TWI406913B - A light-resistant primer device, a method for producing a light-emitting semiconductor device using the undercoat composition, and a light-emitting semiconductor device obtained by the method - Google Patents

Abstract

The invention provides a primer material which has favorable coating property, high adhesion reliability between a sealing resin and a substrate, and high color fastness to light irradiation and heating. The invention also provides a method for producing a light-emitting semiconductor device using the priming paint material. The primer composition contains: (A) at least one silane compound showed by following general formula (1): R<1>XR<2>YSi(R<3>)4-X-Y(1) (wherein, R<1> and R<2> are each independently a hydrogen atom or alkyl containing one or more reactive substituents and 1 to 30 carbon atomics, R<3> is a chlorine atomic, a hydroxyl, or an unsubstituted or substituted alkoxyl or aryloxy containing 1 to 30 carbon atomics, X is an integer of 1 to 2, Y is an integer of 0 to 1, X+Y is an integer of 1 or 2), and/or partial hydrolyzate condensates thereof, (B) a Louis acid organo-aluminium compound and (C) an organic solvent.

Description

Light-resistant primer composition, method for producing light-emitting semiconductor device using the primer composition, and light-emitting semiconductor device obtained by the method

The present invention relates to a light-resistant primer composition, a method for producing a light-emitting semiconductor device using the primer composition, and a light-emitting semiconductor device obtained by the method and a light-emitting semiconductor device using the primer composition.

Due to the high brightness and high output power of the light-emitting diode, the materials constituting the package material and sealing material of the light-emitting diode are in a larger light up to now. Hot load. In recent years, a highly durable material of polyoxymethylene resin has been widely used as a sealing resin of a high-output light-emitting diode (LED). However, the package for mounting LEDs is made of a plurality of materials such as metal and semiconductor materials, and the sealing resin material must have adhesion reliability to various materials. Further, when the LED is driven by light, there is a problem that the color of the undercoat layer is discolored and the light extraction efficiency of the LED is lowered at a high temperature. Further, the primer containing a highly active compound has a limited coating treatment time, which causes problems in the production work surface. In order to solve such problems, there have been reports of primers (Patent Documents 1 and 2) on the combination of a decyl alcohol condensation catalyst and a decane coupling agent, but the coating workability of the primer coating of the LED is adhered. The primers that are compatible with both reliability and discoloration are not described.

[Patent Document 1] Special Opening 2004-339450

[Patent Document 2] Special Opening 2005-093724

Therefore, an object of the present invention is to provide a primer material which has excellent coating workability, high adhesion reliability between a sealing resin and a substrate, and high discoloration resistance to light irradiation and heating.

Further, the object of the present invention is to provide a method for producing a higher performance light-emitting semiconductor device by using the primer composition.

In order to solve this problem, the inventors of the present invention have found that the combination of an organoaluminum compound of a Lewis acid, a specific decane coupling agent, and an organic solvent can solve the above problems and further complete the present invention.

That is, as a means for solving the above problems, the first aspect of the present invention provides (A) the following general formula (1) R ¹ _X R ² _Y Si(R ³ ) _4-XY (1) (wherein R ¹ and R ^{2 each} independently represent a hydrogen atom or an alkyl group having 1 or more carbon atoms which may have one or more reactive substituents, and R ³ represents a chlorine atom, a hydroxyl group or an unsubstituted carbon number of 1 to 30. Or substituted alkoxy or aryloxy, X is an integer of 1 to 2, Y is an integer of 0 to 1, and X + Y is an integer of 1 or 2) and/or such at least one decane compound a partial hydrolysis condensate, (B) a Lewis acidic organoaluminum compound, and (C) an organic solvent, and a primer composition.

The second aspect of the present invention provides that the primer composition is applied to After being mounted on the surface of the light-emitting semiconductor device on the pre-molded package, the surface of the light-emitting semiconductor device is coated to form a primer composition layer, and after the addition reaction-curable polyfluorene is applied to the primer composition layer, The element is overmolded with a resin seal.

By using the primer composition of the present invention, the coating of the primer can be improved, the time of the drying step can be utilized, the workability can be improved, and the adhesion reliability of the sealing resin to the substrate can be improved. Moreover, since the coating layer of the primer composition has chemical and physical stability, the primer layer still has discoloration resistance even under the light irradiation conditions. This makes it possible to realize a light-emitting semiconductor device having a long life and high reliability.

Hereinafter, the present invention will be described in more detail.

[Bottom coating composition] [(A) decane coupling agent]

As the component (A), the general formula (1): R ¹ _X R ² _Y Si(R ³ ) _4-XY (1) (wherein R ¹ and R ² independently represent a hydrogen atom, or may be The alkyl group having one or more reactive substituents has 1 to 30 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 15 carbon atoms, and R ³ represents a chlorine atom, a hydroxyl group or an unsubstituted carbon atom number of 1 to 30. Or substituted alkoxy or aryloxy, X is an integer of 1 to 2, Y is an integer of 0 to 1, and X + Y is an integer of 1 or 2) and/or such at least one decane compound Part of the hydrolysis condensate.

Further, when R ¹ and R ^{2 are} not simultaneously a hydrogen atom (that is, at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms which may have one or more reactive substituents) .

In the general formula (1), when both of R ¹ and R ² or one of them is an alkyl group, a carbon atom number of 1 in a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group is preferred. An example of an alkyl group of ~18.

The alkyl group represented by R ¹ or R ² may have one or more reactive substituents. Examples of the reactive substituents include an epoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a thio group, an amine group, a cyano group, and an isocyano group.

More specifically, it is an epoxy group or an alkyl group having an epoxy group such as glycidyl group, β-glycidoxyethyl group, α-glycidoxypropyl group, β-glycidoxy group Propyl, γ-glycidoxypropyl, α-glycidoxybutyl, β-glycidoxybutyl, γ-glycidoxybutyl, δ-glycidoxy Butyl, (3,4-epoxycyclohexyl)methyl, β-(3,4-epoxycyclohexyl)ethyl, γ-(3,4-epoxycyclohexyl)propyl, Examples of δ-(3,4-epoxycyclohexyl)butyl and the like.

The alkyl group which is an oxetane group is, for example, (3-ethyloxetan-3-yl)propyl group and the like.

The alkyl group having an acryloxy group is exemplified by an acryloxymethyl group, a β-propylene methoxyethyl group, a β-acryloxypropyl group, and a γ-acryloxypropyl group.

As the alkyl group having a methacryloxy group, for example, methacryloxymethyl group, β-methacryloxyethyl group, β-methacryloxypropyl group, γ-methyl propylene Examples of methoxypropyl groups and the like.

An alkyl group having a thiol group, for example, a thiomethyl group, a β-hydrothioethyl group, a β-hydrothiopropyl group, a γ-hydrothiopropyl group, and the like, and an alkyl group having a mercapto group, such as : aminomethyl, β-aminoethyl, β-aminopropyl, γ-aminopropyl, N-(β-aminoethyl)γ-aminopropyl, N-phenyl-γ - Aminopropyl and the like.

Examples of the alkyl group having a mercapto group include a cyanomethyl group, a β-cyanoethyl group, a β-cyanopropyl group, and a γ-cyanopropyl group. Examples of the substituent having an isocyano group include an isocyanomethyl group, a β-isocyanoethyl group, a β-isocyanopropyl group, and a γ-isocyanopropyl group.

In the general formula (1), R ³ represents a chlorine atom, a hydroxyl atom or an unsubstituted or substituted alkoxy group or aryloxy group having 1 to 30 carbon atoms.

The unsubstituted or substituted alkoxy group having 1 to 30 carbon atoms is preferably, for example, a lower alkoxy group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as a methoxy group. Unsubstituted alkoxy group, methoxymethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tri-butoxy group, cyclohexyloxy group, etc. An alkoxy group substituted with an alkoxy group such as an oxyethoxy group, an ethoxymethoxy group or an ethoxyethoxy group.

The unsubstituted or substituted aryloxy group having 1 to 30 carbon atoms is preferably one having two or two aromatic rings, for example, having 6 to 18 carbon atoms, particularly 6 to 12 carbon atoms. : phenyloxy, o, m, p-tolyloxy, dimethylphenyloxy, o, m, p-ethylphenyloxy, Examples of a methoxy group, a phenylethyloxy group, a naphthyloxy group, a biphenylyloxy group, a decyloxy group and the like.

[(B) organoaluminum compound]

The Lewis acid organoaluminum compound used as the component (B) is considered to be a sterol condensation catalyst in the primer composition of the present invention, preferably the following general formula (2): R ⁴ _x Al (OR ⁵ ) _3-X (2) (wherein x is an integer of 0 to 3, and when x is 1 to 3, R ⁴ independently represents a carbon number of 30 or less (that is, a carbon number of 1 to 30) Preferably, it is 1 to 15, more preferably an alkoxy group of 1 to 10, an ethyl fluorenyl group, an ethoxylated group (i.e., a pyruvate group); and a R ⁵ group of 1 to 15 carbon atoms. An organoaluminum compound represented by an unsubstituted or substituted alkyl or aryl group. In the general formula (2) of the above organoaluminum compound, the unsubstituted or substituted alkyl or aryl group of R ⁵ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and third. An example of an alkyl group having a desired number of carbon atoms of from 1 to 15 and particularly preferably from 1 to 10, such as a butyl group or a cyclohexyl group. Further, an aryl group having an ideal carbon number of 6 to 18, such as a phenyl group, a fluorophenyl group, a β-naphthyl group or a fluorenyl group, is preferred.

An alkoxy group of R ⁴ and an unsubstituted or substituted alkoxy group of OR ⁵ or an aryloxy group which is the same as the one represented by R ^{3 of} the general formula (1), an unsubstituted or substituted alkoxy group or an unsubstituted or substituted group. Examples of aryloxy groups.

Specific examples of the above organoaluminum compound include: tris(2-butoxy)aluminum, trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tris(2-propoxy)aluminum, and tributoxide. Base aluminum, tris(t-butoxy aluminum), tris(cyclohexyloxy)aluminum, acetamethylene dimethoxyaluminum, acetamethylene diethoxyaluminum, ethenyldipropoxyaluminum, Ethyl bis(di-propoxy)aluminum, acetamidodibutoxyaluminum, acetamylbis(t-butoxy)aluminum, acetamylbis(t-butoxy)aluminum , ethoxylated dimethoxy aluminum, ethoxylated diethoxy aluminum, ethoxylated dipropoxy aluminum, ethoxylated bis(second-propoxy) aluminum, ethoxylated Examples of dibutoxy aluminum, ethoxylated bis(second-butoxy)aluminum, ethoxylated bis(tris-butoxy)aluminum, and the like. Preferred is tris(2-butoxy)aluminum.

(B) The component may be used alone or in combination of two or more kinds of Lewis acidic organoaluminum compounds.

In the composition of the present invention, the mass ratio of the component (A) to the component (B) is preferably 1 or less, and the mass ratio of the component (A) to the component (B) is 1 to 0.01, or even 0.8 to 0.1, particularly 0.7. ~0.2 will greatly expand the coating workability, that is, the range of available time (use time or limit) in the drying step from the application of the primer to the end of drying is more desirable.

[Organic solvents]

As the organic solvent used for the component (C), various known organic solvents can be used, and those having high effects can be used, for example, n-pentane, n-hexane, n-heptane, isooctane, A hydrocarbon solvent having 5 to 15 carbon atoms such as cyclopentane or cyclohexane. It is also possible to use a solvent containing a hetero atom (that is, a solvent containing a hetero atom other than carbon or hydrogen), such as ethanol, propanol, butanol or a ring. An alcohol-based, ether-based or ester-based solvent such as hexanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, ethyl acetate or butyl acetate. Further, a fluorine-containing solvent such as a fluoroalkane or a fluoroalkane can also be used. More preferably, an aromatic carbocyclic solvent having 5 to 15 carbon atoms such as benzene, toluene, xylene or pyridine or an aromatic complex ring-based solvent can be used.

As an ideal example of an aromatic carbocyclic solvent, the general formula (3): An example of an organic solvent formed by the compound shown.

In the above formula (3), the substituents of R ⁶ , R ⁷ and R ^{8 are} , for example, independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a decylamino group or an amine group. In the case of a halogen atom, R ⁶ , R ⁷ and R ^{8 are} particularly preferably a combination of a hydrogen atom and an alkyl group.

The above alkyl group may be a linear, branched or cyclic alkyl group such as methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl or iso- Butyl, second-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl Base, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2, 2-Dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl 1,1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl , 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-positive -pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl -n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-B 2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl , 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl- Cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl , 2-n-propyl-cyclopropyl, 1-iso-propyl-cyclopropyl, 2-iso-propyl-cyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2 , 3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2 -ethyl-2-methyl Examples of cyclopropyl, 2-ethyl-3-methylcyclopropyl and the like.

Examples of the alkoxy group of the above formula (3) are: methoxy, ethoxy, n-propoxy, iso-propoxy, C-propoxy, n-butoxy, iso-butyl Oxy, second-butoxy, tert-butoxy, C-butoxy, 1-methyl-C-propoxy, 2-methyl-C-propoxy, pentyloxy, C Examples of a pentyloxy group, a hexyloxy group, and a C-hexyloxy group.

As the base of the above-mentioned (3), such as acetamide (acetamidoamine), ethylcarbonylamine, n-propylcarbonylamine, iso-propylcarbonylamine, Examples of n-butylcarbonylamine groups and the like.

As an amine group of the above formula (3), for example, an amine group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a dimethylamino group, a diethylamino group, Examples of the dipropylamino group, the diiso-propylamino group and the like.

Examples of the halogen atom of the above (3) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

More specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, tert-butanol, n-propanol, second-butanol, isobutanol, n-butanol, and 2 - a monovalent alcohol such as butanol, n-hexanol, 1-pentanol, neopentyl alcohol, cyclopentanol or cyclohexanol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-positive - a propylene glycol monoalkyl ether such as propyl ether, propylene glycol mono-n-butyl ether or propylene glycol mono-second-butyl ether; ethylene glycol monomethyl ether, glycerol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-di-butyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol mono-n-hexyl Ether, 2-phenoxyethanol, 2-( Ethylene glycol monoalkyl ethers such as oxy)ethanol; propylene glycol monoacetate, propylene glycol monopropionate, ethylene glycol monoacetate, ethylene glycol monopropionate, diethylene glycol monoacetate, etc. Alcohols having an ester bond; divalent alcohols such as ethylene glycol, propylene glycol, diethylene glycol, and hexanediol; fluoroalcohol, tetrahydrofuranol, 1-chloro-2-propanol, diacetone alcohol, 2- An example of an alcohol having a substituent other than a hydroxyl group such as cyanoethanol or acetone cyanide epichlorohydrin.

Examples of ester solvents include formates such as ethyl formate and propyl formate; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, and amyl acetate. Acetate such as isoamyl acetate; propionate such as methyl propionate or ethyl propionate; methyl lactate, ethyl lactate, milk a lactic acid ester such as butyl acrylate; an ethyl acetate such as methyl acetate, ethyl acetate or the like; a tyrosyl ester; a heterotyrosyl ester; a phytate; a benzoic acid ester; Malate esters; maleate esters; tartrates; citrate esters; diethylene glycol diesters; carbonated compounds such as diethyl carbonate, ethylene carbonate, propylene carbonate, etc.; Esters; examples of phosphates.

Examples of the amide-based solvent include N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, and the like, N-methyl Examples of cyclic guanamines such as phenyl-2-pyrrolidone.

Examples of the nitro compound-based solvent include an alkyl-substituted nitro compound such as nitromethane, nitroethane, nitropropyl or nitrobenzene.

These organic solvents may be used singly or in combination of two or more kinds, and it is preferable to obtain a high stability stability of the specific primer composition, and it is particularly preferable as an aromatic compound solvent.

[Method of Manufacturing Light-Emitting Semiconductor Device]

The method for fabricating a light-emitting semiconductor device according to the present invention is characterized in that after the primer composition is applied onto the surface of the light-emitting semiconductor device of the device packaged on the pre-molded package, after drying, a primer composition layer covering the surface of the light-emitting semiconductor device is formed. After the addition reaction-hardening type polyoxynoxy resin is applied to the primer composition layer, the element is subjected to resin sealing of the outer molding.

In the manufacturing method, the reaction rate of R ³ in the general formula (1) represented by the primer layer formed on the surface of the light-emitting semiconductor element is 50 to 90%, preferably 55 to 80%. More preferably, in the range of 60 to 75%, it is preferable to perform external molding resin sealing by addition reaction hardening type polyoxyl resin. Here, the "reaction rate of R ³ " means the unreacted R ³ remaining after the reaction of the reaction (hydrolysis and further condensation in different cases) is such that the initial molar number of R ³ present in the decane compound is A. The number of ears is B, which is indicated by (1-B/A) × 100 (%). Further, before the use of the primer composition of the present invention, the adhesion reliability and the discoloration resistance surface are preferably in the range of 0 to 49%.

Most of the preformed packages are composed of various materials such as a guide frame, a synthetic resin, a ceramic, and the like, and a highly reliable adhesive can be achieved by using the primer composition of the present invention.

Examples of the light-emitting semiconductor element include a light-emitting diode, a semiconductor laser, an organic EL (electroluminescence), and an inorganic EL.

The method of applying the primer composition to the portion to be sealed is not particularly limited, and it may be carried out by a usual method, and it is usually a method of dropping the primer of the liquid discharge device. Drying after coating can be carried out at 10~40 °C, preferably at room temperature (15~30 °C).

The time from the application of the primer composition to the drying (end) is preferably from 15 minutes to 6 hours, particularly from the limit of 20 minutes to 3 hours (safety factor), and can be sufficiently used after using the composition of the present invention. The coating and drying conditions are set at the limit of this time. More ideally, 30 minutes to 1 hour.

The addition reaction-hardening type polyoxyl resin used as the sealing resin is also not particularly limited.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. The following "parts" represent the meaning of "mass".

[Example 1] (1) Modulation of the composition of the primer

0.5 parts of tris(t-butoxy)aluminum was added to 99.25 parts of toluene under a nitrogen stream, and it was dissolved by vigorous stirring for 5 minutes. Further, 0.25 parts of 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-403) was dissolved in the obtained solution, and vigorously stirred for 5 minutes to obtain a primer composition. . This primer composition was filtered with a pore size (filter pore) of 1 μm under a nitrogen stream before use.

(2) Bottom coating treatment of LED components

The primer composition obtained in (1) is applied to the resin sealing portion of the light-emitting diode element of the package (overmold package) by an ejection device. The solvent contained in the applied primer composition was continuously dried at room temperature for 30 minutes, 1 hour, and 2 hours, and then the primer layer was formed at the sealing portion.

(3) LED seal

5 g of vinyl-terminated polydimethyl decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-35-330A) and 5 g of hydromethyl methoxy oxane placed in a platinum catalyst (Shin-Etsu Chemical industry, trade name X-35-330B) is stirred under vacuum while defoaming. Then, the resin solution was injected into an LED package mold frame by an injection device and treated at 60 ° C for 1 hour, then at 100 ° C for 2 hours, and at 150 ° C for 4 hours to obtain a sealed LED.

(4) Determination of the reactivity of the decane coupling agent of the primer composition

After the primer composition of the present invention was applied to a glass dish and dried under conditions of 30 minutes, 1 hour, and 2 hours, respectively, the obtained cured product was dissolved in heavy chloroform, and the insoluble matter was removed by filtration. After the solution was measured by NMR (nuclear magnetic resonance spectroscopy), the residual amount of methoxydecane was determined from the integral ratio, and the degree of reaction was determined. After repeating the same experiment three times, the degree of reactivity was determined to be within the range of 60 to 70%.

[Comparative Example 1] (coated by titanium primer)

The LED element was sealed by the method of (3) of Example 1 except that the titanium primer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name primer C) was used instead of the primer composition prepared in Example 1.

[assessment]

The sealed LEDs obtained in Example 1 and Comparative Example 1 were subjected to the following conditions.

. Pollution of LED package

. Time limit for coating drying

. Reflow resistance for reflow, and The discoloration resistance of the LED driving under hygroscopic conditions was evaluated according to the following criteria.

Table 1 represents the results of "time limit of coating drying operation" and "peeling resistance to reflow". Table 2 represents the results of "discoloration resistance when the LED is driven under the moisture absorption strip".

(1) Pollution rating of LED package

After the primer coating treatment, the condition of observing the surface state of the LED package by a stereo microscope is divided into four stages.

A: Coating the primer. The dried LED package surface is smooth and transparent.

B: Coating of the primer. The dried LED package surface is smooth and opaque.

C: coating of the primer. The dried LED package surface is rough and transparent.

D: coating of the primer. The dried LED package surface is rough and opaque.

(2) Peel test on LED package of sealing resin

The resin is sealed in a plurality of (n = 1 ~ 16) primer coating. After drying, the LED package was subjected to a hardening reaction, and then maintained in a constant temperature and humidity chamber at 85 ° C and a humidity of 85%, and left for 24 hours. Immediately after removal from the constant temperature and humidity chamber, the heat history (3 times loss) was performed at 260 °C by the IRreflow device. Delivery speed: 40cm/min). The state of the LED package after the treatment was observed by a stereoscopic microscope, and the peeling state of the interface between the LED package and the sealing resin was judged, and the following two stages were determined.

A: The sealing resin sealed in the LED is in close contact with the LED package interface.

B: The sealing resin sealed in the LED is peeled off from the LED package interface.

(3) Perform primer treatment. Sealed LED lighting test

The LED which is initially sealed with a colorless and transparent resin is energized at 85 ° C and a humidity of 85%. The lighting test was carried out in the following three stages to determine the LED coloring state up to 1000 hours.

A: There is almost no discoloration.

B: A little discoloration.

C: Strong discoloration.

From the above results, it was revealed that the titanium-based primer used in Comparative Example 1 was reduced in adhesion under long-term application drying conditions, and discoloration occurred in a short-time LED lighting. Further, when the primer composition of the present invention is used, the LED element can be used in a wide range of coating drying time and is excellent in workability. And there is no discoloration in the LED drive for a long time, and it is highly resistant to discoloration. When the primer composition of the present invention is used, the coating workability, the discoloration resistance, and the peeling resistance surface are excellent.

Claims (5)

A primer composition comprising (A) the following general formula (1) R ¹ _X R ² _Y Si(R ³ ) _4-XY (1) (wherein R ¹ and R ² are independently represented a hydrogen atom or an alkyl group having 1 or more carbon atoms which may have one or more reactive substituents, and R ³ represents a chlorine atom, a hydroxyl group or an unsubstituted or substituted alkoxy group or a aryl group having 1 to 30 carbon atoms. An oxy group, X is an integer of 1 to 2, Y is an integer of 0 to 1, and X + Y is an integer of 1 or 2), and at least one decane compound and/or a partial hydrolysis condensate thereof, B) a Lewis acidic organoaluminum compound and (C) an organic solvent, wherein the mass ratio of the component (A) to the component (B) is 1 or less. For example, in the primer composition of claim 1, wherein the organoaluminum compound of the component (B) is the following general formula (2) R ⁴ _x Al(OR ⁵ ) _3-X (2) (wherein, x An integer of 0 to 3, and when x is 1 to 3, R ⁴ independently represents an alkoxy group having an atomic number of 30 or less, an ethyl fluorenyl group, an ethoxy group, and R ⁵ represents a non-carbon number of 1 to 15. At least one organoaluminum compound represented by a substituted or substituted alkyl group or an aryl group. A method of manufacturing a light-emitting semiconductor device, characterized in that a primer composition as disclosed in claim 1 or 2 is applied to a surface of a light-emitting semiconductor device mounted on a preform package, and dried to form a light-emitting layer The primer layer composition layer on the surface of the semiconductor element is subjected to an addition reaction-hardening type polyoxynoxy resin on the primer composition layer, and then the element is subjected to overmolding resin sealing. The method for producing a light-emitting semiconductor device according to the third aspect of the invention, wherein the reaction rate of R ³ in the decane compound represented by the general formula (1) formed in the primer composition layer of the light-emitting semiconductor device is 50%. In the state of 90%, the overmolded resin is sealed by an addition reaction-hardening type polyoxyl resin. A light-emitting semiconductor device characterized by being manufactured by the method of claim 3 or 4.