JP5000261B2 - Epoxy resin composition and cured epoxy resin - Google Patents

Description

The present invention includes a specific ratio of an alicyclic epoxy resin having a specific structure and obtained by nuclear hydrogenation of a liquid alicyclic epoxy resin and an aromatic epoxy resin at 25 ° C. , And an epoxy resin composition containing an alicyclic epoxy resin having a viscosity at 45 ° C. of a specific value or less. This composition is colorless and transparent, and can provide a cured product excellent in heat resistance, crack resistance, light resistance, and the like, so that it can be used as a coating material, a light curable material, an LED (light emitting diode), and a CCD. It can be used as a sealing material for electrical / electronics related to an optical semiconductor such as a light receiving element.
The present invention also provides an epoxy resin cured product obtained by curing the epoxy resin composition, an optical semiconductor device sealed with the epoxy resin composition, and an adhesive prepared using the epoxy resin composition. About.

  Light emitting devices such as optical semiconductors that are put to practical use in various indoor and outdoor display boards, image reading light sources, traffic signals, large display units, etc., mainly protect the periphery of the light emitting body by sealing with epoxy resin. Yes. The resin used is generally an aromatic epoxy resin such as bisphenol A type, and alicyclic acid anhydrides are widely used as curing agents.

  In recent years, high output, blueening, and whitening of LED elements have been rapidly developed, and light emission with a relatively short wavelength and high output has been performed, and sealing with the above-described aromatic epoxy resin The aromatic ring absorbs light having a short wavelength, so that the sealed resin is deteriorated, and there is a problem that the brightness is lowered and the color is changed due to yellowing.

  Then, LED sealed using the liquid alicyclic epoxy resin obtained by oxidizing a cyclic olefin is proposed (refer patent documents 1 and 2). However, the cured product of this alicyclic epoxy resin is vulnerable to various stresses, easily cracks due to the thermal cycle, etc., and has poor moisture resistance, so the liquid alicyclic epoxy resin alone is not suitable for LED sealing applications. .

  Therefore, liquid nuclear hydrogenated bisphenol A type epoxy resin hydrogenated with aromatic ring is mainly used, alicyclic epoxy resin and phosphorus antioxidant are blended, and sealed with methylhexahydrophthalic anhydride curing agent. LEDs have been proposed (see Patent Document 3). However, although this cured epoxy resin is excellent in colorless transparency, the strength of the cured product is insufficient, the heat cycle resistance is low, and it is suitable for applications for sealing LED elements that require crack resistance. It can not be said.

  On the other hand, the bisphenol A type epoxy resin has excellent properties as a sealing material except that the cured product is colored. In order to take advantage of this property, the improvement of the nuclear hydrogenated bisphenol A type epoxy resin is a resin having a particularly high epoxy equivalent. Has been needed.

  Under such circumstances, a nuclear hydrogenated epoxy resin having a high epoxy equivalent has been proposed (see Patent Document 4). However, the presented conditions are that the epoxy resin is solid and difficult to use for liquid encapsulants used in many transparent encapsulants. Furthermore, the glass transition point of the cured product is low, the heat resistance is insufficient, and the physical properties of the cured product are also unsuitable for use in high-intensity blue or white LEDs.

JP-A-9-213997 JP 2000-196151 A JP 2003-12896 A JP 2005-120357 A

  An object of the present invention is to provide an epoxy resin composition capable of obtaining a cured product which is colorless and transparent, has high heat resistance and strength, and is excellent in heat cycle resistance, and a cured epoxy resin product obtained by curing the epoxy resin composition. Another object of the present invention is to provide an optical semiconductor device sealed with the epoxy resin composition, and an adhesive prepared with the epoxy resin composition.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have obtained by nucleating an alicyclic epoxy resin having a specific structure and a viscosity at 25 ° C. of a specific value or less and an aromatic epoxy resin. When the alicyclic epoxy resin having a specific proportion of the solid alicyclic epoxy resin and having a viscosity at 45 ° C. of a specific value or less is cured, the transparency, heat resistance and strength are high, and heat resistance The inventors have found that a cured product having excellent cycle performance (property capable of suppressing the occurrence of cracks due to a cooling cycle) can be obtained, and the present invention has been completed.

（Ｙは、２価の脂環式炭化水素基；カルボニル基；エステル結合；アミド結合；又は、２価の炭化水素基の１又は２以上と、カルボニル基、エーテル結合、エステル結合及びアミド結合からなる群より選択された少なくとも１つの基とが結合した２価の基を示す。式中に示されるシクロヘキサン環にはアルキル基が結合していてもよい）
で表される脂環式エポキシ樹脂、又は分子内に環状脂肪族骨格及び２以上のエポキシ基を有し且つ２以上のエポキシ基のうち１つのみが環状脂肪族骨格を構成する２つの炭素原子を含んで形成されている脂環式エポキシ樹脂であって、２５℃における粘度が１０００ｍＰａ・ｓ以下の脂環式エポキシ樹脂Ａと、芳香族エポキシ樹脂を核水素化して得られる２５℃で固体であり、エポキシ当量６００〜５０００、核水素化率９６％以上、波長４００ｎｍで測定した光線透過率が８５％以上、軟化温度６０〜１５０℃の脂環式エポキシ樹脂Ｂとを、前者／後者（重量比）＝６０／４０〜７０／３０の割合で含む混合物であって、４５℃における粘度が６００００ｍＰａ・ｓ以下である脂環式エポキシ樹脂と、２５℃における粘度が５００ｍＰａ・ｓ以下の酸無水物と、硬化促進剤とを含有するエポキシ樹脂組成物であり、硬化させて得られるエポキシ樹脂硬化物のガラス転移温度が１７３〜１８５℃であるエポキシ樹脂組成物（以下、「第１のエポキシ樹脂組成物」と称する場合がある）を提供する。 That is, the present invention provides the following formula (1):

(Y is a divalent alicyclic hydrocarbon group; a carbonyl group; an ester bond; an amide bond; or one or more of divalent hydrocarbon groups and a carbonyl group, an ether bond, an ester bond and an amide bond. A divalent group bonded to at least one group selected from the group consisting of: an alkyl group may be bonded to the cyclohexane ring shown in the formula)
Or two carbon atoms having a cyclic aliphatic skeleton and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups constitutes the cyclic aliphatic skeleton. In which the viscosity at 25 ° C. is 1000 mPa · s or less, and obtained by nuclear hydrogenation of an aromatic epoxy resin and solid at 25 ° C. Yes, an alicyclic epoxy resin B having an epoxy equivalent of 600 to 5000, a nuclear hydrogenation rate of 96% or more, a light transmittance measured at a wavelength of 400 nm of 85% or more, and a softening temperature of 60 to 150 ° C. a mixture in a proportion ratio) = 60/40 to 70/30, the cycloaliphatic epoxy resin viscosity at 45 ° C. is not more than 60000mPa · s, a viscosity at 25 ° C. 500 mPa and s following acid anhydride, an epoxy resin composition containing a curing accelerator, an epoxy resin composition a glass transition temperature of the epoxy resin cured product obtained by curing is 173-185 ° C. (hereinafter, " A first epoxy resin composition ”).

（Ｙは、２価の脂環式炭化水素基；カルボニル基；エステル結合；アミド結合；又は、２価の炭化水素基の１又は２以上と、カルボニル基、エーテル結合、エステル結合及びアミド結合からなる群より選択された少なくとも１つの基とが結合した２価の基を示す。式中に示されるシクロヘキサン環にはアルキル基が結合していてもよい）
で表される脂環式エポキシ樹脂、又は分子内に環状脂肪族骨格及び２以上のエポキシ基を有し且つ２以上のエポキシ基のうち１つのみが環状脂肪族骨格を構成する２つの炭素原子を含んで形成されている脂環式エポキシ樹脂であって、２５℃における粘度が１０００ｍＰａ・ｓ以下の脂環式エポキシ樹脂Ａと、芳香族エポキシ樹脂を核水素化して得られる２５℃で固体であり、エポキシ当量６００〜５０００、核水素化率９６％以上、波長４００ｎｍで測定した光線透過率が８５％以上、軟化温度６０〜１５０℃の脂環式エポキシ樹脂Ｂとを、前者／後者（重量比）＝６０／４０〜７０／３０の割合で含む混合物であって、４５℃における粘度が６００００ｍＰａ・ｓ以下である脂環式エポキシ樹脂と、カチオン重合触媒とを含有するエポキシ樹脂組成物であり、硬化させて得られるエポキシ樹脂硬化物のガラス転移温度が１７３〜１８５℃であるエポキシ樹脂組成物（以下、「第２のエポキシ樹脂組成物」と称する場合がある）を提供する。 The present invention also provides the following formula (1):

(Y is a divalent alicyclic hydrocarbon group; a carbonyl group; an ester bond; an amide bond; or one or more of divalent hydrocarbon groups and a carbonyl group, an ether bond, an ester bond and an amide bond. A divalent group bonded to at least one group selected from the group consisting of: an alkyl group may be bonded to the cyclohexane ring shown in the formula)
Or two carbon atoms having a cyclic aliphatic skeleton and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups constitutes the cyclic aliphatic skeleton. In which the viscosity at 25 ° C. is 1000 mPa · s or less, and obtained by nuclear hydrogenation of an aromatic epoxy resin and solid at 25 ° C. Yes, an alicyclic epoxy resin B having an epoxy equivalent of 600 to 5000, a nuclear hydrogenation rate of 96% or more, a light transmittance measured at a wavelength of 400 nm of 85% or more, and a softening temperature of 60 to 150 ° C. a mixture in a proportion ratio) = 60/40 to 70/30, the cycloaliphatic epoxy resin viscosity at 45 ° C. is not more than 60000mPa · s, Epo containing a cationic polymerization catalyst A sheet resin composition, the epoxy resin composition a glass transition temperature of the epoxy resin cured product obtained by curing a one hundred seventy-three to one hundred eighty-five ° C. (hereinafter, may be referred to as "second epoxy resin composition") provide.

  Each of the above epoxy resin compositions may further contain an antioxidant and / or an ultraviolet absorber.

（式中、ｎは１以上の整数である）
で表される芳香族エポキシ樹脂を核水素化して得られる脂環式エポキシ樹脂が含まれる。 In the alicyclic epoxy resin B, the following formula (2)

(Where n is an integer of 1 or more)
The alicyclic epoxy resin obtained by carrying out the nuclear hydrogenation of the aromatic epoxy resin represented by these is contained.

  The present invention further provides a cured epoxy resin obtained by curing the above epoxy resin composition.

The cured epoxy resin preferably has a glass transition temperature of 173 to 185 ° C. Further, it is preferable that the linear expansion coefficient is 55 to 80 ppm, the bending strength is 70 to 125 MPa, the bending elastic modulus is 2075 to 2700 MPa, and the light transmittance measured at a wavelength of 400 nm is 83 to 93%.

  The present invention further provides an optical semiconductor device encapsulated with the epoxy resin composition.

  The present invention also provides an adhesive prepared using the above epoxy resin composition.

  According to the epoxy resin composition of the present invention, a cured product that is colorless and transparent, has high heat resistance and strength, and is excellent in heat cycle resistance can be obtained by curing.

[Epoxy resin composition]
The first epoxy resin composition of the present invention is an alicyclic epoxy resin represented by the formula (1), or has a cyclic aliphatic skeleton and two or more epoxy groups in the molecule, and two or more epoxy groups. An alicyclic epoxy resin in which only one of them is formed to contain two carbon atoms constituting a cycloaliphatic skeleton, and the viscosity at 25 ° C. is 1000 mPa · s or less, A mixture of alicyclic epoxy resin B solid at 25 ° C. obtained by nuclear hydrogenation of an aromatic epoxy resin at a ratio of the former / the latter (weight ratio) = 35/65 to 70/30, The alicyclic epoxy resin whose viscosity in 45 degreeC is 60000 mPa * s or less, the acid anhydride whose viscosity in 25 degreeC is 500 mPa * s or less, and a hardening accelerator are contained. The second epoxy resin composition of the present invention is an alicyclic epoxy resin represented by the formula (1), or a cycloaliphatic skeleton and two or more epoxy groups in the molecule, and two or more epoxy groups. An alicyclic epoxy resin in which only one of them is formed to contain two carbon atoms constituting a cycloaliphatic skeleton, and the viscosity at 25 ° C. is 1000 mPa · s or less, A mixture of alicyclic epoxy resin B solid at 25 ° C. obtained by nuclear hydrogenation of an aromatic epoxy resin at a ratio of the former / the latter (weight ratio) = 35/65 to 70/30, An alicyclic epoxy resin having a viscosity at 45 ° C. of 60000 mPa · s or less and a cationic polymerization catalyst are contained.

  In the above formula (1), Y represents a divalent alicyclic hydrocarbon group; a carbonyl group; an ester bond; an amide bond; or one or more of a divalent hydrocarbon group, a carbonyl group, an ether bond, A divalent group in which at least one group selected from the group consisting of an ester bond and an amide bond is bonded.

  Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, Bivalent cycloalkylene groups (including cycloalkylidene groups) such as 1,4-cyclohexylene and cyclohexylidene groups. Examples of the divalent hydrocarbon group bonded to at least one group selected from the group consisting of a carbonyl group, an ether bond, an ester bond and an amide bond include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, Examples thereof include linear or branched alkylene groups having 1 to 18 carbon atoms (particularly 1 to 10) such as hexamethylene groups, and divalent alicyclic hydrocarbon groups (particularly divalent cycloalkylene groups). .

  In the formula (1), examples of the alkyl group that may be bonded to the cyclohexane ring shown in the formula include carbon numbers such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, and t-butyl group. Examples thereof include 1 to 6 linear or branched alkyl groups. Among these, a methyl group is particularly preferable. The number of alkyl groups bonded to each cyclohexane ring is about 0 to 3.

  The following compound is illustrated as a typical example of the alicyclic epoxy resin represented by Formula (1).

  Said m is an integer of 1-30.

  An alicyclic structure having a cycloaliphatic skeleton and two or more epoxy groups in the molecule, wherein only one of the two or more epoxy groups includes two carbon atoms constituting the cycloaliphatic skeleton. Specific examples of the epoxy resin include the following compounds.

  The viscosity of the alicyclic epoxy resin A at 25 ° C. is 1000 mPa · s or less (for example, 100 to 1000 mPa · s), preferably 200 to 800 mPa · s. The alicyclic epoxy resin A can be used alone or in combination of two or more. As alicyclic epoxy resin A, the alicyclic epoxy resin represented by said Formula (1) is especially preferable.

  The alicyclic epoxy resin A can be produced by a known method or by applying a known method. For example, the alicyclic epoxy resin A is produced by oxidizing (epoxidizing) a corresponding alicyclic olefin compound (cyclic olefin compound) with an aliphatic percarboxylic acid (peracetic acid or the like). In this case, those produced using a substantially anhydrous aliphatic percarboxylic acid are preferable in that they have a high epoxidation rate (see JP-A-2002-275169).

  In the present invention, together with the alicyclic epoxy resin A, an alicyclic epoxy resin in which an epoxy group is formed without sharing the carbon atoms constituting the cycloaliphatic skeleton may be used. As such an epoxy resin, for example, a liquid nuclear hydrogen type epoxy resin [trade names “YX-8000”, “YX-8034” (manufactured by Japan Epoxy Resin Co., Ltd.), product name “HBE-100” (manufactured by Shin Nippon Rika Co., Ltd.) ), Trade name “ST-3000” (manufactured by Tohto Kasei)], diglycidyl ether of cyclohexanedimethanol [trade name “DME-100” (manufactured by Shin Nippon Chemical Co., Ltd.)], trade names “EHPE-3150”, “GT-” 401 "," GT-403 "," GT-301 "," GT-302 "(manufactured by Daicel Chemical Industries) and the like.

  The alicyclic epoxy resin B is not particularly limited as long as it is a solid epoxy resin obtained at 25 ° C. obtained by nuclear hydrogenation of an aromatic epoxy resin, but bisphenol A type epoxy resin or bisphenol F type epoxy resin is nuclear hydrogenated. The alicyclic epoxy resin obtained is preferably an alicyclic epoxy resin obtained by nuclear hydrogenation of the aromatic epoxy resin represented by the formula (2). The alicyclic epoxy resin B can be used alone or in combination of two or more. The alicyclic epoxy resin B is generally excellent in transparency.

The alicyclic epoxy resin obtained by nuclear hydrogenation of the aromatic epoxy resin represented by the formula (2) is represented by the following formula (3). n is the same as described above.

  The epoxy equivalent of the alicyclic epoxy resin B is preferably 500 or more, more preferably 550 or more, and particularly preferably 600 or more. The epoxy equivalent is preferably 5000 or less, more preferably 4500 or less, and particularly preferably 4000 or less. The epoxy equivalent of the alicyclic epoxy resin B is determined by the epoxy equivalent of the aromatic epoxy resin as a raw material and the decomposition rate of the epoxy group that occurs as a side reaction at the time of nuclear hydrogenation. The rate of epoxy group decomposition is the ratio of the epoxy group decomposed to other functional groups such as hydroxyl groups, calculated from the theoretical epoxy equivalent when only the aromatic ring is hydrogenated and the actual epoxy equivalent of the hydrogenated product Can be obtained. The decomposition rate of the epoxy group of the resulting alicyclic epoxy resin B is preferably 50% or less, more preferably 30% or less, and particularly preferably 20% or less. When the decomposition rate of the epoxy group is large, the heat resistance of the cured product tends to decrease.

  The nuclear hydrogenation rate of the alicyclic epoxy resin B is preferably 96% or more, but it is preferably 98% or more particularly when stability to light is required. The upper limit of the hydrogenation rate is 100%. When the nuclear hydrogenation rate is less than 96%, when the epoxy resin composition of the present invention is used for sealing, for example, a nitride semiconductor LED, it absorbs light having a short wavelength and the resin deteriorates with time. In some cases, the emission luminance may be significantly reduced due to yellowing.

  In addition, if the softening temperature of the alicyclic epoxy resin B is too low, the alicyclic epoxy resin B tends to be sticky or easily fused, and workability may be reduced. On the other hand, if it is too high, a high temperature is required at the time of mixing with another epoxy resin, a curing agent, or the like, so that workability, economy, and the like are likely to deteriorate. Therefore, the softening temperature is preferably 60 to 150 ° C, more preferably 65 to 140 ° C. A higher softening temperature alicyclic epoxy resin can be produced using a high molecular weight aromatic epoxy resin having a large epoxy equivalent as a raw material.

  The light transmittance of the alicyclic epoxy resin B at a wavelength of 400 nm is preferably 85% or more (particularly 90% or more). When the light transmittance is low, the transparency of the cured product is also lowered, making it unsuitable for optical materials.

  It is preferable that the alicyclic epoxy resin B does not contain an alkali metal element or a group 15 element of the periodic table as much as possible. For example, the total content of alkali metal elements and group 15 elements of the periodic table in the alicyclic epoxy resin B is desirably 10 ppm by weight or less. Such an alicyclic epoxy resin does not substantially contain a basic substance, and thus, for example, when used as an electric / electronic material, it is possible to prevent deterioration of characteristics and various problems and troubles.

  In addition, the alicyclic epoxy resin B has a lower melt viscosity and improved fluidity than the raw material aromatic epoxy resin. For example, when compared with the melt viscosity at 150 ° C., the viscosity of the alicyclic epoxy resin is usually 70% or less with respect to the melt viscosity of the raw material aromatic epoxy resin.

  The alicyclic epoxy resin B that is solid at 25 ° C. used in the present invention can be produced, for example, by the method described in JP-A-2005-120357. That is, an aromatic epoxy resin having an epoxy equivalent of 500 to 10,000 (preferably 600 to 6000) and preferably a total content of alkali metal elements and Group 15 elements of the periodic table of 10 ppm by weight or less (particularly, bisphenol A type epoxy resin). And / or bisphenol F-type epoxy resin) can be produced by, for example, nuclear hydrogenation in the presence of a catalyst containing a platinum group element.

  As a commercial item applicable to alicyclic epoxy resin B, brand name "YL-7170" (made by Japan Epoxy Resin Co., Ltd.), brand name "ST-4000D" (made by Toto Kasei Co., Ltd.), etc. are mentioned. These are alicyclic epoxy resins obtained by nuclear hydrogenation of the aromatic epoxy resin represented by the formula (2).

  The epoxy resin composition of this invention may contain alicyclic epoxy resins other than the said alicyclic epoxy resin A and the alicyclic epoxy resin B as needed.

  In the epoxy resin composition of the present invention, the ratio of the alicyclic epoxy resin A and the alicyclic epoxy resin B in the alicyclic epoxy resin is the former / the latter (weight ratio) = 35/65 to 70/30. It is. When the ratio is smaller than 35/65, the glass transition temperature of the cured product is low, and the ultraviolet resistance, heat deterioration resistance, etc. are inferior. Moreover, since an alicyclic epoxy resin becomes high viscosity or solid, it becomes unsuitable as a casting material. On the other hand, when the ratio exceeds 70/30, the heat cycle resistance of the cured product is lowered, and cracking is likely to occur due to a cold cycle or the like.

  The total amount of alicyclic epoxy resin A and alicyclic epoxy resin B in the epoxy resin composition of the present invention is usually 50% by weight or more, preferably 70% by weight or more, based on the total alicyclic epoxy resin. Preferably it is 90 weight% or more, Most preferably, it is 95 weight% or more, and an alicyclic epoxy resin may be comprised only with the alicyclic epoxy resin A and the alicyclic epoxy resin B substantially.

  The viscosity at 45 ° C. of the alicyclic epoxy resin (mixture) in the epoxy resin composition of the present invention is 60000 mPa · s or less (for example, 1000 to 60000 mPa · s). When this viscosity exceeds 60,000 mPa · s, the viscosity of the entire epoxy resin composition also increases, handling properties decrease, and it is unsuitable as a casting material.

  The epoxy resin composition of the present invention includes an acid anhydride (curing agent) having a viscosity at 25 ° C. of not more than 500 mPa · s and a curing accelerator, or a cationic polymerization catalyst in order to cure the alicyclic epoxy resin.

  Examples of the acid anhydride having a viscosity at 25 ° C. of 500 mPa · s or less include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, And cyclic aliphatic acid anhydrides such as trialkyltetrahydrophthalic anhydride. Among these, it is particularly preferable to use a hydrogenated cycloaliphatic anhydride such as hexahydrophthalic anhydride or methylhexahydrophthalic anhydride from the viewpoint of improving the light resistance of the epoxy resin composition. Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and the like are not preferable because coloring tends to occur in the cured product. Acid anhydrides having a viscosity at 25 ° C. of 500 mPa · s or less can be used alone or in combination of two or more.

  Examples of the curing accelerator include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-azabicyclo [4. 3.0] tertiary amines such as nonene-7 and salts thereof; phosphonium salts, imidazoles, organic phosphine compounds or salts thereof; metal soaps such as zinc octylate and tin octylate. A hardening accelerator can be used individually or in combination of 2 or more types.

  The use ratio of the acid anhydride as the curing agent for the epoxy resin is, for example, 50 to 120 parts by weight, preferably 60 to 110 parts by weight with respect to 100 parts by weight of the alicyclic epoxy resin (mixture) in the epoxy resin composition. Within the range of the part. Moreover, the usage-amount of the said hardening accelerator is 0.1-5 weight part with respect to 100 weight part of alicyclic epoxy resins (mixture) in an epoxy resin composition, Preferably it is 0.2-2 weight part. is there.

In this invention, you may use the said acid anhydride and another hardening | curing agent together as needed. Examples of other curing agents include Bronsted acid salts such as amine BF ₃ complex compounds, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts and phosphonium salts, adipic acid, sebacic acid, terephthalic acid, trimellitic acid and And polycarboxylic acids such as carboxyl group-containing polyesters. Phenol resins, resols, and amine curing agents are not preferred because the cured product is colored yellow or red. Also, organic acid hydrazides such as dicyandiamides, adipic acid dihydrazide and phthalic acid dihydrazide have low reactivity with liquid alicyclic epoxy resins and are not preferred as curing agents.

  As the cationic polymerization initiator, an active energy ray cationic polymerization initiator that generates a cationic species or Bronsted acid by active energy rays, or a thermal cationic polymerization initiator that generates a cationic species or Bronsted acid by heat can be used. . Cationic polymerization initiators can be used alone or in combination of two or more.

Examples of the active energy ray cationic polymerization initiator include metal fluoroboron complex salts and boron trifluoride complex compounds described in US Pat. No. 3,379,653; bis (perfluoroalkyl) described in US Pat. No. 3,586,616. Sulfonyl) methane metal salts; aryldiazonium compounds described in US Pat. No. 3,708,296; aromatic onium salts of Group VIa elements of the periodic table described in US Pat. No. 4,058,400; described in US Pat. Aromatic onium salts of group Va elements of the periodic table; dicarbonyl chelates of group IIIa to Va elements of the periodic table described in US Pat. No. 4068091; thiopyrylium salts described in US Pat. No. 4,139,655; MF ^6- Kagei that is described in JP 4161478 (Where M is an element selected from phosphorus, antimony and arsenic); Group VIb element compounds of the periodic table; arylsulfonium complex salts described in US Pat. No. 4,231,951; described in US Pat. No. 4,256,828 Aromatic iodonium complex salts and aromatic sulfonium complex salts; R. Watt et al., “The Bis [4- (diphenylsulfonio) described in Journal of Polymer Science, Polymer Chemistry, Vol. 22, p. 1789 (1984)”. Phenyl] sulfide-bis-hexafluorometal salts (for example, phosphate, arsenate, antimonate, etc.) Also, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can be used. These active energy ray cationic polymerization initiators can be used alone or in combination of two or more.

  Preferred active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements of the periodic table. Some of these salts are commercially available. For example, “FX-512” (3M), “UVR-6990” and “UVR-6974” (Union Carbide), “UVE-1014” and “UVE-1016” [General Electric ( General Electric Company], "KI-85" [Degussa], "SP-150" and "SP-170" (Asahi Denka Co., Ltd.), "Sun Aid SI-60L", "Sun Aid SI-80L" And “Sun Aid SI-100L” (Sanshin Chemical Industry Co., Ltd.).

  Examples of the thermal cationic polymerization initiator include cationic or protonic acid catalysts such as triflic acid salt, boron trifluoride ether complex compound, boron trifluoride and the like. A preferable thermal cationic polymerization initiator is a triflate, and examples thereof include diethylammonium triflate and triethylatriflate available as “FC-520” from 3M Corporation. Moreover, among aromatic onium salts used as active energy ray cationic polymerization initiators, there are those that generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators. For example, “Sun-Aid SI-60L”, “Sun-Aid SI-80L” and “Sun-Aid SI-100L” (Sanshin Chemical Industry Co., Ltd.) are available. These thermal cationic polymerization initiators can be used alone or in combination of two or more.

  Among these active energy rays and thermal cationic polymerization initiators, onium salts are preferable in terms of handling properties and a balance between latency and curability, and among them, diazonium salts, iodonium salts, sulfonium salts, and phosphonium salts. Is particularly preferable in that it has an excellent balance between handleability and latency.

  The usage-amount of a cationic polymerization initiator is 0.1-10 weight part with respect to 100 weight part of alicyclic epoxy resins (mixture) in the epoxy resin composition of this invention, Preferably it is 0.3-4 weight part. It is.

  Even when any epoxy resin curing agent is used, if the amount of use is outside the preferred range, the balance of hue, heat resistance and moisture resistance of the cured epoxy resin is deteriorated, which is not preferable.

  Adding an antioxidant to the epoxy resin composition of the present invention, particularly the epoxy resin composition used for a light emitting device encapsulant, to prevent oxidative deterioration during heating is effective in obtaining a cured product with less coloration. Is preferable. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part of alicyclic epoxy resins (mixture) in the epoxy resin composition of this invention, Preferably it is 0.01-0.5. Parts by weight.

  Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl- 6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspir B Bisphenols such as [5,5] undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl- High molecular phenols such as 4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and tocophenol are exemplified.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

  Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.

  These antioxidants can be used alone, but it is particularly preferable to use a combination of two or more, such as phenol / sulfur or phenol / phosphorus.

  If necessary, other components can be added to the epoxy resin composition of the present invention. Examples of the component include epoxy resins other than those described above, such as 2- to 6-functional heterocyclic epoxy resins such as triglycidyl isocyanurate; metal oxides such as aluminum oxide and magnesium oxide, fine powder silica, fused silica, crystalline silica, and the like Silica compounds, transparent fillers such as glass beads, metal hydroxides such as aluminum hydroxide, and other powdery reinforcing agents and fillers such as kaolin, mica, quartz powder, graphite, molybdenum disulfide; titanium dioxide, molybdenum Colorants or pigments such as red, bitumen, ultramarine, cadmium yellow, cadmium red and organic dyes; flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds; ultraviolet absorbers, ion adsorbents, coupling agents, mold release agents And the like.

  Epoxy resins other than the above, powdery reinforcing agents and fillers are blended within a range that does not impair the transparency of the epoxy resin composition of the present invention, and the alicyclic epoxy resin (mixture) in the epoxy resin composition of the present invention. ) For example, 100 parts by weight or less, preferably 10 to 100 parts by weight is appropriate for each 100 parts by weight. The amount of additives such as a colorant or pigment, a flame retardant, an ultraviolet absorber, an ion adsorbent, a coupling agent, a release agent, etc. is used for the alicyclic epoxy resin (mixture) 100 in the epoxy resin composition of the present invention. The amount is, for example, not more than 30 parts by weight, preferably about 0.01 to 30 parts by weight with respect to parts by weight.

  Furthermore, the epoxy resin composition of the present invention can be blended with various curable monomers, oligomers and synthetic resins other than the epoxy resin for the purpose of improving the properties of the cured epoxy resin. For example, diols such as polyether diol, polyester diol, polycarbonate diol, triols, tetraols, vinyl ethers, oxetane compounds, fluororesins, acrylic resins, silicone resins, etc. Can do. The compounding ratio of these compounds and resins is in an amount that does not impair the original properties of the epoxy resin composition of the present invention, for example, 100 parts by weight of an alicyclic epoxy resin (mixture) in the epoxy resin composition of the present invention. The amount is preferably 50 parts by weight or less.

  The epoxy resin composition of the present invention can be produced by using a known method. For example, a predetermined amount of alicyclic epoxy resin A, alicyclic epoxy resin B, the specific acid anhydride and curing accelerator, or cationic polymerization catalyst, and optionally used additives (antioxidants, ultraviolet rays, etc.) It can be prepared by blending an absorbent and the like, and stirring and mixing while excluding bubbles under vacuum heating. The temperature at the time of stirring and mixing is preferably set to 10 to 60 ° C. If the set temperature at the time of preparation is less than 10 ° C., the viscosity is high, and uniform stirring and mixing operations are likely to be difficult. If the temperature exceeds 60 ° C., a curing reaction may occur, and it becomes difficult to obtain a normal epoxy resin composition. . When stirring and mixing, use a general-purpose device such as a uniaxial or multi-axial extruder, kneader, or dissolver equipped with a decompression device, for example, by stirring and mixing for about 5 to 30 minutes. Also good.

  The epoxy resin composition thus obtained has a cured product that is colorless and transparent, has high heat resistance and strength, excellent heat cycle resistance, and high adhesion, so that it is particularly a sealing material for electric and electronic parts, for example, insulation. Although it can be used as a material or the like, it can be suitably used as a sealing material for an optical semiconductor device such as an LED element or an adhesive.

  The optical semiconductor element is sealed by injecting the epoxy resin composition prepared as described above into a predetermined mold and heat-curing (or photocuring) under predetermined conditions. Thereby, the optical semiconductor device in which the optical semiconductor element is sealed with the epoxy resin composition of the present invention is obtained. The curing temperature is, for example, 100 to 200 ° C, preferably 100 to 190 ° C, and more preferably 100 to 180 ° C.

[Hardened epoxy resin]
The cured epoxy resin of the present invention is obtained by curing the epoxy resin composition of the present invention with, for example, light and / or heat. The cured epoxy resin of the present invention has the following physical properties, for example.
-Glass transition temperature measured by TMA: 130-185 ° C (especially 135-185 ° C)
-Average linear expansion coefficient from 50 ° C to 100 ° C: 50-80ppm
Flexural modulus: 2075-2675 MPa (especially 2075-2675 MPa)
・ Bending strength: 70 to 125 MPa
-Adhesive strength: 250-400 MPa
-Light transmittance at 400 nm is 83 to 93%

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by this. In addition, the viscosity of the alicyclic epoxy resin, the glass transition temperature (Tg) of the cured product of the epoxy resin composition, the linear expansion coefficient, the bending strength, the adhesive strength, the ultraviolet resistance, the heat deterioration resistance, the moisture absorption rate (water absorption rate) and Measurement and evaluation of thermal shock resistance (crack resistance) were performed by the following methods.

(viscosity)
The viscosity at 25 ° C. or 45 ° C. was measured using an E-type viscometer.

(Glass transition temperature Tg (° C) and linear expansion coefficient)
It was measured by the TMA method (heating rate 5 ° C./min). The measurement was performed under the trade name “TMA / SS6100” manufactured by Seiko Instruments Inc. The linear expansion coefficient measured the average linear expansion coefficient between 50 to 100 degreeC.

(Light transmittance)
The transmittance of the hydrogenated epoxy resin and the cured epoxy resin at 400 nm was measured with a trade name “UV-2450” manufactured by Shimadzu Corporation.

(Bending strength test)
Using a product name “RTC-1350A” manufactured by Orientec Co., Ltd., bending strength and bending elastic modulus were measured according to JIS K7171.

(Adhesive strength test)
An adhesive strength test was performed according to JIS K6850 using a product name “RTC-1350A” manufactured by Orientec Co., Ltd.

(UV resistance)
The YI value (Yellowness Index) of the cured product after irradiation with ultraviolet light for 72 hours at an irradiation intensity of 0.4 kW / m ² and a black panel temperature of 63 ° C. was measured using a metering weather meter (manufactured by Daipla Intes). .

(Heat resistance degradation)
The transmittance of 400 nm of the cured epoxy resin after heating at 120 ° C. for 72 hours was measured with a product name “UV-2450” manufactured by Shimadzu Corporation.

(Hygroscopic rate)
The moisture absorption rate (water absorption rate) (%) of a cured disc-shaped epoxy resin having a thickness of 1 mm and a diameter of 30 mm after being left at 23 ° C. for 24 hours was measured.

(Thermal shock resistance (crack resistance))
An LED lead frame (EME2003-ver2 / Enomoto) and an epoxy resin composition were used to form a bullet-type LED, and a thermal shock test was performed using a thermal shock tester (TSE-11 / ESPEC). . A thermal shock test was performed at a cycle of 170 ° C. to −75 ° C. shown in Table 1 below, and the cured product was stopped when a crack occurred, and the “crack resistance” of the cycle in which the crack occurred was shown as an average value.

Production Example 1 (Preparation of nuclear hydrogenation catalyst)
625 mg of 40 wt% rhodium chloride (manufactured by NE Chemcat) is dissolved in 20 g of water, and 4.75 g of commercially available graphite (“HSAG100” manufactured by TIMCAL, specific surface area 130 m ² / g) is added to the obtained aqueous rhodium chloride solution. Was impregnated with an aqueous rhodium chloride solution. An aqueous solution in which 0.78 g of 28% by weight of ammonia water was dissolved in 6 ml of water was added, and immobilization treatment was performed at room temperature. The obtained solid product was separated by filtration, sufficiently washed with ion exchanged water, and dried at 50 ° C. to obtain an unreduced rhodium / graphite catalyst supporting 5% by weight of rhodium.

Synthesis example 1
In the autoclave, the content of each element of bisphenol A type solid epoxy resin ("Epicoat 1003" manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 741, Li, Na, K, N, P is 1 ppm or less, Content: 5 ppm or less, light transmittance at 400 nm: 96%, light transmittance at 340 nm: 65%, melt viscosity: 2700 mPa · s, one-step process product) 200 g, ethyl acetate 200 g, production example 1 as hydrogenation catalyst 1 g of unreduced 5 wt% rhodium / graphite catalyst (0.5 wt% epoxy resin, 0.025 wt% rhodium vs. epoxy resin) obtained in the above was charged, and the autoclave was purged with nitrogen and then purged with hydrogen . Thereafter, a nuclear hydrogenation reaction was performed at 110 ° C. and a hydrogen pressure of 8 MPa for 1.8 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate, added with 4 g of magnesium oxide, stirred and mixed at room temperature for 30 minutes, and then filtered. After completion of the filtration, ethyl acetate in the reaction solution was recovered by distillation, the solvent was removed at 160 ° C. and a pressure of 100 MPa, the solution was extracted, and then cooled to obtain a hydrogenated epoxy resin (alicyclic epoxy resin). The resulting hydrogenated epoxy resin (alicyclic epoxy resin) is a colorless and transparent solid, with a nuclear hydrogenation rate of 99.2%, an epoxy equivalent of 943, an epoxy group decomposition rate of 15%, and a light transmission of 400 nm. The rate was 98%, the softening temperature was 73 ° C., and the melt viscosity was 1610 mPa · s.

Example 1
Alicyclic epoxy resin (trade name “CEL-2021P”, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd., viscosity 237 mPa · s at 25 ° C.) 70 parts by weight And 30 parts by weight of an alicyclic epoxy resin (epoxy resin 1: hydrogenated epoxy resin obtained in Synthesis Example 1) were mixed at 90 ° C. under a nitrogen stream in a flask equipped with a stirrer. The product name “Ricacid MH-700” (manufactured by Shin Nippon Chemical Co., Ltd., methylhexahydrophthalic anhydride, viscosity 53 mPa · s at 25 ° C.) is used as a curing agent in 100 parts by weight of the resulting alicyclic epoxy resin mixture. 2 parts by weight, 0.5 part by weight of trade name “U-CAT 18X” (manufactured by San Apro) as a curing accelerator, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol as an antioxidant A part was added, and mixing was performed using Ryotaro Foam (manufactured by Shinky Corporation) to obtain an epoxy resin composition. The viscosity of the alicyclic epoxy resin mixture at 45 ° C. was 2870 mPa · s.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

Example 2 (referred to as “Reference Example 1”)
45 parts by weight of alicyclic epoxy resin (trade name “CEL-2021P”), 50 parts by weight of alicyclic epoxy resin (epoxy resin 1: hydrogenated epoxy resin obtained in Synthesis Example 1), and alicyclic epoxy 5 parts by weight of a resin (trade name “CEL-3000”, 1,2: 8,9-diepoxy limonene, manufactured by Daicel Chemical Industries, Ltd., viscosity 11 mPa · s at 25 ° C.) under a nitrogen stream in a flask equipped with a stirrer, Mix at 90 ° C. To 100 parts by weight of the resulting alicyclic epoxy resin mixture, 0.8 part by weight of a trade name “SANAID SI-100L” (manufactured by Sanshin Chemical Industry Co., Ltd., sulfonium salt cationic polymerization catalyst) as a cationic polymerization catalyst was added. Mixing was performed using Awatake Rentaro (made by Shinki Co., Ltd.) to obtain an epoxy resin composition. The viscosity of the alicyclic epoxy resin mixture at 45 ° C. was 33800 mPa · s.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

Example 3 (referred to as “Reference Example 2”)
40 parts by weight of an alicyclic epoxy resin (trade name “CEL-2021P”) and an alicyclic epoxy resin (epoxy resin 2: trade name “YL7170”, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 1009, nuclear hydrogenation rate 98 %, 400 nm light transmittance is 93%, solid at 25 ° C.) was mixed at 90 ° C. under a nitrogen stream in a flask equipped with a stirrer. To 100 parts by weight of the resulting alicyclic epoxy resin mixture, 62.6 parts by weight of the trade name “Ricacid MH-700” as the curing agent and 0.5 parts by weight of the trade name “U-CAT 18X” as the curing accelerator. Then, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol was added as an antioxidant, and the mixture was mixed using a foam-removal taro (manufactured by Sinky Corporation) to obtain an epoxy resin composition. The viscosity of the alicyclic epoxy resin mixture at 45 ° C. was 53500 mPa · s.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

Example 4 (referred to as “Reference Example 3”)
90 parts by weight of 50 parts by weight of an alicyclic epoxy resin (trade name “CEL-2021P”) and 50 parts by weight of an alicyclic epoxy resin (epoxy resin 2: trade name “YL7170”) in a flask with a stirrer under a nitrogen stream Mixed at ° C. To 100 parts by weight of the resulting alicyclic epoxy resin mixture, 72.9 parts by weight of a trade name “Ricacid MH-700” as a curing agent and 0.5 parts by weight of a trade name “U-CAT 18X” as a curing accelerator Then, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol was added as an antioxidant, and the mixture was mixed using a foam-removal taro (manufactured by Sinky Corporation) to obtain an epoxy resin composition. The viscosity of the alicyclic epoxy resin mixture at 45 ° C. was 13760 mPa · s.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

Example 5
90 parts by weight of an alicyclic epoxy resin (trade name “CEL-2021P”) and 40 parts by weight of an alicyclic epoxy resin (epoxy resin 2: trade name “YL7170”) in a flask equipped with a stirrer under a nitrogen stream Mixed at ° C. To 100 parts by weight of the resulting alicyclic epoxy resin mixture, 84.0 parts by weight of the trade name “Ricacid MH-700” as a curing agent and 0.5 parts by weight of the trade name “U-CAT 18X” as a curing accelerator. Then, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol was added as an antioxidant, and the mixture was mixed using a foam-removal taro (manufactured by Sinky Corporation) to obtain an epoxy resin composition. The viscosity of the alicyclic epoxy resin mixture at 45 ° C. was 4200 mPa · s.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

Example 6 (referred to as “Reference Example 4”)
45 parts by weight of an alicyclic epoxy resin (trade name “CEL-2021P”) and an alicyclic epoxy resin (epoxy resin 3: trade name “ST-4000D”, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 696, nuclear hydrogenation rate The light transmittance at 97% and 400 nm was 91%, solid at 25 ° C.) was mixed at 55 ° C. in a flask equipped with a stirrer under a nitrogen stream at 90 ° C. To 100 parts by weight of the resulting alicyclic epoxy resin mixture, 67.3 parts by weight of the trade name “Ricacid MH-700” as a curing agent and 1.0 part by weight of the trade name “U-CAT 18X” as a curing accelerator Then, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol was added as an antioxidant, and the mixture was mixed using a foam-removal taro (manufactured by Sinky Corporation) to obtain an epoxy resin composition. The viscosity of the alicyclic epoxy resin mixture at 45 ° C. was 58500 mPa · s.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

Comparative Example 1
100 parts by weight of alicyclic epoxy resin (epoxy resin 2: trade name “YL7170”), 23 parts by weight of trade name “Licacid MH-700” as a curing agent, and trade name “U-CAT 18X” as a curing accelerator 1.0 part by weight, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol as an antioxidant is added, and mixing is carried out using a foam removal Ryotaro (Sinky), and an epoxy resin A composition was obtained. The viscosity of the alicyclic epoxy resin at 45 ° C. was a solid and could not be measured.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

Comparative Example 2
90 parts by weight of an alicyclic epoxy resin (trade name “CEL-2021P”) and 80 parts by weight of an alicyclic epoxy resin (epoxy resin 2: trade name “YL7170”) in a flask equipped with a stirrer under a nitrogen stream Mixed at ° C. To 100 parts by weight of the resulting alicyclic epoxy resin mixture, 1.0 part by weight of a trade name “SANAID SI-100L” (manufactured by Sanshin Chemical Industry Co., Ltd., sulfonium salt-based cationic polymerization catalyst) as a cationic polymerization catalyst, antioxidant As an agent, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol was added, and mixing was carried out using Foaming Rentaro (manufactured by Shinky Corp.) to obtain an epoxy resin composition. The viscosity at 45 ° C. of the alicyclic epoxy resin mixture was too high to be measured.
The epoxy resin composition obtained as described above was cast into a predetermined mold, and the primary curing was cured at 100 ° C. for 3 hours, and the secondary curing was cured at 150 ° C. for 3 hours to obtain each test piece. The evaluation results of this cured product are shown in Table 2.

  As shown in the above table, the cured epoxy resin obtained in the examples has a high glass transition temperature, transparency, mechanical strength, adhesive strength, UV resistance, heat deterioration resistance, water absorption, thermal shock resistance. It was excellent in any of these characteristics. On the other hand, an epoxy resin composition containing only a solid alicyclic epoxy resin as an alicyclic epoxy resin as a comparative example or a very high proportion of a solid epoxy resin is unsuitable as a casting material, Moreover, since the cured product has a low glass transition temperature and is inferior in heat deterioration resistance, it is not suitable for high-brightness LEDs with a large calorific value, and also inferior in ultraviolet resistance.

Claims (9)

Following formula (1)

(Y is a divalent alicyclic hydrocarbon group; a carbonyl group; an ester bond; an amide bond; or one or more of divalent hydrocarbon groups and a carbonyl group, an ether bond, an ester bond and an amide bond. A divalent group bonded to at least one group selected from the group consisting of: an alkyl group may be bonded to the cyclohexane ring shown in the formula)
Or two carbon atoms having a cyclic aliphatic skeleton and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups constitutes the cyclic aliphatic skeleton. In which the viscosity at 25 ° C. is 1000 mPa · s or less, and obtained by nuclear hydrogenation of an aromatic epoxy resin and solid at 25 ° C. Yes, an alicyclic epoxy resin B having an epoxy equivalent of 600 to 5000, a nuclear hydrogenation rate of 96% or more, a light transmittance measured at a wavelength of 400 nm of 85% or more, and a softening temperature of 60 to 150 ° C. a mixture in a proportion ratio) = 60/40 to 70/30, the cycloaliphatic epoxy resin viscosity at 45 ° C. is not more than 60000mPa · s, a viscosity at 25 ° C. 500 mPa s The following acid anhydrides and, an epoxy resin composition containing a curing accelerator, an epoxy resin composition a glass transition temperature of the epoxy resin cured product obtained by curing is 173-185 ° C.. Following formula (1)

(Y is a divalent alicyclic hydrocarbon group; a carbonyl group; an ester bond; an amide bond; or one or more of divalent hydrocarbon groups and a carbonyl group, an ether bond, an ester bond and an amide bond. A divalent group bonded to at least one group selected from the group consisting of: an alkyl group may be bonded to the cyclohexane ring shown in the formula)
Or two carbon atoms having a cyclic aliphatic skeleton and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups constitutes the cyclic aliphatic skeleton. In which the viscosity at 25 ° C. is 1000 mPa · s or less, and obtained by nuclear hydrogenation of an aromatic epoxy resin and solid at 25 ° C. Yes, an alicyclic epoxy resin B having an epoxy equivalent of 600 to 5000, a nuclear hydrogenation rate of 96% or more, a light transmittance measured at a wavelength of 400 nm of 85% or more, and a softening temperature of 60 to 150 ° C. a mixture in a proportion ratio) = 60/40 to 70/30, the cycloaliphatic epoxy resin viscosity at 45 ° C. is not more than 60000mPa · s, Epo containing a cationic polymerization catalyst Shi is a resin composition, the epoxy resin composition a glass transition temperature of the epoxy resin cured product obtained by curing a one hundred seventy-three to one hundred eighty-five ° C..   Furthermore, the epoxy resin composition of Claim 1 or 2 containing antioxidant and / or a ultraviolet absorber. The alicyclic epoxy resin B is represented by the following formula (2)

(Where n is an integer of 1 or more)
The epoxy resin composition according to any one of claims 1 to 3, which is an alicyclic epoxy resin obtained by nuclear hydrogenation of an aromatic epoxy resin represented by formula (1). The epoxy resin hardened | cured material obtained by hardening the epoxy resin composition as described in any one of Claims 1-4 . The cured epoxy resin product according to claim 5, wherein the glass transition temperature is 173 to 185 ° C. The cured epoxy resin according to claim 5 or 6 , wherein the linear expansion coefficient is 55 to 80 ppm, the bending strength is 70 to 125 MPa, the bending elastic modulus is 2075 to 2700 MPa, and the light transmittance measured at a wavelength of 400 nm is 83 to 93%. The optical semiconductor device sealed using the epoxy resin composition in any one of Claims 1-4 . The adhesive agent prepared using the epoxy resin composition in any one of Claims 1-4 .