TWI836086B - Primer composition and optical semiconductor device using same - Google Patents

Abstract

The subject of the present invention is to provide a primer composition and a semiconductor device using the primer composition. The primer composition enhances the additive reaction of a substrate mounted with an optical semiconductor element and seals the optical semiconductor element. The hardened polysiloxane composition improves the adhesion of the hardened material, prevents corrosion of the metal electrodes formed on the substrate, and improves the heat resistance and flexibility of the primer itself. The solution is a primer composition that adheres a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction-hardening polysiloxane composition that seals the optical semiconductor element, and contains: (A) Including at least one of acrylate and methacrylate having one or more SiH groups in one molecule, at least one of acrylate and methacrylate having one or more alkoxy groups in one molecule, and not having SiH group and a copolymer of at least one of alkoxy acrylate and methacrylate, (B) solvent, and (C) cerium compound.

Description

Primer composition and photo-semiconductor device using the same

The present invention relates to a primer composition for bonding a substrate on which an optical semiconductor element is mounted to a cured product of an addition reaction curing type polysilicone composition for sealing the optical semiconductor element, and an optical semiconductor device using the primer composition.

A light-emitting diode (LED) lamp known as an optical semiconductor device is composed of an LED mounted on a substrate sealed with a sealing material containing a transparent resin. As this sealing material, epoxy resin-based compositions have been widely used in the past.

However, epoxy resin-based sealing materials are prone to cracking or yellowing due to the increase in heat generation due to the miniaturization of semiconductor packages or the increase in brightness of LEDs in recent years or the shortening of the wavelength of light, resulting in poor reliability. reduce.

Therefore, from the viewpoint of having excellent heat resistance, a polysiloxane composition is used as a sealing material (Patent Document 1). In particular, the addition reaction curable polysiloxane composition can be cured in a short time by heating, so it has good productivity and is suitable as a sealing material for LEDs (Patent Document 2).

However, the adhesion between the substrate (resin or electrode) on which the LED is mounted and the sealing material including the cured product of the addition reaction curing type polysilicone composition is not sufficient.

In addition, since polysiloxane compositions generally have excellent gas permeability, they are easily affected by the external environment. When an LED lamp is exposed to sulfur compounds or exhaust gases in the atmosphere, the sulfur compounds will penetrate the hardened material of the polysiloxane composition, and the metal electrodes on the substrate sealed by the hardened material, especially the Ag electrode, will be damaged over time. Sexual corrosion and then turn black. As a countermeasure against this, it has been developed to use a polymer of acrylate containing SiH, or a copolymer with acrylate, a copolymer with methacrylate, or a copolymer with acrylate and methacrylate. Or a polysilazane compound to inhibit blackening of the primer (Patent Documents 3 to 5). However, a primer that will inhibit blackening even more is still required. Furthermore, when an acrylic polymer containing SiH is used, the heat resistance of the primer film is insufficient, which leads to resin deterioration around LED elements where high current flows in recent years. In contrast, polysilazane compounds have excellent heat resistance, but the film they form is relatively hard. Therefore, when applied to a mounting substrate on which many LED elements called polycrystal wafers are mounted, the film is easily broken.

In order to solve the above problems, the inventors have developed a primer composition that improves the adhesion between the substrate on which LED components are mounted and the cured product of the addition reaction curing type polysilicone composition that seals the LED components, prevents corrosion of the metal electrode formed on the substrate, and improves the heat resistance and flexibility of the primer itself, and an LED device using the primer composition. However, in recent years, the heat resistance of the primer film is still insufficient under the high-density mounting and high-current driven LED components, which causes resin degradation around the LED components, thus requiring a more heat-resistant primer composition. [Prior technical literature] [Patent literature]

[Patent Document 1] Japanese Patent Publication No. 2000-198930 [Patent Document 2] Japanese Patent Publication No. 2004-292714 [Patent Document 3] Japanese Patent Publication No. 2010-168496 [Patent Document 4] Japanese Patent Publication No. 2012-144652 [Patent Document 5] Japanese Patent Publication No. 2014-157849

[Problem to be solved by the invention]

The present invention is completed to solve the above-mentioned problems. Its purpose is to provide a primer composition that improves the adhesion between a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curing polysilicone composition that seals the optical semiconductor element, prevents corrosion of a metal electrode formed on the substrate, and greatly improves the heat resistance and flexibility of the primer itself, and an optical semiconductor device using the primer composition. [Means for solving the problem]

In order to achieve the above-mentioned problem, the present invention provides a primer composition, which is a primer composition for bonding a substrate mounted with an optical semiconductor element and a cured product of an addition reaction curing type polysilicone composition for sealing the aforementioned optical semiconductor element, and is characterized by containing: (A) a copolymer, which includes: at least one of an acrylate and a methacrylate having one or more SiH groups in one molecule, at least one of an acrylate and a methacrylate having one or more alkoxy groups in one molecule, and at least one of an acrylate and a methacrylate having no SiH groups and no alkoxy groups; (B) a solvent; and (C) a bismuth compound.

Such a primer composition improves the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curing polysilicone composition that seals the optical semiconductor element, prevents corrosion of the metal electrode formed on the substrate, and improves the heat resistance and flexibility of the primer itself.

The aforementioned primer composition preferably contains (D) a zinc compound.

When the primer composition further contains (D) a zinc compound, it can further prevent corrosion of the metal electrode formed on the substrate.

In addition, the blending amount of the component (B) is preferably 70% by mass or more of the entire primer composition.

By containing 70% by mass or more of component (B), a primer composition with better workability is obtained.

The component (C) is a trivalent or tetravalent bismuth complex, and preferably contains 1 to 10,000 ppm of the component (C) in terms of bismuth metal relative to the total mass of the solid component of the component (A).

By using the aforementioned barium complex as the aforementioned component (C) and setting the blending amount of the aforementioned component (C) to the aforementioned range, the heat resistance of the primer itself can be further improved.

Where the component (D) is a zinc complex, it is preferred that the component (D) contains 1 to 10,000 ppm of zinc metal relative to the total mass of the solid content of the component (A).

Since the component (D) is a zinc complex and the blending amount of the component (D) is within the range described above, the sulfurization resistance of the primer film can be further improved.

The primer composition preferably further contains (E) a silane coupling agent.

By containing the silane coupling agent, the primer composition can further improve the adhesion between the substrate and the cured product of the addition reaction curing type polysilicone composition.

The present invention also provides an optical semiconductor device, wherein a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curing type polysilicone composition for sealing the optical semiconductor element are bonded together by the primer composition.

If such an optical semiconductor device uses the primer composition of the present invention, since the substrate and the cured product of the addition reaction curing polysilicone composition are strongly bonded, corrosion of the metal electrode formed on the substrate can be prevented, so it has high reliability.

In addition, the aforementioned optical semiconductor element may be a light-emitting diode.

Therefore, the optical semiconductor device of the present invention can be suitably used as a light-emitting diode.

In addition, the aforementioned substrate may be made of polyamide, fiber-reinforced plastic, ceramic, polysilicone, polysilicone modified polymer, or liquid crystal polymer.

Since the optical semiconductor device of the present invention has excellent primer adhesion, it can be used even with such a substrate without impairing the adhesion.

Furthermore, the cured product of the aforementioned addition reaction curing type polysilicone composition is preferably in a rubbery state.

The hardened product of such an addition reaction hardening polysiloxane composition has stronger adhesion and can more effectively prevent corrosion of metal electrodes, especially Ag electrodes, formed on the substrate. [Effects of the invention]

As described above, the primer composition of the present invention can improve the adhesion between the substrate on which the optical semiconductor element is mounted and the hardened material of the addition reaction curable polysiloxane composition for sealing the optical semiconductor element. It is a primer composition that simultaneously prevents corrosion of the metal electrodes formed on the substrate and improves the heat resistance and flexibility of the primer itself. Optical semiconductor devices using this primer composition become highly reliable.

As mentioned above, there has been a demand for the development of a substrate that can improve the adhesion of a hardened product of an addition reaction curable polysiloxane composition that seals the optical semiconductor element on a substrate on which the optical semiconductor element is mounted, and at the same time prevent the metal electrodes formed on the substrate from coming into contact with each other. Development of a primer composition that prevents corrosion and improves the heat resistance and flexibility of the primer itself.

As a result of repeated and careful examination of the above-mentioned subject, the inventors found that if it is a primer composition containing a copolymer and a cerium compound, wherein the copolymer contains an acrylate and methacrylic acid having more than one SiH group in one molecule At least one of esters, at least one of acrylate and methacrylate having one or more alkoxy groups in one molecule, and at least one of acrylate and methacrylate that does not have SiH group and alkoxy group , it is possible to firmly adhere the substrate on which the optical semiconductor element is mounted to the cured product of the addition reaction curable polysiloxane composition that seals the optical semiconductor element, and to prevent metal electrodes, especially Ag electrodes, from being formed on the substrate. The corrosive primer composition is used to complete the present invention.

That is, the present invention is a primer composition for bonding a substrate on which an optical semiconductor element is mounted to a cured product of an addition reaction curing type polysilicone composition for sealing the optical semiconductor element, and contains (A) a copolymer comprising at least one of an acrylate and a methacrylate having one or more SiH groups in one molecule, at least one of an acrylate and a methacrylate having one or more alkoxy groups in one molecule, and at least one of an acrylate and a methacrylate having no SiH groups and no alkoxy groups; (B) a solvent; and (C) a bismuth compound.

The present invention is described in detail below, but the present invention is not limited thereto.

<Primer composition> The primer composition of the present invention contains the following components (A), (B) and (C) as essential components.

The following describes the components of the primer composition of the present invention.

[(A) ingredient] The component (A) contained in the primer composition of the present invention is a copolymer, which includes: at least one of acrylate and methacrylate having one or more SiH groups in one molecule, and one or more alkoxylates having one or more alkoxy groups in one molecule. At least one of acrylate and methacrylate that has a group, and at least one of acrylate and methacrylate that does not have a SiH group and an alkoxy group.

The component (A) of the copolymer can be obtained by polymerizing the corresponding monomer (ester described below) using a free radical polymerization initiator such as 2,2'-azobisisobutyronitrile (AIBN).

The primer composition containing component (A) imparts sufficient adhesion to the substrate and electrode on which the optical semiconductor element is mounted, forms a flexible film on the substrate, and inhibits the formation of metal electrodes (especially Ag electrodes). ) is corroded over time.

The amount of component (A) to be blended is not particularly limited as long as it is soluble in the amount of component (B) described below, but is preferably 30% by mass or less of the total composition (the total of components (A) to (C) etc.), more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass. If the content is 30% by mass or less, the surface of the obtained film can be prevented from being uneven, and sufficient performance as a primer can be obtained.

Acrylates and methacrylates having one or more SiH groups per molecule Examples of acrylates and methacrylates having one or more SiH groups per molecule include compounds having a structure represented by the following formula (1) . (In the formula, R is a hydrogen atom or a methyl group, R ¹ is a monovalent organic group, and R ² is a divalent organic group. n is 0, 1 or 2.)

In addition, compounds having a structure represented by the following formula (2) or the following formula (3) among diorganopolysiloxanes can also be exemplified. (In the formula, R, R ¹ , and R ² have the same meanings as above. l is 0 or a positive integer, and m is a positive integer. The order of arrangement of the siloxane units in parentheses is arbitrary.)

(In the formula, R, R ¹ , and R ² have the same meanings as above. o and p are positive integers. The order of arrangement of the siloxane units in parentheses is arbitrary.)

Here, the monovalent organic group represented by R ¹ is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly an unsubstituted or substituted monovalent hydrocarbon group having 1 to 3 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, etc. Cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, aryl groups such as phenyl, tolyl, stubble, naphthyl, etc., benzyl, phenylethyl, and phenylpropyl Aralkyl groups, etc., or those in which part or all of the hydrogen atoms of these groups are replaced by halogen atoms such as fluorine, bromine, chlorine, cyano groups, etc., such as chloromethyl, chloropropyl, bromoethyl, tribromoethyl, etc. Fluoropropyl, cyanoethyl, etc. ^R1 is preferably methyl, ethyl or phenyl, with methyl being particularly preferred.

As the divalent organic group represented by R ² , a non-substituted or substituted divalent alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms, is preferred. As the divalent alkyl group, there can be mentioned alkylene groups such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-propylene, cyclohexylene, n-octylene, and arylene groups such as phenylene and naphthylene. R ² is preferably ethylene or n-propylene, and particularly preferably n-propylene.

One type of acrylate and methacrylate having one or more SiH groups per molecule may be used alone, or two or more types may be used in combination.

Acrylates and Methacrylates Having One or More Alkoxy Groups in One Molecule Examples of acrylates and methacrylates having one or more alkoxy groups in one molecule include compounds having a structure represented by the following formula (4). (In the formula, R, R ¹ and R ² have the same meanings as above. R ³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. q is 0, 1 or 2.)

Furthermore, compounds having a structure represented by the following formula (5) or the following formula (6) among diorganopolysiloxanes can also be exemplified. (In the formula, R, R ¹ , R ² , and R ³ have the same meanings as above. r is 0 or a positive integer, and s is a positive integer. The order of the siloxane units enclosed by brackets is arbitrary.)

(In the formula, R, R ¹ , R ² and R ³ have the same meanings as above. t and u are positive integers. The order of the siloxane units in brackets is arbitrary.)

Here, the organic groups represented by ^R1 and ^R2 include the same as those mentioned above. The monovalent hydrocarbon group having 1 to 4 carbon atoms represented by ^R3 includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc., and methyl or ethyl is preferred.

The acrylate and methacrylate having one or more alkoxy groups in 1 molecule may be used individually by 1 type, or may use 2 or more types together.

Acrylates and methacrylates without SiH groups and alkoxy groups Examples of acrylates that do not have a SiH group and an alkoxy group include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isopentyl acrylate, and n-hexyl acrylate. Ester, isooctyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, etc.

Examples of the methacrylate having no SiH group and no alkoxy group include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isononyl methacrylate, n-decyl methacrylate, and isodecyl methacrylate.

Among the above examples, an alkyl acrylate or an alkyl methacrylate having an alkyl group having 1 to 12 carbon atoms, especially an alkyl acrylate or alkyl methacrylate having an alkyl group having a carbon number of 1 to 4 is preferred. One or more of these may be used alone. You can also use 2 or more types together.

[(B)Component] The component (B) of the solvent is not particularly limited as long as it can dissolve the above-mentioned component (A) constituting the primer composition of the present invention and any components described below, and known organic solvents can be used.

Examples of the solvent include, for example, aromatic hydrocarbon solvents such as xylene, toluene, and benzene; aliphatic hydrocarbon solvents such as heptane and hexane; and halogenated hydrocarbons such as trichlorethylene, perchlorethylene, and methylene chloride. Solvents, ester solvents such as ethyl acetate, 1-propylene glycol methyl ether acetate, etc., ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, etc., ethanol, isopropyl alcohol, butanol, etc. Alcohol-based solvents, light petroleum (Ligroin), cyclohexanone, diethyl ether, rubber volatile oil, polysiloxane-based solvents, etc. Among them, ethyl acetate, 1-propylene glycol methyl ether acetate, hexane, and acetone are more suitable.

The component (B) may be used alone or in combination of two or more to form a mixed solvent, depending on the evaporation rate of the primer composition during coating.

The blending amount of component (B) is not particularly limited, but it is preferably 70% by mass or more of the total primer composition (total of components (A) to (C), etc.), more preferably 80 to 99.99% by mass, and more Preferably, it is 90~99.9% by mass. If the blending amount of component (B) is 70% by mass or more, the primer composition will have better workability during coating and drying. For example, when forming a primer film on a substrate described later, the film can be It is uniform and does not cause film breakage due to unevenness on the surface, thereby conferring sufficient performance as a primer.

[(C)Component] Component (C) is a cerium compound, which has the effect of improving heat resistance, light resistance, crack resistance, etc. without greatly impairing the transparency of the primer composition of the present invention. Examples of the cerium compound include cerium complexes, composite metal complexes containing cerium, cerium oxide, and inorganic or organic acid salts of cerium, in which trivalent or tetravalent cerium is used as the central metal and an alcohol or The diketone is preferably a cerium complex as a ligand or a composite metal complex containing cerium.

(C) Component is not particularly limited as long as it is soluble in the mixture of the above-mentioned (A) component and (B) component. Examples include 2-methoxyethoxycerium(IV), ginseng(isopropyl) Cerium cyclopentadienyl), cerium (cyclopentadienyl) cerium, cerium (1,2,3,4-tetramethyl-2,4-cyclopentadienyl)cerium (III), cerium oxalate (III), cerium (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione)cerium (III), four (2, 2,6,6,-tetramethyl3-5-heptanedione)cerium(IV), 2,4-pentanedionecerium(III), trifluoroacetylpyruvate cerium(III), Ginseng (acetyl pyruvic acid) cerium (III), etc. Among them, trivalent cerium complexes are preferred because of their high heat resistance imparting effect. Specific examples include ginseng(cyclopentadienyl)cerium and ginseng(acetylpyruvate)cerium(III).

The blending amount of the cerium compound is preferably 1 ppm or more in terms of cerium metal relative to the total mass of the solid content of component (A), and more preferably 10 ppm or more. The upper limit of the aforementioned blending amount is preferably 10,000 ppm or less, more preferably 1,000 ppm or less. When the aforementioned blending amount of the cerium compound is 1 ppm or more, sufficient heat resistance and light resistance of the primer composition can be obtained. In addition, if the aforementioned blending amount of the cerium compound is 10,000 ppm or less, the transparency of the cured primer will not be impaired. The component (C) may be added after being dissolved in the solvent exemplified as the component (B) in advance. (C) Component system may be used individually by 1 type, and may be used in combination of 2 or more types.

[Component (D)] Component (D) is a zinc compound, which has the effect of improving heat resistance, light resistance, crack resistance, and sulfidation resistance without significantly impairing the transparency of the primer composition of the present invention. As the zinc compound, zinc oxide powder or an inorganic acid salt of zinc may be used. From the viewpoint of achieving good surface smoothness when applying the primer composition, a zinc complex having a zinc atom as a central metal and an alcohol or a diketone as a ligand, or a composite metal complex containing zinc is preferred.

The component (D) is not particularly limited as long as it is soluble in the mixture of the components (A) to (C) above, and examples thereof include diethyl zinc, diphenyl zinc, tert-butoxy zinc, i-propoxy zinc, 2-methoxyethoxy zinc, zinc dibenzoate, zinc oxalate, zinc 2-ethylhexanoate, bis(2,4-pentanedione)zinc(II), zinc hexafluoroacetylacetonate, bis(2,2,6,6,-tetramethyl-3,5-heptanedione)zinc(II), and the like. Among them, divalent zinc complexes are preferred due to their high heat resistance-imparting effect, and specific examples thereof include bis(2,4-pentanedione)zinc(II), hexafluoroacetylacetonate zinc, and bis(2,2,6,6,-tetramethyl-3,5-heptanedione)zinc(II).

The blending amount of component (D) is preferably 1 ppm or more in terms of zinc metal relative to the total mass parts of the solid content of component (A), and more preferably 10 ppm or more. The upper limit is preferably 10,000 ppm or less, more preferably 1,000 ppm or less. By ensuring a concentration of 1 ppm or above, sufficient heat resistance and light resistance can be obtained. In addition, if it is below 10,000 ppm, the transparency of the hardened primer will not be impaired. (D) The component may be added after being dissolved in a solvent in advance. Examples include a method of uniformly mixing with a mixer at normal temperature or under heating. The solvent in which component (D) is dissolved in advance may be the same as or different from component (B).

[(E)INGREDIENT] In the primer composition of the present invention, a silane coupling agent may be further blended as the (E) component.

As the silane coupling agent, general silane coupling agents may be used, for example, vinyl-containing silane coupling agents such as vinyl trimethoxy silane and vinyl triethoxy silane, epoxy-containing silane coupling agents such as glycidoxypropyl trimethoxy silane, (meth)acryloxy-containing silane coupling agents such as methacryloxypropyl trimethoxy silane and acryloxypropyl trimethoxy silane, butylyl-containing silane coupling agents such as butylpropyl trimethoxy silane, etc. Among them, vinyl trimethoxy silane and methacryloxypropyl trimethoxy silane are preferred.

When the component (E) is used, the blending amount is preferably 0.05 to 10% by mass of the total primer composition (the total of the components (A) to (E) etc.), and more preferably 0.1 to 3% by mass. If the blending amount of the component (E) is 0.05% by mass or more, the adhesion-improving effect becomes sufficient. However, even if the blending amount exceeds 10% by mass, no further adhesion-improving effect can be obtained, so it is preferably 10% by mass or less.

[Other ingredients] In addition to the above-mentioned components, the primer composition of the present invention may also be blended with other optional components as necessary. For example, as metal corrosion inhibitors, benzotriazole, butylated hydroxytoluene, hydroquinone or derivatives thereof may be blended.

Benzotriazole, dibutylhydroxytoluene, hydroquinone or their derivatives are used when LED lamps are exposed to harsh external environments, such as sulfur compounds in the atmosphere that have penetrated the sealing materials of optical semiconductor devices (addition reaction hardening In the case of a hardened product of a polysiloxane composition), the corrosion of the metal electrode, especially the Ag electrode, on the substrate sealed by the sealing material will be more effectively suppressed.

When the metal corrosion inhibitor is added, the blending amount is preferably 0.005 to 1 part by weight, and more preferably 0.01 to 0.5 parts by weight, relative to 100 parts by weight of the total of components (A) to (C) or components (A) to (D).

Furthermore, as other optional components, phosphors, reinforcing fillers, dyes, pigments, heat-resistant improving agents, antioxidants, adhesion accelerators, etc. can also be added.

[Production method of primer composition] An example of a method for producing the primer composition of the present invention is to uniformly mix the above-mentioned (A), (B), (C) components and any of the above-mentioned components as necessary using a mixer at normal temperature or under heating. methods etc.

<Optical semiconductor device> The present invention also provides an optical semiconductor device, which is a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curing type polysilicone composition that seals the optical semiconductor element are bonded together by the aforementioned primer composition. The following is an explanation of one aspect of the optical semiconductor device of the present invention with reference to the drawings.

FIG1 is a cross-sectional view of an optical semiconductor device (LED lamp) showing an example of the optical semiconductor device of the present invention. The optical semiconductor device (LED lamp) 1 is a substrate 4 on which an LED 3 as an optical semiconductor element is mounted and a cured material 5 of an addition reaction curing type polysilicone composition that seals the LED 3 are bonded together by the above-mentioned primer composition 2. A metal electrode 6 such as an Ag electrode is formed on the substrate 4, and an electrode terminal (not shown) of the LED 3 and the metal electrode 6 are electrically connected by a bonding wire 7.

Examples of materials constituting the substrate 4 include polyamide, various fiber-reinforced plastics, ceramics, polysiloxane, polysiloxane modified polymers, liquid crystal polymers, and the like.

The cured product 5 of the addition reaction curing type silicone composition is obtained by curing the addition reaction curing type silicone composition, and is preferably a transparent cured product, and more preferably a rubber. As the above-mentioned addition reaction curing type silicone composition, a conventionally known one at least comprising: a vinyl-containing organic polysiloxane, an organic hydrogen polysiloxane as a crosslinking agent, and a platinum-based catalyst as an addition reaction catalyst can be used. Furthermore, the above-mentioned addition reaction curing type silicone composition can also be added with a reaction inhibitor, a coloring agent, a flame retardant imparting agent, a heat resistance improving agent, a plasticizer, a reinforcing silica, an adhesion imparting agent, etc. as other arbitrary components.

As a method for manufacturing the optical semiconductor device (LED lamp) 1 shown in FIG. 1 , the following method can be exemplified. On a substrate 4 on which a metal electrode 6 such as an Ag electrode is formed by Ag electroplating in advance, an optical semiconductor element such as an LED 3 is bonded by a bonding agent, and the electrode terminal (not shown) of the LED 3 is electrically connected to the metal electrode 6 in advance by a bonding wire 7. Thereafter, after cleaning the substrate 4 on which the LED 3 is mounted as necessary, a primer composition 2 is applied to the substrate 4 using a coating device such as a spin coater or a sprayer, and the solvent in the primer composition 2 is volatilized by heating, air drying, etc., thereby forming a film preferably less than 10 μm, more preferably 0.1 to 5 μm thick. After forming the primer film, an addition reaction curing type silicone composition is applied using a dispenser or the like, and is left at room temperature or heated to cure, thereby sealing the LED 3 with a rubber-like cured product 5 .

In this way, by using the primer composition of the present invention containing the aforementioned components (A) to (C) or (A) to (D), it is possible to firmly adhere to the substrate on which optical semiconductor elements such as LEDs are mounted. It is a hardened product of an addition reaction-hardening polysiloxane composition and can provide highly reliable optical semiconductor devices, especially LED lamps.

Furthermore, even when the LED lamp is exposed to an excessively harsh external environment and the sulfur compounds in the atmosphere have penetrated into the cured polysilicon composition, the use of the primer composition of the present invention can suppress the corrosion of the metal electrode on the substrate, especially the Ag electrode.

In addition, the optical semiconductor device of the present invention can be suitably used as an LED. In the above aspect, LED has been used as an example of the optical semiconductor element in the description. In addition, it can also be applied to, for example, photoelectric crystals and photodiodes. , CCD, solar cell modules, EPROM, optocoupler, etc. [Example]

Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1] 40 parts by mass of methyl methacrylate, 10 parts by mass of SiH-containing methacrylate represented by the following formula (7), 6 parts by mass of methoxy-containing methacrylate represented by the following formula (8), 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were stirred under heating at 90° C. for 6 hours to prepare a solution containing a copolymer.

[Synthesis example 2] 40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylate represented by the above formula (7), and methoxy group-containing methacrylic acid represented by the above formula (8) were heated and stirred at 90°C. 4 parts by mass of ester, 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were added for 6 hours to prepare a solution containing the copolymer.

[Synthesis example 3] 40 parts by mass of methyl methacrylate, 19 parts by mass of SiH-containing methacrylate represented by the above formula (7), and methoxy group-containing methacrylic acid represented by the above formula (8) were heated and stirred at 90°C. 1 part by mass of ester, 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were added for 6 hours to prepare a solution containing the copolymer.

[Synthesis Example 4] 40 parts by mass of methyl methacrylate, 14 parts by mass of the SiH-containing methacrylate represented by the above formula (7), 5 parts by mass of the methacrylate containing a methoxy group represented by the following formula (9), 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were stirred with heating at 90°C for 6 hours to prepare a solution containing a copolymer.

[Synthesis Example 5] 40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing acrylate represented by the following formula (10), and methoxy group-containing ester represented by the above formula (8) were heated and stirred at 90°C. 4 parts by mass of methacrylate, 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were added for 6 hours to prepare a solution containing the copolymer.

[Synthesis Example 6] 40 parts by mass of methyl methacrylate, 14 parts by mass of the SiH-containing methacrylate represented by the above formula (7), 4 parts by mass of the methoxy-containing acrylate represented by the following formula (11), 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were stirred with heating at 90°C for 6 hours to prepare a solution containing a copolymer.

[Comparative synthesis example 1] 40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing acrylate represented by the above formula (7), 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were heated and stirred at 90°C. 6 hours to prepare a solution containing the copolymer.

[Examples 1 to 6] In the copolymers synthesized in the above-mentioned Synthesis Examples 1 to 6, 50 ppm of bis(acetylpyruvate) bis(III) as the bis(iodide) compound (C) was added in terms of bis(iodide) relative to the total mass of the solid components of the component (A), and the 1-propylene glycol methyl ether acetate of the component (B) was used for dilution in such a manner that the non-volatile content of the entire primer composition was 8%, thereby obtaining a primer composition. Using the obtained primer composition, various physical properties (appearance, penetration, adhesion (adhesion strength) and corrosion resistance) were measured by the evaluation method shown below, and the results are shown in Table 1. The physical properties shown in Table 1 are values measured at 23°C.

[Examples 7 to 13] In the copolymers synthesized in the above-mentioned Synthesis Examples 1 to 6, tetrakis(2,2,6,6-tetramethyl-3-5-heptanedione)indium(IV) was added as the indium compound (C) in an amount of 50 ppm in terms of indium relative to the total mass of the solid components of the component (A). In Examples 7 to 12, bis(2,2,6,6-tetramethyl-3,5-heptanedione)zinc(II) was blended as the zinc compound (D) in an amount of 50 ppm in terms of zinc relative to the total mass of the solid components of the component (A). However, in Example 13, the zinc compound (D) was not blended, and 1-propylene glycol methyl ether acetate as the component (B) was used to dilute the primer composition so that the nonvolatile content of the entire primer composition was 8%, thereby obtaining a primer composition. Using the primer composition obtained, various physical properties (appearance, transmittance, adhesion (adhesion strength) and corrosion resistance) were measured by the evaluation methods shown below, and the results are shown in Table 3. The physical properties shown in Table 3 are values measured at 23°C.

[Appearance] The primer composition was applied to a glass slide with a brush to a thickness of 2 μm, dried at 60°C for 30 minutes, and then dried at 180°C for 30 minutes. An addition reaction curing type silicone rubber composition (KER-2600 manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a thickness of 2 mm on the primer composition, cured at 150°C for 1 hour, and its appearance was observed.

[Transmittance test] The primer composition was applied to a glass slide with a brush to a thickness of 2μm, and dried at 60°C for 30 minutes to form a primer composition film. The transmittance (initial transmittance) of the glass slide with the primer composition film at a wavelength of 400nm was measured and the glass slide was measured as a blank control, and this was set to 100%. Next, the glass slide with the primer composition film was heat-treated at 180°C for 500 hours, and the transmittance after the heat treatment was measured in the same way as above, and the change relative to the initial transmittance was calculated.

[Adhesion (adhesion strength) test] A test piece 11 for adhesion test was prepared as shown in Fig. 2. That is, the primer composition was applied to each side of two Al substrates 12 and 13 (manufactured by KDS, 25 mm wide) to a thickness of 0.01 mm, left at 60°C for 30 minutes, and dried at 180°C to form primer composition films 14 and 15. The surfaces of the Al substrates having the primer composition films 14 and 15 formed thereon were made to face each other, and the ends thereof were made to overlap by 10 mm, and an addition reaction curing type silicone rubber composition (KER-2600 manufactured by Shin-Etsu Chemical Co., Ltd.) was sandwiched therebetween with a thickness of 2 mm. The addition reaction curing type silicone rubber composition was cured by heating at 150°C for 30 minutes, thereby producing a test piece including two Al substrates bonded together (bonding area 25 mm×10 mm=250 mm ² ) by a cured product 16 of the silicone rubber composition. The Al substrates 12 and 13 of the test piece were oriented with their respective ends facing opposite directions (directions of arrows in FIG. 2 ), and the test piece was stretched at a speed of 50 mm/min using a tensile testing machine (Autograph, manufactured by Shimadzu Corporation) to determine the bonding strength per unit area (MPa).

[Corrosion resistance test] The obtained primer composition is filled into an LED package with a silver electrode at the bottom, placed at 60°C for 30 minutes and dried at 180°C, and then the addition reaction hardening polysiloxane rubber composition is placed on it (KER-2600, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was applied to a thickness of 1 mm and hardened at 150° C. for 2 hours to prepare a test piece having a silicone rubber layer. The test piece was put into a 100cc glass bottle together with 0.1g of sulfur crystal and sealed. Examples 1 to 6 and Comparative Examples 1 to 3 described later were placed at 70°C. Examples 7 to 13 and Comparative Examples described later 4~7 are placed at 90°C, and the corrosion degree of the silver plating after 1 day and 7 days is visually observed, and evaluated based on the following standards. ○: No corrosion (discoloration) △: How much corrosion (discoloration) is there? ×: darken

[Comparative example 1] The above-mentioned adhesiveness (adhesion strength) test and corrosion resistance test were conducted in the same manner as in Example 1 except that the cerium compound (C) was not blended.

[Comparative example 2] The copolymer synthesized in Comparative Synthesis Example 1 was diluted with 1-propylene glycol methyl ether acetate so that the non-volatile content was 8% to obtain a primer composition. The conditions were the same as Example 1. Conduct the above-mentioned adhesiveness (adhesion strength) test and corrosion resistance test accordingly.

[Comparative Example 3] Except that no primer composition was used, the above-mentioned adhesion (adhesion strength) test and corrosion resistance test were carried out in the same manner as in Example 1.

[Comparative example 4] The above-mentioned adhesiveness (adhesion strength) test and corrosion resistance test were conducted in the same manner as in Example 7 except that the cerium compound (C) and the zinc compound (D) were not blended.

[Comparative Example 5] Except that the copolymer synthesized in the comparative synthesis example 1 was diluted with 1-propylene glycol methyl ether acetate so that the non-volatile content was 8% to obtain a primer composition, the above-mentioned adhesion (adhesion strength) test and corrosion resistance test were carried out in the same manner as in Example 7.

[Comparative example 6] The above-mentioned adhesiveness (adhesion strength) test and corrosion resistance test were conducted in the same manner as in Example 7 except that the cerium compound (C) was not blended.

[Comparative Example 7] Except that no primer composition was used, the above-mentioned adhesion (adhesion strength) test and corrosion resistance test were carried out in the same manner as in Example 7.

From the results shown in Tables 1 and 3, it can be clearly understood that Examples 1 to 13 using the primer composition of the present invention are hardened products that strongly bond Al and the addition reaction curing type silicone rubber composition. In addition, in the heat resistance test of the primer composition film applied on the slide glass, there was no discoloration, and there was no change in the film itself, and the heat resistance was also excellent. In the corrosion resistance test of the LED package using the silver electrode, any one of Examples 1 to 12 still maintained a high transmittance after 7 days and showed a high corrosion inhibition effect, and Example 13 showed some corrosion. In particular, Examples 7 to 12, which also include component (D) in addition to components (A) to (C), showed a higher corrosion inhibition effect.

On the other hand, from the results shown in Tables 1 and 2, it can be clearly understood that compared with Example 1, Comparative Example 1 in which the (C) component of the present invention is not added has better wear performance after 180°C × 500 hours. The transmittance is poor. Compared with Examples 1 to 6, Comparative Example 2 using a primer composition different from the primer composition of the present invention has poorer corrosion resistance. Furthermore, compared with Examples 1 to 6, Comparative Example 3, which did not use the primer composition itself, had significantly poorer adhesion and corrosion resistance. In addition, from the results shown in Tables 3 and 4, it can be clearly understood that compared with Example 7, Comparative Example 4 in which the (C) component and (D) component of the present invention are not added has a higher temperature at 180° C. × 500 hours. The penetration rate is poor afterwards. Compared with Examples 7 to 13, Comparative Example 5 using a primer composition different from the primer composition of the present invention has poor adhesion and corrosion resistance. Compared with Example 7, Comparative Example 6, which did not add component (C), had poor penetration after 180°C × 500 hours. Compared with Examples 7 to 13, Comparative Example 7, which did not use the primer composition itself, had significantly poorer adhesion and corrosion resistance.

Furthermore, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure as the technical concept described in the scope of the patent application of the present invention and achieving the same effect are included in the technical scope of the present invention.

1: Optical semiconductor device (LED lamp) 2: Primer composition 3: LED 4: Substrate 5: Cured product of addition reaction curing type silicone composition 6: Metal electrode 7: Bonding wire 11: Test piece 12,13: Al substrate 14,15: Primer composition film 16: Cured product of addition reaction curing type silicone rubber composition

[Figure 1] A cross-sectional view of an LED showing an example of a photoconductor device of the present invention. [Figure 2] An oblique view of a test piece for adhesion testing in an embodiment and a comparative example.

1: Optical semiconductor device (LED lamp)

2: Primer composition

3:LED

4:Substrate

5: Hardened product of addition reaction hardening polysiloxane composition

6: Metal electrode

7:Joining line

Claims (10)

A primer composition, which is a primer composition that adheres a substrate on which an optical semiconductor element is mounted to a hardened product of an addition reaction curable polysiloxane composition that seals the optical semiconductor element, and is characterized by containing: (A) A copolymer containing at least one of acrylate and methacrylate having one or more SiH groups in one molecule, and at least one of acrylate and methacrylate having one or more alkoxy groups in one molecule , and, at least one of alkyl acrylate and alkyl methacrylate without SiH group and alkoxy group; (B) solvent; and (C) cerium compound; wherein, the aforementioned molecule has more than one SiH At least one of the acrylate and methacrylate of the base is a compound having a structure represented by the following formula (1), or has the following formula (2) or the following formula (3) in diorganopolysiloxane ); at least one of the acrylate and methacrylate having one or more alkoxy groups in one molecule is a compound having a structure represented by the following formula (4), or, in diorganopolysilica Oxane compounds having a structure represented by the following formula (5) or the following formula (6);

(In the formula, R is a hydrogen atom or a methyl group, R ¹ is a 1-valent organic group, R ² is a 2-valent organic group, and n is 0, 1 or 2)

(In the formula, R, R ¹ and R ² have the same meaning as above, l is 0 or a positive integer, m is a positive integer, and the order of the siloxane units in parentheses is arbitrary)

(In the formula, R, R ¹ and R ² have the same meaning as above, o and p are positive integers, and the order of the siloxane units in brackets is arbitrary)

(In the formula, R, R ¹ and R ² have the same meaning as above, R ³ represents a monovalent hydrocarbon group with 1 to 4 carbon atoms, and q is 0, 1 or 2)

(In the formula, R, R ¹ , R ² , and R ³ have the same meanings as above, r is 0 or a positive integer, s is a positive integer, and the order of the siloxane units in parentheses is arbitrary)

(In the formula, R, R ¹ , R ² and R ³ have the same meanings as above, t and u are positive integers, and the order of the siloxane units in brackets is arbitrary). The primer composition of claim 1, wherein the primer composition further contains (D) a zinc compound. For example, in the primer composition of claim 1 or claim 2, the blending amount of the aforementioned component (B) is greater than 70% by mass of the entire primer composition. For example, in the primer composition of claim 1 or claim 2, the aforementioned component (C) is a trivalent or tetravalent bismuth complex, and the aforementioned component (C) contains 1 to 10,000 ppm of bismuth metal relative to the total mass of the solid components of the aforementioned component (A). The primer composition of claim 2, wherein the aforementioned component (D) is a zinc complex, and the aforementioned component (D) contains 1 to 10,000 ppm of zinc metal relative to the total mass of the solid components of the aforementioned component (A). The primer composition of claim 1 or claim 2, wherein the primer composition further contains (E) silane coupling agent. An optical semiconductor device characterized in that a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curing type polysilicone composition that seals the optical semiconductor element are bonded together by a primer composition as described in any one of claims 1 to 6. As in claim 7, the optical semiconductor device, wherein the optical semiconductor element is a light-emitting diode. The optical semiconductor device of claim 7 or claim 8, wherein the constituent material of the substrate is polyamide, fiber-reinforced plastic, ceramic, polysiloxane, polysiloxane modified polymer, or liquid crystal polymer. The optical semiconductor device according to claim 7 or 8, wherein the cured product of the addition reaction curable polysiloxane composition is rubbery.

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