Condensation-curable silicone resin composition and chip mounting material for optical semiconductor device

Abstract

Provided is a condensation-curable silicone resin composition which is capable of obtaining a cured resin having high hardness and resin strength and which has excellent adhesion to a base material. The condensation-curable silicone resin composition is characterized by containing: (A) a polyorganosiloxane represented by formula (1) and having a hydroxyl group and a hydrolyzable group; (B) an organosilicate oligomer which is a partial hydrolytic condensation product of a tetraalkyl orthosilicate; (C) a linear polyorganosiloxane which is represented by formula (2) and which has an epoxy group and a hydrosilyl group in the molecule; and (D) an inorganic filler. CH3Si (OR) a (OH) bO (3-a-b) / 2 (1), # imgabs0 #.

Description

Technical Field

[0001] The present invention relates to a condensation-curable silicone resin composition and a chip mounting material for an opto-semiconductor device. Background Art

[0002] A chip mounting material is used for the purpose of solidifying a semiconductor chip on a substrate, and from the viewpoint of reliability, characteristics of high adhesive strength and high adhesiveness are sought. Among them, as a chip mounting 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 mostly used. However, recently, LED devices equipped with LED chips smaller than 600 μm, which is the standard size, and having a size of 300 μm or less have gradually increased. For the conventional addition-curable resin compositions of the methyl silicone type disclosed in Patent Document 1 and Patent Document 2, there is a problem that the holding force of the LED chip cannot meet the required value. In addition, in the case of an addition-curable resin composition, there is still a technical problem that the use environment is limited when preventing curing inhibition due to the reaction nature.

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

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2018-131583.

[0007] Patent Document 2: International Publication No. 2018 / 155131.

[0008] Patent Document 3: International Publication No. 2017 / 122762. Summary of the Invention

[0009] (I) Technical Problems to be Solved

[0010] In view of the above circumstances, the present invention aims to provide a condensation-curable silicone resin composition that can obtain a resin cured product having high hardness and resin strength and excellent adhesion to a substrate.

[0011] (II) Technical Solution

[0012] In order to solve the above technical problems, the present invention provides a condensation-curable silicone resin composition, which comprises:

[0013] 100 parts by mass of (A) a polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by the following formula (1),

[0014] CH3Si(OR) a (OH) b O (3-a-b) / 2 (1)

[0015] In formula (1), R represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different, and a and b are numbers satisfying 0 < a ≤ 0.4, 0.001 ≤ b ≤ 0.5, and 0.001 < a + b ≤ 0.9;

[0016] 10 to 50 parts by mass of (B) an organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate with respect to 100 parts by mass of the component (A);

[0017] 0.1 to 10 parts by mass of (C) a linear polyorganosiloxane having an epoxy group and a hydrosilyl group represented by the following formula (2) with respect to a total of 100 parts by mass of the components (A) and (B),

[0018]

[0019] In formula (2), R 1 are each independently 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 each independently an organic group having one or more epoxy groups in the substituent, wherein one or more of the said R 1 are hydrogen atoms; and

[0020] 1 to 10 parts by mass of (D) an inorganic filler with respect to 100 parts by mass of the component (A).

[0021] As long as it is the above condensation-curable silicone resin composition, a resin cured product having high hardness and resin strength can be obtained, and the adhesion to a substrate is excellent.

[0022] In the condensation-curable silicone resin composition of the present invention, preferably: the alkyl group of the tetraalkyl orthosilicate of the component (B) has 1 to 6 carbon atoms.

[0023] As long as it is the above condensation-curable silicone resin composition, a resin cured product having higher hardness and resin strength can be easily obtained, and it is also preferred from the viewpoints of reactivity and cost.

[0024] Furthermore, in the condensation-curable silicone resin composition of the present invention, preferably: 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.

[0025] As long as it is the above condensation-curing silicone resin composition, there is no need to worry about appearance turbidity, and sufficient adhesiveness to a substrate can be obtained.

[0026] Furthermore, the condensation-curing silicone resin composition of the present invention preferably contains a condensation-curing catalyst as the component (E).

[0027] As long as it is the above condensation-curing silicone resin composition, it can be effectively cured.

[0028] In addition, the present invention provides a chip mounting material for an optical semiconductor device, which contains the condensation-curing silicone resin composition of the present invention.

[0029] The above chip mounting material for an optical semiconductor device has excellent adhesive strength even in the case of a small-sized LED chip, and thus can provide a highly reliable LED device.

[0030] (III) Advantageous Effects

[0031] According to the condensation-curing silicone resin composition of the present invention, when used as a chip mounting material for an LED, it has excellent adhesive strength even in the case of a small-sized LED chip, and thus can provide a highly reliable LED device. In addition, the possibility of being restricted by the reaction properties in the use environment is low. Therefore, the condensation-curing silicone resin composition of the present invention is extremely useful as a chip mounting material for an LED. Detailed Embodiments

[0032] As described above, there is a demand for developing a condensation-curing silicone resin composition having excellent adhesive strength even in the case of a small-sized LED chip.

[0033] The inventors of the present invention repeatedly conducted in-depth studies on the above technical problems, and as a result, found that a condensation-curing silicone resin composition containing the above components (A), (B), (C), and (D) has excellent adhesiveness to a substrate and can exhibit high adhesive strength even in the case of a small-sized LED chip, thereby completing the present invention.

[0034] That is, the present invention is a condensation-curing silicone resin composition, which contains:

[0035] 100 parts by mass of (A) a polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by the following formula (1),

[0036] CH3Si(OR) a (OH) b O (3-a-b) / 2 (1)

[0037] In formula (1), R represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different, and a and b are numbers satisfying 0 < a ≤ 0.4, 0.001 ≤ b ≤ 0.5, and 0.001 < a + b ≤ 0.9;

[0038] 10 to 50 parts by mass of (B), which is an organosilicate oligomer that is a partially hydrolyzed condensate of tetraalkyl orthosilicate, based on 100 parts by mass of component (A);

[0039] 0.1 to 10 parts by mass of (C), which is a linear polyorganosiloxane having an epoxy group and a hydrosilyl group in the molecule represented by the following formula (2), based on a total of 100 parts by mass of component (A) and component (B);

[0040]

[0041] In formula (2), R 1 independently represents 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 independently represents an organic group having one or more epoxy groups in the substituent, wherein one or more of the R 1 are hydrogen atoms; and

[0042] 1 to 10 parts by mass of (D), which is an inorganic filler, based on 100 parts by mass of component (A).

[0043] Hereinafter, the present invention will be described in detail, but the present invention is not limited to these descriptions.

[0044] [(A) Polyorganosiloxane having a hydroxyl group and a hydrolyzable group]

[0045] Component (A) is a polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by the following formula (1).

[0046] CH3Si(OR) a (OH) b O (3-a-b) / 2 (1)

[0047] In formula (1), R represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different, and a and b are numbers satisfying 0 < a ≤ 0.4, 0.001 ≤ b ≤ 0.5, and 0.001 < a + b ≤ 0.9.

[0048] In the above formula (1), examples of the alkyl group having 1 to 6 carbon atoms represented by R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, etc. Among them, as the above R, methyl is particularly preferred from the viewpoints of reactivity and cost.

[0049] There is no particular limitation on the method for manufacturing the polyorganosiloxane represented by the above formula (1). For example, it can be synthesized by hydrolysis and condensation of the corresponding alkoxysilane under acidic conditions.

[0050] 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 is greater than 0.4, there is a concern that the strength of the obtained cured product will decrease, so it is not preferred.

[0051] 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 will decrease, and if it is greater than 0.5, the storage stability of the cured product will decrease, so it is not preferred.

[0052] In addition, 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.

[0053] In addition, based on the above formula (1), the component (A) of the present invention is a polyorganosiloxane composed only of T units (trifunctional siloxane units).

[0054] The weight-average molecular weight Mw of the above component (A) determined by GPC is preferably 1,000 to 10,000, more preferably 2,000 to 6,000. As long as the molecular weight is 1,000 to 10,000, sufficient resin strength can be obtained as a chip mounting material, and it will be in a practical viscosity range, so it is preferred. In addition, the weight-average molecular weight mentioned in the present invention refers to the weight-average molecular weight obtained by gel permeation chromatography (GPC) measured under the following conditions using polystyrene as a standard substance.

[0055] [Measurement conditions]

[0056] · Eluent: Tetrahydrofuran (THF)

[0057] · Flow rate: 0.6 mL / min

[0058] · Detector: Differential refractive index detector (RI)

[0059] · Column: TSK Guardcolumn SuperH-L

[0060] · TSKgel SuperH4000 (6.0 mm I.D. × 15 cm × 1)

[0061] ·TSKgel SuperH3000 (6.0 mm I.D. × 15 cm × 1)

[0062] ·TSKgel SuperH2000 (6.0 mm I.D. × 15 cm × 1)

[0063] (All are manufactured by Tosoh Corporation)

[0064] ·Column temperature: 40 °C

[0065] ·Sample injection volume: 20 μL (THF solution with a concentration of 0.5 mass%)

[0066] [(B) is an organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate]

[0067] (B) component 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, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, etc. Among them, from the viewpoints of reactivity or cost, methyl or ethyl is particularly preferred.

[0068] The number of monomer units n of the above organosilicate oligomer is not particularly limited, and preferably ranges from 1 ≤ n ≤ 20, more preferably from 3 ≤ n ≤ 10. As long as the number of monomer units n is 20 or less, the viscosity becomes appropriate and the workability of the resin composition is excellent.

[0069] In the condensation-curable silicone resin composition of the present invention, the amount of the above (B) component is 10 to 50 parts by mass, preferably 20 to 45 parts by mass, based on 100 parts by mass of the above (A) component. When it is less than 10 parts by mass, there is a concern that the strength of the resin may decrease, and if it is more than 50 parts by mass, the volatile components generated by the condensation reaction will become excessive, so it is not preferred.

[0070] The method for manufacturing the above organosilicate oligomer is not particularly limited, and it can be synthesized by hydrolytic condensation of the corresponding tetraalkyl orthosilicate under acidic conditions.

[0071] <(C) Linear polyorganosiloxane having an epoxy group and a hydrosilyl group>

[0072] (C) component is a linear polyorganosiloxane represented by the following formula (2) and having an epoxy group and a hydrosilyl group in the molecule.

[0073]

[0074] In formula (2), R 1Each independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an organic group containing an epoxy group, c is a number satisfying 1 ≤ c ≤ 260, and Ep each independently is an organic group having one or more epoxy groups in the substituent, wherein said R 1 One or more of them are hydrogen atoms.

[0075] For the linear polyorganosiloxane represented by the above formula (2), the adhesiveness to the substrate is increased by the effects of the hydrosilyl group in the side chain and the epoxy group at the terminal.

[0076] In the above formula (2), as examples of the alkyl group having 1 to 12 carbon atoms represented by R 1 : methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, etc. can be exemplified. Among them, as the above R 1 , from the perspective of cost, methyl is particularly preferred.

[0077] In the above formula (2), the range of c is a number satisfying 1 ≤ c ≤ 260, preferably in the range of 10 ≤ c ≤ 100. If c is greater than 260, there is a concern that sufficient adhesiveness cannot be imparted, so it is not preferred.

[0078] In addition, the weight average molecular weight of the above component (C) is 1,000 to 20,000, preferably in the range of 4,000 to 10,000. As long as the weight average molecular weight is 20,000 or less, there is no concern about the appearance turbidity of the silicone resin cured product, and as long as the weight average molecular weight is 1,000 or more, sufficient adhesiveness to the substrate can be obtained.

[0079] 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. As long as the epoxy equivalent is 650 g / mol or less, there is no concern about the appearance turbidity of the silicone resin cured product, and as long as the epoxy equivalent is 400 g / mol or more, sufficient adhesiveness to the substrate can be obtained.

[0080] 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) is more than 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 will be turbid, and as long as it is less than 0.1 part by mass, the adhesiveness to the substrate will become insufficient.

[0081] The production method of the above component (C) is not particularly limited. As an example, it can be synthesized by 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.

[0082] Here, the structure of the above polyorganosiloxane compound having a hydrosilyl group at the terminal is not particularly limited, and a linear polyorganosiloxane compound represented by the following chemical formula can be exemplified.

[0083]

[0084] In the above formula (3), R 1 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and c is a number satisfying 1 ≤ c ≤ 260.

[0085] Here, the above epoxy compound having an alkenyl group is not particularly limited, and an epoxy compound represented by the following formula can be exemplified.

[0086]

[0087] [(D) Inorganic filler]

[0088] The component (D) of the present invention is an inorganic filler. Its purpose is to improve the strength of the obtained cured product or to impart thixotropy to improve the coating workability of the chip mounting material. As the inorganic filler, for example, fumed silica, fumed titanium dioxide, etc. can be exemplified. In particular, from the viewpoint of the transparency of the obtained cured product, fumed silica is preferably used as the inorganic filler.

[0089] As the blending amount of the (D) inorganic filler, it is 1 to 10 parts by mass, preferably 2 to 8 parts by mass, relative to 100 parts by mass of the component (A). When it is less than 1 part by mass, there is a concern that sufficient strength cannot be obtained, and when it is more than 10 parts by mass, there is a concern that the viscosity becomes too high, so it is not preferred.

[0090] In particular, when fumed silica is used as the inorganic filler, from the viewpoint of compatibility with the silicone resin, the surface of the silica is preferably treated with a hydrophobic group. As the hydrophobic group, alkylsilyls such as trimethylsilyl or dimethylsilyl can be specifically cited.

[0091] In addition, by performing surface treatment, it also has the effect of suppressing the interaction between the epoxy group contained in the component (C) and the hydrosilyl group on the surface of the fumed silica, and further improving the storage stability. Therefore, as fumed silica, surface treatment is preferably carried out sufficiently. Specifically, fumed silica as follows is preferably used: BET specific surface area is 150 m 2 / g or more and 290 m2 Fumed silica of less than / g, preferably 170 m 2 / g or more and 230 m 2 / g or less of fumed silica. As commercially available products of the fumed silica surface-treated with an alkylsilyl group, there can be mentioned R812 (specific surface area: 230 to 290 m 2 / g) and RX300 (specific surface area: 180 to 220 m 2 / g) surface-treated with trimethylsilyl and manufactured by Nippon Aerosil Co., Ltd., R976 (specific surface area: 225 to 275 m 2 / g) and R976S (specific surface area: 215 to 265 m 2 / g) surface-treated with dimethylsilyl, etc.

[0092] [(E) Condensation curing catalyst]

[0093] The condensation curable silicone composition of the present invention contains the above components (A), (B), (C) and (D) as essential components, and may further contain (E) a condensation curing catalyst, etc. as required. The condensation curing catalyst is a component that promotes the hydrolysis condensation reaction of the hydrolyzable silyl groups such as alkoxysilyl groups and silanol groups contained in the above organopolysiloxane using moisture in the air, promotes the subsequent dehydration condensation reaction between silanols, and further promotes the curing of the composition, and is added in order to efficiently cure the condensation curable silicone composition of the present invention.

[0094] The addition amount of the component (E) is not particularly limited. If it is considered to adjust the curing rate to an appropriate range to produce a cured product having desired physical properties and improve the workability during coating, etc., the amount of the metal element t (ppm) is in the range of 0 ≤ t ≤ 1,000, more preferably 100 ≤ t ≤ 500, as the addition amount relative to 100 parts by mass of the component (A). As long as the amount of the catalyst t is 1,000 or less, appropriate storage stability can also be obtained.

[0095] As the curing catalyst, any curing catalyst that can be used for curing a conventional condensation-curing type composition may be used, and there is no particular limitation. For example, there may be mentioned: organic carboxylates, organic chelate compounds, and alkoxide compounds of metals such as tin, titanium, zirconium, zinc, and aluminum. As the tin compound, there may be mentioned: dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, and dibutyltin dioctoate, etc. As the titanium compound, there may be mentioned: tetraethoxy titanium, tetraisopropyl titanate, tetrabutyl titanate, diisopropoxy bis(acetylacetone) titanium, and diisopropoxy bis(ethylacetoacetate) titanium, etc. As the zirconium catalyst, there may be mentioned: tetrapropoxy zirconium, tetrabutoxy zirconium, zirconium tetraacetylacetonate, and zirconium tetraacetylacetonate, etc. As the zinc compound, there may be mentioned: zinc acetate, zinc acetylacetonate, zinc octoate, zinc laurate, and zinc naphthenate, etc. As the aluminum compound, there may be mentioned: aluminum trihydroxide, aluminum tributoxide, aluminum triacetylacetonate, bis(ethylacetoacetato) monoacetylacetonate aluminum, and aluminum triethylacetoacetate, etc.

[0096] In addition, various additives can be added to the condensation-curing silicone resin composition of the present invention as needed. For example, by various additives, the shrinkage rate during curing and the thermal expansion coefficient, heat resistance, thermal conductivity, antioxidant property, etc. of the obtained cured product can be appropriately adjusted. As the above additives, there may be mentioned: non-reinforcing inorganic fillers other than the above component (D) such as quartz powder, glass fiber, calcium carbonate, magnesium carbonate, aluminum hydroxide, alumina, aluminum nitride, magnesium oxide, and boron nitride; antioxidants such as hydroquinone and 2,6-di-tert-butyl-p-cresol.

[0097] [Curing method]

[0098] The condensation-curing silicone resin composition of the present invention can be cured after being coated on a substrate according to the use, and heating curing is preferably carried out in the temperature range of 60°C to 200°C, more preferably in the temperature range of 100°C to 170°C. As long as the heating temperature is within the above range, there is no need to worry about the reduction of the adhesion strength between the substrate and the resin cured product. In addition, the above heating curing time can be 1 to 4 hours. In addition, a stepwise curing method can also be adopted.

[0099] The condensation-curable silicone resin composition of the present invention, by using the above-mentioned polyorganosiloxane in a specific combination, has excellent adhesion to a substrate compared to a general thermosetting silicone resin composition, and can exhibit high adhesion strength even in the case of a small-sized LED chip. In addition, in the case of a conventional addition-curable type using a platinum catalyst, the use environment is limited when preventing curing inhibition due to the reaction nature. However, the condensation-curable silicone resin composition developed this time can be suitably used for various electronic component applications without being limited by the use environment of the substrate, and specifically can be suitably used as a chip mounting material for an optoelectronic semiconductor device.

[0100] Examples

[0101] Hereinafter, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited thereto.

[0102] In addition, "parts" means "parts by mass", Me means "methyl", Vi means "vinyl", Ep means "1,2-epoxy-4-ethylcyclohexyl", and Ep' means "γ-glycidoxypropyl".

[0103] The weight-average molecular weight means the weight-average molecular weight obtained by GPC measurement measured under the above conditions. In addition, in the following examples, the amount of Si-H groups represents the number of moles of hydrogen atoms directly bonded to silicon atoms in the molecule, which is obtained by 1 1H-NMR measurement using a nuclear magnetic resonance (NMR) measurement device manufactured by Bruker Corporation and quantified with dimethyl sulfoxide (DMSO) as an internal standard.

[0104] Hereinafter, descriptions of the respective components described in Tables 1 and 2 are shown.

[0105] [Component (A)]

[0106] (a-1): 1,200 g of KC-89RP (manufactured by Shin-Etsu Chemical Co., Ltd.), 1,200 g of toluene, 163 g of IPA (isopropanol), and 26 g of methanesulfonic acid were added to a reaction apparatus, and 289 g of distilled water was added dropwise thereto. A hydrolysis reaction was carried out at room temperature for 100 minutes. Then, 26 g of sodium bicarbonate was added dropwise for neutralization. After removing ethanol as a by-product at 72 °C and simultaneously carrying out aging, an organopolysiloxane was synthesized, which is represented by the following chemical formula and has a weight-average molecular weight Mw of 3,900 obtained by GPC measurement.

[0107] CH3Si(OCH3) 0.18 (OH) 0.013 O 2.8 / 2

[0108] [Component (B)]

[0109] (b-1): Tetraethyl orthosilicate oligomer (manufactured by Colcoat Co., Ltd.: ETHYL SILICATE 40, average number of monomer units n = 5)

[0110] (b-2): Tetramethyl orthosilicate oligomer (manufactured by Colcoat Co., Ltd.: METHYL SILICATE 51, average number of monomer units n = 4)

[0111] [Component (C)]

[0112] (c-1): Organopolysiloxane, wherein the siloxane units are represented by 2 mol% of EpMe2SiO 1 / 2 units, 70 mol% of Me2Si 2 / 2 units, 28 mol% of HMeSiO 2 / 2 units, and the weight-average molecular weight Mw obtained by GPC measurement is 6,800 and the epoxy equivalent is 570 g / mol. (c = 98)

[0113] (c-2): Organopolysiloxane, wherein the siloxane units are represented by 3 mol% of Ep’SiO 3 / 2 units, 84 mol% of Me2SiO 2 / 2 units, 13 mol% of ViSiO 3 / 2 units, the weight-average molecular weight is 2,600 and the epoxy equivalent is 950 g / mol.

[0114] (c-3): An organic compound represented by the following formula synthesized by the method described in Japanese Patent Application Laid-Open No. 2012-518610.

[0115]

[0116] [Component (D)]

[0117] (d-1): Fumed silica (manufactured by Nippon Aerosil Co., Ltd.: Aerosil RX-300)

[0118] [Component (E)]

[0119] (e-1): A 1-butanol solution of zirconium alkoxide (manufactured by Matsumoto Fine Chemical Co., Ltd.: ZA-65) with a zirconium content of 2% by mass

[0120] (e-2): Toluene solution of zirconium chelate (manufactured by Matsumoto Fine Chemical Co., Ltd.: ZC-700) with a zirconium content of 2% by mass

[0121] (e-3): Toluene solution of zinc chelate (manufactured by Hope Chemical Co., Ltd.: 22% Octope Zn) with a zinc content of 2% by mass

[0122] [Examples 1 - 5, Comparative Examples 1 - 5]

[0123] Condensation-curing silicone resin compositions of Examples 1 - 5 and Comparative Examples 1 - 5 were prepared according to the blending ratios (values in parts by mass) shown in Tables 1 and 2. For each composition, storage stability, heat resistance, stainability, and adhesiveness were evaluated by the test methods shown below. The measurement results are shown in Tables 1 and 2.

[0124] (a) Storage stability test

[0125] For each of the prepared condensation-curing silicone resin compositions, using a cone-plate rotational viscometer (Toki Sangyo Co., Ltd.: TVE-33H), the viscosity at a temperature of 23°C and a rotational speed of 10 rpm was measured in accordance with Japanese Industrial Standard JIS K 7117-2:1999 and set as the initial value. After storing each condensation-curing silicone resin composition in a sealed state at 23°C for 24 hours, the viscosity of the composition was measured by the same method as the initial value. The ratio of the viscosity measured after storage to the initial viscosity was calculated and used as the pot life.

[0126] (b) Heat resistance test

[0127] After coating each of the prepared condensation-curing silicone resin compositions on a glass substrate to a thickness of 0.18 mm, it was heated at 150°C for 4 hours to form a cured product. The transmittance of each of the formed cured products at 450 nm was measured using a spectrophotometer (manufactured by Hitachi High-Tech Corporation: U-410) and set as the initial value. Then, the cured product was placed in a hot air circulation dryer at 200°C, and the linear transmittance after 48 hours was measured by the same method. The value when the initial value was set to 100% was shown.

[0128] (c) Stainability test

[0129] Weigh 1 g of each of the prepared condensation-curing silicone resin compositions on an aluminum disc, and place a 20 mm × 20 mm gold-plated substrate on the aluminum disc in a manner that does not come into contact with the resin composition. Seal the aluminum disc with aluminum foil, and then heat it at 150 °C for 1 hour using a hot air circulation dryer. Cool the removed aluminum disc to room temperature, and visually confirm the gold-plated surface. Evaluate those without resin deposits on the gold-plated surface as "good (〇)", and those with resin deposits confirmed on the gold-plated surface as "bad (×)".

[0130] (d) Adhesion test

[0131] Apply a specified amount of the prepared condensation-curing silicone resin composition to the center of each cavity of an SMD type 3030 package where the lead frame part is silver-plated, the reflector member is EMC, and it has been cleaned by chemical etching after molding. After die-bonding a small-sized LED chip (manufactured by HC Semitek Co., Ltd.: BA31U-BM (600 μm × 225 μm)), cure it by heating at 150 °C for 4 hours using a hot air circulation dryer. After heating, cool the removed package to 25 °C, and measure the adhesion strength between the LED chip and the silver plating for each condensation-curing silicone resin composition in a test quantity of 10 using an adhesion strength tester (manufactured by Nordson Advanced Technology K.K.: Dage 4000), and calculate the average adhesion strength. In addition, after measurement, observe the silver-plated surface with a microscope and evaluate the residual resin. Evaluate those with an average residual resin on the silver-plated side of 70% or more by area ratio as "good (○)", and those less than 70% as "bad (×)".

[0132] [Table 1]

[0133]

[0134] [Table 2]

[0135]

[0136] From the results of the above evaluation tests, it can be seen that the condensation-curing silicone resin compositions of the present invention (Examples 1 to 5) are excellent in storage stability, heat resistance, and contamination, and show high adhesion strength and a good failure mode showing cohesive failure in the adhesion test of LED chips.

[0137] On the other hand, Comparative Example 1 that does not contain component (C), Comparative Example 5 that does not contain components (B) and (C), and even Comparative Example 2 ((c-2)) and Comparative Example 3 ((c-3)) that contain components (c-2) and (c-3) which are not the (C) component of the present invention showed significantly lower adhesion strength than Examples 1 to 5. In addition, in Comparative Example 4 that contains the (C) component ((c-1)) of the present invention but does not contain component (B), the adhesion strength was also lower than that of Examples 1 to 5.

[0138] Based on the above, it can be seen that the condensation-curable silicone resin composition of the present invention has excellent adhesion to a substrate, and even in the case of a small-sized LED chip, it can exhibit high adhesion strength, can be suitably used for various electronic component applications without being limited by the use environment of the substrate, and can specifically be suitably used as a chip mounting material for opto-semiconductor devices.

[0139] This specification includes the following aspects.

[0140] [1] A condensation-curable silicone resin composition, characterized by comprising:

[0141] 100 parts by mass of (A) a polyorganosiloxane having a hydroxyl group and a hydrolyzable group represented by the following formula (1),

[0142] CH3Si(OR) a (OH) b O (3-a-b) / 2 (1)

[0143] In formula (1), R represents an alkyl group having 1 to 6 carbon atoms, the same or different, and a and b are numbers satisfying 0 < a ≤ 0.4, 0.001 ≤ b ≤ 0.5, and 0.001 < a + b ≤ 0.9;

[0144] 10 to 50 parts by mass of (B) an organosilicate oligomer which is a partial hydrolysis condensate of tetraalkyl orthosilicate with respect to 100 parts by mass of component (A);

[0145] 0.1 to 10 parts by mass of (C) a linear polyorganosiloxane having an epoxy group and a hydrosilyl group in the molecule represented by the following formula (2) with respect to a total of 100 parts by mass of components (A) and (B),

[0146]

[0147] In formula (2), R 1 are each independently 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 each independently an organic group having one or more epoxy groups in the substituent, wherein the R 1one or more of them is a hydrogen atom; and

[0148] The (D) inorganic filler is 1 to 10 parts by mass relative to 100 parts by mass of the (A) component.

[0149] [2] The condensation-curable silicone resin composition according to [1] above, wherein the alkyl group of the tetraalkyl orthosilicate of the (B) component has 1 to 6 carbon atoms.

[0150] [3] The condensation-curable silicone resin composition according to [1] or [2] above, wherein the (C) component has a weight-average molecular weight of 1,000 to 20,000 and an epoxy equivalent of 400 to 650 g / mol.

[0151] [4] The condensation-curable silicone resin composition according to [1], [2] or [3] above, further comprising an (E) condensation-curing catalyst.

[0152] [5] A chip mounting material for an optical semiconductor device, comprising the condensation-curable silicone resin composition according to any one of [1] to [4] above.

[0153] In addition, the present invention is not limited to the above embodiments. The above embodiments are examples, and any technical solutions having substantially the same technical concept as that described in the claims of the present invention and achieving the same technical effects are included in the technical scope of the present invention.

Claims

1. A condensation-curable silicone resin composition, characterized in that Include: 100 parts by mass of (A) 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 formula (1), R represents an alkyl group having 1 to 6 carbon atoms, which may be the same or different, and a and b are numbers satisfying 0<a≤0.4, 0.001≤b≤0.5, and 0.001<a+b≤0.9; 10 to 50 parts by mass of (B) an organosilicate oligomer which is a partial hydrolysis condensation product of a tetraalkyl orthosilicate, based on 100 parts by mass of the component (A); 0.1 to 10 parts by mass of (C) a linear polyorganosiloxane having an epoxy group and a hydrosilyl group in the molecule represented by the following formula (2) based on 100 parts by mass of the total of the components (A) and (B), In formula (2), R 1 are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an organic group containing an epoxy group, c is a number satisfying 1≤c≤260, and Ep is independently an organic group having one or more epoxy groups in the substituent, wherein the R 1 at least one of them is a hydrogen atom; and The amount of the (D) inorganic filler is 1 to 10 parts by mass based on 100 parts by mass of the (A) component.

2. The condensation-curable silicone resin composition according to claim 1, characterized in that The alkyl group of the tetraalkyl orthosilicate of the component (B) has 1 to 6 carbon atoms.

3. The condensation-curable silicone resin composition according to claim 1, characterized in 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.

4. The condensation-curable silicone resin composition according to claim 1, characterized in that It further contains (E) a condensation curing catalyst.

5. A die attach material for an optical semiconductor device, characterized in that: A condensation-curable silicone resin composition comprising the condensation-curable silicone resin composition according to claim 1.

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