JP5541171B2 - Primer composition and optical semiconductor device using the composition - Google Patents

Description

  The present invention provides, for example, a primer composition that firmly bonds a substrate on which an optical semiconductor element such as an LED (light emitting diode) is mounted and a cured product of an addition reaction curable silicone composition that seals the optical semiconductor element, and the primer composition The present invention relates to an optical semiconductor device using the composition.

An LED lamp known as an optical semiconductor device has a light emitting diode (LED) as an optical semiconductor element and has an LED mounted on a substrate sealed with a sealing material made of a transparent resin. As a sealing material for sealing the LED, an epoxy resin-based composition has been widely used.
However, epoxy resin-based encapsulants are prone to cracking and yellowing due to increased heat generation and shorter wavelength of light due to recent miniaturization of semiconductor packages and higher brightness of LEDs, resulting in lower reliability. Was invited.

Therefore, a silicone composition is used as a sealing material from the viewpoint of excellent heat resistance (see, for example, Patent Document 1: JP 2000-198930 A). In particular, the addition reaction curable silicone composition is cured in a short time by heating and thus has high productivity and is suitable as an LED sealing material (see, for example, Japanese Patent Application Laid-Open No. 2004-292714).
However, it cannot be said that the adhesion between the substrate on which the LED is mounted and the sealing material made of the cured product of the addition reaction curable silicone composition is sufficient.

  As a substrate for mounting an LED, a polyphthalamide resin is frequently used because of its excellent mechanical strength, and a primer useful for the resin has been developed (for example, Patent Document 3: Japanese Patent Application Laid-Open No. 2008-179694). See the official gazette). However, for LEDs that require high power, the polyphthalamide resin does not have heat resistance and discolors. Recently, ceramics typified by alumina, which has better heat resistance than the polyphthalamide resin, are used as substrates. There are more and more cases. Peeling is likely to occur between the substrate made of alumina ceramic and the cured product of the addition reaction curable silicone composition.

Moreover, since a silicone composition is generally excellent in gas permeability, it is easy to receive the influence from an external environment. When the LED lamp is exposed to sulfur compounds or exhaust gas in the atmosphere, the sulfur compounds pass through 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.
In addition, the following literature is mentioned with the literature mentioned above as a prior art relevant to this invention.

JP 2000-198930 A JP 2004-292714 A JP 2008-179694 A JP 2010-168596 A JP 2004-339450 A JP 2005-93724 A JP 2007-246803 A

  The present invention has been made in view of the above circumstances, and improves the adhesion between 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. An object of the present invention is to provide a primer composition capable of preventing corrosion of a metal electrode formed thereon, and a highly reliable optical semiconductor device using the composition.

  As a result of intensive studies to achieve the above object, the present inventor mounted an optical semiconductor element by blending a composition with a silazane compound or polysilazane compound containing at least one silazane bond in one molecule. The bonded substrate, particularly an alumina ceramic substrate, and the cured product of the addition reaction curable silicone composition that seals the optical semiconductor element are firmly bonded, and the metal electrode formed on the substrate, particularly the corrosion of the Ag electrode, is corroded. It was found that a primer composition capable of preventing the above was obtained, and further that an optical semiconductor device using the composition had high reliability, which led to the present invention.

（式中、Ａは（メタ）アクリロキシ基含有基、メルカプト基含有基、エポキシ基含有基又はビニル基であり、ａ１、ｂ１は０≦ａ１＜１、０＜ｂ１≦１で、ａ１＋ｂ１＝１を満足する数、ａ２、ｂ２は０＜ａ２＜１、０＜ｂ２＜１で、ａ２＋ｂ２＝１を満足する数、ａ３、ｂ３は０≦ａ３＜１、０＜ｂ３≦１で、ａ３＋ｂ３＝１を満足する数である。）
（Ｂ）溶剤
を含有することを特徴とする光半導体用プライマー組成物。
〔請求項２〕
前記（Ｂ）成分の配合量が組成物全体の７０質量％以上であることを特徴とする請求項１に記載のプライマー組成物。
〔請求項３〕
更に、（Ｃ）シランカップリング剤
を含有することを特徴とする請求項１又は２に記載のプライマー組成物。
〔請求項４〕
請求項１乃至３のいずれか１項に記載のプライマー組成物により、光半導体素子を実装した基板と、前記光半導体素子を封止する付加反応硬化型シリコーン組成物の硬化物とが接着されてなることを特徴とする光半導体装置。
〔請求項５〕
前記光半導体素子が、発光ダイオードであることを特徴とする請求項４に記載の光半導体装置。
〔請求項６〕
前記付加反応硬化型シリコーン組成物の硬化物が、ゴム状であることを特徴とする請求項４又は５に記載の光半導体装置。 Accordingly, the present invention provides a primer composition shown below and an optical semiconductor device using the composition.
[Claim 1]
A primer composition for adhering a substrate comprising polyamide, ceramics, or liquid crystal polymer, 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,
(A) Polysilazane compound selected from the following formula

(In the formula, A is a (meth) acryloxy group-containing group, a mercapto group-containing group, an epoxy group-containing group or a vinyl group, and a1 and b1 are 0 ≦ a1 <1, 0 <b1 ≦ 1, and a1 + b1 = 1. A satisfying number, a2 and b2 are 0 <a2 <1, 0 <b2 <1, and a2 + b2 = 1, a3 and b3 are 0 ≦ a3 <1, 0 <b3 ≦ 1 and a3 + b3 = 1 Satisfied number.)
(B) A primer composition for an optical semiconductor comprising a solvent.
[Claim 2]
2. The primer composition according to claim 1, wherein the blending amount of the component (B) is 70% by mass or more of the entire composition.
[Claim 3]
Furthermore, (C) Silane coupling agent is contained, The primer composition of Claim 1 or 2 characterized by the above-mentioned.
[Claim 4]
4. The primer composition according to claim 1, wherein 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 are bonded together. An optical semiconductor device.
[Claim 5]
The optical semiconductor device according to claim 4, wherein the optical semiconductor element is a light emitting diode.
[Claim 6]
The optical semiconductor device according to claim 4, wherein the cured product of the addition reaction curable silicone composition is rubbery.

  According to the present invention, the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition for sealing the optical semiconductor element is improved, and the metal electrode formed on the substrate is improved. A primer composition capable of preventing corrosion is obtained, and an optical semiconductor device using the composition has high reliability.

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 an adhesive test in the Example of this invention.

<Primer composition>
The primer composition of the present invention comprises:
(A) It contains a silazane compound or polysilazane compound (B) having at least one silazane bond in one molecule. Hereinafter, this primer composition will be described.

[(A) component]
The silazane compound or polysilazane compound having at least one silazane bond in one molecule of the component (A) is a characteristic component of the present invention. For example, for a substrate on which an LED is mounted, particularly a ceramic substrate or a polyamide resin substrate. In addition to providing sufficient adhesion, the metal electrode (especially Ag electrode) formed on the substrate is prevented from corrosion over time.

（式中、Ｒは水素原子又は１価の有機基を示す。） Examples of the compound containing at least one silazane bond in one molecule include compounds having the structure shown below.

(In the formula, R represents a hydrogen atom or a monovalent organic group.)

  Here, as a monovalent organic group of R, a C1-C6, especially a C1-C3 unsubstituted or substituted monovalent hydrocarbon group is preferable. Examples of monovalent hydrocarbon groups include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups, octyl groups and other alkyl groups, cyclohexyl groups, etc. Alkenyl groups such as cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups, etc. , Those in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, such as chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl Groups and the like. R is preferably a hydrogen atom, a methyl group or an ethyl group, particularly preferably a hydrogen atom.

Polysilazane compounds include R ′ ₂ Si (NR) _2/2 units and / or R′Si (NR) _3/2 units (where R is the same as above, R ′ is a monovalent organic group) And a polysilazane compound having a branched structure having R′Si (NR) _3/2 units is preferable.

  Here, as R ′, the same as the unsubstituted or substituted monovalent hydrocarbon group exemplified as the monovalent organic group of R above can be exemplified, but also (meth) acryloxypropyl group, (meth) acryloxy (Meth) acryloxy group-containing group such as methyl group (in the present invention, “(meth) acryloxy” means “acryloyloxy” and / or “methacryloyloxy”, the same shall apply hereinafter), mercaptopropyl group, mercaptomethyl group, etc. Examples include mercapto group-containing groups, glycidoxypropyl groups, epoxy group-containing groups such as glycidoxymethyl groups, and the like. Among these, a (meth) acryloxy group-containing group, a mercapto group-containing group, an epoxy group-containing group, and an alkenyl group are preferable, and a (meth) acryloxy group-containing group is particularly preferable. R ′ may have two or more different R ′ molecules.

  It is preferable that the weight average molecular weight by GPC (gel permeation chromatography) measurement of the said polysilazane compound is 200-10,000, More preferably, it is 500-8,000, Most preferably, it is 1,000-5,000. . If the molecular weight is too small, the film strength may be insufficient, and if it is too large, the solubility in a solvent may be reduced.

（式中、ｍは３〜８の整数であり、Ａは（メタ）アクリロキシ基含有基、メルカプト基含有基、エポキシ基含有基又はビニル基であり、ａ１、ｂ１は０≦ａ１＜１、０＜ｂ１≦１で、ａ１＋ｂ１＝１を満足する数、ａ２、ｂ２は０＜ａ２＜１、０＜ｂ２＜１で、ａ２＋ｂ２＝１を満足する数、ａ３、ｂ３は０≦ａ３＜１、０＜ｂ３≦１で、ａ３＋ｂ３＝１を満足する数である。） Specific examples of the component (A) include those shown below.

(In the formula, m is an integer of 3 to 8, A is a (meth) acryloxy group-containing group, mercapto group-containing group, epoxy group-containing group or vinyl group, and a1 and b1 are 0 ≦ a1 <1,0. <B1 ≦ 1 and a1 + b1 = 1 satisfying number, a2 and b2 satisfy 0 <a2 <1, 0 <b2 <1 and a2 + b2 = 1 satisfying, a3 and b3 satisfy 0 ≦ a3 <1, 0 <B3 ≦ 1 and a3 + b3 = 1 is satisfied.)

（式中、Ａ、ａ１、ｂ１は上記と同じ。） Of these, the following are preferred.

(In the formula, A, a1, and b1 are the same as above.)

  The component (A) can be prepared by a known method. For example, the component (A) can be prepared by excessively reacting ammonia gas with chlorosilane having an organic group with respect to moles of chloro.

  The amount of the component (A) is not particularly limited as long as it is an amount that dissolves in the component (B), but is 30% by mass or less of the entire composition (the total of the components (A) and (B)). More preferably, it is 0.01-20 mass%, More preferably, it is 0.1-10 mass%, Most preferably, it is 0.2-5 mass%. If the content of the component (A) is small, the corrosion prevention of the metal electrode, particularly the Ag electrode may be insufficient. If the content is too large, the surface may be uneven, and the performance as a primer may be insufficient.

[Component (B)]
The solvent of (B) component will not be specifically limited if the said (A) component which comprises this composition, and the arbitrary component mentioned later are melt | dissolved, A well-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, Examples include ester solvents such as ethyl acetate, ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone, alcohol solvents such as ethanol, isopropanol, and butanol, ligroin, cyclohexanone, diethyl ether, rubber volatile oil, and silicone solvents. Of these, ethyl acetate, hexane, and acetone are preferably used.
(B) A component may be used individually by 1 type according to the evaporation rate at the time of primer application | coating operation | work, or may be used as a mixed solvent combining 2 or more types.

  The blending amount of the component (B) is not particularly limited as long as it does not hinder the workability during coating and drying, but is 70% by mass or more of the entire composition (the sum of the components (A) and (B)). More preferably, it is 80-99.99 mass%, More preferably, it is 90-99.9 mass%, Most preferably, it is 95-99.8 mass%. If the blending amount of the component (B) is small, the surface may be uneven, and the performance as a primer may be insufficient, and if it is too large, corrosion prevention of the metal electrode, particularly the Ag electrode, may be insufficient.

[Component (C)]
In the present invention, (C) a silane coupling agent can be further blended. 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 such as glycidoxypropyltrimethoxysilane. -Containing silane coupling agents, (meth) acryloxy group-containing silane coupling agents such as methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltrimethoxysilane, and mercapto group-containing silane coupling agents such as mercaptopropyltrimethoxysilane . Of these, vinyltrimethoxysilane and methacryloyloxypropyltrimethoxysilane are preferred.

  (C) As a compounding quantity when using a component, it is preferable that it is 0.05-10 mass% of the whole composition (the sum total of (A)-(C) component), More preferably, it is 0.1-0.1%. 3% by mass. If the blending amount of the component (C) is too small, the effect of improving the adhesiveness may be insufficient, and if it is too large, the effect of improving the adhesiveness may not be obtained.

[Other ingredients]
The primer composition of this invention can mix | blend other arbitrary components other than the said component as needed. For example, benzotriazole, butylhydroxytoluene, hydroquinone or a derivative thereof can be blended as a metal corrosion inhibitor. Benzotriazole, dibutylhydroxytoluene, hydroquinone or derivatives thereof, LED lamps are exposed to harsh external environments, for example, sulfur compounds in the atmosphere are encapsulated in 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 sealing material, particularly the Ag electrode.
When the metal corrosion inhibitor is added, the blending amount is 0.005 to 1 part by mass, particularly 0.01 to 0.5 part by mass with respect to 100 parts by mass in total of the components (A) and (B). Is preferred.

  Furthermore, as other optional components, reinforcing fillers, dyes, pigments, heat resistance improvers, antioxidants, adhesion promoters, and the like may be added as long as the object of the present invention is not impaired.

[Method for producing primer composition]
Examples of the method for producing the primer composition of the present invention include a method of uniformly mixing the above components (A) and (B) and optional components as necessary with a mixing stirrer at room temperature.

<Optical semiconductor device>
The optical semiconductor device of the present invention is characterized in that 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 are bonded to each other by the primer composition. And The optical semiconductor device of the present invention will be described below with reference to the drawings.

  FIG. 1 is a sectional view of an LED (light emitting diode) lamp showing an example of an optical semiconductor device according to the present invention. In the optical semiconductor device (LED lamp) 1, the substrate 4 on which the LED 3 is mounted as an optical semiconductor element and the cured product 5 of the addition reaction curable silicone composition that seals the LED 3 are bonded to each other by the primer composition 2 described above. ing. 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 resins, various fiber reinforced plastics, ceramics, liquid crystal polymers and the like. In the present invention, ceramics are preferable from the viewpoint of good heat resistance, and alumina ceramics are particularly preferable.

  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 rubbery. As the addition reaction curable silicone composition, those 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. The silicone composition contains a reaction inhibitor, a colorant, a flame retardant, a heat resistance improver, a plasticizer, a reinforcing silica, an adhesion promoter, and the like as other optional components. You may add in the range which does not affect to.

  As a manufacturing method of the optical semiconductor device (LED lamp) 1, 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 in advance by Ag plating, and wire bonding is performed. An electrode terminal (not shown) of the LED 3 and the metal electrode 6 are electrically connected, and then the substrate 4 on which the LED 3 is mounted is cleaned as necessary, and then a coating device such as a spinner or a sprayer is used. After the primer composition 2 is applied to the substrate 4 by, for example, 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 0.01 to 1 μm is formed. To do. After the primer treatment, the addition reaction curable silicone composition is applied with a dispenser or the like, and allowed to stand or heat cure at room temperature 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 the component (A), the substrate on which the optical semiconductor element such as an LED is mounted and the cured product of the addition reaction curable silicone composition are firmly bonded. In addition, a highly reliable optical semiconductor device, particularly an LED lamp can be provided.

  Also, when the LED lamp is exposed to a harsh external environment and sulfur compounds in the atmosphere penetrate into the cured product of the silicone composition, the primer composition can be used on the substrate. Corrosion of metal electrodes, particularly Ag electrodes can be suppressed.

  In the above-described embodiment, the LED is described as an example of the optical semiconductor element. However, other than this, for example, it can be applied to a phototransistor, a photodiode, a CCD, a solar cell module, an EPROM, a photocoupler, and the like. .

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Synthesis Example 1] Synthesis of polysilazane compound Into a 2 L four-necked flask equipped with a serpentine condenser and a thermometer, 1,000 g of ethyl acetate was added, and 3.8 g (0.015 mol) of methacryloyloxypropyltrichlorosilane was added thereto. Then, 41.5 g (0.28 mol) of methyltrichlorosilane was added and stirred in an ice bath. When the inside of the system became 10 ° C. or lower, 15 g (0.89 mol) of ammonia gas was blown in, and the mixture was stirred for 3 hours. After the stirring was completed, ammonium chloride as a by-product was filtered off and finished as a 4% by mass polysilazane solution of ethyl acetate.

When the synthesized polysilazane compound was measured by ²⁹ Si-NMR and ¹ H-NMR, the structure of the polysilazane was as shown below, and the weight average molecular weight determined by GPC measurement (THF solvent) was 2,000.

[Synthesis Example 2] Synthesis of polysilazane compound Into a 2 L four-necked flask equipped with a serpentine condenser and a thermometer, 1,000 g of ethyl acetate was added, and 19 g (0.15 mol) of dimethyldichlorosilane and methyltrichlorosilane were added thereto. 22.5 g (0.15 mol) was added and stirred in an ice bath. When the inside of the system became 10 ° C. or less, 14 g (0.83 mol) of ammonia gas was blown, and stirred for 3 hours. After the stirring was completed, ammonium chloride as a by-product was filtered off and finished as a 4% by mass polysilazane solution of ethyl acetate.

When the synthesized polysilazane compound was measured by ²⁹ Si-NMR and ¹ H-NMR, the structure of the polysilazane was as shown below, and the weight average molecular weight determined by GPC measurement (THF solvent) was 2,000.

[Comparative Synthesis Example 1]
100 parts by weight of methyl methacrylate, 900 parts by weight of ethyl acetate and 0.5 parts by weight of AIBN (2,2′-azobisisobutyronitrile) are heated and stirred at 80 ° C. for 3 hours to contain a methyl methacrylate polymer. A solution was prepared.

[Comparative Synthesis Example 2]
83 parts by weight of methyl methacrylate, 17 parts by weight of γ-methacryloyloxypropyltrimethoxysilane, 900 parts by weight of ethyl acetate, 0.5 parts by weight of AIBN (2,2′-azobisisobutyronitrile) at 80 ° C. for 3 hours A solution containing a methyl methacrylate polymer was prepared by heating and stirring.

[Example 1]
To 100 parts by mass of the ethyl acetate solution of the polysilazane compound prepared in Synthesis Example 1, 1 part by mass of vinyltrimethoxysilane and 0.1 part by mass of hydroquinone were added and stirred 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 methods shown below, and the results are shown in Table 1. The physical properties shown in Table 1 are values measured at 23 ° C.

[appearance]
The obtained primer composition was brush-coated on an alumina ceramic plate to a thickness of 2 μm, allowed to stand at 23 ° C. for 30 minutes and dried, and then an addition reaction curable silicone rubber composition was formed on the primer composition. (Shin-Etsu Chemical Co., Ltd., KER-2700) was applied at a thickness of 2 mm and cured at 150 ° C. for 1 hour, and the appearance was observed.

[Transmissivity test]
The obtained primer composition was brush-coated on a slide glass so as to have a thickness of 2 μm, and allowed to stand at 23 ° C. for 30 minutes to dry, thereby forming a primer composition film. The transmittance at a wavelength of 400 nm of the slide glass on which the primer composition film was formed was measured using air as a blank. Further, the slide glass on which the primer composition film was formed was heat-deteriorated at 150 ° C. for 500 hours, and the transmittance was measured in the same manner as described above.

[Adhesion (adhesion strength) test]
A test piece 11 for adhesion test as shown in FIG. 2 was produced. That is, the obtained primer composition was applied with a thickness of 0.01 mm on one side of each of two alumina ceramic substrates 12 and 13 (KDS Corp., width 25 mm) and left at 23 ° C. for 60 minutes. It was made to dry and the primer composition films 14 and 15 were formed. These alumina ceramic substrates are faced with the surfaces on which the primer composition coatings 14 and 15 are formed so that their end portions overlap each other by 10 mm, during which an addition reaction curable silicone rubber composition (manufactured by Shin-Etsu Chemical Co., Ltd., KER-2700) is sandwiched at a thickness of 1 mm and heated at 150 ° C. for 2 hours to cure the addition reaction curable silicone rubber composition, and the cured product 16 of the silicone rubber composition is bonded (bonding area 25 mm × A test piece made of two alumina ceramic substrates with 10 mm = 250 mm ² ) was produced.
Each end of the alumina ceramic substrates 12 and 13 of this test piece is pulled in the opposite direction (arrow direction in FIG. 2) using a tensile tester (manufactured by Shimadzu Corporation, Autograph) at a pulling speed of 50 mm / min. The adhesive strength per area (MPa) was determined.

[Corrosion test]
The obtained primer composition was brush-coated on a silver-plated plate to a thickness of 2 μm, allowed to stand at 23 ° C. for 30 minutes and dried, and then an addition reaction curable silicone rubber composition (Shin-Etsu Chemical) Kogyo Co., Ltd., KER-2700) was applied at a thickness of 1 mm and cured at 150 ° C. for 1 hour to prepare a test piece having a silicone rubber layer. This test piece is put in a 100 cc glass bottle together with 0.1 g of sulfur crystals, sealed and left at 70 ° C., and the silicone rubber layer of the test piece is peeled off at each time point after 1 day, 8 days, and 12 days, The degree of corrosion of the part where the silicone rubber layer was peeled was visually observed and evaluated according to the following criteria.
○: No corrosion (discoloration) △: Some corrosion (discoloration)
×: Black change

[Example 2]
100 parts by mass of the ethyl acetate solution of the polysilazane compound prepared in Synthesis Example 2 was used as it was to obtain a primer composition. Using this composition, various physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative Example 1]
A direct addition reaction curable silicone rubber composition (manufactured by Shin-Etsu Chemical Co., Ltd., KER-2700) was applied to an alumina ceramic plate and a silver plating plate without applying the primer composition. The physical properties (adhesiveness and corrosiveness) were measured in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative Example 2]
1 part by mass of vinyltrimethoxysilane and 0.1 part by mass of hydroquinone were added to 100 parts by mass of an ethyl acetate solution of the methacrylic acid methyl ester polymer prepared in Comparative Synthesis Example 1 and stirred to obtain a primer composition. Using this composition, various physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative Example 3]
1 part by mass of γ-glycidoxypropyltrimethoxysilane and 1 part by mass of tetra-n-butyl titanate were added to 100 parts by mass of the ethyl acetate solution of the methyl methacrylate polymer prepared in Comparative Synthesis Example 2 and stirred. A primer composition was obtained. Using this composition, various physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

As is apparent from the results in Table 1, the primer compositions of Examples 1 and 2 blended with the polysilazane compound firmly bonded the alumina ceramic and the rubber-like cured product of the addition reaction curable silicone rubber composition. .
In the heat resistance test of the primer composition coating applied to the slide glass, there was no discoloration, no change in the coating itself, and excellent heat resistance.
In addition, in the corrosivity test using a silver plating plate instead of alumina ceramics, both Examples 1 and 2 had no discoloration after 1 day, and there was an effect of suppressing discoloration (corrosion) even after 12 days. It was.

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 Alumina ceramic substrate 14, 15 Primer composition coating 16 Cured product of addition reaction curable silicone rubber composition

Claims (6)

A primer composition for adhering a substrate comprising polyamide, ceramics, or liquid crystal polymer, 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,
(A) Polysilazane compound selected from the following formula

(In the formula, A is a (meth) acryloxy group-containing group, a mercapto group-containing group, an epoxy group-containing group or a vinyl group, and a1 and b1 are 0 ≦ a1 <1, 0 <b1 ≦ 1, and a1 + b1 = 1. A satisfying number, a2 and b2 are 0 <a2 <1, 0 <b2 <1, and a2 + b2 = 1, a3 and b3 are 0 ≦ a3 <1, 0 <b3 ≦ 1 and a3 + b3 = 1 Satisfied number.)
(B) A primer composition for an optical semiconductor comprising a solvent.   2. The primer composition according to claim 1, wherein the blending amount of the component (B) is 70% by mass or more of the entire composition. Furthermore, (C) Silane coupling agent is contained, The primer composition of Claim 1 or 2 characterized by the above-mentioned.   4. The primer composition according to claim 1, wherein 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 are bonded together. An optical semiconductor device.   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, wherein the cured product of the addition reaction curable silicone composition is rubbery.

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