KR20200138039A - Primer composition and optical semiconductor device using the same - Google Patents

Abstract

The present invention provides a primer composition which improves adhesion between a substrate on which an optical semiconductor device is mounted and a cured product of an addition reaction curable silicone composition for sealing the optical semiconductor device, prevents corrosion of a metal electrode formed on a substrate, and improves heat resistance and flexibility of a primer itself, and an optical semiconductor device using the primer composition. The primer composition for bonding a substrate on which an optical semiconductor device is mounted and a cured product of an addition reaction curable silicone composition for sealing the optical semiconductor device comprises: (A) a copolymer including at least one of acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule, at least one of acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule, and at least one of acrylic acid ester and methacrylic acid ester which does not have a SiH group and an alkoxy group; (B) a solvent; and (C) a cerium compound.

Description

A primer composition and an optical semiconductor device using the same TECHNICAL FIELD [0002] The PRIMER COMPOSITION AND OPTICAL 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, a cured product of an addition reaction curable silicone 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 has a configuration in which an LED mounted on a substrate is sealed with a sealing material containing a transparent resin. As this sealing material, conventionally, a composition based on an epoxy resin has been used.

However, in the epoxy resin-based sealing material, cracking and yellowing are apt to occur due to an increase in calorific value or a shorter wavelength of light accompanying the miniaturization of semiconductor packages in recent years and the increase in brightness of LEDs, leading to a decrease in reliability.

Therefore, from the viewpoint of having excellent heat resistance, a silicone composition is used as a sealing material (Patent Document 1). In particular, since the addition reaction curing type silicone composition is cured in a short time by heating, 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 curable silicone composition cannot be said to be sufficient.

Moreover, since the silicone composition is generally excellent in gas permeability, it is easy to be influenced by the external environment. When the LED lamp is exposed to a sulfur compound or exhaust gas in the atmosphere, the sulfur compound or the like penetrates the cured product of the silicone composition, and the metal electrode on the substrate sealed with the cured product, especially the Ag electrode, is corroded with time and turns black. As a countermeasure against this, use a polymer of an acrylic ester containing SiH, a copolymer with an acrylic ester, a copolymer with a methacrylic ester, a copolymer with an acrylic ester and a methacrylic ester, or a polysilazane compound. By doing so, primers (Patent Documents 3 to 5) that suppress black stools have been developed. However, in addition, a primer that further suppresses black stools is required. Further, when an acrylic polymer containing SiH is used, the heat resistance of the primer film is insufficient, and the resin deteriorates around the LED element through which high current flows in recent years. On the other hand, although the polysilazane compound is excellent in heat resistance, since the film to be formed is hard, the film is easily cracked when applied on a mounting substrate on which a large number of LED elements called multichips are mounted.

In order to solve the above, the present inventors improved the adhesion between the substrate on which the LED element is mounted and the cured product of the addition reaction curable silicone composition sealing the LED element, and corrosion of the metal electrode formed on the substrate. A primer composition that prevents and improves the heat resistance and flexibility of the primer itself and an LED device using the primer composition have been developed, but in recent years, high-density mounting and driving of LED elements driven at high currents, the heat resistance of the primer film is still insufficient. And, the resin deteriorates around the LED element, and a heat-resistant primer composition is still required.

Japanese Patent Publication No. 2000-198930 Japanese Patent Publication No. 2004-292714 Japanese Patent Publication No. 2010-168496 Japanese Patent Application Publication No. 2012-144652 Japanese Patent Publication No. 2014-157849

The present invention has been made to solve the above problem, and improves adhesion between the substrate on which the optical semiconductor device is mounted and the cured product of the addition reaction curable silicone composition sealing the optical semiconductor device, and is formed on the substrate. An object of the present invention is to provide a primer composition that prevents corrosion of a metal electrode and significantly improves the heat resistance and flexibility of the primer itself, and an optical semiconductor device using the primer composition.

In order to achieve the above object, in the present invention, as a primer composition for bonding a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition sealing the optical semiconductor element,

(A) At least one of acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule, at least one of acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule, and SiH group and alkoxy group A copolymer containing at least one of an acrylic acid ester and a methacrylic acid ester that does not have, and

(B) a solvent, and

(C) cerium compound

It provides a primer composition containing.

Such a primer composition improves adhesion between the substrate on which the optical semiconductor device is mounted and the cured product of the addition reaction curable silicone composition sealing the optical semiconductor device, and prevents corrosion of the metal electrode formed on the substrate. Also, it improves the heat resistance and flexibility of the primer itself.

It is preferable if the said primer composition further contains (D) zinc compound.

If the primer composition further contains (D) a zinc compound, corrosion of the metal electrode formed on the substrate can be further prevented.

Moreover, it is preferable that the blending amount of the component (B) is 70% by mass or more of the entire primer composition.

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

The component (C) is a trivalent or tetravalent cerium complex, and the component (C) is preferably one containing 1 to 10,000 ppm of cerium metal with respect to the total mass of the solid content of the component (A).

When the component (C) is the cerium complex, and the amount of the component (C) is in the above range, the heat resistance of the primer itself can be further improved.

The component (D) is a zinc complex, and the component (D) is preferably 1 to 10,000 ppm of zinc metal based on the total mass of the solid content of the component (A).

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

It is preferable if the said primer composition further contains (E) a silane coupling agent.

By containing the silane coupling agent in this way, it becomes a primer composition which further improves the adhesion between the substrate and the cured product of the addition reaction curable silicone composition.

In addition, the present invention provides an optical semiconductor device in which a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition for sealing the optical semiconductor element are bonded by the primer composition.

Such an optical semiconductor device using the primer composition of the present invention has high reliability since the substrate and the cured product of the addition reaction curable silicone composition are firmly bonded and corrosion of the metal electrode formed on the substrate can be prevented. Becomes.

Further, the optical semiconductor device can be a light emitting diode.

Thus, the optical semiconductor device of the present invention can be suitably used for light emitting diodes.

Further, the constituent material of the substrate may be polyamide, fiber reinforced plastic, ceramics, silicone, silicone modified polymer, or liquid crystal polymer.

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

Further, it is preferable that the cured product of the addition reaction curable silicone composition is a rubber-like one.

If it is a cured product of such an addition reaction curable silicone composition, it has more robust adhesiveness and can more effectively prevent corrosion of a metal electrode formed on a substrate, particularly an Ag electrode.

As described above, in the case of the primer composition of the present invention, the metal electrode formed on the substrate improves adhesion between the substrate on which the optical semiconductor device is mounted and the cured product of the addition reaction curable silicone composition sealing the optical semiconductor device. It is possible to prevent corrosion of the primer, and also a primer composition that improves the heat resistance and flexibility of the primer itself, and an optical semiconductor device using the primer composition has high reliability.

1 is a cross-sectional view of an LED showing an example of an optical semiconductor device according to the present invention.
Fig. 2 is a perspective view illustrating a test piece for an adhesion test in Examples and Comparative Examples.

As described above, the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition sealing the optical semiconductor element is improved, and corrosion of the metal electrode formed on the substrate is prevented, In addition, there has been a demand for development of a primer composition capable of improving the heat resistance and flexibility of the primer itself.

The inventors of the present invention have repeatedly studied the above problems, and as a result, at least one of acrylic acid esters and methacrylic acid esters having at least one SiH group in one molecule, and acrylic acid esters and methacrylic acid having at least one alkoxy group in one molecule. In the case of a primer composition containing at least one of an acid ester and a cerium compound and a copolymer containing at least one of an acrylic acid ester and a methacrylic acid ester having no SiH group and an alkoxy group, a substrate on which an optical semiconductor element is mounted, and the optical semiconductor The present invention was completed by discovering that the cured product of the addition reaction curable silicone composition that seals the device can be firmly bonded and becomes a primer composition capable of preventing corrosion of the metal electrode formed on the substrate, especially the Ag electrode. .

That is, the present invention is a primer composition for bonding a substrate on which an optical semiconductor device is mounted and a cured product of an addition reaction curable silicone composition for sealing the optical semiconductor device,

(A) At least one of acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule, at least one of acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule, and SiH group and alkoxy group A copolymer containing at least one of an acrylic acid ester and a methacrylic acid ester that does not have, and

(B) a solvent, and

(C) cerium compound

It is a primer composition containing.

Hereinafter, although this invention is demonstrated in detail, this invention is not limited to these.

<Primer composition>

The primer composition of the present invention contains a component (A), a component (B) and a component (C) described later as essential components.

Hereinafter, each component of the primer composition of the present invention will be described.

[(A) component]

Component (A) contained in the primer composition of the present invention is at least one of an acrylic acid ester and methacrylic acid ester having at least one SiH group per molecule, and an acrylic acid ester and methacrylic acid having at least one alkoxy group per molecule. It is a copolymer containing at least one of an ester and at least one of an acrylic acid ester and a methacrylic acid ester having no SiH group and an alkoxy group.

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

The primer composition containing the component (A) imparts sufficient adhesion to the substrate and the electrode on which the optical semiconductor device is mounted, forms a flexible film on the substrate, and forms a metal electrode (especially an Ag electrode). ) To suppress corrosion over time.

The blending amount of the component (A) is not particularly limited as long as it is an amount dissolved in the component (B) described later, but it is preferably 30% by mass or less of the total composition (the sum of components (A) to (C), etc.), and more It is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass. When the content is 30% by mass or less, the occurrence of irregularities on the surface of the resulting film can be prevented, and sufficient performance as a primer can be obtained.

Acrylic acid ester and methacrylic acid ester having at least one SiH group in one molecule

Examples of the acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule include a compound having a structure represented by the following formula (1).

(Wherein, R represents a hydrogen atom or a methyl group, R ¹ represents a monovalent organic group, and R ² represents a divalent organic group. n represents 0, 1, or 2.)

In addition, a compound having a structure represented by the following formula (2) or the following formula (3) in the diorganopolysiloxane can also be illustrated.

(In the formula, R, R ¹ and R ² represent the same meaning as described above. l is 0 or a positive integer, and m is a positive integer. The order of the arrangement of each siloxane unit 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. The order of the arrangement of each siloxane unit 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 1 to 3 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, and cyclohexyl group. Alkenyl groups such as cycloalkyl group, vinyl group, allyl group, and propenyl group, aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group, aralkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group, and these groups Some or all of the hydrogen atoms of are substituted with halogen atoms such as fluorine, bromine, and chlorine, cyano groups, etc., for example, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group, etc. Can be mentioned. As R ¹ , a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group is particularly preferable.

The divalent organic group represented by R ² is preferably an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms. Examples of the divalent hydrocarbon group include alkylene groups such as methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, cyclohexylene group, and n-octylene group, phenylene group, Arylene groups, such as a naphthylene group, are mentioned. As R ² , an ethylene group and an n-propylene group are preferable, and an n-propylene group is particularly preferable.

The acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule may be used alone or in combination of two or more.

Acrylic acid ester and methacrylic acid ester having at least one alkoxy group in one molecule

Examples of the acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule include a compound including a structure represented by the following formula (4).

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

Further, a compound having a structure represented by the following formula (5) or the following formula (6) in the diorganopolysiloxane can also be illustrated.

(In the formula, R, R ¹ , R ² and R ³ have the same meaning as described above. r is 0 or a positive integer, and s is a positive integer. The order of the arrangement of each siloxane unit in parentheses is arbitrary.)

(In the formula, R, R ¹ , R ² and R ³ have the same meaning as above. t and u are positive integers. The order of the arrangement of each siloxane unit in parentheses is arbitrary.)

Here, examples of the organic group represented by R ¹ and R ² include those similar to those described above. Examples of the monovalent hydrocarbon group having 1 to 4 carbon atoms represented by R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, and the like, and methyl group or ethyl group is preferable. .

The acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule may be used alone or in combination of two or more.

Acrylic acid ester and methacrylic acid ester without SiH group and alkoxy group

Examples of acrylic esters having no SiH group and alkoxy group include methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, isopentyl acrylate, -n-hexyl acrylate, isooctyl acrylate, and 2-ethylhexyl acrylate. , Acrylic acid-n-octyl, isononyl acrylate, acrylic acid-n-decyl, and isodecyl acrylate.

As a methacrylic acid ester which does not have a SiH group and an alkoxy group, for example, methyl methacrylate, ethyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, isopentyl methacrylate, methacrylic acid- n-hexyl, isooctyl methacrylate, 2-ethylhexyl methacrylate, -n-octyl methacrylate, isononyl methacrylate, -n-decyl methacrylate, isodecyl methacrylate, and the like. have.

Among the above examples, alkyl acrylate esters and alkyl methacrylates having 1 to 12 carbon atoms in the alkyl group and 1 to 4 carbon atoms in the alkyl group are particularly preferred, and may be used alone or in combination of two or more.

[(B) component]

As the component (B) that is a solvent, it is not particularly limited as long as it dissolves the component (A) and the optional component described later that constitute the primer composition of the present invention, and a known organic solvent can be used.

Examples of the solvent include aromatic hydrocarbon solvents such as xylene, toluene and benzene, aliphatic hydrocarbon solvents such as heptane and hexane, halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene, methylene chloride, ethyl acetate, 1- Ester solvents such as propylene glycol methyl ether acetate, ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone, alcohol solvents such as ethanol, isopropanol and butanol, ligroin, cyclohexanone, diethyl ether, volatilized rubber, silicone type Solvents, etc. are mentioned. Among them, ethyl acetate, 1-propylene glycol methyl ether acetate, hexane, and acetone are suitably used.

The component (B) may be used as a mixed solvent by using one type alone or in combination of two or more depending on the evaporation rate at the time of application of the primer composition.

The blending amount of the component (B) is not particularly limited, but it is preferably 70% by mass or more, more preferably 80 to 99.99% by mass, still more preferably 70% by mass or more of the entire primer composition (total of components (A) to (C), etc.) It is 90 to 99.9 mass %. When the blending amount of the component (B) is 70% by mass or more, it becomes a primer composition with better workability during application and drying, and can be made uniform, for example, when forming a primer film on a substrate described later, When unevenness occurs, there is no cracking of the film, and sufficient performance as a primer is imparted.

[Component (C)]

The component (C) is a cerium compound, and has an effect of improving heat resistance, light resistance, crack resistance, and the like without significantly impairing the transparency of the primer composition of the present invention.

Examples of the cerium compound include cerium complexes, complex metal complexes containing cerium, cerium oxide, inorganic acid salts and organic acid salts of cerium, but cerium complexes containing trivalent or tetravalent cerium as the central metal and alcohol or diketone as ligands. B. A composite metal complex containing cerium is preferred.

Component (C) is not particularly limited as long as it is soluble in the mixture of component (A) and component (B) described above, but cerium(IV)2-methoxyethoxide, tris(isopropylcyclopentadienyl)cerium , Tris(cyclopentadienyl)cerium, tris(1,2,3,4-tetramethyl-2,4-cyclopentadienyl)cerium(III), cerium oxalate(III), tris(6,6,7 ,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)cerium(III), tetrakis(2,2,6,6-tetramethyl-3,5- Heptanedionato)cerium(IV), 2,4-pentanedionatocerium(III), trifluoroacetylacetonatocerium(III), tris(acetylacetonato)cerium(III), and the like. Among them, the trivalent cerium complex has a high heat resistance imparting effect, and is preferable. Specifically, tris(cyclopentadienyl)cerium and tris(acetylacetonato)cerium(III) are mentioned.

The blending amount of the cerium compound is preferably 1 ppm or more, more preferably 10 ppm or more as the cerium metal with respect to the total mass of the solid content of the component (A). The upper limit of the blending amount is preferably 10,000 ppm or less, and more preferably 1,000 ppm or less. When the amount of the cerium compound is 1 ppm or more, sufficient heat resistance and light resistance of the primer composition can be obtained. Further, if the amount of the cerium compound is 10,000 ppm or less, the transparency of the cured primer is not impaired.

The component (C) may be added after dissolving in advance in the solvent illustrated as the component (B).

Component (C) may be used alone or in combination of two or more.

[(D) component]

The component (D) is a zinc compound, and has an effect of improving heat resistance, light resistance, crack resistance, sulfidation resistance, and the like 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 can also be used, but from the viewpoint of improving the smoothness of the surface when the primer composition is applied, zinc is made of a zinc atom as a central metal and an alcohol or diketone as a ligand. A complex or a composite metal complex containing zinc is preferable.

The component (D) is not particularly limited as long as it is soluble in the mixture of components (A) to (C) described above, but diethylzinc, diphenylzinc, zinc tert-butoxide, zinc i-propoxide, zinc 2 -Methoxyethoxide, zinc dibenzoate, zinc oxalate, zinc 2-ethylhexanoate, zinc bis(2,4-pentanedionato)(II), zinc hexafluoroacetylacetonato, bis(2,2, 6,6-tetramethyl-3,5-heptanedionato)zinc (II), etc. are mentioned. Among them, a divalent cerium complex is preferred because of its high heat resistance imparting effect, specifically, bis(2,4-pentanedionato)zinc(II), hexafluoroacetylacetonatozinc, bis(2,2,6) ,6-tetramethyl-3,5-heptanedionato)zinc (II) is mentioned.

The blending amount of the component (D) is, as zinc metal, preferably 1 ppm or more, and more preferably 10 ppm or more, based on the total mass part of the solid content of the component (A). As an upper limit, it becomes like this. Preferably it is 10,000 ppm or less, More preferably, it is 1,000 ppm or less. By securing a concentration of 1 ppm or more, sufficient heat resistance and light resistance can be obtained. Moreover, if it is 10,000 ppm or less, transparency of a cured primer is not impaired.

The component (D) may be added after dissolving in a solvent beforehand, and a method of uniformly mixing with a mixing stirrer under normal temperature or heating can be mentioned. The solvent in which the component (D) is dissolved in advance may be the same as or different from the component (B).

[(E) component]

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

As the silane coupling agent, a general silane coupling agent may be used. For example, a vinyl group-containing silane coupling agent such as vinyl trimethoxysilane and a vinyl triethoxysilane, and an epoxy group-containing silane coupling agent such as glycidoxypropyltrimethoxysilane. , (Meth)acryloxy group-containing silane coupling agents such as methacryloyloxypropyltrimethoxysilane and acryloyloxypropyltrimethoxysilane, mercapto group-containing silane coupling agents such as mercaptopropyltrimethoxysilane, etc. Can be mentioned. Among them, vinyl trimethoxysilane and methacryloyloxypropyl trimethoxysilane are preferable.

When the component (E) is used, the blending amount is preferably 0.05 to 10% by mass, more preferably 0.1 to 3% by mass of the entire primer composition (the sum of components (A) to (E), etc.). When the blending amount of the component (E) is 0.05% by mass or more, the effect of improving the adhesion is sufficient, and even if a value exceeding 10% by mass is blended, a further effect of improving the adhesion is not obtained, so it is preferably 10% by mass or less.

[Other ingredients]

In the primer composition of the present invention, in addition to the above components, other optional components can be blended if necessary. For example, as a metal corrosion inhibitor, benzotriazole, butylhydroxytoluene, hydroquinone or a derivative thereof can be blended.

Benzotriazole, dibutylhydroxytoluene, hydroquinone or a derivative thereof is exposed to the harsh external environment of the LED lamp, and for example, a sulfur compound in the atmosphere makes the sealing material of the optical semiconductor device (cured product of the addition reaction curable silicone composition). In the case of transmission, it is a component that more effectively suppresses corrosion of the metal electrode, particularly the Ag electrode, on the substrate sealed with this sealing material.

When the metal corrosion inhibitor is added, the blending amount is preferably 0.005 to 1 parts by mass, particularly 0.01 to 0.5 parts by mass, based on 100 parts by mass of the total of components (A) to (C) or (A) to (D). It is desirable.

Further, as other optional components, a phosphor, a reinforcing filler, a dye, a pigment, a heat resistance improving agent, an antioxidant, an adhesion promoter, and the like may be added.

[Method for preparing primer composition]

Examples of the method for producing the primer composition of the present invention include a method of uniformly mixing the components (A), (B), and (C), and optionally the optional components under heating at room temperature with a mixing stirrer.

<optical semiconductor device>

In addition, the present invention provides an optical semiconductor device in which a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition for sealing the optical semiconductor element are bonded by the primer composition.

Hereinafter, an aspect of the optical semiconductor device of the present invention will be described with reference to the drawings.

1 is a cross-sectional view of an optical semiconductor device (LED lamp) showing an example of an optical semiconductor device according to the present invention. The optical semiconductor device (LED lamp) 1 includes a substrate 4 on which an LED 3 is mounted as an optical semiconductor element, and a cured product 5 of an addition reaction curable silicone composition sealing the LED 3, as described above. It was bonded with one primer composition (2). Among them, a metal electrode 6 such as an Ag electrode is formed on the substrate 4, and the electrode terminal (not shown) of the LED 3 and the metal electrode 6 are electrically connected with the bonding wire 7 Connected.

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

The cured product 5 of the addition reaction curable silicone composition is obtained by curing the addition reaction curable silicone composition, and is preferably a transparent cured product, and is preferably a rubbery one. As the addition reaction curable silicone composition, one containing at least a conventionally known vinyl group-containing organopolysiloxane, an organohydrogenpolysiloxane as a crosslinking agent, and a platinum-based catalyst as an addition reaction catalyst can be used, and the addition reaction curable silicone composition In addition, as other optional components, a reaction inhibitor, a colorant, a flame retardant imparting agent, a heat resistance improving agent, a plasticizer, a reinforcing silica, an adhesive imparting agent, and the like may be added.

As a manufacturing method of the optical semiconductor device (LED lamp) 1 shown in FIG. 1, the following method can be illustrated.

In advance, an optical semiconductor element such as LED 3 is bonded to the substrate 4 on which the metal electrode 6 such as Ag electrode is formed by Ag plating with an adhesive, and the electrode terminal of the LED 3 is carried out with a bonding wire 7. (Not shown) and the metal electrode 6 are electrically connected, and after that, the substrate 4 on which the LED 3 is mounted is cleaned as necessary, and then a primer such as a spinner or a sprayer is used. After the composition (2) is applied to the substrate (4), the solvent in the primer composition (2) is volatilized by heating, air drying, etc., and a film having a thickness of preferably 10 µm or less, more preferably 0.1 to 5 µm is formed. To form. After forming a film of the primer, the addition reaction curable silicone composition is applied with a dispenser or the like, and allowed to stand at room temperature or heat cured to seal the LED 3 with the rubber-like cured product 5.

As described above, by using the primer composition of the present invention containing components (A) to (C) or components (A) to (D), the substrate on which optical semiconductor devices such as LEDs are mounted and the addition reaction curable silicone composition It is possible to provide an optical semiconductor device, in particular an LED lamp, in which the cured product of is firmly adhered and has high reliability.

In addition, even when the LED lamp is exposed to the harsh external environment and the sulfur compound in the air penetrates into the cured product of the silicone composition, the use of the primer composition of the present invention suppresses corrosion of the metal electrode on the substrate, especially the Ag electrode. can do.

In addition, the optical semiconductor device of the present invention can be suitably used for LEDs, and in the above-described aspect, an LED was used as an example of an optical semiconductor element, but in addition, for example, a phototransistor, a photodiode, a CCD, It can also be applied to solar cell modules, EPROMs, and photocouplers.

[Example]

Synthesis Examples, Examples, and Comparative Examples are shown below, and the present invention is specifically described, 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 methacrylic acid ester represented by the following formula (7), 6 parts by mass of a methoxy group-containing methacrylic acid ester represented by the following formula (8), 1-propylene glycol methyl 230 parts by mass of ether acetate and 0.25 parts by mass of AIBN were heated and stirred 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 methacrylic acid ester represented by the above formula (7), 4 parts by mass of a methoxy group-containing methacrylic acid ester represented by the above formula (8), 1-propylene glycol methyl 230 parts by mass of ether acetate and 0.25 parts by mass of AIBN were heated and stirred at 90° C. for 6 hours to prepare a solution containing a copolymer.

[Synthesis Example 3]

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

[Synthesis Example 4]

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylic acid ester represented by the above formula (7), 5 parts by mass of a methoxy group-containing methacrylic acid ester represented by the following formula (9), 1-propylene glycol methyl 230 parts by mass of ether acetate and 0.25 parts by mass of AIBN were heated and stirred 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 acrylic acid ester represented by the following formula (10), 4 parts by mass of a methoxy group-containing methacrylic acid ester represented by the formula (8), 1-propylene glycol methyl ether acetate 230 mass parts and 0.25 mass parts of AIBN were heated and stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was prepared.

[Synthesis Example 6]

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylic acid ester represented by the above formula (7), 4 parts by mass of a methoxy group-containing acrylic acid ester represented by the following formula (11), 1-propylene glycol methyl ether acetate 230 mass parts and 0.25 mass parts of AIBN were heated and stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was prepared.

[Comparative Synthesis Example 1]

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylic acid ester represented by the above formula (7), 230 parts by mass of 1-propylene glycol methyl ether acetate, 0.25 parts by mass of AIBN were heated and stirred at 90° C. for 6 hours, A solution containing the copolymer was prepared.

[Examples 1 to 6]

In the copolymers synthesized in Synthesis Examples 1 to 6, tris (acetylacetonato) cerium (III) as the cerium compound (C) was added to 50 ppm as cerium based on the total mass of the solid content of the component (A), and It diluted with 1-propylene glycol methyl ether acetate which is (B) component so that non-volatile content might become 8%, and obtained the primer composition.

Using the obtained primer composition, various physical properties (appearance, transmittance, adhesiveness (adhesive strength), and corrosiveness) were measured by the evaluation method shown below, and the results are shown in Table 1. In other words, the physical properties shown in Table 1 are values measured at 23°C.

[Examples 7 to 13]

In the copolymers synthesized in Synthesis Examples 1 to 6, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionato) cerium (IV) as a cerium compound (C) was added as component (A). 50 ppm as cerium based on the total mass part of the solid content of, and in Examples 7 to 12, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zinc (II) as zinc compound (D) 50 ppm of zinc was blended as zinc with respect to the total mass part of the solid content of the component (A). In Example 13, the zinc compound (D) was not blended, and the nonvolatile content of the entire primer composition was 8%. -Diluted with propylene glycol methyl ether acetate to obtain a primer composition.

Using the obtained primer composition, various physical properties (appearance, transmittance, adhesiveness (adhesive strength), and corrosiveness) were measured by the evaluation method shown below, and the results are shown in Table 3. In other words, the physical properties shown in Table 3 are values measured at 23°C.

[Exterior]

The obtained primer composition was brush-coated on a slide glass so as to have a thickness of 2 µm, left to stand at 60°C for 30 minutes to dry, and further dried at 180°C for 30 minutes. On this primer composition, an addition reaction curable silicone rubber composition (made by Shin-Etsu Chemical Co., Ltd., KER-2600) was applied to a thickness of 2 mm and cured at 150° C. for 1 hour, and its appearance was observed.

[Transmittance test]

The obtained primer composition was brush-coated on a slide glass so as to have a thickness of 2 µm, and left to stand at 60°C for 30 minutes to dry, thereby forming a primer composition film. The transmittance (initial transmittance) at a wavelength of 400 nm of the slide glass on which the primer composition film was formed was measured as a blank, and this was set to 100%. Subsequently, the slide glass on which the primer composition film was formed was heat-treated at 180° C. for 500 hours, and the transmittance after the heat treatment was measured in the same manner as described above, and the change in the initial transmittance was obtained.

[Adhesion (adhesion strength) test]

A test piece 11 for an adhesion test as shown in FIG. 2 was prepared. That is, the obtained primer composition was applied to each side of the two Al substrates 12 and 13 (manufactured by KDS, width 25 mm) to a thickness of 0.01 mm, left to stand at 60°C for 30 minutes, and further at 180°C. By drying, the primer composition films 14 and 15 were formed. These Al substrates are made to face the faces on which the primer composition films 14 and 15 are formed, so that their ends overlap 10 mm, and addition reaction curable silicone rubber composition (made by Shin-Etsu Chemical Co., Ltd., KER -2600) was inserted into a thickness of 2 mm and heated at 150° C. for 30 minutes to cure the addition reaction curable silicone rubber composition, and adhered by the cured product 16 of the silicone rubber composition (adhesive area 25 mm×10 mm = 250 A test piece including two Al substrates of mm 2) was prepared.

Each end of the Al substrates 12 and 13 of this test piece was pulled in the opposite direction (direction of the arrow in Fig. 2) at a tensile speed of 50 mm/min using a tensile tester (manufactured by Shimadzu Corporation, Autograph), The adhesive strength (MPa) per unit area was calculated.

[Corrosion resistance test]

The resulting primer composition was filled into an LED package having a silver electrode at the bottom, left at 60° C. for 30 minutes, dried at 180° C., and then an addition reaction curable silicone rubber composition (manufactured by Shin-Etsu Chemical Co., Ltd., KER-2600) was applied to a thickness of 1 mm and cured at 150° C. for 2 hours to prepare a test piece having a silicone rubber layer. This test piece was put in a 100 cc glass bottle with 0.1 g of sulfur crystals, sealed, and in Examples 1 to 6 and Comparative Examples 1 to 3 described later, at 70°C, Examples 7 to 13 and Comparative Examples 4 to 7 described later At, it was left at 90°C, and the degree of corrosion of the silver plating after 1 day and 7 days was visually observed, and evaluated according to the following criteria.

○: No corrosion (discoloration)

△: slight corrosion (discoloration)

×: black side

[Comparative Example 1]

In the same manner as in Example 1, except that the cerium compound (C) was not blended, the above-described adhesion (adhesion strength) test and corrosion resistance test were performed.

[Comparative Example 2]

In the same manner as in Example 1, except that 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%, and a primer composition was obtained, the adhesion (adhesion strength) test And corrosion resistance test.

[Comparative Example 3]

In the same manner as in Example 1, except that the primer composition was not used, the above-described adhesion (adhesion strength) test and corrosion resistance test were performed.

[Comparative Example 4]

In the same manner as in Example 7, except that the cerium compound (C) and the zinc compound (D) were not mixed, the above-described adhesion (adhesion strength) test and corrosion resistance test were performed.

[Comparative Example 5]

In the same manner as in Example 7, except that 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%, and a primer composition was obtained, the adhesion (adhesion strength) test And corrosion resistance test.

[Comparative Example 6]

In the same manner as in Example 7, except that the cerium compound (C) was not blended, the above-described adhesion (adhesion strength) test and corrosion resistance test were performed.

[Comparative Example 7]

In the same manner as in Example 7, except that the primer composition was not used, the above-described adhesion (adhesive strength) test and corrosion resistance test were performed.

As apparent from the results shown in Tables 1 and 3, in Examples 1 to 13 using the primer composition of the present invention, Al and the cured product of the addition reaction curable silicone rubber composition were firmly bonded. In addition, in the heat resistance test of the primer composition film applied to the slide glass, there was no discoloration, no change in the film itself, and excellent heat resistance. In addition, in the corrosion resistance test using an LED package equipped with a silver electrode, all of Examples 1 to 12 maintained a high transmittance even after 7 days elapsed, a high corrosion inhibiting effect was observed, and Example 13 showed some corrosion resistance. . In particular, Examples 7 to 12 including the component (D) in addition to the components (A) to (C) exhibited a higher corrosion inhibitory effect.

On the other hand, as apparent from the results shown in Tables 1 and 2, the transmittance of Comparative Example 1 to which the component (C) of the present invention was not added was inferior to that of Example 1 after 180°C for 500 hours. Comparative Example 2 using a primer composition different from the primer composition of the present invention was inferior in corrosion resistance as compared with Examples 1 to 6. In addition, in Comparative Example 3 in which the primer composition itself was not used, compared with Examples 1 to 6, the adhesion and corrosion resistance were significantly inferior. In addition, as apparent from the results shown in Tables 3 and 4, Comparative Example 4 in which the components (C) and (D) of the present invention were not added, compared to Example 7, the transmittance after 180°C x 500 hours. It was falling. Comparative Example 5 using a primer composition different from the primer composition of the present invention was inferior in adhesion and corrosion resistance as compared with Examples 7 to 13. In Comparative Example 6 in which the component (C) was not added, the transmittance after 180°C x 500 hours was inferior as compared with Example 7. In Comparative Example 7 in which the primer composition itself was not used, compared with Examples 7 to 13, the adhesion and corrosion resistance were significantly inferior.

In other words, the present invention is not limited to the above embodiments. The above-described embodiment is an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operation and effect is 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 curable silicone composition
6: metal electrode
7: bonding wire
11: test piece
12, 13: Al substrate
14, 15: primer composition coating
16: Cured product of addition reaction curable silicone rubber composition

Claims (10)

A primer composition for bonding a substrate on which an optical semiconductor device is mounted and a cured product of an addition reaction curable silicone composition for sealing the optical semiconductor device,
(A) At least one of acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule, at least one of acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule, and SiH group and alkoxy group A copolymer containing at least one of an acrylic acid ester and a methacrylic acid ester that does not have, and
(B) a solvent, and
(C) cerium compound
Primer composition, characterized in that it contains. The primer composition according to claim 1, wherein the primer composition further contains (D) a zinc compound. The primer composition according to claim 1 or 2, wherein the blending amount of the component (B) is 70% by mass or more of the entire primer composition. The method according to claim 1 or 2, wherein the component (C) is a trivalent or tetravalent cerium complex, and the component (C) is 1 to 10,000 as a cerium metal based on the total mass of the solid content of the component (A). A primer composition, characterized in that it contains ppm. The primer composition according to claim 2, wherein the component (D) is a zinc complex, and the component (D) contains 1 to 10,000 ppm as zinc metal with respect to the total mass of the solid content of the component (A). . The primer composition according to claim 1 or 2, wherein the primer composition further contains (E) a silane coupling agent. An optical semiconductor device, wherein a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition for sealing the optical semiconductor element are bonded to each other by the primer composition according to claim 1 or 2. The optical semiconductor device according to claim 7, wherein the optical semiconductor element is a light emitting diode. The optical semiconductor device according to claim 7, wherein the constituent material of the substrate is polyamide, fiber-reinforced plastic, ceramics, silicone, silicon-modified polymer, or liquid crystal polymer. The optical semiconductor device according to claim 7, wherein the cured product of the addition reaction curable silicone composition is in a rubber shape.

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