocarbon group such as an aryl group having 6 to 12 carbon atoms such as a phenyl group or a tolyl group.

  Specific examples of the organopolysiloxane of the general formula (2) include the following.

（上記式において、ｋ，ｍは、０≦ｋ＋ｍ≦５００を満足する整数であり、好ましくは５≦ｋ＋ｍ≦２５０で、０≦ｍ／（ｋ＋ｍ）≦０．５を満足する整数である。）

(In the above formula, k and m are integers satisfying 0 ≦ k + m ≦ 500, preferably 5 ≦ k + m ≦ 250, and integers satisfying 0 ≦ m / (k + m) ≦ 0.5.)

  The organopolysiloxane of the above formula (2) includes, for example, cyclic diorganopolysiloxanes such as cyclic dimethylpolysiloxane, cyclic diphenylpolysiloxane, and cyclic methylphenylpolysiloxane constituting the main chain, and divinyltetramethyldisiloxane constituting the terminal group. It can be obtained by alkali equilibration reaction with disiloxane such as siloxane, dimethyltetravinyldisiloxane, hexavinyldisiloxane, diphenyltetravinyldisiloxane, divinyltetraphenyldisiloxane, etc. Minutes are not contained.

  The organopolysiloxane of the above formula (2) is preferably blended in the component (A) in an amount of 0 to 70% by mass, more preferably 5 to 65% by mass, and still more preferably 5 to 60% by mass. A tack | tuck will remain on the hardened | cured material surface, and there exists a possibility that light transmittance may be impaired by adhesion of dust etc.

  The non-covalent double bond group in component (A) is about 1 to 50 mol%, preferably 2 to 40 mol%, more preferably about 5 to 30 mol% of the total monovalent hydrocarbon group. If the amount is too small, a cured product cannot be obtained. If the amount is too large, the mechanical properties may deteriorate. The aromatic group is 0 to 95 mol%, preferably 10 to 90 mol%, more preferably about 20 to 80 mol% of the total monovalent hydrocarbon group. When an appropriate amount of the aromatic group is contained in the resin, there are advantages that the mechanical properties are good and the production is easy. Another advantage is that the refractive index can be controlled by introducing an aromatic group.

  Next, the component (B) of the resin composition of the present invention is an organohydrogenpolysiloxane. This organohydrogenpolysiloxane acts as a crosslinking agent, and includes a SiH group in the component and a non-covalent double bond-containing group (typically an alkenyl group) such as a vinyl group in the component (A). Are cured to form a cured product. Such organohydrogenpolysiloxanes only need to have two or more hydrogen atoms (that is, SiH groups) bonded to silicon atoms in one molecule.

  In addition, the organohydrogenpolysiloxane has an aromatic hydrocarbon group, thereby increasing compatibility when the organosilicon compound having a non-covalent double bond group as the component (A) has a high refractive index, A transparent cured product can be provided.

  Accordingly, in the organohydrogenpolysiloxane of the component (B), an organohydrogenpolysiloxane having an aromatic monovalent hydrocarbon group can be included as a part or all of the component (B).

  In addition, in the organohydrogenpolysiloxane of the component (B), the organohydrogenpolysiloxane having a glycidyl structure can be included as part or all of the component (B), and the organohydrogenpolysiloxane contains a glycidyl structure. By having a group, a sealing resin composition for optical semiconductors having high adhesion to the substrate can be provided.

Examples of the organohydrogenpolysiloxane include, but are not limited to, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogen Siloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-glycidoxypropyl-1,3,5 7-tetramethylcyclotetrasiloxane, 1-glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends Trimethylsiloxy-blocked dimethylsiloxane Methyl hydrogen siloxane copolymer, both ends dimethyl hydrogen siloxy group-capped dimethyl polysiloxane, both ends dimethyl hydrogen siloxy group capped dimethyl siloxane / methyl hydrogen siloxane copolymer, both ends trimethyl siloxy group capped methyl hydrogen siloxane From diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, trimethoxysilane polymer, (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit And a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units and (C ₆ H ₅ ) SiO _3/2 units.

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

  The molecular structure of this organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number (or degree of polymerization) of silicon atoms in one molecule is 2 or more. Preferably, about 2 to 1,000, more preferably about 2 to 300 can be used.

  The blending amount of the organohydrogenpolysiloxane of the component (B) is such that silicon atom-bonded hydrogen in the component (B) per non-covalent double bond group (typically alkenyl group) of the component (A) It is preferable to include an amount sufficient to give 0.75 to 2.0 atoms (SiH groups).

The component (C) of the resin composition of the present invention is a platinum-based catalyst, and typical examples thereof include chloroplatinic acid, alcohol-modified chloroplatinic acid, and a platinum complex having a chelate structure.
The blending amount is a catalytic amount, and is usually 1 to 1,000 ppm as platinum metal with respect to the component (A).

  The silicone resin composition of the present invention contains the above-described components (A) to (C) as essential components, and various silane coupling agents may be added thereto as necessary. For example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2 (amino Ethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy Run, 3-aminopropyltriethoxysilane, N- phenyl-3-aminopropyl trimethoxysilane, and the like 3-mercaptopropyltrimethoxysilane, trimethoxysilane, etc. tetramethoxysilane and its oligomers and the like. It is also possible to use a mixture of these. The blending amount is preferably 10% by mass or less (0 to 10% by mass), particularly 5% by mass or less (0 to 5% by mass) of the entire composition.

  Further, as other components, these transparent resin compositions include, for example, BHT and vitamin B as antioxidants as well as known discoloration inhibitors such as organic, as long as the performance of the apparatus is not deteriorated. Phosphorus-based discoloration inhibitors, photodegradation inhibitors such as hindered amines, vinyl ethers, vinylamides, epoxy resins, oxetanes, allyl phthalates, vinyl adipates, etc. as reactive diluents, fumed silica, Reinforcing fillers such as precipitated silica, flame retardants, phosphors, organic solvents, and the like may be added to form a sealing resin composition. Moreover, you may color with a coloring component.

  The silicone resin composition of the present invention can be obtained by sufficiently mixing the above components (A), (B), (C) and other optional components.

  The silicone resin composition of the present invention is used for sealing an optical semiconductor element, and the optical semiconductor is not limited to this. For example, a light emitting diode, a phototransistor, a photodiode, a CCD, a solar cell module, an EPROM In particular, light-emitting diodes are effectively used.

  In this case, as a sealing method, a conventional method according to the type of the optical semiconductor is adopted, but the curing condition of the resin composition of the present invention is from several tens of seconds in a temperature range from room temperature to about 200 ° C. Although a time range of several days can be considered, it is preferably about 1 minute to 10 hours in a temperature range of 80 to 180 ° C.

  The optical semiconductor device coated and protected with the cured product of the resin composition for encapsulating an optical semiconductor element of the present invention is excellent in heat resistance, moisture resistance and light resistance of the device, and is excellent in reliability without corroding the device. An optical semiconductor device can be provided, and the industrial merit is great.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited to the following Example. In addition, molecular weight shows the weight average molecular weight of polystyrene conversion in GPC (gel permeation chromatography analysis).

[Synthesis Example 1]
A mixture of 54.0 g (55 mol%) of phenyltrichlorosilane, 24.7 g (15 mol%) of dimethyldichlorosilane and 148.4 g (30 mol%) of methylvinyldichlorosilane was mixed with 250 g of water heated to 80 ° C. and 100 g of toluene. The mixture was added dropwise over 1 hour with stirring. After completion of dropping, the mixture was refluxed for 2 hours to obtain a toluene solution of a cohydrolyzed condensate. The solution was allowed to stand, cooled to room temperature, the aqueous layer was removed, and then the toluene layer was washed with water until the extracted water became neutral. To the obtained toluene solution of organic polyorganosiloxane (organic layer 1), KOH was added in an amount 20 times the amount of chloro and refluxed for 2 hours. After the reaction, the mixture was neutralized with trimethylchlorosilane and washed with water until the toluene layer became neutral (organic layer 2). The organic layer 2 was dehydrated and then filtered to remove impurities. Toluene was removed from the filtrate (under reduced pressure) to obtain the desired component (A) polyorganosiloxane (molecular weight; 3,300) (resin 1).

[Synthesis Example 2]
A mixture of 108.9 g (55 mol%) of phenyltrimethoxysilane, 18.0 g (15 mol%) of dimethyldimethoxysilane and 39.6 g (30 mol%) of methylvinyldimethoxysilane was added to 80 g of 20% aqueous HCl solution and toluene heated to 80 ° C. The mixture was added dropwise to 160 g of the mixed solvent with stirring for 1 hour. After completion of dropping, the mixture was refluxed for 2 hours to obtain a toluene solution of a cohydrolyzed condensate. The solution was allowed to stand, cooled to room temperature, the aqueous layer was removed, and then the toluene layer was washed with water until the extracted water became neutral. 0.05 g of KOH was added to the obtained toluene solution of polyorganosiloxane and refluxed for 2 hours. After the reaction, the mixture was neutralized with trimethylchlorosilane and washed with water until the toluene layer became neutral. The aqueous layer was removed, the toluene layer was dehydrated, and then filtered to remove impurities. Toluene was removed from the filtrate (under reduced pressure) to obtain the desired component (A) polyorganosiloxane (molecular weight: 3,000) (resin 2).

[Comparative Synthesis Example 1]
A mixture of 54.0 g (55 mol%) of phenyltrichlorosilane, 24.7 g (15 mol%) of dimethyldichlorosilane and 148.4 g (30 mol%) of methylvinyldichlorosilane was added to 500 g of water and toluene previously heated to 80 ° C. in a flask. The mixture was added dropwise to 200 g of the mixed solvent over 1 hour with stirring. After completion of the addition, the mixture was further refluxed for 2 hours to obtain a toluene solution of a cohydrolyzed condensate. After this solution is allowed to stand and cool to room temperature, the separated aqueous layer is removed, followed by mixing with water, stirring, and leaving to stand, and the toluene layer is neutralized by removing the aqueous layer. Until the reaction was stopped. The obtained toluene solution of polyorganosiloxane was filtered to remove impurities, and then toluene was removed by distillation under reduced pressure to obtain polyorganosiloxane (molecular weight: 5,100) (Comparative Resin 1).

[Comparative Synthesis Example 2]
A polyorganosiloxane (molecular weight: 4,500) was obtained by cohydrolysis of 55 mol% phenyltrichlorosilane, 15 mol% phenylmethyldichlorosilane, and 30 mol% methylvinyldichlorosilane in the same procedure as in Comparative Synthesis Example 1 (Comparative resin) 2).

[Comparative Synthesis Example 3]
In the same procedure as in Comparative Synthesis Example 1, polyorganosiloxane (molecular weight: 2,900) was obtained by cohydrolysis of 45 mol% phenyltrichlorosilane, 15 mol% dimethyldichlorosilane, 15 mol% methylvinyldichlorosilane, and 25 mol% trimethylchlorosilane. Obtained (Comparative Resin 3).

[Comparative Synthesis Example 4]
1,1,3,3-tetramethyldisiloxane 53.6 g (22 mol%), diphenyldimethoxysilane 195.2 g (45 mol%) and 1,3,5,7-tetramethylcyclotetrasiloxane 144.0 g (33 mol%) Concentrated sulfuric acid (17.8 g) and pure water (15.4 g) were sequentially added at 10 ° C. and stirred for 12 hours to cause hydrolysis and equilibration reactions. To this reaction solution, 5.9 g of water and 195.8 g of toluene were added and stirred to stop the reaction. Then, water was mixed, stirred and allowed to stand, and the water washing operation of removing the aqueous layer was performed with the toluene layer. I went until it became neutral. Furthermore, the organohydrogenpolysiloxane obtained by removing toluene by vacuum distillation was filtered to remove impurities to obtain polyorganosiloxane (molecular weight: 800) (Comparative Resin 4).

[Comparative Synthesis Example 5]
In the same procedure as Comparative Synthesis Example 4, 1,1,1,3,3,3-hexamethyldisiloxane 30 mol%, diphenyldimethoxysilane 40 mol%, 1,3,5,7-tetramethylcyclotetrasiloxane 30 mol% The polyorganosiloxane (molecular weight: 600) was obtained by hydrolysis and equilibration reaction (Comparative Resin 5).

[Comparative Synthesis Example 6]
In the same procedure as in Comparative Synthesis Example 1, polyorganosiloxane (molecular weight; 3,800) was obtained by cohydrolysis of 45 mol% of phenyltrichlorosilane, 15 mol% of methyldichlorosilane, 15 mol% of methylvinyldichlorosilane, and 25 mol% of trimethylchlorosilane. Obtained (Comparative Resin 6).

[Comparative Synthesis Example 7]
The organic layer 1 described in Synthesis Example 1 was neutralized by adding sodium ethoxide corresponding to the chloro content, and then a water washing operation was performed until the toluene layer became neutral. After removing impurities by filtration, toluene was removed under reduced pressure to obtain polyorganosiloxane (molecular weight; 2,700) (Comparative Resin 7).

  Next, an example of preparing a sealing resin is shown. In the following examples, the resin a as the component (A) is represented by the following formula (a), and the organohydrogenpolysiloxane b-1 as the component (B) is represented by the following formula (b-1). b-2 is represented by the following formula (b-2). In the following formulae, Me represents a methyl group.

[Seal Resin Preparation Example 1]
Resin 1 as component (A), b-1 as component (B), H-Si (in component B) / Vi-Si (in component A) = 1.2, and (C) As a component, 200 ppm of platinum catalyst was uniformly mixed (Vi represents a vinyl group. The same applies hereinafter).

[Seal Resin Preparation Example 2]
Resin 2 as component (A), b-1 as component (B), H-Si (in component B) / Vi-Si (in component A) = 1.2, and (C) As a component, 200 ppm of platinum catalyst was uniformly mixed.

[Seal Resin Preparation Example 3]
As the component (A), the resin 1 and the resin a are mixed at a mass ratio of 100: 20, and as the component (B), b-1 is H-Si (in the component B) / Vi-Si (in the component A) = 1. Further, 200 ppm of a platinum catalyst was uniformly mixed as the component (C).

[Seal Resin Preparation Example 4]
(A) Component 2 is resin 2 and resin a in a mass ratio of 100: 20, (B) component is b-1, H-Si (in component B) / Vi-Si (in component A) = 1. Further, 200 ppm of a platinum catalyst was uniformly mixed as the component (C).

[Seal Resin Preparation Example 5]
Resin 1 as component (A), a mixture of b-1 and b-2 in a mass ratio of 6: 4 as component (B), H-Si (in component B) / Vi-Si (in component A) = Also, 200 ppm of platinum catalyst was uniformly mixed as the component (C) so as to be 1.2.

[Seal Resin Preparation Example 6]
Resin 2 as the component (A), a mixture of b-1 and b-2 in the mass ratio 6: 4 as the component (B), H-Si (in the component (B)) / Vi-Si ((A) In the component), 200 ppm of platinum catalyst was uniformly mixed as the component (C) so as to be 1.2.

[Comparative sealing resin preparation example 1]
The comparative resin 1 and the comparative resin 4 were mixed uniformly with a platinum catalyst of 200 ppm so that the mass ratio was 80:20.

[Comparative sealing resin preparation example 2]
Comparative resin 2 and comparative resin 5 were mixed uniformly so that the mass ratio was 75:25 and platinum catalyst was 200 ppm.

[Comparative sealing resin preparation example 3]
Comparative resin 1 and comparative resin 5 were mixed uniformly so that the mass ratio was 75:25 and platinum catalyst was 200 ppm.

[Comparative sealing resin preparation example 4]
The comparative resin 3 and the comparative resin 6 were mixed uniformly with 200 ppm of platinum catalyst so that the mass ratio was 10:90.
(Quantification of hydroxyl and chloro contents)
In each composition prepared in sealing resin preparation examples 1 to 6 and comparative sealing resin examples 1 to 4, a mixed composition of the component (A) and the component (B) before adding the component (C) (platinum catalyst) The content of chloro and the amount of hydroxyl groups were determined. The results are shown in Table 1.

［実施例１］
（腐食試験）
封止樹脂調製例１〜６及び比較封止樹脂調製例１〜４で調製した樹脂組成物を３ｃｍ×３ｃｍ×１ｍｍの大きさに１５０℃，４時間で硬化させた。この硬化物（試験片）をアルミシャーレ上におき、１５０℃雰囲気下に２４時間放置した。その後、試験片に接していたアルミシャーレの表面状態を観察し、アルミが腐食し、白く変色しているか否かを調べた。結果を表２に示す。

[Example 1]
(Corrosion test)
The resin compositions prepared in Sealing Resin Preparation Examples 1 to 6 and Comparative Sealing Resin Preparation Examples 1 to 4 were cured to a size of 3 cm × 3 cm × 1 mm at 150 ° C. for 4 hours. This cured product (test piece) was placed on an aluminum petri dish and allowed to stand in an atmosphere at 150 ° C. for 24 hours. Thereafter, the surface state of the aluminum petri dish that was in contact with the test piece was observed to examine whether the aluminum was corroded and turned white. The results are shown in Table 2.

[Example 2]
(Storage stability test)
In each resin composition prepared in sealing resin preparation examples 1 to 6 and comparative sealing resin preparation examples 1 to 4, mixing of component (A) and component (B) before adding component (C) (platinum catalyst) The composition was left at 30 ° C. for 10 days and the change was observed.

［実施例３］
ＬＥＤパッケージによる封止樹脂の評価を行った。
（評価方法）
発光半導体パッケージ
発光素子として、ＩｎＧａＮからなる発光層を有し、主発光ピークが４７０ｎｍのＬＥＤチップを搭載した、図１に示すような発光半導体装置を使用した。ここで、１が筐体、２が発光素子、３，４がリード電極、５がダイボンド材、６が金線、７が封止樹脂である。封止樹脂７の硬化条件は１５０℃，４時間である。
耐湿及び赤外線リフローの試験方法
作製した発光半導体装置１０個を、８５℃，８５％の恒温恒湿室に２４時間入れた後、赤外線リフロー装置（２６０℃）を３回通し、外観の変化を観察した。結果を表４に示す。なお、樹脂のクラックやＬＥＤパッケージからの剥離が確認されたものをＮＧとしてカウントした。

[Example 3]
Evaluation of the sealing resin by the LED package was performed.
(Evaluation methods)
As the light emitting semiconductor package light emitting element, a light emitting semiconductor device as shown in FIG. 1 having a light emitting layer made of InGaN and mounting an LED chip having a main light emission peak of 470 nm was used. Here, 1 is a 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 sealing resin. The curing conditions for the sealing resin 7 are 150 ° C. and 4 hours.
Moisture resistance and infrared reflow test method 10 light-emitting semiconductor devices were placed in a constant temperature and humidity chamber at 85 ° C and 85% for 24 hours, and then passed through an infrared reflow device (260 ° C) three times to observe changes in appearance. did. The results are shown in Table 4. In addition, the thing by which the crack of resin and peeling from the LED package were confirmed was counted as NG.

It is sectional drawing of the light emitting diode which shows the surface mount type semiconductor light-emitting device (what the light emitting element was die-bonded on the insulating housing | casing) used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Case 2 Light emitting element 3, 4 Lead electrode 5 Die bond material 6 Gold wire 7 Sealing resin

Claims (6)

(A) The following average composition formula (1)
(R ¹ SiO _3/2 ) _a (R ² R ³ SiO) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (SiO _4/2 ) _d (1)
(Wherein R ^{1 to} R ⁶ each represent the same or different monovalent hydrocarbon group, 1 to 50 mol% of the total monovalent hydrocarbon group is an alkenyl group, and a, b, c and d are It is a positive number indicating the molar ratio of each siloxane unit, a / (a + b + c + d) = 0.40-0.95, b / (a + b + c + d) = 0.05-0.60, c / (a + b + c + d) = 0-0 .05, d / (a + b + c + d) = 0 to 0.10, a + b + c + d = 1.0.)
(A) 30 to 100% by mass of the total component (A) , and
The following general formula (2)
^{R 7 R 8 R 9 SiO- (} R 10 R 11 SiO) e - (R 12 R 13 SiO) f -SiR 7 R 8 R 9 (2)
(Wherein R ⁷ represents a non-covalent double bond group-containing monovalent hydrocarbon group, R ^{8 to} R ¹³ each represent the same or different monovalent hydrocarbon group, of which R ¹² and / or R ¹³ represents an aromatic monovalent hydrocarbon group, an integer of 0 ≦ e + f ≦ 500, and an integer of 0 ≦ e ≦ 500 and 0 ≦ f ≦ 250.
0 to 70% by mass of the whole component (A)
Organosilicon compound having two or more alkenyl groups in one molecule consisting of,
(B) The following formula

An organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one or two or more molecules selected from 0.75 to 0.75 silicon atom-bonded hydrogen atoms per alkenyl group of component (A) Enough to give ~ 2.0 ,
(C) An optical semiconductor element encapsulating material comprising a catalytic amount of a platinum-based catalyst as an essential component, and the organopolysiloxanes of the component ( A) and the component (B) do not contain silanol. (C) The optical-semiconductor element sealing material of Claim 1 whose total chloro content in the composition except a component is 30 ppm or less. 3. The optical semiconductor device according to claim 1, wherein in the organopolysiloxane represented by the formula (1) of the component (A), at least one of R ^{1 to} R ⁶ is the same or different aromatic monovalent hydrocarbon group. sealing material. The organopolysiloxane represented by the formula (1) of the component (A) is an organoxysilane represented by the following formulas (3) to (6): 0.40 to 0.95, 0.05 to 0.60, It is used in a molar ratio of 0 to 0.05, 0 to 0.10, or chlorosilanes represented by the following formulas (7) to (10) are respectively 0.40 to 0.95 and 0.05 to 0.60. using a molar ratio of 0～0.05,0～0.10, these silanes acid hydrolysis, followed by any one of claims 1 to 3, those obtained by alkaline condensation The optical semiconductor element sealing material of description.
R ¹ Si (OR ¹⁴ ) ₃ (3)
R ² R ³ Si (OR ¹⁴ ) ₂ (4)
R ⁴ R ⁵ R ⁶ SiOR ¹⁴ (5)
Si (OR ¹⁴ ) ₄ (6)
R ¹ SiCl ₃ (7)
R ² R ³ SiCl ₂ (8)
R ⁴ R ⁵ R ⁶ SiCl (9)
SiCl ₄ (10)
(In the formula, R ^{1 to} R ⁶ are as described above. R ¹⁴ represents a monovalent hydrocarbon group.) The optical semiconductor element sealed with the hardened | cured material of the optical semiconductor element sealing material of any one of Claims 1-4 . The light emitting diode sealed with the hardened | cured material of the optical-semiconductor element sealing material of any one of Claims 1-4 .

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