JP2018060856A - Coating composition and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the adhesiveness of a substrate with an optical semiconductor element mounted thereon, and a cured product of an addition reaction curing type polyorganosiloxane composition for sealing the element and to prevent the corrosion of metal electrodes on the substrate.SOLUTION: A coating composition of the present invention comprises: (A) 100 parts of a polyorganosiloxane including a terminal blocked with a hydroxyl group or alkoxy group, and having a viscosity of 20-1,000,000 mPa s (at 23°C); (B) 0.1-20 parts of a tri- or tetra-functional silane compound and/or its partial hydrolysis condensate; (C) 0.01-15 parts of a cured catalyst; and (D) 0.0001-10 parts of a triazole compound. A cured product of the coating composition serves to bond a substrate with an optical semiconductor element mounted thereon with a cured product of an addition reaction curing type polyorganosiloxane composition sealing the element.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a coating composition and an optical semiconductor device, and more particularly to bond a substrate on which an optical semiconductor element is mounted to a cured product of an addition reaction curable polyorganosiloxane composition that seals the optical semiconductor element. And an optical semiconductor device in which the substrate and the cured product of the addition reaction curable polyorganosiloxane composition are bonded using the coating composition.

  An optical semiconductor device (for example, an LED lamp) having an optical semiconductor element such as a light emitting diode (LED) has a structure in which an LED mounted on a substrate is sealed with a transparent sealing material. Conventionally, a composition mainly composed of epoxy resin has been widely used as a sealing material. However, cracking and yellowing occur due to an increase in the amount of heat generated due to the recent increase in brightness of LEDs and the shortening of light emission wavelength. It was easy to do and caused a decrease in reliability.

  Therefore, as an encapsulant for optical semiconductor devices, an addition reaction curable polyorganosiloxane composition that is excellent in heat resistance and cures in a short time is used instead of an epoxy resin composition. Hereinafter, the “polyorganosiloxane composition” is also referred to as “silicone composition”. The “cured product of the silicone composition” is also referred to as “silicone cured product”.

  However, the addition reaction curable silicone cured product has not sufficiently good adhesion to the substrate on which the LED is mounted. In particular, a substrate made of polyphthalamide (PPA) resin is often used as a substrate for mounting an LED because of its excellent mechanical strength, but the adhesion between the PPA resin and the cured silicone is poor. For this reason, there is a problem that the cured product easily peels off.

  Moreover, since the cured silicone has a high gas permeability, the optical semiconductor element sealed with the addition reaction curable silicone cured product is easily affected by the external environment. For example, when an optical semiconductor device such as an LED lamp is exposed to a corrosive gas such as a sulfur compound (for example, hydrogen sulfide, sulfuric acid gas) in the atmosphere, the corrosive gas passes through the cured silicone and the substrate The upper metal electrode, particularly the silver (Ag) electrode, corrodes over time and turns black.

  In order to cope with such problems of corrosion of the Ag electrode and adhesion failure with the resin substrate, a primer composition containing an acrylic ester polymer, an alkoxysilane having an epoxy group, a platinum compound, and a solvent is used. An optical semiconductor device in which a substrate and an addition reaction curable silicone cured product are bonded has been proposed (see, for example, Patent Document 1).

  However, in the optical semiconductor device described in Patent Document 1, the adhesiveness between the silicone cured product and the metal electrode formed on the substrate was insufficient. Therefore, corrosion of the Ag electrode under an environment containing corrosive gas could not be sufficiently prevented. Moreover, since there was turbidity (or cloudiness) at the interface with the primer layer of the silicone cured product, the light transmission from the optical semiconductor element was not good. Furthermore, since the primer composition described in Patent Document 1 contains an organic solvent, there is a problem that not only the peripheral substrate is affected but also the working environment is deteriorated.

Japanese Patent No. 5090000

  The present invention has been made to solve these problems, and improves the adhesion between a substrate on which an optical semiconductor element is mounted and an addition reaction curable silicone cured material that seals the optical semiconductor element, and the substrate. It is an object of the present invention to provide a coating composition capable of preventing corrosion of a metal electrode formed thereon, and a highly reliable optical semiconductor device using the same.

The coating composition of the present invention comprises
(A) 100 parts by mass of a polyorganosiloxane whose molecular chain terminal is blocked with a hydroxyl group or an alkoxy group and has a viscosity at 23 ° C. of 20 to 1,000,000 mPa · s;
(B) General formula: R ¹ _n Si (OR ² ) _4-n (1)
Wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ² is the same or different unsubstituted monovalent hydrocarbon group, and n is 0 or 1. 0.1 to 20 parts by mass of a trifunctional or tetrafunctional silane compound and / or a partially hydrolyzed condensate thereof,
(C) 0.01-15 parts by mass of a curing catalyst;
(D) a composition containing 0.0001 to 10 parts by mass of a triazole compound,
The cured product of the composition adheres a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable polyorganosiloxane composition that seals the optical semiconductor element.

  The optical semiconductor device of the present invention is formed on a substrate on which the optical semiconductor element is mounted, a cured product of an addition reaction curable polyorganosiloxane composition that seals the optical semiconductor element, and the substrate. And a coating adhesive layer for adhering the cured product of the addition reaction curable polyorganosiloxane composition, the coating adhesive layer comprising a cured product of the coating composition of the present invention. Features.

  The coating composition of the present invention contains a component (corrosion prevention component) having a high effect of trapping corrosive gas and forms a cured product having good adhesion to a resin such as a PPA resin and a metal. . Therefore, according to the coating composition of the present invention, the adhesion between the substrate on which the optical semiconductor element is mounted and the metal electrode formed on the substrate and the cured silicone that seals the optical semiconductor element is improved. A highly reliable optical semiconductor device can be provided in which corrosion of the metal electrode in an environment containing a corrosive gas is prevented.

  Further, the cured product of the coating composition of the present invention (hereinafter also referred to as coating cured product) has good adhesion and adhesiveness with the addition reaction curable silicone cured product that seals the optical semiconductor element, and The addition reaction curable silicone cured product has no turbidity (or cloudiness) at the bonding interface with the coating cured product, and has high light transmittance at the interface between them, so that an optical semiconductor device with high luminous efficiency can be obtained.

It is sectional drawing which shows typically an example of a structure of the optical semiconductor device of this invention. It is a figure which shows roughly the method of the adhesive test in an Example.

  Embodiments of the present invention will be described below.

[Coating composition]
In the first embodiment of the present invention, (A) 100 parts by mass of a polyorganosiloxane whose molecular chain end is blocked with a hydroxyl group or an alkoxy group and whose viscosity (23 ° C.) is 20 to 1,000,000 mPa · s, (B) Trifunctional or tetrafunctional silane compound and / or its partial hydrolysis condensate 0.1-20 parts by mass, (C) curing catalyst 0.01-15 parts by mass, (D) triazole compound It is a coating composition containing 0.0001-10 mass parts, respectively. The cured product (coating composition) of the coating composition of the embodiment strongly bonds the substrate on which the optical semiconductor element is mounted and the addition reaction curable silicone cured product that seals the optical semiconductor element.
Hereinafter, each component contained in the coating composition of 1st Embodiment is demonstrated.

<(A) Terminal hydroxyl group or alkoxy group-blocked polyorganosiloxane>
The component (A) is a polyorganosiloxane whose molecular chain end is blocked with a hydroxyl group (hydroxyl group) or an alkoxy group, and is a base component of the coating composition of the embodiment. If the viscosity of the component (A) is too low, the rubber elasticity of the cured product will be low, and if it is too high, the workability of coating will be reduced. . The viscosity is preferably 50 to 500,000 mPa · s, particularly preferably 100 to 100,000 mPa · s.

The molecular structure of the polyorganosiloxane is preferably a straight chain represented by the following general formula (2), but may have a partially branched structure.

In the formula (2), R ³ represents a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other, and R ⁴ is _a monovalent organic group represented by —ZSiR ⁵ _3-a Xa. Represents a group. Here, Z represents oxygen (oxo group) or a divalent hydrocarbon group, and R ⁵ represents a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from each other. X represents a hydroxyl group (hydroxyl group) or an alkoxy group, and a is an integer of 1 to 3. Moreover, m is a number which makes the viscosity at 23 degreeC of the said (A) component the range of 20-1,000,000 mPa * s.

R ³ includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group; alkenyl group such as vinyl group and allyl group; phenyl group And aryl groups such as tolyl group and xylyl group; and aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group. In addition, hydrogen atoms of these hydrocarbon groups are substituted with other atoms or groups, that is, halogens such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group A substituted hydrocarbon group such as a cyanoalkyl group such as a 3-cyanopropyl group. Since the synthesis is easy and the component (A) has a low viscosity for the molecular weight, the composition before curing has good coating properties, and the cured product has good physical properties. preferably R ³ over 85% of all are methyl groups, and more preferably substantially all of the R ³ is a methyl group.

In particular, when imparting heat resistance, radiation resistance, cold resistance, etc. to the composition, a necessary amount of phenyl group as a part of R ³ , and when imparting oil resistance and solvent resistance, R ³ When a 3,3,3-trifluoropropyl group or 3-cyanopropyl group is added as a part of the surface, or a surface having paintability is imparted, a long chain alkyl group or an aralkyl group is added as a part of R ³ . It can be arbitrarily selected depending on the purpose, for example, in combination with a methyl group.

The terminal group R ^{4 of the} component (A) is a silicon-functional siloxy unit represented by the formula: —ZSiR ⁵ _3-a X _a and having at least one hydroxyl group or hydroxyl group that is a silicon functional group. is there. Therefore, the component (A) has at least one hydroxyl group (hydroxyl group) or alkoxy group X at both ends of the molecule.

In the terminal group R ⁴ , R ⁵ bonded to the silicon atom is a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from each other, and examples thereof are the same as those described above for R ³ . R ³ may be the same as or different from R ³ . A methyl group or a vinyl group is preferred because synthesis is easy and the reactivity of the hydrolyzable group X is excellent. Z is a divalent oxygen (oxy group) or a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group such as a methylene group, an ethylene group and a trimethylene group; a phenylene group and the like. Is done. In view of easy synthesis, an oxy group or an ethylene group is preferable, and an oxy group is particularly preferable.

X is a hydroxyl group (hydroxyl group) or an alkoxy group present in at least one of R ⁴ as a terminal group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The plurality of alkoxy groups may be the same or different.

In the terminal group R ⁴ , the number a of the hydroxyl group or alkoxy group X is preferably 1 to 3. A silicon-functional polydiorganosiloxane in which X is a hydroxyl group is a ring-opening polymerization or ring-opening copolymerization of a cyclic diorganosiloxane low monomer such as octamethylcyclosiloxane in the presence of water using an acidic catalyst or an alkaline catalyst. And by introducing a hydroxyl group bonded to a silicon atom into the terminal of the linear polydiorganosiloxane.

The silicon-functional polydiorganosiloxane in which X is an alkoxy group can be synthesized, for example, by condensing a silane having two or more arbitrary alkoxy groups with a polyorganosiloxane having a hydroxyl group at the terminal. In this case, since one alkoxy group of the silane is consumed by the condensation reaction, the number of X in the terminal group R ⁴ of the polyorganosilosan obtained by the reaction is the alkoxy group of the alkoxy group-containing silane used. One less than the number of.

Examples of the siloxy group at the end of the molecular chain blocked with a hydroxyl group include a dimethylhydroxysiloxy group and a methylphenylhydroxysiloxy group. Examples of the siloxy group at the end of the molecular chain blocked with an alkoxy group include vinyl dimethoxysiloxy group, methyldimethoxysiloxy group, trimethoxysiloxy group, methyldiethoxysiloxy group, triethoxysiloxy group and the like.
Specific examples of the component (A) include the following polyorganosiloxanes in which these siloxy groups are bonded to at least one terminal of a molecular chain, that is, dimethylpolysiloxane, methylethylpolysiloxane, methyloctylpolysiloxane, methyl Vinyl polysiloxane, methylphenyl polysiloxane, methyl (3,3,3-trifluoropropyl) polysiloxane, copolymer of dimethylsiloxane and methylphenylsiloxane, dimethylsiloxane and methyl (3,3,3-trifluoropropyl) Examples include siloxane copolymers.

  As the component (A), the terminal hydroxyl group or alkoxy group-blocked polyorganosiloxane may be used alone or in combination of two or more.

<(B) Silane compound and / or partial hydrolysis condensate thereof>
In the coating composition of the embodiment, the (B) component silane compound and / or a partial hydrolysis condensate thereof is represented by the formula: R ¹ _n Si (OR ² ) _4-n (1) A trifunctional or tetrafunctional silane compound and / or a partially hydrolyzed condensate thereof, and acts as a crosslinking agent for the component (A).

In formula (1), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from each other. Examples thereof include the same groups as R ³ in the formula (2) representing the component (A). All statements relating to R ³ also apply to R ¹ . R ² is an unsubstituted monovalent hydrocarbon group which may be the same as or different from each other. Examples of R ² include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. R ¹ and R ² are preferably a methyl group, an ethyl group, or a propyl group. n is 0 or 1.

  Such a partial hydrolysis-condensation product of a trifunctional or tetrafunctional silane compound preferably has 3 to 20 Si atoms, more preferably 4 to 15 molecules. If the number of Si is less than 3, sufficient curability cannot be obtained. Moreover, when Si number exceeds 20, sclerosis | hardenability and the mechanical characteristic of hardened | cured material will fall. As the silane compound and its partial hydrolysis condensate as component (B), one type may be used alone, or two or more types may be mixed and used.

  (B) The compounding quantity of a component is 0.1-20 mass parts with respect to 100 mass parts of said (A) component, Preferably it is 0.5-15 mass parts. If the amount is less than 0.1 part by mass, crosslinking is not sufficiently performed and not only a cured product having low hardness is obtained, but also the storage stability of the composition containing the crosslinking agent becomes poor. If it exceeds 20 parts by mass, the shrinkage rate during curing increases, and the physical properties of the cured product decrease.

<(C) Curing catalyst>
The curing catalyst as component (C) serves to promote the condensation reaction of the hydroxyl group (hydroxyl group) and / or alkoxy group of component (A) and the crosslinking reaction by component (B) to promote curing of the composition. It is a catalyst.
(C) As a curing catalyst, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, diisopropoxy-bis (ethyl acetoacetate) titanium, diisopropoxy bis (methyl acetoacetate) titanium, diisopropoxy bis (acetylacetate) Organic titanium compounds such as nato) titanium, dibutoxybis (ethylacetoacetate) titanium, dimethoxybis (ethylacetoacetate) titanium; carboxylic acid metals such as iron octoate, manganese octoate, zinc octoate, tin naphthate, tin caprylate, tin oleate Salt: Dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethyl Organotin compounds such as xoxide, dibutylbis (triethoxysiloxy) tin, dioctyltin dilaurate; such as tetraethoxytitanium, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, triethoxyaluminum Organic aluminum; organic zirconium compounds such as zirconium tetraacetylacetonate, tetraisopropoxyzirconium, tetrabutoxyzirconium, tributoxyzirconium acetylacetonate, and tributoxyzirconium stearate are exemplified. These may be used individually by 1 type, and may mix and use 2 or more types.
An organotitanium compound is preferred because it has a large catalytic ability in the presence of a small amount and a composition with few impurities can be obtained. In particular, titanium chelates such as 1,3-diisopropoxy-bis (ethylacetoacetate) titanium and 1,3-dipropoxybis (acetylacetonato) titanium are preferable.

  (C) The compounding quantity of the curing catalyst which is a component is 0.01-15 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.1-10 mass parts. If it is less than 0.01 parts by mass, it does not sufficiently act as a curing catalyst, and it takes a long time to cure. Conversely, when it exceeds 15 parts by mass, there is no effect corresponding to the blending amount, which is uneconomical. In addition, the storage stability is lowered.

<(D) Triazole compound>
The triazole compound as the component (D) is an addition reaction curable silicone in which an optical semiconductor device such as an LED lamp is exposed to a severe external environment, and a corrosive gas such as a sulfur compound in the atmosphere is a sealing material. It is a component having an effect of preventing corrosion of a metal electrode on a substrate, particularly an Ag electrode, when passing through a cured product (cured silicone for sealing).

Examples of triazole compounds include benzotriazole and derivatives thereof, such as 1,2,3-benzotriazole, tolyltriazole, carboxybenzotriazole, sodium benzotriazole, sodium tolyltriazole, benzotriazole butyl ester, naphthotriazole, chlorobenzotriazole, and the like; 1,2,4-triazole and its derivatives, such as 1,2,4-triazole, 1-methyl-1,2,4-triazole, 1,3-diphenyl-1,2,4-triazole, 5-amino -3-methyl-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1,2,4-triazole-3-carboxylic acid, 1-phenyl-1,2,4-triazole- 5-one, 1-phenylurazole and the like are exemplified. . These triazole compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The use of 1,2,3-benzotriazole is most preferred because it has a great effect of preventing corrosion of the Ag electrode.

  The compounding quantity of a triazole compound is 0.0001-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.001-5 mass parts. If the blending amount is less than 0.0001 parts by mass, corrosion of metal electrodes such as Ag electrodes cannot be sufficiently prevented. When the blending amount exceeds 10 parts by mass, the stability and curability of the composition are lowered, and the mechanical properties and the like of the resulting cured product are adversely affected.

<(E) Unreactive polyorganosiloxane>
The coating composition of the embodiment includes (E) an unreactive polyorganosiloxane in order to adjust the viscosity of the composition and further enhance the effect of preventing corrosion of the metal electrode by corrosive gas contained in the atmosphere. Can be blended.

  The unreacted polyorganosiloxane of component (E) is a polyorganosiloxane that does not substantially contain a functional group (for example, a hydroxyl group or an alkoxy group) bonded to a silicon atom and therefore does not react with the component (A). is there. The unreactive polyorganosiloxane preferably has a viscosity at 23 ° C. of 10 mPa · s or more and lower than the viscosity of the component (A) in order to prevent bleeding and volatilization from the cured product. In order to prevent bleeding after separation and curing, the organic group in the side chain is preferably the same type as the component (A).

  (E) 1-50 weight part is preferable with respect to 100 weight part of (A) component, and, as for the compounding quantity of unreactive polyorganosiloxane, 3-30 weight part is more preferable. If the amount is less than 1 part by weight, the effect of blending cannot be sufficiently obtained. Conversely, if it exceeds 50 parts by weight, the mechanical properties of the cured product may be adversely affected.

<(F) Adhesiveness imparting agent>
The coating composition of the present invention can contain (F) an adhesion-imparting agent. (F) As an adhesion imparting agent, for example, an isocyanurate compound having a dialkoxysilylpropyl group or a trialkoxysilylpropyl group can be used. In particular, tris (N-trialkoxysilylpropyl) isocyanurate is preferable.

  (F) As an adhesion-imparting agent, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyltriacetamidosilane, N- (2-amino) Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxy Silane, substituted or unsubstituted amino group-containing silane such as N, N-dimethyl-3-aminopropyltrimethoxysilane; 3-glycidoxytrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 3,4-epoxy Epoxy like cyclohexylethyltrimethoxysilane Xy group-containing silanes; isocyanato group-containing silanes such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropylmethyldimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (Meth) acryloxy group-containing silanes such as acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane; mercapto group-containing silanes such as 3-mercaptopropyltrimethoxysilane; and 3-chloropropyltrimethoxysilane Such halogen atom-containing silanes can also be blended.

  From the viewpoint of compatibility with the composition, the adhesiveness-imparting agent that is the component (F) is preferably blended in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 0.01 parts by mass, the effect of improving the adhesiveness is small and the onset thereof is slow. Moreover, when it mix | blends exceeding 5 mass parts, not only the isolation | separation in storage but shrinkage | contraction of hardened | cured material will arise, but storage stability and workability | operativity will deteriorate. In addition, yellowing may occur. (F) As for the compounding quantity of an adhesive provision agent, the range of 0.1-2 mass parts is more preferable with respect to 100 mass parts of (A) component.

<Other ingredients>
In addition to the components (A) to (F), additives such as a thixotropy imparting agent, a viscosity modifier, a heat resistance improver, and a flame retardant are added to the coating composition of the embodiment to inhibit the effects of the present invention. In the range not to be, it can mix | blend as needed.

  The coating composition of the embodiment does not contain an organic solvent such as benzene, toluene, xylene, heptane, hexane, trichloroethylene, methylene chloride, ethyl acetate, ethanol, isopropyl alcohol, and butyl alcohol. Since the organic solvent is not contained, there is an advantage that the adverse effect on the support base material of the optical semiconductor device and the deterioration of the working environment are not caused.

  The coating composition of 1st Embodiment is obtained by mixing each component of (A)-(F) and the said arbitrary component uniformly in the state which interrupted moisture. The order of addition of each component is not particularly limited, but after the component (A) is diluted with the component (E), the remaining component (B), component (C), component (D), (F) It is preferable to add components and other optional components. The obtained composition can be used as a so-called one-packaging room temperature curable composition that is stored as it is in a closed container and cured only by exposure to moisture in the air during use. Also, for example, a so-called multi-packaging type in which (B) a crosslinking agent and (C) a curing catalyst are prepared as separate compositions, stored in appropriate two or three separate containers, and mixed at the time of use. It can also be used as a room temperature curable composition.

  A coating composition according to an embodiment of the present invention includes (A) a polyorganosiloxane having a predetermined viscosity blocked with a hydroxyl group or an alkoxy group, (B) a trifunctional or tetrafunctional silane compound, and / or Because it contains a partial hydrolysis condensate and a curing catalyst such as (C) an organotitanium compound, it forms a cured product with excellent adhesion to resins such as PPA resin and metals such as Ag. To do. Further, since the coating composition of the embodiment contains a triazole compound having a high effect of trapping corrosive gas such as sulfur compound, discoloration or corrosion of metal such as silver by corrosive gas due to the cured product. Is prevented.

  Therefore, the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition (sealing silicone cured product) that seals the device are cured with the cured product of the coating composition (coating curing). The substrate and the cured silicone cured product are firmly bonded, and corrosion of the metal electrode formed on the substrate is prevented, and a highly reliable optical semiconductor device is obtained.

  Moreover, since the adhesiveness between the cured coating and the cured silicone for sealing is good, the occurrence of cracks at the interface between them is also suppressed. Furthermore, since there is no turbidity or cloudiness at the bonding interface between the cured coating and the cured silicone for sealing, and the light transmittance is high, an optical semiconductor device with high luminous efficiency can be obtained.

  Conventionally, in liquid crystal display devices (LCD) and plasma display panels (PDP), it is bonded to silicon atoms as a coating material for preventing corrosion and migration of electrodes and wiring due to corrosive gas contained in the atmosphere. Condensation reaction curable polyorgano, which contains a polyorganosiloxane having a functional group such as a hydroxyl group or an alkoxy group, a crosslinking agent such as a trifunctional silane, a curing catalyst, and an imidazole compound or thiazole compound as a corrosion inhibitor. A siloxane composition has been proposed (see, for example, JP-A-2006-152181). Also, a condensation reaction curable polyorgano, which contains a silicon functional group-containing polyorganosiloxane, a trifunctional silane or a tetrafunctional silane, a curing catalyst, and 1,2,4-triazole or a derivative thereof as a corrosion inhibitor. A siloxane composition has also been proposed (see, for example, JP-A-2006-206817).

  However, all these compositions are subject to corrosion of the metal layer due to the high gas permeability of the cured product of the composition itself, assuming that the composition is applied onto the metal layer such as electrodes and wiring. From such a viewpoint, an imidazole compound or a thiazole compound, or 1,2,4-triazole or a derivative thereof has been selected from such a viewpoint. In these prior arts, there has been no technical idea of improving adhesion to a metal layer and improving adhesion to a resin substrate.

  The coating composition of the present invention is a condensation reaction curable silicone composition containing a triazole compound which is not listed as a corrosion preventing component for a metal layer in the prior art, and such a composition is mounted on an optical semiconductor element. The substrate is used as a material for bonding the cured product of the addition reaction curable silicone composition (sealing silicone cured product) that seals the element.

  The cured product of the silicone composition has sufficient heat resistance, whether it is a cured product of a condensation reaction curable silicone composition or a cured product of an addition reaction curable silicone composition. Since the adhesiveness to various metals, plastics, and resin base materials is not sufficient, it has not been considered to laminate cured products of compositions having different curing reaction mechanisms. Therefore, in the present invention, the technical idea of using a cured product of a condensation reaction curable coating composition as an underlayer of a cured product of an addition reaction curable silicone composition for sealing an optical semiconductor element is easy from the prior art. It is not something that is recalled.

  Next, an optical semiconductor device according to a second embodiment of the present invention will be described. This optical semiconductor device is formed on a substrate on which an optical semiconductor element is mounted, a cured product of an addition reaction curable silicone composition that seals the optical semiconductor element (cured silicone cured product), A coating adhesive layer for adhering the substrate and the cured silicone cured product; And a coating adhesion layer consists of hardened | cured material (coating hardened | cured material) of the coating composition of 1st Embodiment mentioned above, It is characterized by the above-mentioned.

  An optical semiconductor device according to a second embodiment will be described with reference to the drawings. FIG. 1 is a cross-sectional view of an LED lamp which is an example of an optical semiconductor device.

  The optical semiconductor device 1 includes a substrate 3 on which an LED 2 is mounted as an optical semiconductor element, and a cured product 4 of an addition reaction curable silicone composition that seals the LED 2. A metal electrode 5 such as an Ag electrode is formed on the LED mounting surface of the substrate 3, and an electrode terminal (not shown) of the LED 2 and the metal electrode 5 are electrically connected by a bonding wire 6. . Moreover, the coating cured product 7 is formed on the substrate 3 having the metal electrode 5, and the substrate 3 and the cured product 4 of the addition reaction curable silicone composition are bonded by the coating cured product 7. .

  Examples of the constituent material of the substrate 3 include PPA resin, various fiber reinforced plastics, and ceramics. PPA resin is particularly preferable because of its high mechanical strength.

The cured product 4 of the addition reaction curable silicone composition can be obtained, for example, by curing an addition reaction curable silicone composition containing a vinyl group-containing polyorganosiloxane, polyorganohydrogensiloxane, and a platinum-based catalyst. A transparent cured product is preferred.
Here, “transparent” means that light generated from an optical semiconductor element such as the LED 2 is substantially transmitted, and specifically, means that the light transmittance is 90% or more. In addition, there is no specific prescription | regulation about the light transmittance of the sealing material of an optical semiconductor element, and it is so dominant that the light transmittance is high, but depending on a use, it may be used even about 80%.

  The addition reaction curable silicone composition includes, as optional components, a reaction inhibitor, a colorant, a flame retardant, a heat resistance improver, a plasticizer, reinforcing silica, an adhesion promoter, etc. You may add in the range which does not affect property. Moreover, it is also possible to contain the fluorescent substance which generate | occur | produces visible light by being excited by light emission from an optical semiconductor element as a wavelength adjusting agent.

Addition reaction curable silicone compositions include: (a) Bonded to silicon atoms in the molecule from the viewpoints of physical properties such as transparency, hardness, and tensile strength of cured products, and adhesion and adhesion to cured cured products. A polyorganosiloxane having two or more alkenyl groups having a viscosity of 100 to 100,000 mPa · s at 23 ° C., and (b) having two or more hydrogen atoms bonded to silicon atoms in one molecule. Polyorganohydrogensiloxane, an amount of 0.1 to 4.0 hydrogen atoms in this component per alkenyl group in component (a), and (c) a catalyst for a platinum-based catalyst A composition containing the amount is preferred.
Hereinafter, components contained in a preferable addition reaction curable silicone composition will be described.

<(A) component>
The molecular structure of the polyorganosiloxane having two or more alkenyl groups as component (a) includes linear, branched, cyclic, etc., but the main chain basically consists of repeating diorganosiloxane units. A straight chain in which both ends of the molecular chain are blocked with a triorganosiloxy group is preferable.

  The alkenyl group bonded to the silicon atom in the component (a) has 2 to 8 carbon atoms, more preferably 2 to 8 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, and heptenyl group. There are 4 alkenyl groups. A vinyl group is particularly preferable. When the polyorganosiloxane as the component (a) is linear, the alkenyl group may be bonded to the silicon atom at either the molecular chain terminal or the middle, but both the molecular chain terminal and the middle And may be bonded to a silicon atom.

  Examples of the organic group bonded to the silicon atom other than the alkenyl group in component (a) include, for example, an alkyl group, particularly an alkyl group having 1 to 10 carbon atoms; an aryl group, particularly an aryl group having 6 to 14 carbon atoms; Group: an unsubstituted or halogen-substituted monovalent hydrocarbon group such as a halogenated alkyl group. A methyl group or a phenyl group is particularly preferable.

  The viscosity (23 ° C.) of the component (a) is preferably 100 to 100,000 mPa · s, and particularly preferably 500 to 10,000 mPa · s.

  Specific examples of the component (a) include: a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer at both ends of a molecular chain, a trimethylsiloxy group-capped methylvinylpolysiloxane at both ends of a molecular chain, and a trimethylsiloxy group-capped dimethyl at both molecular chains. Siloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of molecular chain, dimethylvinylsiloxy group-blocked methylvinylpolysiloxane with molecular chain at both ends, dimethylvinylsiloxy group-blocked dimethyl with molecular chain at both ends Siloxane / methyl vinyl siloxane copolymer, both ends of molecular chain dimethyl vinyl siloxy group blocked dimethyl siloxane / methyl vinyl siloxane / methyl phenyl siloxane copolymer, tri chain siloxy at both ends of molecular chain Blocked dimethylpolysiloxane.

<(B) component>
The polyorganohydrogensiloxane as component (b) acts as a crosslinking agent for component (a). There is no restriction | limiting in particular in the molecular structure of (b) component, Polyorganohydrogensiloxane, such as linear, cyclic, and branched, can be used. It is also possible to use a three-dimensional network (resin-like) polyorganohydrogensiloxane.

  The polyorganohydrogensiloxane of component (b) has 2 or more, preferably 3 or more hydrogen atoms bonded to silicon atoms, that is, hydrosilyl groups (Si-H groups) in one molecule. When the polyorganohydrogensiloxane as the component (b) is linear, the Si-H group may be located only at one of the molecular chain terminal or the middle part, or may be located at both of them. Good. The number (degree of polymerization) of silicon atoms in one molecule of the component (b) is 2 to 1,000, more preferably 3 to 100.

  Specific examples of the component (b) include molecular chain both ends trimethylsiloxy group-capped methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group. Blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both molecular chain ends, dimethylpolysiloxane / methylhydrogensiloxane copolymer blockade at both ends of molecular chain dimethylhydrogensiloxy group Combined, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends of molecular chain, dimethylhydrosiloxy group-blocked methylphenyl at both ends of molecular chain Include the polysiloxane.

  The blending amount of the polyorganohydrogensiloxane as the component (b) is the effective curing amount of the component (a), and in particular, the Si-H group of the component (b) is an alkenyl group in the component (a) (for example, (Vinyl group) is used at a blending amount of 0.1 to 4.0, more preferably 1.0 to 3.0. If it is less than 0.1, the curing reaction does not proceed, and it may be difficult to obtain a cured product. If it exceeds 4.0, a large amount of unreacted Si—H groups remain in the cured product. Therefore, the physical properties of the cured product may change over time.

<(C) component>
The platinum-based catalyst as the component (c) is a catalyst that promotes the addition reaction (hydrosilylation reaction) between the alkenyl group in the component (a) and the Si—H group in the component (b). As the component (c), chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum complex having an olefin, a vinyl group-containing siloxane, or an acetylene compound as a ligand can be used.

  The amount of component (c) is not particularly limited as long as it is an amount effective as a catalyst for the hydrosilylation reaction. The total amount of the component (a) and the component (b) is 0.1 to 1,000 ppm, more preferably 1 to 500 ppm, and still more preferably 1 to 20 ppm in terms of platinum element. When the blending amount is within this range, sufficient curing is obtained as a result of acceleration of the addition reaction, which is economically advantageous.

  In addition to the components (a) to (c), an adhesion-imparting agent can be added to the addition reaction curable silicone composition. As the adhesion imparting agent, the isocyanurate compound having a dialkoxysilylpropyl group or trialkoxysilylpropyl group described as the (F) adhesion imparting agent that can be contained in the coating composition of the first embodiment is used. Can be mentioned. Further, substituted or unsubstituted amino group-containing silanes, epoxy group-containing silanes, isocyanato group-containing silanes, (meth) acryloxy group-containing silanes, mercapto group-containing silanes described as adhesiveness-imparting agents other than isocyanurate compounds, and Halogen atom-containing silanes can also be included.

  Furthermore, a well-known additive can be mix | blended with an addition reaction curable silicone composition as needed. For example, reinforcing fillers such as fumed silica, non-reinforcing fillers such as calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, zinc oxide, wavelength adjusting agents such as fluorescent substances, It can mix | blend suitably in the range which does not impair the objective of this invention. Blends such as fumed silica and wavelength adjusting agents are preferred.

  This addition reaction curable silicone composition is prepared by uniformly mixing the above-mentioned components, but the curability can be arbitrarily adjusted by adding a reaction inhibitor. Curing reaction inhibitors include acetylene alcohols such as 3-methyl-1-butyn-3-ol, 2-phenyl-3-butyn-2-ol, and maleic acid derivatives such as diallyl maleate. . By using such a reaction inhibitor, it can be used as one liquid.

Moreover, it can also be divided and stored in two liquids so that curing does not proceed, and the two liquids can be mixed and cured during use. In the case of the two-component mixing type, it is necessary to avoid using the same packaging for the polyorganohydrogensiloxane (b) component and the platinum catalyst (c) component because of the risk of dehydrogenation reaction. .
The viscosity of the addition reaction curable silicone composition thus obtained is preferably 100 to 50,000 mPa · s, particularly preferably 300 to 10,000 mPa · s, as measured by a rotational viscometer at 23 ° C.

  The addition reaction curable silicone composition is cured by heating as necessary. The curing conditions are not particularly limited, but are usually cured at 40 to 200 ° C., preferably 60 to 170 ° C. for 1 minute to 10 hours, preferably about 30 minutes to 6 hours.

  The optical semiconductor device 1 shown in FIG. 2 is manufactured by the following method. That is, an optical semiconductor element such as an LED 2 is bonded to a substrate 3 on which a metal electrode 5 such as an Ag electrode is previously formed by Ag plating, and an electrode terminal (not shown) of the LED 2 and the metal electrode 5 are bonded by wire bonding. Are electrically connected. Next, after the substrate 3 on which the LED 2 is mounted is cleaned as necessary, a coating composition is applied onto the substrate 3 using a known coating apparatus, and then cured at room temperature, preferably 500 μm or less, more Preferably, the cured coating 7 having a thickness of 50 to 300 μm is formed. Thereafter, an addition reaction curable silicone composition is applied onto the coating cured product 7 with a dispenser or the like, and left or heated and cured at room temperature to seal the LED 2. Form.

  Thus, using the coating composition of the present invention, a cured coating is formed on a substrate on which an optical semiconductor element such as an LED is mounted, and a cured product of an addition reaction curable silicone composition (a cured silicone for sealing). By forming the product, the substrate and the cured silicone cured product can be favorably bonded. Moreover, since the adhesiveness between the cured coating and the cured silicone for sealing is good and cracks are not generated at the interface or the like, a highly reliable optical semiconductor device, particularly an LED lamp can be obtained.

  Further, even if the LED lamp is exposed to a harsh external environment and corrosive gas in the air permeates through the inside of the silicone cured product for sealing, the corrosive gas is captured by the cured coating product of the present invention. Corrosion of the metal electrode (Ag electrode) on the substrate is suppressed.

  In the above-described embodiment, the LED is used as an example of the optical semiconductor element. However, the present invention can be applied to, for example, a phototransistor, a photodiode, a CCD, a solar cell module, an EPROM, and a photocoupler.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. Note that “part” means “part by mass”, and the viscosity is a value at 23 ° C. and a relative humidity of 50%.

Example 1
(A1) 52.6 parts of polydimethylsiloxane blocked at both ends of the molecular chain with a trimethoxysiloxy group (hereinafter also referred to as α, ω-bis (trimethoxysiloxy) polydimethylsiloxane) (viscosity 100 mPa · s) (A2) In a mixture with 22.5 parts of α, ω-bis (trimethoxysiloxy) polydimethylsiloxane (viscosity 700 mPa · s) blocked at both ends of the molecular chain with a trimethoxysiloxy group, (E) molecular chain Polydimethylsiloxane (viscosity 50 mPa · s) 15.0 parts blocked at both ends with trimethylsiloxy groups, (B) 7.5 parts of methyltrimethoxysilane, (C) diisopropoxy-bis (ethylacetoacetate) titanium 2.25 parts, (F) 1,3,5-tris (N-trimethoxysilylpropyl) isocyanurate 0.15 parts, and (D 1) 0.1 part of 1,2,3-benzotriazole was added and mixed under moisture blocking until uniform to obtain a coating composition.

Examples 2-4
Each component shown in Table 1 was blended in the composition shown in the same table and mixed in the same manner as in Example 1 to obtain a coating composition.

Comparative Example 1
Component (D) ((D1) 1,2,3-benzotriazole and (D2) 1,2,4-triazole) was not blended, and each component shown in Table 1 was blended in the composition shown in the same table. And it mixed similarly to Example 1 and obtained the coating composition.

  About the coating composition obtained in Examples 1-4 and Comparative Example 1, the test shown below was done and the characteristic was measured and evaluated. The results are shown in Table 1.

[Adhesion test]
The coating compositions obtained in Examples 1 to 4 and Comparative Example 1 were each applied to two substrates to a thickness of 0.1 mm (100 μm), and 3 in an atmosphere of 23 ° C. and 50% RH. It was left for days to cure. Next, as shown in FIG. 2, an addition reaction curable silicone rubber composition (product name: TSE3033, manufactured by Momentive Performance Materials, Inc.) is 1 mm thick on a pair of substrates 11 and 12 on which a cured film is formed. After being applied so as to be sandwiched between (adhesive area 25 mm × 10 mm), it was cured by heating at 150 ° C. for 1 hour to form a cured product layer 13. Thus, a test piece for adhesion test was produced.

  As the substrates 11 and 12, a PPA resin substrate (manufactured by Solvay Specialty Polymers Japan Co., Ltd., trade name: Amodel) and an epoxy glass substrate (manufactured by Shin-Kobe Electric Co., Ltd., trade name: epoxy glass KFL-GES) were used. .

  Next, the substrates 11 and 12 of the produced test pieces were pulled at a tensile speed of 10 mm / min in the direction of the arrow (see FIG. 2) using a tensile tester (manufactured by Shimadzu Corporation, Autograph). 12 was peeled off. And the ratio of the part which carried out the cohesive failure (breaking in the part of silicone rubber) in the hardened | cured material layer 13 of the board | substrates 11 and 12 peeled off was measured as a cohesive failure rate. The cohesive failure rate of 80% or more was evaluated as ◯, the cohesive failure rate of 40-80% was evaluated as Δ, and the cohesive failure rate of 40% or less was evaluated as ×.

[Corrosion test]
The coating compositions obtained in Examples 1 to 4 and Comparative Example 1 were applied to a thickness of 0.1 mm (100 μm) on a silver plated plate and left in an atmosphere of 23 ° C. and 50% RH for 3 days. And cured. Next, an addition reaction curable silicone rubber composition (TSE3033) was applied to a thickness of 0.1 mm (100 μm) on the cured film, and then cured by heating at 150 ° C. for 1 hour to prepare a test piece.

  Next, the produced test piece was sealed in a 100 cc glass bottle together with 0.1 g of sulfur crystals and left at 70 ° C. Then, after a predetermined time (1 day, 7 days, 14 days), the cured film and the silicone rubber layer were peeled off, and the degree of corrosion (discoloration) on the surface of the silver-plated plate was visually observed. The surface of the silver-plated plate was evaluated as ○ when there was no corrosion and discoloration, Δ when there was some corrosion (discoloration), and × when there was black discoloration.

[Adhesion of bonding interface]
The coating compositions obtained in Examples 1 to 4 and Comparative Example 1 were applied on a PPA resin substrate at a thickness of 100 μm and allowed to cure in an atmosphere of 23 ° C. and 50% RH for 3 days. On the cured film thus formed, an addition reaction curable silicone rubber composition (TSE3033) was applied in a thickness of 1 mm and cured by heating at 150 ° C. for 1 hour. Subsequently, the interface between the thus formed silicone rubber cured layer and the cured film of the underlying coating composition was visually observed. The case where the adhesiveness at the bonding interface between the cured silicone rubber layer and the underlying cured film was good was evaluated as ◯, and the case where there was peeling or cracking and the adhesiveness was poor was evaluated as ×. In addition, when the cured silicone rubber layer is observed with the naked eye and the cured silicone rubber layer is clearly visible through the cured silicone rubber layer, ○ (Clear), the underlying cured film appears cloudy or cloudy X (Hazy), and the case where the underlying cured film appeared slightly cloudy was evaluated as Δ.

Comparative Example 2
On the silver-plated plate, an addition reaction curable silicone rubber composition (TSE3033) was applied at a thickness of 1 mm without applying a coating composition, and cured by heating at 150 ° C. for 1 hour to prepare a test piece. . And the said corrosivity test was done with respect to the test piece produced in this way. The results are shown in Table 2.
In addition, when this silicone rubber cured layer was visually observed from above, it was transparent to the interface with the substrate.

Comparative Example 3
83 parts of methyl methacrylate, 17 parts of γ-methacryloxypropyltrimethoxysilane, 200 parts of a mixed solvent of IPA (isopropyl alcohol) and ethyl acetate, 0.5 part of AIBN (2,2′-azobisisobutyronitrile) The mixture was heated and stirred at 80 ° C. for 3 hours to prepare a solution containing a methyl methacrylate polymer.

  Next, after 300 parts of the methyl methacrylate polymer-containing solution thus obtained was diluted with 1800 parts of a mixed solvent of IPA, ethyl acetate and toluene, 25 parts of γ-glycidoxypropyltrimethoxysilane and alcohol of chloroplatinic acid were used. 11 parts of a solution (Pt content 1.8%) (92 ppm as platinum amount) and 11 parts of tetra-n-butyl titanate were added and stirred to obtain a primer composition.

  A test piece was prepared in the same manner as in Example 1 by using the above-described primer composition instead of the coating composition obtained in Example 1.

Comparative Examples 4-6
Instead of the coating composition obtained in Example 1, the following coating materials were used, and test pieces were produced in the same manner as in Example 1.
In Comparative Example 4, organic solvent type printed circuit board coating material Hemiseal 1B51 (Air Brown Co., Ltd.) mainly composed of polyolefin resin, and in Comparative Example 5, organic solvent type printed circuit board coating material mainly composed of polyurethane resin. In Hemiseal 1A27NS (Air Brown Co., Ltd.) and Comparative Example 6, an organic solvent type printed circuit board coating material Hemiseal 1B73 (Air Brown Co., Ltd.) mainly composed of acrylic resin was used.

  The test pieces produced in Comparative Examples 3 to 6 were subjected to an adhesion test and a corrosive test by the above methods. In Comparative Example 3, the adhesion at the bonding interface between the cured silicone rubber layer and the substrate and the appearance of the substrate are shown. In Comparative Examples 4 to 6, the adhesion at the bonding interface between the coating film of the coating material and the cured silicone rubber layer. The appearance of the coating film as the base was examined in the same manner as described above. The results are shown in Table 2.

From Table 1 and Table 2, the following can be understood.
That is, (A) a polyorganosiloxane having a molecular chain terminal blocked with an alkoxy group and having a viscosity of 20 to 1,000,000 mPa · s as a main component, and (B) a trifunctional or tetrafunctional silane compound and / or The coating compositions of Examples 1 to 4 containing the partially hydrolyzed condensate, (C) a curing catalyst, and (D) a triazole compound at a predetermined ratio, the cured product (coating cured product) is a PPA resin or the like In addition to firmly bonding the substrate and the cured product (silicone rubber cured layer) of the addition reaction curable silicone rubber composition, the adhesion and adhesion between the cured coating and the cured silicone rubber layer are good. In addition, there is no turbidity or cloudiness at the bonding interface between the cured cured product and the silicone rubber cured layer, and the light transmittance of the interface is high. Furthermore, it turns out that corrosion by the corrosive gas of a silver plating board is fully prevented by the hardened | cured material of the coating composition of Examples 1-4.

  On the other hand, when the coating composition of Comparative Example 1 which is a condensation reaction curable silicone composition containing no triazole compound is used, the adhesion between the PPA resin substrate and the silicone rubber cured layer is poor, and silver plating is used. Insufficient corrosion prevention of the plate. Furthermore, there is some turbidity or cloudiness at the bonding interface between the cured cured product and the cured silicone rubber layer, and the light transmittance at the interface is low.

  Further, in Comparative Example 2 in which the silicone rubber cured layer was directly formed without applying the coating composition of the example on the silver plated plate, significant corrosion and discoloration occurred on the surface of the silver plated plate.

  In Comparative Example 3 using an acrylic primer composition instead of the coating composition of Example and Comparative Example 6 using a coating material mainly composed of an acrylic resin, the adhesion between the cured silicone rubber layer and the substrate is Although good, the corrosion prevention of the silver-plated plate is insufficient, and corrosion and discoloration have occurred on the surface of the silver-plated plate over time. Further, the interface between the cured silicone rubber layer and the substrate or coating material layer is cloudy or cloudy, resulting in a decrease in light transmission.

  Furthermore, in Comparative Example 4 using a coating material mainly composed of a polyolefin resin instead of the coating composition of the example, and in Comparative Example 5 using a coating material mainly composed of a polyurethane resin, corrosion prevention of the silver plated plate is prevented. It is insufficient, and corrosion and discoloration occur on the surface of the silver-plated plate. Further, the interface between the coating material layer and the silicone rubber cured layer is cloudy or cloudy, and the light transmittance at the interface is low.

  According to the coating composition of the present invention, the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition for sealing the optical semiconductor element can be satisfactorily adhered to each other, and formed on the substrate. Therefore, it is possible to provide an optical semiconductor device that prevents corrosion of the formed metal electrode and has high luminous efficiency and high reliability.

  DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device, 2 ... LED, 3 ... Board | substrate, 4 ... Hardened | cured material of addition reaction hardening type silicone composition, 5 ... Metal electrode, 6 ... Bonding wire, 7 ... Coating hardened | cured material.

Claims (10)

(A) 100 parts by mass of a polyorganosiloxane whose molecular chain terminal is blocked with a hydroxyl group or an alkoxy group and has a viscosity at 23 ° C. of 20 to 1,000,000 mPa · s;
(B) General formula: R ¹ _n Si (OR ² ) _4-n (1)
Wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ² is the same or different unsubstituted monovalent hydrocarbon group, and n is 0 or 1. 0.1 to 20 parts by mass of a trifunctional or tetrafunctional silane compound and / or a partially hydrolyzed condensate thereof,
(C) 0.01-15 parts by mass of a curing catalyst;
(D) a composition containing 0.0001 to 10 parts by mass of a triazole compound,
A cured composition of the composition adheres a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable polyorganosiloxane composition that seals the optical semiconductor element.   The coating composition according to claim 1, wherein the (D) triazole compound is 1,2,3-benzotriazole or a derivative thereof.   The coating composition according to claim 1 or 2, which does not contain an organic solvent. A substrate on which an optical semiconductor element is mounted, a cured product of an addition reaction curable polyorganosiloxane composition for sealing the optical semiconductor element, and the substrate and the addition reaction curable polyorganosiloxane composition formed on the substrate. It is an optical semiconductor device having a coating adhesive layer that adheres a cured product of the product,
4. The optical semiconductor device, wherein the coating adhesive layer is made of a cured product of the coating composition according to any one of claims 1 to 3.   The optical semiconductor device according to claim 4, wherein the cured product of the addition reaction curable polyorganosiloxane composition is transparent. The addition reaction curable polyorganosiloxane composition is:
(A) 100 parts by mass of a polyorganosiloxane having 2 or more alkenyl groups bonded to silicon atoms in the molecule and having a viscosity at 23 ° C. of 100 to 100,000 mPa · s;
(B) A polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule, the amount of the hydrogen atoms in the component is 0.1 per alkenyl group in the component (a). An amount of 1 to 4.0,
(C) The optical semiconductor device according to claim 4 or 5, which contains a catalytic amount of a platinum-based catalyst.   The optical semiconductor device according to claim 4, wherein the optical semiconductor element is a light emitting diode.   The optical semiconductor device according to claim 4, wherein the constituent material of the substrate is a polyphthalamide resin.   The optical semiconductor device according to claim 4, wherein the substrate has a metal electrode on a mounting surface of the optical semiconductor element.   The optical semiconductor device according to claim 9, wherein the metal electrode is a silver electrode.

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