TW201922886A - Transparent liquid thermosetting resin composition, optical material bonding agent and optical semiconductor device having high transparency, adhesive strength, good workability, and excellent storage stability - Google Patents

Abstract

The present invention provides a transparent liquid thermosetting resin composition, comprising: a liquid thermosetting resin (A) having a refractive index of 1.40 to 1.55; and (B) nano silicon dioxide having an average primary particle diameter of 1 to 50 nm, and being subject to an alkylsilane treatment by an alkoxydecane containing an alkyl group having 4 or more carbon atoms.

Description

Transparent liquid thermosetting resin composition, adhesive for optical material, and optical semiconductor device

The present invention relates to a transparent liquid thermosetting resin composition, an optical material adhesive comprising the transparent liquid thermosetting resin composition, and an optical semiconductor device comprising the optical material adhesive. .

A liquid thermosetting resin which is an optical material such as a sealing material or an adhesive used for an optical semiconductor or the like is required to have excellent workability and storage stability in addition to high transparency. For example, if it is an adhesive used for an optical semiconductor such as an LED (Light Emitting Diode), it is required to be accurately applied to a small amount of area, and it is required to have a coating amount or a coating shape stability, and an LED element. The reduction in positional offset. When the coating amount is insufficient or the shape is unstable, the side fillet is not sufficiently formed, and then the strength is lowered, and peeling occurs during wire bonding or in the brightness test. Further, when the position of the element is shifted, the wire cannot be accurately bonded to the electrode pad. Further, in order to improve productivity, high-speed coating is required, but it is required that drawing does not occur even under high-speed coating conditions. It is known that the above particles can be improved by dispersing the nanoparticles in the resin and imparting thixotropy by the cohesive force of the particles. However, when the nanoparticles are dispersed in the resin, there is a problem that the difference in refractive index between the nanoparticles and the resin and insufficient dispersion cause a large decrease in transparency and a decrease in light extraction efficiency of the optical semiconductor. Further, since the nanoparticles dispersed by the change over time are agglomerated with each other, the viscosity is increased, and the workability such as drawing is deteriorated.

Previously, the dispersibility in the resin was improved by performing surface treatment of the nanoparticles (for example, Patent Documents 1 to 3). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei.

[The problem that the invention wants to solve]

However, even if the surface-treated nanoparticle is used, it is difficult to produce a transparent cured product because the refractive index of the nanoparticle and the resin are different and the dispersibility is insufficient. Further, even when the surface of the nanoparticle is treated to improve the compatibility with the resin and to be dispersed to a degree of transparency, depending on the type of the surface treatment agent, the cohesive force of the nanoparticles is also lost, and the liquid cannot be liquid. The resin imparts sufficient thixotropy and is inferior in workability. Further, even in the case where the surface treatment of the nanoparticles is performed, there is a case where the nanoparticles are agglomerated due to a change with time, and the viscosity is increased, so that the drawing or coating shape is inferior and the workability is also inferior.

The present invention has been made in view of such an actual situation, and an object of the present invention is to provide a transparent liquid thermosetting resin composition which has high transparency and high strength, has excellent workability, and is excellent in storage stability, and includes the transparent An adhesive for an optical material of a liquid thermosetting resin composition, and an optical semiconductor device obtained by bonding an element with an adhesive for the optical material. [Technical means to solve the problem]

In order to solve the above problems, the inventors of the present invention have repeatedly tried hard to find a transparent liquid obtained by dispersing an alkyl sulfonium alkyl group-treated nano cerium oxide into a liquid thermosetting resin having a specific refractive index. The thermosetting resin composition solves the above problems, thereby completing the present invention. The present invention has been completed based on this finding.

That is, the present invention provides the following [1] to [4]. [1] A transparent liquid thermosetting resin composition comprising: (A) a liquid thermosetting resin having a refractive index of 1.40 to 1.55; and (B) nano cerium oxide having an average primary particle diameter It is 1 to 50 nm, and is treated with an alkoxydecane having an alkyl group having 4 or more carbon atoms as an alkylalkylene group. [2] The transparent liquid thermosetting resin composition according to the above [1], wherein the component (A) is any one of a polysiloxane resin and an epoxy resin. [3] An adhesive for an optical material, comprising the transparent liquid thermosetting resin composition according to the above [1] or [2]. [4] An optical semiconductor device comprising the optical semiconductor element which is followed by the adhesive for an optical material described in the above [3]. [Effects of the Invention]

According to the present invention, it is possible to provide a transparent liquid thermosetting resin composition having high transparency and high strength, excellent workability, and excellent storage stability, and opticals comprising the transparent liquid thermosetting resin composition. An adhesive for the material and an optical semiconductor device formed by bonding the optical material with an adhesive.

The invention will be described in detail below. [Transparent liquid thermosetting resin composition] The transparent liquid thermosetting resin composition of the present invention is characterized by comprising: (A) a liquid thermosetting resin having a refractive index of 1.40 to 1.55; and (B) The nano cerium oxide has an average primary particle diameter of 1 to 50 nm and is treated with an alkoxy decane having an alkyl group having 4 or more carbon atoms as an alkyl decyl group.

First, each component of the transparent liquid thermosetting resin composition (hereinafter also simply referred to as "thermosetting resin composition") of the present invention will be described. [(A) Liquid thermosetting resin having a specific refractive index] The liquid thermosetting resin of the component (A) used in the present invention is liquid at normal temperature (25 ° C) and has a refractive index of 1.40. ~1.55 thermosetting resin. In order to obtain a refractive index of less than 1.40, it is necessary to introduce a functional group containing fluorine or the like, but the cost is high and the wettability with the substrate is lowered, which may cause a decrease in the strength of the bonding. Therefore, in the present invention, the refractive index of the liquid thermosetting resin of the component (A) is set to 1.40 or more. Further, when the refractive index exceeds 1.55, the transparency of the cured product is lowered. From such a viewpoint, the refractive index of the liquid thermosetting resin of the component (A) is preferably from 1.42 to 1.53. The above refractive index can be measured using a refractometer (for example, an Abbe refractometer).

The liquid thermosetting resin as the component (A) is not particularly limited as long as it is liquid at normal temperature (25 ° C) and has a refractive index of 1.40 to 1.55, and transparency, heat resistance, and adhesion are considered. In particular, a polyoxyxylene resin or an epoxy resin is more preferably a polyoxyxene resin from the viewpoint of transparency.

The polyoxyxylene resin may be a siloxane having a siloxane bond (Si-O-Si) and having two or more sclerosing reactive groups. For example, a resin having a main skeleton of methyl polyoxygen (refractive index of 1.40) may be mentioned. ～1.42), a resin having a main skeleton of methyl polyfluorene and a methyl group of a methyl polyfluorene, which is substituted with a phenyl group (refractive index of 1.42 to 1.55), and a part of a decane bond is changed to an alkyl chain. Or a resin of ethylene glycol chain (refractive index 1.42 to 1.49). Examples of the shape include linear polyfluorene oxide, branched polyfluorene oxide, cyclic polyfluorene oxide, ladder sesquiterpene oxide, random sesquiterpene oxide, and cage sesquiterpene oxide.

As a curing method of the polyoxyxylene resin, a hydroquinone alkylation reaction in which a resin having a hydrofluorenylalkyl group (-SiH) and a carbon-carbon double bond is carried out in the presence of a hydroquinone alkylation catalyst; a polycondensation reaction of a base resin in the presence of a polycondensation catalyst; a radical reaction of a carbon-carbon double bond using an organic peroxide; and a reactive group such as an epoxy group, an amine group, a hydroxyl group or a carboxyl group introduced into the resin skeleton And the method of hardening, and the like. These may be used alone or in combination of two or more. From the viewpoint of curing time, heat resistance, and storage stability, a hydroquinone alkylation reaction is preferred.

Further, if the polyoxyxene resin satisfies the refractive index of 1.40 to 1.55, an organic compound may be introduced into the polyfluorene oxide resin. For example, by introducing an organic compound into the resin skeleton by a hydroquinone alkylation reaction, the original heat resistance and ultraviolet resistance of the polyoxynoxy resin can be impaired to improve the toughness and adhesion. The organic compound is preferably a compound represented by the following formula (1) from the viewpoint of heat resistance and adhesion.

[Chemical 1]

In the formula, R ¹ represents a hydrogen atom, an unsaturated hydrocarbon group, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a group having an epoxy group, and R ² each independently represents an unsaturated hydrocarbon group, and each of them may be the same or different.

The unsaturated hydrocarbon group of R ¹ and R ² preferably has 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a (meth)acrylonitrile group, a propenyl group, and a butenyl group. Here, the (meth)acryl fluorenyl group means an acryl fluorenyl group or a methacryl fluorenyl group. Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms and preferably 1 to 5 carbon atoms in R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Further, examples of the epoxy group-containing group include an epoxy group and a glycidyl group.

Specific examples of the compound represented by the above formula (1) include triallyl isocyanurate, diallyl glycidyl isocyanurate, diallyl isocyanurate, and isocyanide. Diallyl urate, tris(2-propenyloxy) isocyanurate, trimethylallyl isocyanurate, triallyl isocyanurate prepolymer, triallyl cyanuric acid, etc. . These may be used alone or in combination of two or more. Among these, from the viewpoint of wafer shear strength, heat resistance, and ultraviolet resistance, triallyl isocyanurate, diallyl glycidyl isocyanurate, and diallyl isocyanurate are preferred. Methyl ester.

Examples of the epoxy resin include hydrogenated bisphenol A type or F type epoxy resin (refractive index 1.48 to 1.52), alicyclic epoxy resin (refractive index 1.48 to 1.51), and isomeric cyanuric acid skeleton. Epoxy resin (refractive index 1.48 to 1.55), epoxy resin having a polyfluorene skeleton (refractive index 1.43 to 1.50), and the like. Among them, from the viewpoint of heat resistance and adhesion, an alicyclic epoxy resin, an epoxy resin having an iso-cyanuric acid skeleton, and an epoxy resin having a polyfluorene skeleton are preferable.

Commercially available, Celloxide 2021P, Celloxide 2081, EHPE3150, EHPE3150CE (above manufactured by Daicel Co., Ltd.), TEPIC-G, TEPIC-S, TEPIC-HP, TEPIC-L, TEPIC-PAS B26L, TEPIC-PAS B22 , TEPIC-FL, TEPIC-VL, TEPIC-UC (above manufactured by Nissan Chemical Industry Co., Ltd.), KF-105, X-22-163, X-22-169, X-22-173 (above is Shin-Etsu Chemical) Industrial Co., Ltd.), BY16-855, SF8411, SF8413, FZ-3720, BY16-839, SF-8421 (above manufactured by Dow Corning Toray Co., Ltd.), TSF4730, YF3965 (above manufactured by Momentive Performance Materials), etc. .

In the case where an epoxy resin is used as the liquid thermosetting resin of the component (A), it is preferred to blend a curing agent. Examples of the curing agent include acid anhydrides, amines, imidazoles, phenols, dicyandiamide, and acid generators of sulfonium salts. From the viewpoint of heat resistance and adhesion, it is preferably an acid generator of an acid anhydride or a phosphonium salt, and when it is mixed and stored, it is more preferably an acid generator of a phosphonium salt from the viewpoint of viscosity stability. . As a commercial item, SAN-AID SI-45, SAN-AID SI-45L, SAN-AID SI-60, SAN-AID SI-60L, SAN-AID SI-80, SAN-AID SI-80L, SAN-AID SI-100, SAN-AID SI-100L, SAN-AID SI-110, SAN-AID SI-110L, SAN-AID SI-150, SAN-AID SI-150L, SAN-AID SI-300, SAN -AID SI-360, SAN-AID SI-B2A, SAN-AID SI-B3A, SAN-AID SI-B3, SAN-AID SI-B4, SAN-AID SI-B5 (above is Sanxin Chemical Industry Co., Ltd. Manufactured, TA-100, TA-120, TA-160 (above, manufactured by San-Apro Co., Ltd.), CO454, C2363, D2685 (above, manufactured by Tokyo Chemical Industry Co., Ltd.).

The content of the curing agent is preferably 0.1 to 3.0 parts by mass, more preferably 0.2 to 2.5 parts by mass, per 100 parts by mass of the epoxy resin.

[(B) Nano cerium oxide treated by an alkyl sulfonyl group having an alkoxy decane having an alkyl group having 4 or more carbon atoms] The alkyl decyl group treated by the component (B) used in the present invention The nanometer cerium oxide has an average primary particle diameter of 1 to 50 nm and is treated with an alkoxy decane having an alkyl group having 4 or more carbon atoms as an alkyl decyl group. By using a nano cerium oxide which has been subjected to alkyl alkyl group treatment using an alkoxy decane having an alkyl group having 4 or more carbon atoms, the adhesion and workability of the thermosetting resin composition can be improved, and the reflow-resistant welding can be improved. Sex.

When the average primary particle diameter of the alkyl cerium-substituted nano cerium oxide of the component (B) is less than 1 nm, the viscosity of the thermosetting resin composition is extremely increased. If it exceeds 50 nm, There is a possibility that the transparency of the cured product of the thermosetting resin composition is lowered. From this point of view, the average primary particle diameter of the alkylphosphonium-treated nano cerium oxide of the component (B) is preferably from 2 to 40 nm, more preferably from 3 to 30 nm. Here, the average primary particle diameter is a number average particle diameter. The average primary particle diameter of the component (B) was randomly selected from 100 primary particles, and the major axis and the minor axis of each primary particle were measured by a scanning electron microscope (SEM, Scanning Electron Microscope), and the average value was obtained.

The synthesis method of the nano cerium oxide is not particularly limited, and examples thereof include a VMC (Vaperized Metal Combustion) method for burning cerium powder, a method for producing water glass as a raw material, and an alkoxide. A method of manufacturing a raw material, and the like.

The method for subjecting the nano cerium oxide to an alkyl sulfonyl group by an alkoxy decane having an alkyl group having 4 or more carbon atoms can be carried out by a known method, and is not particularly limited. The alkoxydecane is not particularly limited as long as it has an alkyl group having 4 or more carbon atoms. For example, a trialkoxysilane represented by the following formula (2) can be preferably used.

[Chemical 2] (wherein R ³ is an alkyl group having 4 or more carbon atoms; and R ^{4 is} each independently an alkyl group having 1 to 4 carbon atoms; and a plurality of R ^{4 's} may be the same or different)

R ³ is an alkyl group having 4 or more carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and examples thereof include a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and 12 Alkyl, tetradecyl, hexadecyl, octadecyl, and the like. Among them, from the viewpoint of imparting thixotropy, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group is preferred.

Examples of the alkyl group having 1 to 4 carbon atoms of R ⁴ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tributyl group. Among them, from the viewpoint of availability, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

Specific examples of the trialkoxysilane represented by the above formula (2) include butyltrimethoxydecane, pentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, and anthracene. Trimethoxy decane, dodecyl trimethoxy decane, hexadecyl trimethoxy decane, octadecyl trimethoxy decane, butyl triethoxy decane, pentyl triethoxy decane, hexyl Triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, dodecyl triethoxy decane, cetyl triethoxy decane, octadecyl triethoxy Decane and so on. These may be used alone or in combination of two or more.

Further, the trialkoxydecane represented by the above formula (2) can be obtained as a decane coupling agent. As a commercial item of the above-mentioned decane coupling agent, H0789 (hexyl trimethoxy decane), T2875 (octyl trimethoxy decane), D4704 (decyl triethoxy decane), D3383 (dodecyl trimethyl) Oxydecane), H1376 (hexadecyltrimethoxydecane), O0256 (octadecyltrimethoxydecane), P0736 (pentyltriethoxydecane), H1158 (hexyltriethoxydecane), D5197 (fluorenyltriethoxydecane), O0171 (octyltriethoxydecane), D1510 (dodecyltriethoxydecane), O0165 (octadecyltriethoxydecane) (above Tokyo Chemical Industry Co., Ltd.) and so on.

The content of the decane coupling agent is preferably from 3 to 20 parts by mass based on 100 parts by mass of the nano cerium oxide. By containing a decane coupling agent in this range, the surface treatment of nano cerium oxide can be sufficiently performed.

In addition, as a commercial product of the surface-treated nano-cerium oxide, AEROSIL (registered trademark) R805, AEROSIL (registered trademark) R816, AEROSIL (registered trademark) VP NKC130, AEROSIL (registered trademark) VP NK 200 (above is manufactured by Nippon Aerozil Co., Ltd.) and the like.

The content of the alkyl cerium oxide-treated nano cerium oxide of the component (B) is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass per 100 parts by mass of the liquid thermosetting resin of the component (A). The mass part is further preferably 3 to 6 parts by mass. By setting the content of the component (B) to 1 part by mass or more, thixotropy can be imparted, and when it is 10 parts by mass or less, workability can be maintained and thixotropy can be imparted.

[Other components] The transparent liquid thermosetting resin composition of the present invention may contain, in addition to the above components (A) and (B), within the scope of the object and effect of the present invention, for example, from the viewpoint of improving transparency. Adding an antioxidant; adding a hardening inhibitor, a solvent, an anti-seepage agent, etc. from the viewpoint of improving workability.

In the transparent liquid thermosetting resin composition of the present invention, the content of the component (A) and the component (B) is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

The method for producing the transparent liquid thermosetting resin composition of the present invention is not particularly limited, and examples thereof include a homogeneous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. A method such as a bead mill or the like, in which a component (A), a component (B), and other components to be blended are mixed at room temperature (25 ° C) or under heating.

The curing temperature of the transparent liquid thermosetting resin composition of the present invention is not particularly limited. The curing temperature of the transparent liquid thermosetting resin composition is preferably from 80 ° C to 200 ° C, more preferably from 100 ° C to 180 ° C, still more preferably from 110 ° C to 160 ° C. When the curing temperature is 80 ° C or more, the hardening of the thermosetting resin composition is sufficiently performed. Moreover, when the hardening temperature is 200 ° C or less, thermal deterioration of the peripheral member can be suppressed.

[Binder for Optical Material] The adhesive for optical material of the present invention comprises the above-mentioned transparent liquid thermosetting resin composition and is then used in an optical semiconductor element, and the viscosity and thixotropy can be adjusted by a coating method. Examples of the coating method of the adhesive for an optical material of the present invention include stamping, dispensing, screen printing, spin coating, and the like.

The viscosity measured by a rotational viscometer using an adhesive for an optical material of the present invention is preferably 150 Pa∙s or less, more preferably 100 Pa∙s or less, still more preferably 70 Pa∙s or less. The light transmittance of the cured product obtained by curing the optical material of the present invention with an adhesive is preferably 70% or more, more preferably 75% or more, still more preferably 80% or more. Moreover, the adhesive strength of the cured product obtained by curing the optical material with an adhesive is preferably 2.5 N or more, more preferably 5.0 N or more, still more preferably 5.5 N or more. Further, the viscosity, the light transmittance, and the adhesion strength can be measured by the methods described in the examples.

[Optical semiconductor device] The optical semiconductor device of the present invention includes an optical semiconductor element which is followed by the above-mentioned adhesive for an optical material. Specific examples of the optical semiconductor device of the present invention include a light-emitting diode device, a semiconductor laser device, and a photocoupler. Such an optical semiconductor device can be suitably used, for example, as a backlight for a liquid crystal display or the like; a light source for illumination, various sensors, a printer, and a photocopier; a light source for a vehicle; a signal lamp; a display lamp; a display device; A light source of a illuminator; a display, a decoration, various lamps, and switching elements.

The light-emitting element which is the above-mentioned optical semiconductor element is not particularly limited as long as it is a light-emitting element using a semiconductor. In the case where the light-emitting element is a light-emitting diode, for example, a structure in which a semiconductor material for LED form is laminated on a substrate can be cited. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

Examples of the material of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as needed. Examples of the material of the buffer layer include GaN, AlN, and the like. [Examples]

Next, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples.

(Synthesis Example 1: Synthesis of Polyoxon Resin 1) Addition of triallyl isocyanurate to a 300 mL four-neck separable flask equipped with a nitrogen gas introduction tube, a thermocouple, and a dropping funnel (Tokyo Chemical Industry Co., Ltd.) Manufactured) 95.9 g, platinum/vinylmethylcyclodecane complex-3% vinylmethylcyclodecane solution 0.033 g. The temperature was raised to 80 ° C for 1 hour from the normal temperature (25 ° C), and 1,3,5,7-tetramethylcyclotetraoxane was added dropwise over 30 minutes while maintaining the temperature in the reaction vessel at 80 ° C (and Wako Pure Chemical Industries Co., Ltd.) 104.1 g. After the completion of the dropwise addition, the temperature was gradually raised to 110 ° C in a non-reactive uncontrolled manner, and cooling was carried out at a time point of 5 Pa∙s, and a polyoxynoxy resin 1 as a colorless transparent viscous liquid was synthesized in a yield of 99%. The synthesized polyoxyxene resin 1 had a refractive index of 1.46.

(Synthesis Example 2: Synthesis of Polyoxymethylene Resin 2) Addition of 1,3-divinyltetramethyldioxane to a 300 mL four-neck separable flask equipped with a nitrogen gas introduction tube, a thermocouple, and a dropping funnel (manufactured by Tokyo Chemical Industry Co., Ltd.) 91.9 g, triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.1 g, platinum/vinylmethylcyclodecane complex-3% vinyl The base cycloxane solution was 0.033 g. The temperature was raised to 80 ° C for 1 hour from the normal temperature (25 ° C), and 1,3,5,7-tetramethylcyclotetraoxane was added dropwise over 30 minutes while maintaining the temperature in the reaction vessel at 80 ° C (and Light Pure Medicine Industry Co., Ltd. manufactured by 98.9 g. After the completion of the dropwise addition, the temperature was gradually raised to 110 ° C in a non-reactive manner, and cooling was carried out at a time point of 5 Pa∙s, and a polyoxynoxy resin 2 as a colorless transparent viscous liquid was synthesized in a yield of 99%. The synthesized polyoxyxene resin 2 had a refractive index of 1.43.

(Preparation of Epoxy Resin 1) 80 g of Celloxide 2021P (manufactured by Daicel Co., Ltd., refractive index: 1.50) and 20 g of EHPE 3150 (manufactured by Daicel Co., Ltd., which is a solid, a refractive index was not measured) were mixed. The refractive index after mixing was 1.50. Further, 2 g of SAN-AID SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.) as a curing agent and 0.06 g of SI-S (manufactured by Sanshin Chemical Industry Co., Ltd.) as an auxiliary agent were mixed.

(Preparation of Epoxy Resin 2) 75 g of Celloxide 2021P (manufactured by Daicel Co., Ltd., refractive index: 1.50) and 25 g of TEPIC-PAS B26L (manufactured by Nissan Chemical Industries, Ltd., refractive index: 1.51) were mixed. The refractive index after mixing was 1.50. Further, 2 g of SAN-AID SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.) as a curing agent and 0.06 g of SI-S (manufactured by Sanshin Chemical Industry Co., Ltd.) as an auxiliary agent were mixed.

(Material of Epoxy Resin 3) 2 g of SAN-AID SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.) as a hardener in 100 g of YL983U (manufactured by Mitsubishi Chemical Co., Ltd., refractive index: 1.58) As an auxiliary agent, SI-S (manufactured by Sanshin Chemical Industry Co., Ltd.) was 0.06 g.

(Example 1) 5 parts by mass of the alkane as the component (B) is blended with respect to 100 parts by mass of the polyoxyxylene resin 1 synthesized in Synthesis Example 1 of the liquid thermosetting resin as the component (A). Nano-cerium oxide-based nano-cerium oxide 1 (AEROSIL (registered trademark) 200, manufactured by Nippon Aerozil Co., Ltd.), which is obtained by dispersing the nano-cerium dioxide by a ceramic three-roll mill, and is prepared and implemented. The transparent liquid thermosetting resin composition of Example 1.

(Examples 2 to 13 and Comparative Examples 1 to 10) A transparent liquid thermosetting resin composition was prepared in the same manner as in Example 1 by blending the respective parts by mass of the components shown in Table 1. Furthermore, in Table 1, the blank column indicates that it is not allocated.

The details of the nano cerium oxides 1 to 12 described in Table 1 are as follows. [(B) component: nano cerium oxide] ∙nano cerium oxide 1: obtained by alkyl decyl treatment of AEROSIL (registered trademark) 200 (manufactured by Nippon Aerozil Co., Ltd.) using hexyltrimethoxy decane (carbon number 6), average primary particle diameter: 12 nm ∙ nanometer ruthenium dioxide 2: AEROSIL (registered trademark) R805 (manufactured by Nippon Aerozil Co., Ltd., trade name, alkyl decyl group, carbon number 8), average Primary particle size: 12 nm ∙n2 二3: AEROSIL (registered trademark) VP NK 200 (manufactured by Nippon Aerozil Co., Ltd., trade name, alkyl decyl treatment, carbon number 16), average primary particle size: 16 Nm ∙n2 二2: Alkyl decyl group obtained by AEROSIL (registered trademark) 200 (manufactured by Nippon Aerozil Co., Ltd.) by octadecyltrimethoxydecane (carbon number 18), averaged once Particle size: 12 nm ∙n2 二9: obtained by alkyl decyl treatment of AEROSIL (registered trademark) 200 (manufactured by Nippon Aerozil Co., Ltd.) using decyltrimethoxydecane (carbon number 10), Average primary particle size: 12 nm ∙ nanometer dioxin矽10: Alkyl decyl treatment of AEROSIL (registered trademark) 90G (manufactured by Nippon Aerozil Co., Ltd.) by decyltrimethoxydecane (carbon number 10), average primary particle diameter: 20 nm ∙ nanometer Cerium oxide 11: obtained by subjecting YA050C (manufactured by Admatechs Co., Ltd.) to alkyl decyl group treatment (carbon number 10) using decyltrimethoxydecane, average primary particle diameter: 50 nm [(B) Nano cerium oxide] ∙ nano cerium oxide 5: AEROSIL (registered trademark) 200 (manufactured by Nippon Aerozil Co., Ltd., without alkyl decyl treatment), average primary particle size: 12 nm ∙ nanometer cerium oxide 6: AEROSIL (registered trademark) RX200 (alkyl decyl treatment: carbon number 1), average primary particle diameter: 12 nm ∙ nanometer ruthenium dioxide 7: using propyltrimethoxy decane to AEROSIL (registered trademark) 200 ( Nippon Aerozil Co., Ltd.) obtained by alkyl decyl group treatment (carbon number 3), average primary particle size: 12 nm ∙ nanometer 二8: AEROSIL (registered trademark) RY200S (manufactured by Nippon Aerozil Co., Ltd. , dimethyl polyoxane treatment), Uniform particle size: 16 nm ∙n2 二12: obtained by alkyl decyl treatment of YA100C (manufactured by Admatechs Co., Ltd.) with decyltrimethoxydecane (carbon number 10), average primary particle size : 100 nm The average primary particle diameter of the above-mentioned nano cerium oxide was determined by scanning electron microscopy (SEM) to determine the major axis and minor axis of 100 primary particles, and the average value was obtained.

The paste characteristics, the evaluation of the cured product characteristics, and the pilot experiment of the transparent liquid thermosetting resin composition obtained in each of the above Examples and Comparative Examples were carried out. Furthermore, the evaluation results are shown in Table 1.

<Paste characteristics> (1) Refractive index The refractive index at 589 nm was measured using an Abbe refractometer (DR-M2) manufactured by Atago Co., Ltd.

(2) Viscosity, thixotropy, and viscosity change rate Viscosity (Pa∙s) was measured at 25 ° C and 0.5 rpm using a viscometer (TPE-100H) manufactured by Toki Sangyo Co., Ltd. Further, the viscosity was measured at 25 ° C and 5 rpm, and the thixotropy was determined from the ratio of the viscosity at 0.5 rpm. Further, the rate of change in viscosity after standing for 24 hours was also measured at room temperature (25 ° C).

(3) Bonding workability (drawing, coating appearance) The wafer was bonded to the LED substrate by a press stamping method using an automatic die bonder manufactured by Kosaka Research Institute Co., Ltd. It is confirmed whether or not the wire is produced when the paste is applied. Further, it was confirmed whether or not the coating amount was insufficient, the diffusion of the resin, the positional shift of the wafer, and the scattering of the resin during the pressing, and the evaluation was performed based on the following criteria. A: The coating amount was sufficient, and the diffusion of the resin, the positional shift of the wafer, and the scattering of the resin during the pressing were not confirmed. C: At least one of insufficient coating amount, diffusion of resin, displacement of the wafer, and scattering of resin during pressing was confirmed.

<Characteristics of cured product> (4) Transmittance The transmittance of 400 nm of a 1 mm thick plate-like cured product was measured using an ultraviolet-visible spectrophotometer (V-570) manufactured by JASCO Corporation. In the case of the cured product, the above-mentioned thermosetting resin composition was poured into a unit prepared by sandwiching a polyxylene oxide sheet having a thickness of 1 mm between two glass plates as a spacer, and performing at 100 ° C for 1 hour. It was heated and then produced by heating at 150 ° C for 1 hour.

(5) Adhesive strength Next, the strength of the wafer was measured at room temperature (25 ° C) using a bonding strength tester (4000plus) manufactured by Nordson Advanced Technology Co., Ltd. The test piece was produced by adhering a 0.3 mm □ Si wafer to a silver-plated copper frame using the above-mentioned thermosetting resin composition, and heating at 150 ° C for 1 hour.

(Intermediate test) (6) Wire bonding property Using an automatic die bonder manufactured by Kosaka Research Co., Ltd., the blue light-emitting device was mounted on an LED substrate by the above-mentioned thermosetting resin composition, and hardened at 150 ° C. 2 hours. Next, wire bonding was performed by a wire bonding machine manufactured by Kulicke & Soffa Japan Co., Ltd., and evaluated according to the following criteria. A: It is possible to perform wire bonding C: positional displacement and/or peeling

(7) Reflow resistance The LED device produced in the same manner as in (6) was heated by a hot plate at 260 ° C for 1 minute, and then the presence or absence of component peeling was confirmed by ultrasonic flaw detection (SAT). When n=10, two or more peelers are regarded as C, and no peelers are regarded as A.

(8) Conduction test The LED device produced in the same manner as in the above (6) was energized with a forward current of 20 mA, and it was confirmed by ultrasonic inspection (SAT) whether or not peeling occurred after 10,000 hours of energization. When n=10, two or more peelers are regarded as C, and no peelers are regarded as A.

[Table 1] Table 1 Unit Example Comparative Example 1234567891011121312345678910 Transparent Liquid Thermosetting Resin Composition (A) Liquid Thermosetting Resin Polyoxymethylene Resin 1 part by mass 100100100100100100100100100100100100100 Polyoxyl resin 2 parts by mass 100100100 Epoxy resin 1 Parts by mass 100100100100 Epoxy resin 2 parts by mass 100100100 (A) Component liquid thermosetting resin epoxy resin 3 parts by mass 100 (B) Alkyl fluorenyl treated nano cerium oxide nano cerium oxide 1 Parts by mass 5 nm ceria 2 parts by mass 5 nm ceria 3 parts by mass 55555 nm ceria 4 parts by mass 5 nm ceria 9 parts by mass 5555 nm ceria 10 parts by mass 5 nm Cerium oxide 11 parts by mass of the nanometer bismuth dioxide nano cerium oxide other than the 5 (B) component 5 parts by mass 5 nanometer cerium oxide 6 parts by mass 5 nanometer cerium oxide 7 parts by mass 5 nanometer cerium oxide 8 parts by mass of 5 nm ceria 12 parts by mass 5 paste characteristic refractive index 589 nm-1.461.461.461.461.431.501.501.461.431.501.501.461.461.461.431.501.501.461.461.461.501.581.46 Viscosity 0.5 rpmPa∙s313045343765663833585819155511501315806775.0 rpmPa∙s1011121110141 41110131276551113121214156 Thixotropy 0.5 rpm/5.0 rpm-3.12.73.83.13.74.64.73.53.34.54.82.72.51.01.01.01.03.81.11.35.74.51.2 Viscosity change rate rt/24 h%<3<3<3<3<3 <3<3<3<3<3<3<3<3<3<3<3<350<5<5<3<5<5 viscous workability drawing - no generation, no generation, no generation, no generation No generation no generation no generation no generation no generation no generation no generation no generation no generation no generation no generation no generation no generation no generation no generation no generation no coating appearance - AAAAAAAAAAAAACCCCCCCAAC hardening property transmittance 400 nm/1 Mmt%8788858589767886887779757091928989898886635128Next strength 25 °C, 0.3 mm□ Ag-plated Cu frame N5.85.76.15.92.57.98.15.92.57.98.15.24.72.20.72.72.72.43.43.43.77.97.53.4 Intermediate test wire bonding - AAAAAAAAAAAAAACAAAAAAAA resistant Solderability - AAAAAAAAAAAAACACCACCAAC power-on test - AAAAAAAAAAAAACCCCACCACC

The transparent liquid thermosetting resin compositions of Examples 1 to 13 containing the components (A) and (B) were not drawn, and were excellent in coating appearance. Therefore, workability and storage stability were excellent. Moreover, the cured product of the thermosetting resin composition had high transparency and adhesion strength, and was excellent in reflow resistance, and no peeling was observed at the time of wire bonding and after the energization test. [Industrial availability]

The transparent liquid thermosetting resin composition of the present invention has high transparency and adhesion, and has excellent workability, and is excellent in storage stability. Therefore, it is useful for a member requiring transparency such as an optical semiconductor device.

Claims (4)

A transparent liquid thermosetting resin composition comprising: (A) a liquid thermosetting resin having a refractive index of 1.40 to 1.55; and (B) nano cerium oxide having an average primary particle diameter of 1 to ～ 50 nm, and treated with an alkoxydecane having an alkyl group having 4 or more carbon atoms as an alkylalkyl group. The transparent liquid thermosetting resin composition of claim 1, wherein the component (A) is any one of a polysiloxane resin and an epoxy resin. An adhesive for an optical material comprising the transparent liquid thermosetting resin composition of claim 1 or 2. An optical semiconductor device comprising an optical semiconductor element followed by an adhesive for an optical material according to claim 3.