TW202003729A - Primer composition and optical semiconductor device using the same having good adhesion between the substrate and the polysiloxane composition to prevent corrosion of metal electrodes - Google Patents

Abstract

An object of the present invention is to provide a primer composition for improving the adhesion between a substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction-curing polysiloxane composition that seals the optical semiconductor element, preventing corrosion of metal electrodes formed on the substrate, and improving the heat resistance and flexibility itself, and also provides an optical semiconductor device using the primer composition. To achieve the object, the primer composition is provided to adhere a substrate on which an optical semiconductor element is mounted with a cured product of an addition reaction-curing polysiloxane composition that seals the optical semiconductor element, which comprises (A) a copolymer composed of 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 at least one of acrylate and methacrylate having no SiH group and no alkoxy group, and (B) a solvent.

Description

Primer composition and optical semiconductor device using the same

The present invention relates to a primer composition followed by a substrate on which an optical semiconductor element is constructed, and a cured product of an addition reaction hardening type polysiloxane composition that seals the aforementioned optical semiconductor element, and the use of the primer composition Light semiconductor device.

It is known that a light-emitting diode (LED) lamp as an optical semiconductor device is a structure in which an LED mounted on a substrate is sealed with a sealing material made of transparent resin. This sealing material has been a composition of epoxy resin bases used in the past.

However, in epoxy resin-based sealing materials, cracking or yellowing is likely to occur due to increased heat generation or shorter wavelength of light accompanying the miniaturization of semiconductor packages or the increase in brightness of LEDs in recent years, which invites trust The decrease in sex.

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 hardening type polysiloxane composition is hardened 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) that constitutes the LED and the sealing material composed of the cured product of the addition reaction-curing polysiloxane composition cannot be said to be sufficient.

In addition, the polysilicone composition is generally excellent in gas permeability, so it is easily affected by the external environment. When the LED lamp is exposed to sulfur compounds or exhaust gas in the atmosphere, the sulfur compounds will pass through the hardened product of the polysilicon composition, and over time the metal electrode on the substrate sealed by the hardened material, especially the Ag electrode Corrosion to make it black. The countermeasures for this have been the development of polymers containing acrylates of SiH or copolymers with acrylates, copolymers with methacrylates, copolymers of acrylates and methacrylates, or by using polysilicon Primers to inhibit blackening by using aza compounds (Patent Documents 3 to 5). 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 where high current flows in recent years. In contrast, although the polysilazane compound has excellent heat resistance, the formed film is hard, so when it is coated on a multi-wafer mounting substrate on which many optical semiconductor elements are mounted, the film is easily broken. [Prior Technical Literature] [Patent Literature]

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

[Problems to be solved by the invention]

The present invention is made to solve the above-mentioned problems, and its object is to provide improved adhesion between a substrate on which an optical semiconductor element is built and an addition reaction hardening type polysiloxane composition that seals the optical semiconductor element, and prevents A primer composition that corrodes metal electrodes formed on a substrate and improves the heat resistance/flexibility of the primer itself, and an optical semiconductor device using the primer composition. [Means to solve the problem]

In order to achieve the above-mentioned problems, in the present invention, a primer composition is provided, which is A primer composition, which contains a substrate on which an optical semiconductor element is constructed, and a hardened product of an addition reaction hardening type polysiloxane composition that seals the aforementioned optical semiconductor element, which contains (A) At least one of acrylates and methacrylates having more than one SiH group in one molecule, and at least one of acrylates and methacrylates having more than one alkoxy group in one molecule, and not having A copolymer composed of at least one of acrylate and methacrylate of SiH group and alkoxy group, and (B) Solvent.

If it is such a primer composition, it will improve the adhesion between the substrate on which the optical semiconductor element is constructed and the cured product of the addition reaction hardening type polysiloxane composition that seals the optical semiconductor element, and prevent formation on the substrate Corrosion of the metal electrode, and improve the heat resistance/flexibility of the primer itself.

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

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

Furthermore, the primer composition preferably further contains (C) Silane coupling agent.

By containing the silane coupling agent in this way, it becomes a primer composition that further improves the adhesion between the substrate and the cured product of the addition reaction hardening type polysiloxane composition.

Furthermore, the present invention provides an optical semiconductor device comprising a substrate equipped with an optical semiconductor element, and a cured product of an addition reaction hardening type polysiloxane composition that seals the optical semiconductor element, by the primer composition The author was taken over.

In the case of such an optical semiconductor device using the primer composition of the present invention, the substrate and the cured product of the addition reaction-curing polysiloxane composition are firmly adhered to prevent the metal electrode formed on the substrate Corrosion, so it has high reliability.

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

In this way, the optical semiconductor device of the present invention can be suitably used as a light emitting diode.

In addition, the constituent material of the substrate may be polyamide, fiber-reinforced plastic, ceramic, polysiloxane, polysiloxane-modified polymer, or liquid crystal polymer.

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

Furthermore, the cured product of the addition reaction hardening type polysiloxane composition is preferably rubber-like.

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

As described above, if it is the primer composition of the present invention, the adhesion between the substrate of the optical semiconductor device and the cured product of the addition reaction hardening type polysiloxane composition that seals the optical semiconductor device can be improved. It also prevents corrosion of the metal electrode formed on the substrate and becomes a primer composition that improves the heat resistance/flexibility of the primer itself, and the optical semiconductor device using the primer composition becomes highly reliable By.

As described above, the adhesion between the substrate on which the optical semiconductor element is constructed and the cured product of the addition reaction hardening type polysiloxane composition that seals the optical semiconductor element can be improved, and the corrosion of metal electrodes formed on the substrate can be prevented, In addition, the development of a primer composition that improves the heat resistance/flexibility of the primer itself is in demand.

The inventors of the present invention have repeated in-depth studies on the above-mentioned problems and found that if it contains at least one of acrylates and methacrylates having more than one SiH group in one molecule, it has more than one alkoxy group in one molecule. The primer composition of a copolymer composed of at least one of acrylate and methacrylate of a group and at least one of acrylate and methacrylate without a SiH group and an alkoxy group becomes a The substrate containing the optical semiconductor element is firmly adhered to the hardened product of the addition reaction hardening type polysiloxane composition that seals the optical semiconductor element, and can prevent corrosion of the metal electrode formed on the substrate, especially the Ag electrode The present invention is completed by the primer composition.

That is, the present invention is a primer composition, which is A primer composition, which contains a substrate on which an optical semiconductor element is constructed, and a hardened product of an addition reaction hardening type polysiloxane composition that seals the aforementioned optical semiconductor element, which contains (A) At least one of acrylates and methacrylates having more than one SiH group in one molecule, and at least one of acrylates and methacrylates having more than one alkoxy group in one molecule, and not having A copolymer composed of at least one of acrylate and methacrylate of SiH group and alkoxy group, and (B) Solvent.

The present invention will be described in detail below, but the present invention is not limited to these.

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

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

[(A) ingredient] The component (A) contained in the primer composition of the present invention is composed of at least one of acrylate and methacrylate having one or more SiH groups in one molecule and one or more alkoxy groups in one molecule A copolymer composed of at least one of acrylate and methacrylate, and at least one of acrylate and methacrylate without SiH groups and alkoxy groups.

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

The primer composition containing such component (A) provides sufficient adhesion to the substrate and electrode constituting the optical semiconductor element, and forms a flexible film on the substrate to suppress metal electrodes (especially Ag Electrode) corrosion over time.

(A) The blending amount of the component is not particularly limited as long as the amount of the (B) component to be described later is dissolved, and is preferably 30% by mass of the entire composition (total of (A), (B) components, etc.) Below, it is more preferably 0.01 to 20% by mass, and still more preferably 0.1 to 10% by mass. If the content is 30% by mass or less, generation of irregularities on the surface of the obtained film can be prevented, and sufficient performance as a primer can be obtained.

(式中，R表示氫原子或甲基、R¹ 表示1價有機基、R² 表示2價有機基。n為0、1，或2)。Acrylates and methacrylates having more than one SiH group in one molecule Acrylates and methacrylates having more than one SiH group in one molecule include compounds having a structure represented by the following formula (1).

(In the formula, 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 is 0, 1, or 2).

(式中，R、R¹ 、R² 表示與上述相同意義。l為0或正整數、m為正整數。附有括弧之各矽氧烷單位之排列順序不固定)。In addition, a compound having a structure represented by the following formula (2) or the following formula (3) in diorganopolysiloxane can also be exemplified.

(In the formula, R, R ¹ and R ^{2 have} the same meaning as above. ^l is 0 or a positive integer and m is a positive integer. The arrangement order of each siloxane unit with parentheses is not fixed).

(式中，R、R¹ 、R² 表示與上述相同意義。o、p為正整數。附有括弧之各矽氧烷單位之排列順序不固定)。

(In the formula, R, R ¹ and R ^{2 have} the same meaning as above. o and p are positive integers. The arrangement order of the siloxane units with brackets is not fixed).

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. Monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl and other alkyl groups; cyclohexyl and the like Cycloalkyl; alkenyl such as vinyl, allyl, propenyl, etc.; aryl such as phenyl, tolyl, xylyl, naphthyl; benzyl, phenylethyl, phenylpropyl, etc. Aralkyl, etc., or a part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl , Cyanoethyl, etc. R ^{1 is} preferably methyl, ethyl, or phenyl, and particularly preferably methyl.

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. Divalent hydrocarbon groups include methylene, ethylidene, n-propylene, n-butylene, n-pentylyl, n-hexyl, cyclohexyl, n-octyl and the like. Base; phenylene, naphthyl, etc. R ^{2 is} preferably ethylidene or n-propylene, and particularly preferably n-propylene.

Acrylates and methacrylates having more than one SiH group in one molecule can be used alone or in combination of two or more.

(式中，R、R¹ 、R² 表示與上述相同意義。R³ 表示碳數1~4之1價烴基。q為0、1，或2)。Acrylates and methacrylates having more than one alkoxy group in one molecule Acrylates and methacrylates having more than one alkoxy group in one molecule include the structure represented by the following formula (4) Compound.

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

(式中，R、R¹ 、R² 、R³ 表示與上述相同意義。r為0或正整數、s為正整數。附有括弧之各矽氧烷單位之排列順序不固定)。In addition, a compound having a structure represented by the following formula (5) or the following formula (6) in diorganopolysiloxane can also be exemplified.

(In the formula, R, R ¹ , R ² , and R ^{3 have} the same meaning as above. r is 0 or a positive integer, and s is a positive integer. The arrangement order of each siloxane unit with parentheses is not fixed).

(式中，R、R¹ 、R² 、R³ 表示與上述相同意義。t、u為正整數。附有括弧之各矽氧烷單位之排列順序不固定)。

(In the formula, R, R ¹ , R ² , and R ^{3 have} the same meaning as above. t and u are positive integers. The arrangement order of each siloxane unit with parentheses is not fixed).

Here, the organic group represented by R ¹ and R ² may be the same as described above. The monovalent hydrocarbon group having 1 to 4 carbon atoms represented by R ³ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc., preferably methyl or ethyl .

Acrylates and methacrylates having more than one alkoxy group in one molecule can be used alone or in combination of two or more.

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

Methacrylates that do not have SiH groups and alkoxy groups include, for example, methyl methacrylate, ethyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, and isoamyl methacrylate Ester, methacrylic acid-n-hexyl ester, isooctyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid-n-octyl ester, isononyl methacrylate, methacrylic acid-n -Decyl ester, isodecyl methacrylate, etc.

In the above examples, alkyl acrylates and alkyl methacrylates having 1 to 12 carbon atoms in the alkyl group, especially 1 to 4 carbon atoms in the alkyl group are preferred, and one type may be used alone or two or more types may be used in combination .

[(B) ingredient] The component (B) of the 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 components described below, 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, and methylene chloride; and acetic acid Ester solvents such as ethyl ester and 1-propanediol methyl ether acetate; ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone; alcohol solvents such as ethanol, isopropanol and butanol; Petroleum, cyclohexanone, diethyl ether, volatile oil of rubber, polysiloxane-based solvents, etc. Among them, ethyl acetate, 1-propanediol methyl ether acetate, hexane, and acetone are particularly suitable.

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

(B) The blending amount of the components is not particularly limited, but it is preferably 70% by mass or more of the entire primer composition (total of (A), (B) components, etc.), more preferably 80 to 99.99% by mass, It is more preferably 90 to 99.9% by mass. (B) If the blending amount of the components is 70% by mass or more, it becomes a primer composition with better workability at the time of coating and drying, for example, when forming a primer film on a substrate described later, it may be uniform It does not cause the film to be cracked due to the unevenness on the surface, and it is to impart sufficient performance as a primer.

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

The silane coupling agent may be a general silane coupling agent, and examples thereof include vinyl-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; glycidoxypropyltrimethoxy Silane and other silane coupling agents containing epoxy groups; methacryl oxypropyl trimethoxy silane, propylene oxypropyl trimethoxy silane and other (meth) propylene oxy silane coupling agents ; Mercaptopropyl trimethoxy silane and other silane coupling agents containing mercapto groups, etc. Among them, vinyl trimethoxy silane and methacryl propyl trimethoxy silane are particularly preferred.

When the (C) component 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 (total of (A) to (C) components, etc.). (C) If the blending amount of the components is 0.05% by mass or more, the effect of improving the adhesiveness becomes sufficient, and even if the blending exceeds a value of 10% by mass, no further effect of improving the adhesiveness is obtained, so 10 is preferable Mass% or less.

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

Benzotriazole, dibutylhydroxytoluene, hydroquinone or its derivatives are used when LED lamps are exposed to severe external environments, for example, sulfur compounds in the atmosphere penetrate the sealing material of the optical semiconductor device (addition reaction hardening type) In the case of a hardened polysiloxane composition), it is more effective to suppress the corrosion of the metal electrode, especially the Ag electrode, on the substrate sealed by the sealing material.

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

Furthermore, as other optional components, phosphors, reinforcing fillers, dyes, pigments, heat resistance improvers, antioxidants, adhesion promoters, and the like may be added.

[Manufacturing method of primer composition] The method for producing the primer composition of the present invention may include a method of uniformly mixing the above-mentioned components (A) and (B) and any of the above-mentioned optional components by a mixer at room temperature or under heating.

<Optical Semiconductor Device> Furthermore, the present invention provides an optical semiconductor device comprising a substrate equipped with an optical semiconductor element, and a cured product of an addition reaction hardening type polysiloxane composition that seals the optical semiconductor element, by the primer composition And the recipient. 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 of the present invention. An optical semiconductor device (LED lamp) 1 is a substrate 4 in which an LED 3 as an optical semiconductor element is structured, and a cured product 5 of an addition reaction hardening type polysiloxane composition that seals the LED 3, and is composed of the above primer Object 2 is given to the author. Among them, 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 the material constituting the substrate 4 include polyamide, various fiber-reinforced plastics, ceramics, polysiloxane, polysiloxane-modified polymers, and liquid crystal polymers.

The hardened product 5 of the addition reaction hardening type polysiloxane composition is obtained by hardening the addition reaction hardening type polysiloxane composition, preferably a transparent hardened product, and more preferably a rubbery one . As the addition reaction hardening type polysiloxane composition, a platinum-based contact containing at least a conventionally known vinyl-containing organic polysiloxane, an organic hydrogen polysiloxane containing a crosslinking agent, and an addition reaction catalyst can be used In addition, the above addition reaction hardening type polysiloxane composition may also include reaction inhibitors, colorants, flame retardant imparting agents, heat resistance improvers, plasticizers, reinforcing silica, adhesiveness The imparting agent and the like are optional components.

The manufacturing method of the optical semiconductor device (LED lamp) 1 shown in FIG. 1 can exemplify the following method. An optical semiconductor element such as an LED 3 is previously bonded to the substrate 4 on which a metal electrode 6 such as an Ag electrode is formed by Ag plating with an adhesive, and the electrode terminal (not shown) of the LED 3 and the metal electrode 6 are previously connected by a bonding wire 7 After being electrically connected, after cleaning the substrate 4 with the LED 3 as needed, the primer composition 2 is applied to the substrate 4 with a coating device such as a spinner or a sprayer, etc. Air drying or the like evaporates the solvent in the primer composition 2 to form a coating having a thickness of preferably 10 μm or less, and more preferably 0.1 to 5 μm. After the coating of the primer is formed, the addition reaction hardening type polysiloxane composition is applied with a dispenser or the like, left at room temperature or cured by heating, and the LED 3 is sealed with a rubber-like hardened material 5.

In this manner, by using the primer composition of the present invention containing the aforementioned components (A) and (B), the substrate on which the optical semiconductor device such as an LED is constructed and the addition reaction hardening type polysiloxane composition The hardened material is firmly attached, and a highly reliable optical semiconductor device, particularly an LED lamp, can be provided.

In addition, even if the LED lamp is exposed to a severe external environment, when sulfur compounds in the atmosphere pass through the hardened product of the above polysiloxane composition, the use of the primer composition of the present invention can suppress the substrate Corrosion of metal electrodes, especially Ag electrodes.

Furthermore, the optical semiconductor device of the present invention can be suitably used as an LED. In the above-mentioned aspect, the LED is used as an example of the optical semiconductor element. However, it can also be applied to photoelectric crystals and optical diodes. Body, CCD, solar cell module, EPROM, photocoupler, etc. [Example]

Synthesis examples, examples, and comparative examples are shown below to specifically illustrate the present invention, 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), and methoxy group-containing methacrylate represented by the following formula (8) 6 parts by mass, 230 parts by mass of 1-propanediol methyl ether acetate, and 0.25 parts by mass of AIBN were heated and stirred at 90°C for 6 hours to prepare a copolymer-containing solution.

[Synthesis Example 2] 40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylate represented by the above formula (7), 4 parts by mass of methoxy-containing methacrylate represented by the above formula (8), 1- 230 parts by mass of propylene glycol methyl 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 methacrylate represented by the above formula (7), 1 part by mass of methoxy-containing methacrylate represented by the above formula (8), 1- 230 parts by mass of propylene glycol methyl 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 methacrylate represented by the above formula (7), and methoxy-containing methacrylate represented by the following formula (9) 5 parts by mass, 230 parts by mass of 1-propanediol methyl ether acetate, and 0.25 parts by mass of AIBN were heated and stirred at 90°C for 6 hours to prepare a copolymer-containing solution.

[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 4 parts by mass of methoxy-containing methacrylate represented by the above formula (8) Parts, 230 parts by mass of 1-propanediol methyl 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 6] 40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylate represented by the above formula (7), and 4 parts by mass of methoxy-containing acrylate represented by the following formula (11) Parts, 230 parts by mass of 1-propanediol methyl 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.

[Comparative Synthesis Example 1] 40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylate represented by the above formula (7), 230 parts by mass of 1-propanediol methyl ether acetate, and 0.25 parts by mass of AIBN were heated at 90°C After stirring for 6 hours, a solution containing a 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-propanediol methyl ether acetate to make the non-volatile content 8% to obtain a primer composition (Examples 1 to 6) , Comparative Example 1).

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

[Exterior] The bristle of the obtained primer composition was applied to a glass slide to a thickness of 2 μm, and was left to stand at 60°C for 30 minutes to dry, and further dried at 180°C for 30 minutes. An addition reaction hardening type silicone rubber composition (manufactured by Shin-Etsu Chemical Co., Ltd., KER-2600) was coated on the primer composition to a thickness of 2 mm, and cured at 150° C. for 1 hour, and the appearance was observed.

[Transmittance test] The bristle of the obtained primer composition was applied on a glass slide to a thickness of 2 μm, and left at 60° C. for 30 minutes to be dried to form a primer composition film. Using the glass slide as a blank sample, the transmittance (initial transmittance) of the glass slide on which the primer composition film was formed at a wavelength of 400 nm was measured, and it was 100%. Next, the glass slide on which the coating film of the primer composition was formed was heat-treated at 180° C.×500 hours, and the transmittance after the heat treatment was measured in the same manner as described above to determine the change from the initial transmittance.

[Adhesion (adhesion strength) test] A test piece 11 for an adhesion test as shown in FIG. 2 was produced. That is, on the single surfaces of the two Al substrates 12, 13 (manufactured by KDS, 25 mm in width), the primer composition obtained was applied to a thickness of 0.01 mm, and was left at 60° C. for 30 minutes and further at 180 It was dried at ℃ to form the coating films 14 and 15 of the primer composition. Put these Al substrates so that the coating films 14 and 15 on which the primer composition is formed face each other, and overlap these ends by 10 mm, and sandwich a 2 mm thick addition reaction hardening type polysiloxane rubber composition therebetween (Manufactured by Shin-Etsu Chemical Industry Co., Ltd., KER-2600), heated at 150°C for 30 minutes, to harden the addition reaction hardening type silicone rubber composition, to produce a cured product 16 made of silicone rubber composition Next (adjacent area 25 mm×10 mm=250 mm ² ) a test piece composed of two Al substrates. The ends of the Al substrates 12 and 13 of this test piece were stretched in the opposite direction (arrow direction in FIG. 2) at a stretching speed of 50 mm/min using a tensile tester (manufactured by Shimadzu Corporation, Autograph) to obtain each Adhesive strength per unit area (MPa).

[Corrosion resistance test] The resulting primer composition was filled in an LED package with a silver electrode at the bottom, left at 60°C for 30 minutes, and dried at 180°C, and an addition reaction hardening type polysiloxane rubber composition (Shin-Etsu Chemical Co., Ltd.) was coated on it. Industrial Co., Ltd., KER-2600) is 1 mm thick and cured at 150°C for 2 hours to produce a test piece with 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 placed at 70° C., and the degree of corrosion of silver plating after 1 day and 7 days was visually observed and evaluated on the basis of the following criteria. ○: No corrosion (discoloration) △: How much corrosion (discoloration) ×: Blackened

[Comparative Example 2] The above-mentioned adhesion (adhesion strength) test and corrosion resistance test were performed in the same manner as in Examples 1 to 6 and Comparative Example 1 except that the primer composition was not used.

As is apparent from the results shown in Table 1, in Examples 1 to 6 using the primer composition of the present invention, Al and the addition reaction hardening type silicone rubber composition were firmly bonded to the hardened material. Furthermore, in the heat resistance test of the film of the primer composition applied to the glass slide, there was no discoloration, the film itself did not change, and the heat resistance was also excellent. In addition, in the corrosion resistance test using the LED package equipped with the silver electrode, all of Examples 1 to 6 did not change color even after 7 days passed, and a high corrosion suppression effect was seen.

On the other hand, Comparative Example 1 using a primer composition different from the primer composition of the present invention has poor adhesion and corrosion resistance compared to Examples 1 to 6. In addition, in Comparative Example 2 which does not use the primer composition itself, compared to Examples 1 to 6, the adhesiveness and corrosion resistance are significantly poor.

Furthermore, the present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiments are examples, and have substantially the same structure as the technical idea described in the patent application scope of the present invention, and exert 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‧‧‧ Hardened product of addition reaction hardening type polysiloxane composition 6‧‧‧Metal electrode 7‧‧‧bond wire 11‧‧‧Test piece 12, 13‧‧‧Al substrate 14, 15‧‧‧ Primer composition coating 16‧‧‧hardened product of addition reaction hardening type silicone rubber composition

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

1‧‧‧Optical semiconductor device (LED lamp)

2‧‧‧ Primer composition

3‧‧‧LED

4‧‧‧ substrate

5‧‧‧ Hardened product of addition reaction hardening type polysiloxane composition

6‧‧‧Metal electrode

7‧‧‧bond wire

Claims (7)

A primer composition, which is a primer composition in which a substrate on which an optical semiconductor element is built, and a hardened product of an addition reaction hardening type polysiloxane composition that seals the aforementioned optical semiconductor element are attached, and its characteristics To contain (A) At least one of acrylates and methacrylates having more than one SiH group in one molecule, and at least one of acrylates and methacrylates having more than one alkoxy group in one molecule, and not having A copolymer composed of at least one of acrylate and methacrylate of SiH group and alkoxy group, and (B) Solvent. 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 according to claim 1 or claim 2, wherein the primer composition further contains (C) Silane coupling agent. An optical semiconductor device, characterized in that a substrate on which an optical semiconductor element is constructed, and a hardened product of an addition reaction hardening type polysiloxane composition that seals the optical semiconductor element are provided by, for example, claim 1 to claim 3 The primer composition of any of the following items. The optical semiconductor device according to claim 4, wherein the aforementioned optical semiconductor element is a light emitting diode. The optical semiconductor device according to claim 4 or claim 5, wherein the constituent material of the aforementioned substrate is polyamide, fiber-reinforced plastic, ceramic, polysiloxane, polysiloxane-modified polymer, or liquid crystal polymer. The optical semiconductor device according to claim 4 or claim 5, wherein the cured product of the addition reaction hardening type polysiloxane composition is rubber-like.

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