Condensation-curable silicone resin composition and die attach material for optical semiconductor apparatus

Abstract

To provide a condensation-curable silicone resin composition that produces a resin cured product with high hardness and high resin strength, and has excellent adhesion capability to substrates.SOLUTION: A condensation-curable silicone resin composition includes: (A) a polyorganosiloxane having a hydroxyl group and a hydrolysable group represented by the following formula (1), CH3Si(OR)a(OH)bO(3-a-b) / 2 (1); (B) an organosilicate oligomer which is a partially hydrolyzed condensate of tetraalkyl orthosilicate; (C) a linear polyorganosiloxane having an epoxy group and a hydrosilyl group in the molecule, represented by the following formula (2); and (D) an inorganic filler.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a condensation-curable silicone resin composition and a die attach material for an optical semiconductor device.

Background Art

[0002] A die attach material is used for the purpose of solidifying a semiconductor chip on a substrate, and characteristics such as high adhesive strength and high adhesiveness are required from the viewpoint of reliability. Among them, as a die attach material for an LED chip, an addition-curable silicone resin composition such as a methyl silicone-based one having high heat resistance and light resistance is often used. However, recently, LED devices equipped with LED chips of 300 μm or less, which are smaller than the 600 μm LED chips used as the standard size, have emerged. In the conventional methyl silicone-based addition-curable resin compositions disclosed in Patent Document 1 and Patent Document 2, there is a problem that the holding force of the LED chip cannot satisfy the required value. In addition, in the case of an addition-curable resin composition, there remains a problem that the use environment is limited in order to prevent curing inhibition due to the nature of the reaction.

[0003] On the other hand, a method of using a conventional condensation-curable silicone resin composition as disclosed in Patent Document 3 as a die attach material for an LED device has been disclosed. However, problems have been pointed out particularly in the instability of the adhesive strength and the fracture mode of the resin in the adhesion test in the case of small-sized LED chips, and an improvement in the adhesive strength is also desired.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a condensation-curable silicone resin composition capable of obtaining a resin cured product having high hardness and high resin strength and excellent adhesion to a substrate.

Means for Solving the Problems

[0006] In order to solve the above problems, the present invention provides (A) The following formula (1) CH3Si(OR) a (OH) b O (3-a-b) / 2 (1) (In the formula, R represents the same or different alkyl groups having 1 to 6 carbon atoms, and is a number satisfying 0 < a ≦ 0.4, 0.001 ≦ b ≦ 0.5, and 0.001 < a + b ≦ 0.9.) Polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by: 100 parts by mass, (B) Organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate: 10 to 50 parts by mass with respect to 100 parts by mass of component (A), (C) The following formula (2)

Chemical formula

[0007] With such a condensation-curing silicone resin composition, a resin cured product having high hardness and resin strength can be obtained, and it also has excellent adhesion to a substrate.

[0008] In the condensation-curing silicone resin composition of the present invention, it is preferable that the alkyl group of the tetraalkyl orthosilicate as the component (B) has 1 to 6 carbon atoms.

[0009] With such a condensation-curing silicone resin composition, it is easier to obtain a product with higher hardness and resin strength, and it is also preferable in terms of reactivity and cost.

[0010] Furthermore, in the condensation-curing silicone resin composition of the present invention, it is preferable that the weight average molecular weight of the component (C) is 1,000 to 20,000 and the epoxy equivalent is 400 to 650 g / mol.

[0011] With such a condensation-curing silicone resin composition, there is no risk of clouding of the appearance, and sufficient adhesiveness to the substrate can be obtained.

[0012] Furthermore, it is preferable that the condensation-curing silicone resin composition of the present invention contains a condensation-curing catalyst as the component (E).

[0013] With such a condensation-curing silicone resin composition, it can be cured efficiently.

[0014] Furthermore, the present invention provides a die attach material for an optical semiconductor device containing the condensation-curing silicone resin composition of the present invention.

[0015] Such a die attach material for an optical semiconductor device can provide a highly reliable LED device because it has excellent adhesion strength even for a small-sized LED chip.

Effects of the Invention

[0016] According to the condensation-curing silicone resin composition of the present invention, when used as a die attach material for LEDs, even for small-sized LED chips, it can provide a highly reliable LED device because of its excellent adhesive strength. Also, due to the nature of the reaction, the possibility of the use environment being restricted is low. Therefore, the condensation-curing silicone resin composition of the present invention is extremely useful as a die attach material for LEDs.

Embodiments for Carrying Out the Invention

[0017] As described above, there has been a demand for the development of a condensation-curing silicone resin composition having excellent adhesive strength even for small-sized LED chips.

[0018] As a result of intensive studies on the above problems, the present inventors have found that a condensation-curing silicone resin composition containing the components (A), (B), (C), and (D) has excellent adhesion to a substrate and can exhibit high adhesive strength even in small-sized LED chips, and thus completed the present invention.

[0019] That is, the present invention is (A) The following formula (1) CH3Si(OR) a (OH) b O (3-a-b) / 2 (1) (In the formula, R represents the same or different alkyl groups having 1 to 6 carbon atoms, and a is a number satisfying 0 < a ≤ 0.4, 0.001 ≤ b ≤ 0.5, and 0.001 < a + b ≤ 0.9.) Polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by: 100 parts by mass, (B) Organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate: 10 to 50 parts by mass with respect to 100 parts by mass of component (A), (C) The following formula (2)

Chemical formula

[0020] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.)

[0021] [(A) Polyorganosiloxane having a hydroxyl group and a hydrolyzable group] The (A) component is a polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by the following formula (1). CH3Si(OR) a (OH) b O (3-a-b) / 2 (1) (In the formula, R represents the same or different alkyl groups having 1 to 6 carbon atoms, and 0 < a ≦ 0.4, 0.001 ≦ b ≦ 0.5, 0.001 < a + b ≦ 0.9 are satisfied.)

[0022] In the above formula (1), examples of the alkyl group having 1 to 6 carbon atoms represented by R 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, a cyclohexyl group, and the like. Among them, as the above R, a methyl group is particularly preferable from the viewpoints of reactivity and cost.)

[0023] The method for producing the polyorganosiloxane represented by the above formula (1) is not particularly limited. For example, it can be synthesized by hydrolysis and condensation of the corresponding alkoxysilane under acidic conditions.)

[0024] In the above formula (1), the content a of the hydrolyzable group (OR) directly bonded to the silicon atom is 0 < a ≤ 0.4, preferably 0.05 ≤ a ≤ 0.3. If a exceeds 0.4, the strength of the resulting cured product may decrease, which is not preferable.

[0025] In the above formula (1), the content b of the hydroxyl group (OH) directly bonded to the silicon atom is 0.001 ≤ b ≤ 0.5, preferably 0.005 ≤ b ≤ 0.4. If b is less than 0.001, the reactivity decreases, and if it exceeds 0.5, the storage stability of the cured product decreases, which is not preferable.

[0026] Also, the content a + b of the hydroxyl group and the hydrolyzable group directly bonded to the silicon atom constituting the main chain structure of the polymer is in the range of 0.001 < a + b ≤ 0.9, preferably 0.06 ≤ a + b < 0.8.

[0027] As is clear from the above formula (1), the component (A) of the present invention is a polyorganosiloxane composed only of T units (trifunctional siloxane units).

[0028] The weight average molecular weight Mw of the above component (A) by GPC is preferably 1,000 to 10,000, more preferably 2,000 to 6,000. If the molecular weight is in the range of 1,000 to 10,000, sufficient resin strength can be obtained as a die attach material, and a practical viscosity range is achieved, which is preferable. In addition, the weight average molecular weight referred to in the present invention means the weight average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) measured under the following conditions.

[0029] [Measurement conditions] · Developing solvent: Tetrahydrofuran (THF) · Flow rate: 0.6 mL / min · Detector: Differential refractive index detector (RI) · Column: TSK Guardcolumn SuperH-L ·TSKgel SuperH4000 (6.0 mm I.D. × 15 cm × 1) ·TSKgel SuperH3000 (6.0 mm I.D. × 15 cm × 1 ·TSKgel SuperH2000 (6.0 mm I.D. × 15 cm × 1 (All are manufactured by Tosoh Corporation) ·Column temperature: 40 °C ·Sample injection volume: 20 μl (THF solution with a concentration of 0.5 mass%)

[0030] [(B) Organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate] Component (B) is an organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate. The alkyl group preferably has 1 to 6 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, etc. Among them, from the viewpoints of reactivity or cost, methyl group or ethyl group is particularly preferable.

[0031] The number of monomer units n of the above organosilicate oligomer is not particularly limited, but preferably in the range of 1 ≤ n ≤ 20, more preferably in the range of 3 ≤ n ≤ 10. If the number of monomer units n is 20 or less, the viscosity becomes appropriate and the handleability of the resin composition is excellent.

[0032] In the condensation curable silicone resin composition of the present invention, the amount of the above component (B) is 10 to 50 parts by mass, preferably 20 to 45 parts by mass, based on 100 parts by mass of the above component (A). If it is less than 10 parts by mass, the strength of the resin may decrease, and if it exceeds 50 parts by mass, the volatile components due to the condensation reaction become excessive, which is not preferable.

[0033] The production method of the above organosilicate oligomer is not particularly limited, and it can be synthesized by hydrolysis condensation of the corresponding tetraalkyl orthosilicate under acidic conditions.

[0034] <Linear polyorganosiloxane having an epoxy group and a hydrosilyl group> (C) component is a linear polyorganosiloxane having an epoxy group and a hydrosilyl group in the molecule, represented by the following formula (2). [Chemical formula] (In formula (2), R 1 is, independently of one another, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an epoxy group-containing organic group, c is a number satisfying 1 ≦ c ≦ 260, and Ep is, independently of one another, an organic group having one or more epoxy groups in the substituent. However, one or more of the above R 1 are hydrogen atoms.)

[0035] The linear polyorganosiloxane represented by the above formula (2) has improved adhesion to the substrate due to the effects of the hydrosilyl group in the side chain and the epoxy group at the end.

[0036] In the above formula (2), examples of the alkyl group having 1 to 12 carbon atoms represented by R 1 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, a cyclohexyl group, an octyl group, a nonyl group, a decyl group, etc. Among them, from the viewpoint of cost, the methyl group is particularly preferable as the above R 1 .

[0037] The range of c in the above formula (2) is a number satisfying 1 ≦ c ≦ 260, preferably in the range of 10 ≦ c ≦ 100. If c exceeds 260, sufficient adhesion may not be imparted, which is not preferable.

[0038] Further, the weight average molecular weight of the above (C) component is 1,000 to 20,000, preferably in the range of 4,000 to 10,000. If the weight average molecular weight is 20,000 or less, there is no fear that the appearance of the silicone resin cured product will become cloudy, and if the weight average molecular weight is 1,000 or more, sufficient adhesion to the substrate can be obtained.

[0039] Furthermore, the epoxy equivalent of the above component (C) is preferably in the range of 400 to 650 g / mol, more preferably in the range of 500 to 600 g / mol. If the epoxy equivalent is 650 g / mol or less, there is no risk of clouding the appearance of the silicone resin cured product, and if the epoxy equivalent is 400 g / mol or more, sufficient adhesiveness to the substrate can be obtained.

[0040] In the condensation-curable silicone resin composition of the present invention, the amount of the above component (C) is 0.1 to 10 parts by mass, preferably 1.0 to 8 parts by mass, based on 100 parts by mass in total of the above components (A) and (B). When the amount of the above component (C) exceeds 10 parts by mass based on 100 parts by mass in total of the above components (A) and (B), the appearance of the silicone resin cured product becomes cloudy, and if it is less than 0.1 part by mass, the adhesiveness to the substrate becomes insufficient.

[0041] The production method of the above component (C) is not particularly limited, but as an example, it can be synthesized by a hydrosilylation reaction of a polyorganosiloxane compound having a hydrosilyl group at the terminal and an epoxy compound having an alkenyl group in the presence of a catalyst.

[0042] Here, the structure of the polyorganosiloxane compound having a hydrosilyl group at the terminal is not particularly limited, but a linear polyorganosiloxane compound represented by the following formula can be exemplified.

Chemical formula

[0043] Here, the epoxy compound having an alkenyl group is not particularly limited, but an epoxy compound represented by the following formula can be exemplified.

Chemical formula

[0044] [(D) Inorganic filler] Component (D) of the present invention is an inorganic filler. The purpose is to improve the strength of the resulting cured product or to impart thixotropy to improve the coating workability of the diattach material. Examples of the inorganic filler include fumed silica, fumed titanium dioxide, etc. In particular, from the viewpoint of the transparency of the resulting cured product, it is preferable to use fumed silica as the inorganic filler.

[0045] (D) The blending amount of the inorganic filler is 1 to 10 parts by mass, preferably in the range of 2 to 8 parts by mass, based on 100 parts by mass of component (A). If it is less than 1 part by mass, sufficient strength may not be obtained, and if it exceeds 10 parts by mass, the viscosity may become excessively large, which is not preferable.

[0046] In particular, when using fumed silica as the inorganic filler, from the viewpoint of compatibility with the silicone resin, it is preferable that the silica surface is treated with a hydrophobic group. Specific examples of the hydrophobic group include alkylsilyl groups such as trimethylsilyl group and dimethylsilyl group.

[0047] Also, by surface treatment, it is possible to suppress the interaction between the epoxy group contained in the component (C) and the hydroxysilyl group on the surface of fumed silica, and there is also an effect of improving the storage stability. For this reason, as fumed silica, those that are sufficiently surface-treated are preferable. Specifically, the BET specific surface area is 150 m 2 / g or more and 290 m 2 / g or less, preferably 170 m 2 / g or more and 230 m 2 / g or less of fumed silica is preferably used. As commercially available fumed silica surface-treated with the above alkylsilyl group, R812 (specific surface area 230 - 290 m 2 / g) and RX300 (specific surface area 180 - 220 m 2 / g) surface-treated with a trimethylsilyl group of Nippon Aerosil Co., Ltd., and R976 (specific surface area 225 - 275 m 2 / g), R976S (specific surface area 215 - 265 m 2 / g), etc.

[0048] [(E) Condensation curing catalyst] The condensation curable silicone composition of the present invention contains the above-mentioned components (A), (B), (C) and (D) as essential components, but may contain (E) a condensation curing catalyst and the like as required. The condensation curing catalyst promotes the reaction in which hydrolyzable silyl groups such as alkoxysilyl groups and silanol groups contained in the above organopolysiloxane are hydrolytically condensed with moisture in the air, and then promotes the dehydration condensation reaction between silanols, and as a result, it is a component that promotes the curing of the composition, and is added to efficiently cure the condensation curable silicone composition of the present invention.

[0049] The addition amount of the component (E) is not particularly limited, but considering adjusting the curing rate to an appropriate range to produce a cured product with desired physical properties and improving the workability during coating, etc., the amount of the metal element t (ppm) as the addition amount relative to 100 parts by mass of the component (A) is in the range of 0 ≦ t ≦ 1,000, preferably 100 ≦ t ≦ 500 is even more preferable. If the catalyst amount t is 1,000 or less, appropriate storage stability can also be obtained.

[0050] The curing catalyst is not particularly limited as long as it is a curing catalyst used for curing general condensation-curing type compositions. For example, there may be mentioned organic carboxylates of metals such as tin, titanium, zirconium, zinc, and aluminum, organic chelate compounds, and alkoxide compounds. Examples of the tin compound include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, and dibutyltin dioctoate. Examples of the titanium compound include tetraethoxytitanium, tetraisopropyl titanate, tetrabutyl titanate, diisopropoxybis(acetylacetonate)titanium, and diisopropoxybis(ethyl acetoacetate)titanium. Examples of the zirconium catalyst include tetrapropoxyzirconium, tetrabutoxyzirconium, tetraacetylacetonate zirconium, and tetraacetylacetonate zirconium. Examples of the zinc compound include zinc acetate, zinc acetylacetonate, zinc octylate, zinc laurate, and zinc naphthenate. Examples of the aluminum compound include aluminum trihydroxide, aluminum tributoxide, aluminum triacetylacetonate, aluminum bis(ethyl acetoacetate)monoacetylacetonate, and aluminum triethyl acetoacetate. and so on.

[0051] In addition, various additives may be added to the condensation-curing silicone resin composition of the present invention as necessary. For example, the shrinkage rate during curing, and the coefficient of thermal expansion, heat resistance, thermal conductivity, oxidation resistance, etc. of the resulting cured product can be appropriately adjusted by various additives. Such additives include non-reinforcing inorganic fillers other than the above component (D) such as quartz powder, glass fiber, calcium carbonate, magnesium carbonate, aluminum hydroxide, alumina (aluminum oxide), aluminum nitride, magnesium oxide, and boron nitride, and antioxidants such as hydroquinone and 2,6-tert-butyl-p-cresol.

[0052] [Curing Method] The condensation-curing silicone resin composition of the present invention can be cured after being applied onto a substrate according to the intended use, and preferably can be heat-cured in the temperature range of 60°C to 200°C, more preferably in the temperature range of 100°C to 170°C. If the heating temperature is within the above range, there is no risk of a decrease in the adhesive strength between the substrate and the resin cured product. The heating curing time may be 1 to 4 hours, and a step curing method may also be adopted.

[0053] By using the above polyorganosiloxane in a specific combination, the condensation-curing silicone resin composition of the present invention is excellent in adhesion to a substrate compared with ordinary thermosetting silicone resin compositions, and can exhibit high adhesive strength even in small-sized LED chips. In addition, in the case of a general addition-curing type using a platinum catalyst, the use environment is limited in order to prevent curing inhibition due to the nature of the reaction. However, the condensation-curing silicone resin composition developed this time can be suitably used for various electronic component applications regardless of the use environment of the substrate. Specifically, it can be suitably used as a die attach material for optical semiconductor devices.

Examples

[0054] Hereinafter, the present invention will be specifically described using Examples and Comparative Examples, but the present invention is not limited thereto.

[0055] Note that "parts" means "parts by mass", Me means "methyl group", Vi means "vinyl group", Ep means "1,2-epoxy-4-ethylcyclohexyl group", and Ep' means "γ-glycidoxypropyl group", respectively.

[0056] The weight average molecular weight refers to the weight average molecular weight measured by GPC measurement under the conditions described above. In the following Examples, the amount of Si-H groups indicates the number of moles of hydrogen atoms directly bonded to silicon atoms in the molecule, and is quantified by 1H-NMR measurement using a nuclear magnetic resonance (NMR) measurement apparatus manufactured by Bruker Corporation with dimethyl sulfoxide (DMSO) as an internal standard. 1 It is a value quantified with dimethyl sulfoxide (DMSO) as an internal standard by 1H-NMR measurement.

[0057] The components listed in Tables 1 and 2 are described below.

[0058] [Component (A)] (a-1): 1,200g of KC-89RP (Shin-Etsu Chemical Co., Ltd.), 1,200g of toluene, 163g of IPA, and 26g of methanesulfonic acid were charged into a reactor, and 289g of distilled water was added dropwise to carry out a hydrolysis reaction at room temperature for 100 minutes. After that, 26g of sodium bicarbonate was added dropwise to neutralize. After maturing while removing the by-product alcohol at 72°C, the remaining solvent was removed to synthesize an organopolysiloxane with a weight average molecular weight Mw of 3,900 as measured by GPC, which is represented by the following formula. CH3Si(OCH3) 0.18 (OH) 0.013 O 2.8 / 2

[0059] [(B) Component] (b-1): Tetraethyl orthosilicate oligomer (manufactured by Colcoat Co., Ltd.: Ethyl silicate 40, average number of monomer units n = 5) (b-2): Tetramethyl orthosilicate oligomer (Colcoat Co., Ltd.: Methyl silicate 51, average number of monomer units n = 4)

[0060] [(C) component] (c-1): The siloxane unit is EpMe2SiO 1 / 2 The unit is 2 mol%, Me2Si 2 / 2 The unit is 70 mol%, HMeSiO 2 / 2 An organopolysiloxane having a unit of 28 mol%, a weight average molecular weight Mw of 6,800 as measured by GPC, and an epoxy equivalent of 570 g / mol. (c=98) (c-2): The siloxane unit is Ep'SiO 3 / 2 Units: 3 mol%, Me2SiO 2 / 2 The unit is 84 mol%, ViSiO 3 / 2 is represented by 13 mol %, the weight average molecular weight is 2,600, and the epoxy equivalent is 950 g / mol. (c-3): An organic compound represented by the following formula synthesized by the method described in Japanese Patent Publication No. 2012-518610. [Chemical formula]

[0061] [Component (D)] (d-1): Fumed silica (manufactured by Nippon Aerosil Co., Ltd.: Aerosil RX-300)

[0062] [Component (E)] (e-1): A 1-butanol solution containing 2% by mass of zirconium of zirconium alkoxide (manufactured by Matsumoto Fine Chemical Co., Ltd.: ZA-65) (e-2): A toluene solution containing 2% by mass of zirconium of zirconium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd.: ZC-700) (e-3): A toluene solution containing 2% by mass of zinc of zinc chelate (manufactured by Hope Pharmaceutical Co., Ltd.: 22% OctoP Zn)

[0063] [Examples 1-5, Comparative Examples 1-5] The condensation-curable silicone resin compositions of Examples 1-5 and Comparative Examples 1-5 were prepared according to the compounding ratios (values are in parts by mass) shown in Tables 1 and 2. For each of these compositions, the storage stability, heat resistance, contamination resistance, and adhesiveness were evaluated by the test methods shown below. The measurement results are shown in Tables 1 and 2.

[0064] (a) Storage stability test For each of the prepared condensation-curable silicone resin compositions, using a cone-plate type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.: TVE-33H), in accordance with JIS K 7117-2:1999, the viscosity at a temperature of 23°C and a rotational speed of 10 rpm was measured and taken as the initial value. After storing each condensation-curable silicone resin composition in a sealed state at 23°C for 24 hours, the viscosity of the composition was measured in the same manner as the initial value. The ratio of the viscosity measured after storage to the initial viscosity was calculated and taken as the pot life.

[0065] (b) Heat resistance test After applying each of the prepared condensation-curing silicone resin compositions onto a glass substrate to a thickness of 0.18 mm, it was heated at 150 °C for 4 hours to prepare a cured product. The transmittance of each prepared cured product at 450 nm was measured with a spectrophotometer (manufactured by Hitachi High-Technologies Corporation: U-410), and this was taken as the initial value. Thereafter, the cured product was placed in a hot air circulation dryer at 200 °C and left for 48 hours, and then the linear transmittance was measured in the same manner. The value when the initial value was taken as 100% was shown.

[0066] (c) Contamination test 1 g of each of the prepared condensation-curing silicone resin compositions was weighed onto an aluminum dish, and a 20 mm × 20 mm gold-plated substrate was placed on the aluminum dish so as not to contact the resin composition. The aluminum dish was sealed with aluminum foil and heated at 150 °C for 1 hour using a hot air circulation dryer. The taken-out aluminum dish was cooled to room temperature and the surface of the placed gold plating was visually confirmed. Those with no resin deposits on the gold plating surface were rated as "good (〇)", and those with confirmed resin deposits were rated as "not acceptable (×)".

[0067] (d) Adhesion test The lead frame part was silver-plated, the reflector member was EMC, and a predetermined amount of the prepared condensation-curing silicone resin composition was applied to the center of each cavity of an SMD type 3030 package that was washed by chemical etching after molding. After die-bonding a small-sized LED chip (manufactured by HC Semitek Corporation: BA31U-BM (600 μm × 225 μm)), it was heated and cured at 150 °C for 4 hours using a hot air circulation dryer. After heating, the taken-out package was cooled to 25 °C, and the adhesion strength between the LED chip and the silver plating was measured 10 times for each condensation-curing silicone resin cured product with a bond tester (manufactured by Nordson Advanced Technology: Dage4000), and the average adhesion strength was calculated. Further, after the measurement, the silver plating surface was observed with a microscope and the resin residue was evaluated. Those with an average resin residue on the silver plating side of 70% or more by area ratio were rated as "good (〇)", and those less than 70% were rated as "not acceptable (×)".

[0068]

Table 1

[0069]

Table 2

[0070] As a result of the above evaluation tests, the condensation-curing silicone resin compositions of the present invention (Examples 1 to 5) are excellent in storage stability, heat resistance and contamination resistance, and showed high adhesive strength and a good fracture mode showing cohesive failure in the adhesive property test of LED chips. On the other hand, Comparative Example 1 not containing component (C), Comparative Example 5 not containing components (B) and (C), and further Comparative Example 2 ((c-2)) and Comparative Example 3 ((c-3)) containing components (c-2) and (c-3) which are not the component (C) of the present invention showed significantly lower adhesive strength compared to Examples 1 to 5. Also, in Comparative Example 4 which contains the component (C) ((c-1)) of the present invention but does not contain the component (B), a lower adhesive strength was shown compared to Examples 1 to 5.

[0071] From the above, it was found that the condensation-curing silicone resin composition of the present invention is excellent in adhesiveness to a substrate, exhibits high adhesive strength even in small-sized LED chips, and can be suitably used for various electronic component applications regardless of the use environment of the substrate. Specifically, it was found that it can be suitably used as a die attach material for optical semiconductor devices.

[0072] This specification includes the following aspects. [1]: (A) The following formula (1) CH3Si(OR) a (OH) b O (3-a-b) / 2 (1) (In the formula, R represents the same or different alkyl groups having 1 to 6 carbon atoms, and is a number satisfying 0 < a ≤ 0.4, 0.001 ≤ b ≤ 0.5, and 0.001 < a + b ≤ 0.9.) A polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by: 100 parts by mass, (B) Organosilicate oligomer, which is a partial hydrolysis condensate of tetraalkyl orthosilicate: 10 to 50 parts by mass with respect to 100 parts by mass of component (A), (C) The following formula (2) [Chemical formula] (In formula (2), R 1 are, independently of each other, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an epoxy group-containing organic group, c is a number satisfying 1 ≦ c ≦ 260, and Ep are, independently of each other, an organic group having one or more epoxy groups in the substituent. However, one or more of the said R 1 are hydrogen atoms.) A linear polyorganosiloxane having an epoxy group and a hydrosilyl group in the molecule, represented by: 0.1 to 10 parts by mass with respect to 100 parts by mass of the total of component (A) and component (B), (D) Inorganic filler: 1 to 10 parts by mass with respect to 100 parts by mass of component (A) A condensation-curable silicone resin composition, characterized by containing the above. [2] The condensation-curable silicone resin composition according to [1] above, characterized in that the alkyl group of tetraalkyl orthosilicate of component (B) has 1 to 6 carbon atoms. [3] The condensation-curable silicone resin composition according to [1] or [2] above, characterized in that the weight average molecular weight of component (C) is 1,000 to 20,000 and the epoxy equivalent is 400 to 650 g / mol. [4] The condensation-curable silicone resin composition according to [1], [2] or [3] above, characterized by further containing (E) a condensation-curing catalyst. [5] A die attach material for an optical semiconductor device, characterized by containing the condensation-curable silicone resin composition according to any one of [1] to [4] above.

[0073] Note that the present invention is not limited to the above-described embodiments. The above-described embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims

1. (A)The following formula (1): CH ３ Si(OR) ａ (OH) ｂ O （３－ａ－ｂ）／２ (1) (In the formula, R represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different, and a is a number satisfying 0 < a ≤ 0.4, 0.001 ≤ b ≤ 0.5, and 0.001 < a + b ≤ 0.9.) A polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by: 100 parts by mass (B) An organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate: 10 to 50 parts by mass with respect to 100 parts by mass of component (A) (C) The following formula (2): 【Chemical 1】 (In formula (2), R １ is, independently of one another, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an epoxy group-containing organic group, c is a number satisfying 1 ≦ c ≦ 260, and Ep is, independently of one another, an organic group having one or more epoxy groups in the substituent. However, one or more of the said R １ are hydrogen atoms.) A linear polyorganosiloxane having an epoxy group and a hydrosilyl group in the molecule, represented by: 0.1 to 10 parts by mass with respect to 100 parts by mass of the total of components (A) and (B) (D) An inorganic filler: 1 to 10 parts by mass with respect to 100 parts by mass of component (A) A condensation curable silicone resin composition, characterized by containing the above components.

2. The condensation curable silicone resin composition according to Claim 1, wherein the alkyl group of the tetraalkyl orthosilicate of component (B) has 1 to 6 carbon atoms.

3. The condensation curable silicone resin composition according to Claim 1, wherein the weight average molecular weight of component (C) is 1,000 to 20,000, and the epoxy equivalent is 400 to 650 g / mol.

4. The condensation curable silicone resin composition according to Claim 1, further characterized by containing (E) a condensation curing catalyst.

5. A die attach material for an optical semiconductor device, characterized by containing the condensation curable silicone resin composition according to Claim 1.

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