JP6966381B2 - Primer composition and optical semiconductor device using it - Google Patents

Description

The present invention is a primer composition for adhering a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition that seals the optical semiconductor element, and an optical semiconductor device using the primer composition. Regarding.

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 made of a transparent resin. As this encapsulant, an epoxy resin-based composition has been widely used.

However, with epoxy resin-based encapsulants, cracking and yellowing are likely to occur due to the increase in calorific value and the shortening of the wavelength of light due to the recent miniaturization of semiconductor packages and the increase in brightness of LEDs, resulting in a decrease in reliability. Was invited.

Therefore, a silicone composition is used as a sealing material because it has excellent heat resistance (Patent Document 1). In particular, the addition reaction curing type silicone composition is highly productive because it cures in a short time by heating, and is suitable as an LED encapsulant (Patent Document 2).

However, it cannot be said that the adhesiveness between the substrate (resin or electrode) on which the LED is mounted and the encapsulant made of the cured product of the addition reaction curable silicone composition is sufficient.

Further, since the silicone composition generally has excellent gas permeability, it is easily affected by the external environment. When an LED lamp is exposed to a sulfur compound in the atmosphere, exhaust gas, etc., the sulfur compound or the like permeates the cured product of the silicone composition, and the metal electrode on the substrate sealed with the cured product, particularly the Ag electrode. Corrodes over time and turns black. As a countermeasure against this, a polymer of an acrylic acid ester containing SiH, a copolymer with an acrylic acid ester, a copolymer with a methacrylic acid ester, a copolymer of an acrylic acid ester and a methacrylic acid ester, or a polysilazane compound. Primers (Patent Documents 3 to 5) that suppress blackening by using the above have been developed. However, when an acrylic polymer containing SiH is used, the heat resistance of the primer film is insufficient, and the resin deteriorates around the semiconductor element in which a high current flows in recent years. On the other hand, although the polysilazane compound has excellent heat resistance, the film formed is hard, so that the film is easily cracked when applied on a mounting substrate on which a large number of optical semiconductor elements called multichips are mounted.

Japanese Unexamined Patent Publication No. 2000-198930 Japanese Unexamined Patent Publication No. 2004-292714 Japanese Unexamined Patent Publication No. 2010-168496 Japanese Unexamined Patent Publication No. 2012-144652 Japanese Unexamined Patent Publication No. 2014-157894

The present invention has been made to solve the above problems, and improves the adhesiveness between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition that seals the optical semiconductor element. At the same time, it is an object of the present invention to provide a primer composition that prevents corrosion of a metal electrode formed on a substrate and improves the heat resistance and flexibility of the primer itself, and an optical semiconductor device using the primer composition. And.

In order to achieve the above problems, in the present invention,
A primer composition for adhering a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition that encloses the optical semiconductor element.
(A) At least one of an acrylic acid ester and a methacrylic acid ester having one or more SiH groups in one molecule, and at least one of an acrylic acid ester and a methacrylic acid ester having one or more alkoxy groups in one molecule. , A copolymer consisting of at least one of an acrylic acid ester and a methacrylic acid ester having no SiH group and an alkoxy group, and
(B) Solvent,
Provided is a primer composition containing the above.

Such a primer composition improves the adhesiveness between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition that encloses the optical semiconductor element, and also on the substrate. It prevents corrosion of the metal electrode formed in the primer and improves the heat resistance and flexibility of the primer itself.

Further, 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% by mass or more of the component (B), a primer composition having better workability can be obtained.

In addition, the primer composition further
(C) Silane coupling agent,
It is preferable that it contains.

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

Further, in the present invention, 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 that encloses the optical semiconductor element are bonded by the primer composition. I will provide a.

In such an optical semiconductor device using the primer composition of the present invention, the substrate and the cured product of the addition reaction curable silicone composition are firmly adhered to each other, and the metal electrode formed on the substrate is formed. Since corrosion can also be prevented, it has high reliability.

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

As described above, the optical semiconductor device of the present invention can be suitably used for a light emitting diode.

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 adhesiveness of the primer is excellent, even such a substrate can be used without impairing the adhesiveness.

Further, it is preferable that the cured product of the addition reaction curable silicone composition is in the form of rubber.

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

As described above, the primer composition of the present invention improves the adhesiveness between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition that encloses the optical semiconductor element. It is a primer composition that can prevent corrosion of the metal electrodes formed on the substrate and improve the heat resistance and flexibility of the primer itself, and the optical semiconductor device using the primer composition is highly reliable. It will have sex.

It is sectional drawing of the LED lamp which shows an example of the optical semiconductor device which concerns on this invention. It is a perspective view explaining the test piece for adhesiveness test in an Example and a comparative example.

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 that seals the optical semiconductor element is improved, and the metal electrodes formed on the substrate are corroded. There has been a demand for the development of a primer composition capable of preventing the above-mentioned problems and improving the heat resistance and flexibility of the primer itself.

As a result of diligent studies on the above-mentioned problems, the present inventors have made at least one of an acrylic acid ester and a methacrylic acid ester having one or more SiH groups in one molecule, and one or more alkoxy groups in one molecule. If it is a primer composition containing a copolymer consisting of at least one of an acrylic acid ester and a methacrylic acid ester having a SiH group and at least one of an acrylic acid ester and a methacrylic acid ester having no SiH group and an alkoxy group, the optical semiconductor element. The substrate on which the ester is mounted and the cured product of the addition reaction curable silicone composition that encloses the optical semiconductor element can be firmly adhered to prevent corrosion of the metal electrode formed on the substrate, especially the Ag electrode. We have found that it is possible to obtain a primer composition, and have completed the present invention.

That is, the present invention
A primer composition for adhering a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition that encloses the optical semiconductor element.
(A) At least one of an acrylic acid ester and a methacrylic acid ester having one or more SiH groups in one molecule, and at least one of an acrylic acid ester and a methacrylic acid ester having one or more alkoxy groups in one molecule. , A copolymer consisting of at least one of an acrylic acid ester and a methacrylic acid ester having no SiH group and an alkoxy group, and
(B) Solvent,
It is a primer composition containing.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

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

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

[(A) component]
The component (A) contained in the primer composition of the present invention includes at least one of an acrylic acid ester and a methacrylic acid ester having one or more SiH groups in one molecule, and one or more alkoxy groups in one molecule. It is a copolymer composed of at least one of an acrylic acid ester and a methacrylic acid ester having a SiH group 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), which is a copolymer, can be obtained by polymerizing the corresponding monomer (ester described later) with a radical polymerization initiator such as 2,2'-azobisisobutyronitrile (AIBN). can.

The primer composition containing such a component (A) imparts sufficient adhesiveness to the substrate and the electrode on which the optical semiconductor element is mounted, and forms a flexible film on the substrate to form a metal. It suppresses corrosion of electrodes (particularly Ag electrodes) over time.

The blending amount of the component (A) is not particularly limited as long as it dissolves in the component (B) described later, but is 30% by mass or less of the entire composition (total of the components (A), (B), etc.). 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 obtained film can be prevented, and sufficient performance as a primer can be obtained.

（式中、Ｒは水素原子又はメチル基、Ｒ^１は１価の有機基、Ｒ^２は２価の有機基を表す。ｎは０、１、又は２である。） Acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule Acrylic acid ester and methacrylic acid ester having one or more SiH groups in one molecule are represented by the following formula (1). Examples include compounds containing a structure.

(In the formula, R represents a hydrogen atom or a methyl group, R ¹ represents a monovalent organic group, R ² represents a divalent organic group. N is 0, 1, or 2.)

（式中、Ｒ、Ｒ^１、Ｒ^２は上記と同様の意味を表す。ｌは０又は正の整数、ｍは正の整数である。括弧が付された各シロキサン単位の配列順は不定である。） Further, a compound having a structure represented by the following formula (2) or the following formula (3) in the diorganopolysiloxane 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, m is a positive integer. The arrangement order of each siloxane unit in parentheses is indefinite. be.)

（式中、Ｒ、Ｒ^１、Ｒ^２は上記と同様の意味を表す。ｏ、ｐは正の整数である。括弧が付された各シロキサン単位の配列順は不定である。）

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

Here, ^{as the monovalent organic group represented by R 1} , an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms is preferable. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, an octyl group and the like, an alkyl group, a cyclohexyl group and the like. Alkenyl group such as cycloalkyl group, vinyl group, allyl group, propenyl group, aryl group such as phenyl group, trill group, xylyl group and naphthyl group, aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group. , Part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, cyano groups, etc., such as chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl. The group etc. can be mentioned. The R ^1, a methyl group, an ethyl group, a phenyl group is preferable, a methyl group is particularly preferred.

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

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.

（式中、Ｒ、Ｒ^１、Ｒ^２は上記と同様の意味を表す。Ｒ^３は炭素数１〜４の１価の炭化水素基を表す。ｑは０、１、又は２である。） Acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule The acrylic acid ester and methacrylic acid ester having one or more alkoxy groups in one molecule are represented by the following formula (4). Examples include compounds containing a structure.

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

（式中、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３は上記と同様の意味を表す。ｒは０又は正の整数、ｓは正の整数である。括弧が付された各シロキサン単位の配列順は不定である。） Further, a compound having a structure represented by the following formula (5) or the following formula (6) in the diorganopolysiloxane 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. Arrangement order of each siloxane unit in parentheses. Is indefinite.)

（式中、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３は上記と同様の意味を表す。ｔ、ｕは正の整数である。括弧が付された各シロキサン単位の配列順は不定である。）

(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 arrangement of each siloxane unit in parentheses is undefined.)

Here, examples of the organic group represented by ^{R 1} and R ^{2 include the same as above.} Examples of the monovalent hydrocarbon group having 1 to 4 carbon atoms represented by R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group and the like, and a methyl group. Alternatively, an ethyl group is preferable.

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

Examples of the methacrylic acid ester having no SiH group and an alkoxy group include methyl methacrylate, ethyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, isopentyl methacrylate, -n-hexyl methacrylate, isooctyl methacrylate and methacrylic acid. Examples thereof include -2-ethylhexyl acid acid, -n-octyl methacrylate, isononyl methacrylate, -n-decyl methacrylate, and isodecyl methacrylate.

Among the above examples, acrylic acid alkyl esters and methacrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms are preferable, and one type alone or two or more types are used in combination. You may.

[(B) component]
The component (B) which is a solvent is not particularly limited as long as it dissolves the above-mentioned component (A) constituting the primer composition of the present invention and any component described later, and a known organic solvent is used. can do.

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 and methylene chloride, and acetic acid. Ester-based solvents such as ethyl and 1-propylene glycol methyl ether acetate, ketone-based solvents such as methylisobutylketone and methylethylketone, alcohol-based solvents such as ethanol, isopropanol and butanol, ligroin, cyclohexanone, diethyl ether, rubber volatile oil and silicone-based Examples include solvents. Of these, ethyl acetate, 1-propylene glycol methyl ether acetate, hexane and acetone are preferably used.

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

The blending amount of the component (B) is not particularly limited, but is preferably 70% by mass or more, more preferably 80 to 99.99, based on the entire primer composition (total of the components (A), (B), etc.). It is by mass, more preferably 90 to 99.9% by mass. When the blending amount of the component (B) is 70% by mass or more, the primer composition has better workability during coating and drying, and is made uniform, for example, when forming a primer film on a substrate described later. It is possible to prevent the film from cracking due to the unevenness of the surface, and to give sufficient performance as a primer.

[(C) component]
A silane coupling agent can be further added to the primer composition of the present invention as the component (C).

The silane coupling agent may be a general silane coupling agent, for example, a vinyl group-containing silane coupling agent such as vinyltrimethoxysilane or vinyltriethoxysilane, or an epoxy group-containing agent such as glycidoxypropyltrimethoxysilane. Examples thereof include a (meth) acryloxy group-containing silane coupling agent such as a silane coupling agent, methacryloyloxypropyltrimethoxysilane, and acryloyloxypropyltrimethoxysilane, and a mercapto group-containing silane coupling agent such as mercaptopropyltrimethoxysilane. Of these, vinyltrimethoxysilane and methacryloyloxypropyltrimethoxysilane are preferable.

When the component (C) is used, the blending amount is preferably 0.05 to 10% by mass, more preferably 0.% by mass of the entire primer composition (total of the components (A) to (C) and the like). It is 1 to 3% by mass. If the blending amount of the component (C) is 0.05% by mass or more, the adhesiveness improving effect is sufficient, and even if a value exceeding 10% by mass is blended, a further adhesiveness improving effect cannot be obtained. It is preferably 10% by mass or less.

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

Benzotriazole, dibutyl hydroxytoluene, hydroquinone or its derivatives are exposed to the harsh external environment of LED lamps, for example, sulfur compounds in the atmosphere are used as encapsulants for optical semiconductor devices (cured products of addition reaction curable silicone compositions). ) Is a component that more effectively suppresses corrosion of the metal electrode on the substrate sealed with the encapsulant, particularly the Ag electrode, when it has passed through.

When the metal corrosion inhibitor is added, the blending amount is preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the total of the components (A) and (B), and particularly 0.01 to 0.5. It is preferably parts by mass.

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

[Manufacturing method of primer composition]
Examples of the method for producing the primer composition of the present invention include a method of uniformly mixing the above-mentioned components (A) and (B) and, if necessary, the above-mentioned optional components with a mixing stirrer at room temperature or heating.

<Optical semiconductor device>
Further, in the present invention, 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 that encloses the optical semiconductor element are bonded by the primer composition. I will provide a.
Hereinafter, one aspect of the optical semiconductor device of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view of an optical semiconductor device (LED lamp) showing an example of the optical semiconductor device according to the present invention. In the optical semiconductor device (LED lamp) 1, 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 that seals the LED 3 are bonded to each other by the primer composition 2 described above. It is a thing. Of these, 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 by a bonding wire 7.

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

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 rubber-like. preferable. As the addition reaction curing type silicone composition, a conventionally known vinyl group-containing organopolysiloxane, an organohydrogenpolysiloxane as a cross-linking agent, and a platinum-based catalyst as an addition reaction catalyst can be used. Further, in the above-mentioned addition reaction curable silicone composition, as other optional components, a reaction inhibitor, a colorant, a flame retardant imparting agent, a heat resistance improving agent, a plasticizing agent, a reinforcing silica, an adhesive imparting agent and the like are added. It may be added.

As a method for manufacturing the optical semiconductor device (LED lamp) 1 shown in FIG. 1, the following method can be exemplified.
An optical semiconductor element such as an LED 3 is bonded to a substrate 4 on which a metal electrode 6 such as an Ag electrode is formed by Ag plating in advance with an adhesive, and an electrode terminal (not shown) of the LED 3 and a metal electrode 6 are bonded by a bonding wire 7. After that, the substrate 4 on which the LED 3 is mounted is cleaned as necessary, and then the primer composition 2 is applied to the substrate 4 with a coating device such as a spinner or a sprayer. The solvent in the primer composition 2 is volatilized by heating, air drying, or the like to form a film having a thickness of preferably 10 μm or less, more preferably 0.1 to 5 μm. After forming the primer film, the addition reaction curable silicone composition is applied with a dispenser or the like, left at room temperature or heat-cured, and the LED 3 is sealed with the rubber-like cured product 5.

As described above, by using the primer composition of the present invention containing the above-mentioned components (A) and (B), a substrate on which an optical semiconductor element such as an LED is mounted and a cured product of an addition reaction curable silicone composition are used. Can provide highly reliable optical semiconductor devices, especially LED lamps, which are firmly adhered to each other.

Further, even when the LED lamp is exposed to a harsh external environment and sulfur compounds in the atmosphere permeate into the cured product of the above silicone composition, the primer composition of the present invention can be used for the substrate. Corrosion of the above metal electrode, especially the Ag electrode, can be suppressed.

The optical semiconductor device of the present invention can be suitably used for LEDs, and in the above aspect, an LED has been described as an example of an optical semiconductor element, but other than this, for example, a phototransistor and a photodiode. , CCD, solar cell module, EPROM, photocoupler and the like.

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 methacrylic acid ester represented by the following formula (7), 6 parts by mass of methoxy group-containing methacrylic acid ester represented by the following formula (8), 1-propylene glycol methyl ether. 230 parts by mass of 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 methoxy group-containing methacrylic acid ester represented by the above formula (8), 1-propylene glycol methyl ether. 230 parts by mass of 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 methoxy group-containing methacrylic acid ester represented by the above formula (8), 1-propylene glycol methyl ether. 230 parts by mass of 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 methoxy group-containing methacrylic acid ester represented by the following formula (9), 1-propylene glycol methyl ether. 230 parts by mass of 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 methoxy group-containing methacrylic acid ester represented by the above formula (8), 1-propylene glycol methyl ether. 230 parts by mass of 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 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 methoxy group-containing acrylic acid ester represented by the following formula (11), 1-propylene glycol methyl ether. 230 parts by mass of 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.

[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, and 0.25 parts by mass of AIBN are heated and stirred at 90 ° C. for 6 hours. , A solution containing the copolymer was prepared.

[Examples 1 to 6, Comparative Example 1]
The copolymers synthesized in the above Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 were diluted with 1-propylene glycol methyl ether acetate so that the non-volatile content was 8% to obtain a primer composition (Examples 1 to 6). , Comparative Example 1).

Using the obtained primer composition, various physical properties (appearance, transmittance, adhesiveness (adhesive strength) and corrosiveness) were measured by the evaluation methods shown below, and the results are shown in Tables 1 and 2. The physical properties shown in Tables 1 and 2 are values measured at 23 ° C.

[exterior]
The obtained primer composition was brushed onto a slide glass to a thickness of 2 μm, left at 60 ° C. for 30 minutes to dry, and further dried at 180 ° C. for 30 minutes. An addition reaction curable silicone rubber composition (KER-2600, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto this primer composition 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 brushed onto a slide glass to a thickness of 2 μm, left at 60 ° C. for 30 minutes and dried to form a primer composition film. The transmittance (initial transmittance) of the slide glass on which the primer composition film was formed at a wavelength of 400 nm was measured with the slide glass as a blank, and this was taken as 100%. Next, 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 above to determine the change with respect to the initial transmittance.

[Adhesiveness (adhesive strength) test]
A test piece 11 for an adhesion test as shown in FIG. 2 was produced. That is, the obtained primer composition was applied to one side of each of the two Al substrates 12 and 13 (manufactured by KDS Co., Ltd., width 25 mm) to a thickness of 0.01 mm, left at 60 ° C. for 30 minutes, and further. It was dried at 180 ° C. to form primer composition coatings 14 and 15. These Al substrates are opposed to the surfaces on which the primer composition coatings 14 and 15 are formed so that their ends overlap by 10 mm, and an addition reaction curing type silicone rubber composition (manufactured by Shin-Etsu Chemical Co., Ltd., KER) is provided between them. -2600) is sandwiched between 2 mm thick and heated at 150 ° C. for 30 minutes to cure the addition reaction curable silicone rubber composition, which is then bonded to the cured silicone rubber composition 16 (adhesion area 25 mm × 10 mm). = 250 mm ² ) A test piece made of two Al substrates was produced.
The ends of the Al substrates 12 and 13 of this test piece are pulled in opposite directions (in the direction of the arrow in FIG. 2) using a tensile tester (manufactured by Shimadzu Corporation, Autograph) at a tensile speed of 50 mm / min, and the unit area is The adhesive strength (MPa) per unit was determined.

[Corrosion resistance test]
The obtained primer composition is filled in an LED package having a silver electrode at the bottom, left at 60 ° C. for 30 minutes, dried at 180 ° C., and then added reaction-curable silicone rubber composition (Shin-Etsu Chemical Co., Ltd.). KER-2600, manufactured by KER-2600 Co., Ltd.) 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 placed in a 100 cc glass bottle together with 0.1 g of sulfur crystals, sealed and left at 70 ° 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) △: Some corrosion (discoloration)
×: Black change

[Comparative Example 2]
The adhesiveness (adhesive strength) test and corrosion resistance test were carried out in the same manner as in Examples 1 to 6 and Comparative Example 1 except that the primer composition was not used.

As is clear from the results shown in Table 1, in Examples 1 to 6 using the primer composition of the present invention, Al and the cured product of the addition reaction curable silicone rubber composition are firmly adhered to each other. Further, 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. Further, in the corrosion resistance test using the LED package equipped with the silver electrode, no discoloration was observed even after 7 days had passed in any of Examples 1 to 6, and a high corrosion suppressing effect was observed.

On the other hand, Comparative Example 1 using a primer composition different from the primer composition of the present invention was inferior in adhesiveness and corrosion resistance as compared with Examples 1 to 6. Further, in Comparative Example 2 in which the primer composition itself was not used, the adhesiveness and corrosion resistance were significantly inferior to those in Examples 1 to 6.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any of the above-described embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

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 (7)

A primer composition for adhering a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition that encloses the optical semiconductor element.
(A) At least one of an acrylic acid ester and a methacrylic acid ester having one or more SiH groups in one molecule, and at least one of an acrylic acid ester and a methacrylic acid ester having one or more alkoxy groups in one molecule. , A copolymer consisting of at least one of an acrylic acid ester and a methacrylic acid ester having no SiH group and an alkoxy group, and
(B) Solvent,
A primer composition characterized by containing. The primer composition according to claim 1, wherein the blending amount of the component (B) is 70% by mass or more of the entire primer composition. The primer composition further
(C) Silane coupling agent,
The primer composition according to claim 1 or 2, wherein the primer composition comprises. The substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curing type silicone composition that encloses the optical semiconductor element are adhered to each other by the primer composition according to any one of claims 1 to 3. An optical semiconductor device characterized by being made. The optical semiconductor device according to claim 4, wherein the optical semiconductor element is a light emitting diode. The optical semiconductor device according to claim 4 or 5, wherein the constituent material of the substrate is polyamide, fiber reinforced plastic, ceramics, silicone, silicone-modified polymer, or liquid crystal polymer. The optical semiconductor device according to any one of claims 4 to 6, wherein the cured product of the addition reaction curable silicone composition is in the form of rubber.

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