TWI465487B - Resin composition for sealing optical semiconductor - Google Patents

Description

Resin composition for optical semiconductor sealing

The present invention relates to a silicone modified epoxy resin composition for sealing an optical semiconductor element which is excellent in heat resistance test and particularly excellent in crack resistance.

Conventionally, a transparent epoxy resin composition has been widely used as an optical semiconductor element sealing resin for sealing an optical semiconductor element. The component of the epoxy resin composition for optical semiconductor sealing usually contains an alicyclic epoxy resin, a curing agent, and a curing catalyst, and is formed by a molding method such as casting molding or transfer molding. The epoxy resin composition for sealing the optical semiconductor is introduced into a mold in which the optical semiconductor element is placed and cured, and the optical semiconductor element is sealed (Patent Document 1 and Patent Document 2).

However, recently, as the brightness and power of blue-emitting diodes (LEDs) and white LEDs are getting higher and higher, LED elements sealed with conventional transparent epoxy resins appear to have wavelengths over time. The problem of discoloration (yellowing) with shorter blue light or ultraviolet light. Moreover, problems such as high water absorption rate and poor moisture durability are also pointed out.

Therefore, those skilled in the art have also proposed a resin composition for coating protection of an optical semiconductor element. The resin composition for coating protection of the optical semiconductor element includes at least two carbons having reactivity with SiH groups in one molecule. - an organic compound or a fluorenone resin having a carbon double bond, contained in one molecule to There are two SiH-based ruthenium compounds and a hydrosilylation catalyst (Patent Document 3, Patent Document 4).

However, such an anthrone-based cured product has a drawback in that if it is to be improved in crack resistance, the surface of the cured product usually has a tack which is likely to adhere to dust and impair the light transmittance. In order to solve these problems, those skilled in the art have proposed to use a high hardness fluorenone resin for the purpose of protecting coating (Patent Document 5, Patent Document 6). However, the case type light-emitting semiconductor device in which the light-emitting element is disposed in a ceramic and/or plastic case and filled with the fluorenone resin inside the case has the following problem, because These high hardness fluorenone resins have insufficient toughness and adhesiveness. Therefore, in the thermal shock test at -40 ° C to 120 ° C, the fluorenone resin is peeled off from the ceramic or plastic of the casing, or cracks are generated.

Further, as a composition having the possibility of compensating for these disadvantages, a composition containing an epoxy resin and an anthrone resin has been proposed (Patent Document 7 and Patent Document 8), but such a composition also has insufficient adhesion or cause The problem of photodegradation and discoloration. Further, in order to increase the strength of the resin and to improve the ultraviolet resistance, it has been proposed to use a cation hardening catalyst to halose a siloxane compound having an epoxy group and/or an oxetanyl group. A method of hardening a silsesquioxane compound (Patent Document 9), but there are problems such as corrosion and coloring caused by onium ions or the like generated by the cation hardening catalyst to be used. In addition, a phase B of a combination of a sesquioxanes and a hydrogenated epoxy resin was proposed. (B-Stage) Resin composition (Patent Document 10), but such a resin composition using a hydrogenated epoxy resin has a problem of poor ultraviolet resistance. Further, a composition comprising an organopolysiloxane containing an isocyanuric acid derivative group and an epoxy resin is proposed (Patent Document 11), and an organic polysiloxane is generally used as a phenol resin for sealing a semiconductor. ), an additive in an epoxy resin. However, this epoxy resin composition is not used for transparent sealing of LEDs, and is also limited to a linear skeleton with respect to the indole skeleton, and does not mention the molecular weight distribution of anthrone.

[Patent Document 1] Japanese Patent No. 3241338

[Patent Document 2] Japanese Patent Laid-Open No. 7-25987

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-327126

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-338833

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-314139

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2002-314143

[Patent Document 7] Japanese Patent Laid-Open Publication No. SHO 52-107049

[Patent Document 8] Japanese Patent No. 3396652

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2004-238589

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2005-263869

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2004-99751

The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide an epoxy resin composition for sealing an optical semiconductor element which is excellent in heat resistance and light resistance and which is mainly excellent in crack resistance.

The inventors of the present invention have diligently studied in order to achieve the stated object, and have found that The anthrone-modified epoxy compound represented by the following formula (1) can form a cured product excellent in heat resistance, light resistance, and crack resistance.

In other words, the present invention relates to a resin composition for optical semiconductor sealing, which comprises the following components (A), (B) and (C):

(A) 100 parts by weight of an anthrone-modified epoxy compound having two or more epoxy groups in one molecule and represented by the following formula (1) and having a degree of dispersion of 1.0 to 1.2

(R ^{1 is} independently of each other, and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R ² is a group represented by the following formula (2) or (3), and a and b are selected from an integer One or more integers from 0 to 20)

[Chemical 3]

(B) Hardener 0.1 parts by mass to 100 parts by mass

(C) The curing catalyst is 0.05 parts by mass to 3 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

The fluorenone-modified epoxy resin composition for optical semiconductor element sealing of the present invention is intended to reduce the difference in thermal expansion strain between the high molecular weight body and the low molecular weight body by controlling the molecular weight distribution of the fluorenone, thereby eliminating the entire composition. Thermal expansion strain. As a result, sealing of an optical semiconductor element excellent in crack resistance and excellent in heat resistance and light resistance was achieved.

The above description is only an overview of the technical solutions of the present invention, and the technical means of the present invention can be more clearly understood and can be implemented in accordance with the contents of the specification. Hereinafter, the preferred embodiments of the present invention will be described in detail below.

I. (A) anthrone-modified epoxy compound and its production method

The anthrone-modified epoxy compound of the present invention is characterized in that it has two or more epoxy groups in one molecule, and is represented by the following formula (1), and has a degree of dispersion of 1.0 to 1.2, more preferably 1.0 to 1.1.

[Chemical 4]

R ² is represented by the following formula (2) or formula (3).

R ^{1 is} independent of each other and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a norbornyl group. An aryl group such as a cycloalkyl group or a phenyl group, or the like, and a 3,3,3-trifluoropropyl group, a 3-hydroxypropyl group, a 3-aminopropyl group or the like obtained by substituting these groups with a halogen group or an amino group. . Among these monovalent hydrocarbon groups, a methyl group, a phenyl group, and preferably 90 mol% or more of all R ¹ are a methyl group.

In the formula (1), a and b are one or more integers selected from the integers 0 to 20, and a and b are preferably integers of 0 to 10. If a and b exceed the above upper limit value, it is difficult to fractionate, which is not preferable.

Examples of the hydrocarbon group having 1 to 12 carbon atoms which may have an organocarbomethoxy group which may have a substituent include an organomethylalkoxy group which may have a substituent, a methylene group, an ethylene group, and a propylene group. A group formed by bonding such as propylene or butylene.

The (A) anthrone-modified epoxy compound is represented, for example, by the following formula.

The compound represented by the formula (1) can be easily produced by controlling the degree of dispersion to 1 to 1.2, preferably 1 to 1.1, by the following formula (4) with respect to separation distillation or fractional distillation. a nonoxyl 1 mol, 1-allyl-3,5-diglycidyl isocyanurate or a vinylcyclohexene monoxide having hydrosilyl groups at both ends (ie 1,2-epoxy-4-vinylcyclohexane) is 1.5 to 2.5 moles, preferably 2.0 to 2.1 moles, and is heated to 80 ° C to 150 ° C using a hydrogenation sulfonation catalyst such as a platinum catalyst. The compound is allowed to react.

Wherein R ¹ , R ² , a, and b are as described above.

If the amount of 1-allyl-3,5-diglycidyl isocyanurate or ethylene oxide cyclohexene is less than the lower limit, a large amount of unreacted hydrofluorenyl group remains. It becomes a cause of foaming when the composition of the siloxane is hardened. In addition, if the upper limit is exceeded, unreacted 1-allyl-3,5-diglycidyl isocyanurate or ethylene oxide cyclohexene remains in the system, thus in terms of cost. In terms of features, it is a problem.

The platinum catalyst is typically a 2% octanol solution of chloroplatinic acid, and this solution is used in an amount of 5 ppm to 50 ppm of platinum. The desired compound can be synthesized in a high yield by reacting at 80 ° C to 100 ° C for 1 hour to 8 hours. Further, as the solvent of the reaction, a solvent such as an aromatic or ketone system can be used.

As the fluorenone containing a hydrofluorenyl group at both terminals whose degree of dispersion is controlled in the present invention, the following fluorenone can be represented as a representative.

[Chemistry 9]

N≒3, the dispersion is 1.02

n≒4, the dispersion is 1.08

n≒8, the dispersion is 1.06

The two-terminal hydroquinone-containing fluorenone used in the present invention may be used singly or in combination.

In particular, in order to obtain a hard and rigid cured product, the two-terminal hydroquinone-containing anthrone having a controlled degree of dispersion used in the present invention is preferably a compound represented by the above formula (5) or (6). In order to be strong and soft The soft cured product is preferably a compound represented by the above formula (7). Further, it is preferred to use a mixture of an anthrone containing a hydrofluorenyl group having a degree of dispersion of 1.0 to 1.2. The fluorenone modified epoxy compound of the present invention can be effectively used as various additives, coupling agents, and tackifiers in addition to being used as a main component of an epoxy resin composition.

II. Resin composition for optical semiconductor sealing

Hereinafter, the resin composition for optical semiconductor sealing of the present invention will be described.

The resin composition for optical semiconductor sealing of the present invention contains the above-mentioned (A) anthrone-modified epoxy compound, a curing agent, and a curing accelerator as essential components.

(B) hardener

A hardener is used in order to form a crosslink by reacting with an epoxy group. The curing agent may be any of an amine-based curing agent, a phenol-based curing agent, and an acid-based curing agent which are generally used, and is preferably an acid anhydride-based curing agent from the viewpoints of light transmittance and heat resistance.

Examples of the acid anhydride-based hardener include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic dianhydride. , hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or 4-methyl-hexahydrophthalic anhydride and six a mixture of hydrogen phthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, Norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, and the like. The amount of the curing agent (B) is from 0.5 equivalents to 1.5 equivalents, preferably from 0.8 equivalents to 1.2 equivalents, per equivalent of the epoxy group. This corresponds to 0.1 part by mass to 100 parts by mass, preferably 20 parts by mass to 80 parts by mass, per 100 parts by mass of the component (A).

(C) hardening catalyst

In order to allow the hardening reaction to be completed smoothly and in a short time, a hardening catalyst is used. The hardening catalyst is preferably one or two or more kinds of quaternary phosphonium salts, and it is particularly preferable to use a quaternary phosphonium salt containing a compound represented by the following formula (8) and/or a compound represented by the following formula (9). One or two or more. Thereby, it is possible to produce a cured product which is transparent, has no surface adhesion, and does not change color due to reflow. Specific examples of the quaternary phosphonium salt other than the compound represented by the following formula (8) and formula (9) include "U" manufactured by San-Apro Co., Ltd., which is a quaternary phosphonium bromide salt. -CAT 5003”.

It is also possible to use the catalyst together with other hardening catalysts. This Examples of the hardening catalyst include an organophosphine-based hardening catalyst such as triphenylphosphine or diphenylphosphine, and 1,8-diazabicyclo(5,4,0)undecene-7 (1,8-). Third amine hardening catalyst such as diazabicyclo(5,4,0)undecen-7), triethanolamine, benzyldimethylamine, 2-methylimidazole, 2-phenyl Imidazoles such as 4-methylimidazole.

The amount of the curing catalyst (C) is preferably 0.05 parts by mass to 3 parts by mass based on 100 parts by mass of the total of the components (A) and (B). If the compounding amount of the hardening catalyst is less than the lower limit value, there is a possibility that a sufficient effect of promoting the reaction between the epoxy resin and the hardener may not be obtained. Further, when the amount of the curing catalyst is more than the above upper limit, there is a possibility that discoloration occurs during hardening or during the reflow test.

(D) Epoxy resin

A conventional epoxy resin having two or more epoxy groups in one molecule can be added in a range in which the properties of the epoxy resin are not deteriorated. In the epoxy resin, an epoxy resin having two epoxy groups in one molecule may be exemplified by a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, Cresol novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin An aromatic epoxy resin; a hydrogenated epoxy resin obtained by hydrogenating an aromatic ring of the various epoxy resins; a dicyclopentadiene type epoxy resin, an alicyclic epoxy resin, and isocyanuric acid Non-aromatic epoxy resin such as triglycidyl ester; It is not limited to the resin to have at least two epoxy groups in the molecule. These epoxy resins may be used singly or in combination of two or more. In order to prevent deterioration due to light when sealing a light-emitting semiconductor device such as an LED, it is preferable to use a non-aromatic epoxy such as a hydrogenated epoxy resin, an alicyclic epoxy resin or a triglycidyl isocyanurate. Resin.

The amount of the epoxy resin is 0.1 parts by mass to 90 parts by mass, preferably 0.1 parts by mass to 30 parts by mass, per 100 parts by mass of the total of the components (A) and (B). If the compounding amount of the hardening catalyst is less than the lower limit value, the hardening becomes slow. Further, if the compounding amount of the hardening catalyst exceeds the above upper limit value, discoloration is caused.

(E) Antioxidants

In the present invention, in order to increase the heat resistance of the resin, 0.01 parts by mass to 1.0 part by mass of the antioxidant may be blended with 100 parts by mass of the total of the components (A) and (B). The antioxidant is preferably a hindered phenol-based antioxidant, and for example, tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid]pentaerythritol ester, N, N can be exemplified. '-Bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl)propanediamine (N,N'-propane-1,3-diylbis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionamide]), thiobisethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate](thiodiethylene bis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, 6, 6'-di-t-butyl-2,2'-thiobis-p-cresol, N,N'-bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoid Hexamethylenediamine, 3,5-di-t-butyl-4-hydroxyphenylpropionic acid Benzenepropanoic acid (3,5-bis(1,1-dimethylethyl)-4-hydroxy-, C7-9-branched alkyl ester), [[3,5-bis(1,1-dimethylethyl) Diethyl 4-hydroxyphenyl]methyl]phosphonate, 2,2'-ethylenebis[4,6-di-t-butylphenol], 3,3',3",5,5 ',5"-hexa-t-butyl-a, a', a"-(meslic trimethylbenzene-2,4,6-triyl)tri-p-cresol, bis[[[3,5-di Calcium (1,1-dimethylethyl)-4-hydroxyphenyl]methyl]diethyl]phosphonate, 4,6-bis(octylthiomethyl)o-cresol, 4,6-double (dodecylthiomethyl) o-cresol, ethylene bis(oxyethylene) bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], six Methylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6-trione, 1,3,5-tris[(4-t-butyl-3-hydroxy-2,6-dimethylphenyl) 1,1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 6,6'-di-t-butyl-4,4'-thio-bis (intermediate Reaction product of phenol), diphenylamine, N-phenylaniline and 2,4,4-trimethylpentene, 2,6-di-t-butyl-4-(4,6-bis(octyl sulphur) 1,3,5-triazin-2-ylamino)phenol, 3,4-dihydro-2,5,7,8-tetra 2-(4,8,12-trimethyltridecyl)-2H-1-benzopyran-6-ol, 2',3-bis[[3-[3,5-di Tributyl-4-hydroxyphenyl]propanyl]]propane, 3,3'-thiodipropionic acid dodecyl ester, 3,3'-thiodipropionic acid dioctadecane Base ester and the like.

As the antioxidant, a phosphorus-based antioxidant can also be used, and, for example, triphenyl phosphite or bis[2,4-di(1,1-dimethylethyl)-6-methylphenyl]phosphite ethyl ester can be exemplified. , tris(2,4-di-t-butylphenyl)phosphite, 4,4'-[1,1'-biphenyl]ylidene diphosphonic acid-tetra[2,4-di-third Phenyl] ester (tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4'-diylbisphosphonite), 2,2',2"-nitrogen [triethyl-tris[ 3,3',5,5'-tetrabutyl butyl -1,1,-biphenyl-2,2'-diyl]phosphite, [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphoric acid Diethyl ester and the like.

(F) UV absorber

In order to improve the light resistance of the resin, 0.01 parts by mass to 1.0 part by mass of a hindered amine-based ultraviolet absorber may be blended with 100 parts by mass of the total of the components (A) and (B). The heat-resistant deterioration agent can be exemplified by 2,2,4,4-tetramethyl-7-oxa-3,20-diazaspiro[5.1.11.2]-docosane-21-one, 2 ,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazabispiro[5.1.11.2]-docosane-20-propionic acid lauryl ester 2,2,4,4-Tetramethyl-21-oxo-7-oxa-3,20-diazabispiro[5.1.11.2]-docosane-20-propionic acid tetradecane Base, [{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butylmalonic acid di(1,2,2,6,6-penta 4--4-acridinyl) ester, bis(2,2,6,6-tetramethyl-4-acridinyl) sebacate, poly[{6-(1,1,3,3-tetra Methyl butyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-acridinyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-acridinyl)imin}], 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl -1-phenylethyl)phenol, 2,2',2"-nitro-[triethyl-tris[3,3',5,5'-tetra-tert-butyl-1,1'-linked Benzene-2,2'-diyl]]phosphite, 2-(2H-benzotriazol-2-yl)-4,6-di-p-pentylphenol, and the like.

(G) phosphor

In order to convert the resin to an emission wavelength such as a blue LED or an ultraviolet LED (UVLED), various well-known phosphor powders may be added. As a representative yellow phosphor, it is particularly advantageous to contain a formula A ₃ B ₅₀ O ₁₂ :M (wherein component A has a selected from the group consisting of yttrium (Y), yttrium (Gd), yttrium (Tb), At least one element selected from the group consisting of lanthanum (La), lanthanum (Lu), selenium (Se), and lanthanum (Sm), the component B having a composition selected from the group consisting of aluminum (Al), gallium (Ga), and indium (In) At least one element in the group, the component M having at least one selected from the group consisting of cerium (Ce), praseodymium (Er), chromium (cr), cerium (Nd), and cerium (Er) A phosphor particle composed of a group of garnets of the element). A phosphor for use in a light-emitting diode element containing a white-emitting diode that emits blue light is suitable for a Y ₃ Al ₅ O ₁₂ :Ce phosphor and/or (Y, Gd, Tb) ₃ (Al, Ga) ₅ O ₁₂ : Ce phosphor. Examples of other phosphors include CaGa ₂ S ₄ :Ce ³⁺ and SrGa ₂ S ₄ :Ce ³⁺ , YAlO ₃ :Ce ³⁺ , YGaO ₃ :Ce ³⁺ , Y(Al,Ga)O ₃ :Ce ³⁺ , Y ₂ SiO ₅ : Ce ^3+, and the like. Further, in order to form a mixed color of light, an aluminate doped with a rare earth group or an orthosilicate doped with a rare earth group may be suitably used in addition to these phosphors. The phosphor may be blended in an amount of 0.1 part by mass to 100 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

(H) tackifier

In order to increase the adhesiveness of the resin, 0.01 parts by mass to 1.0 part by mass of the fluorenyl decane-based coupling agent may be blended with 100 parts by mass of the total of the components (A) and (B).

(I) inorganic filler

In order to obtain the effect of the LED light-diffusing effect and the precipitation of the phosphor, the resin may be adjusted to have a coefficient of expansion of 0.01 to 100 parts by mass based on 100 parts by mass of the total of the components (A) and (B). Inorganic filler. As the inorganic filler, silica, titanium oxide, zinc oxide, aluminum oxide, calcium carbonate or the like can be added as appropriate.

The resin composition of the present invention can be suitably used as a coating protective material for coating a protective optical semiconductor element. In this case, examples of the device include a light-emitting diode (LED), an organic electroluminescence device (organic EL), a laser diode, an LED array, and the like.

The composition of the present invention is suitable for use in a box-type light-emitting semiconductor device, that is, it is suitable for disposing a light-emitting element in a ceramic and/or plastic housing, covering the element disposed in the housing to fill the composition of the present invention. After being placed in the casing, it is hardened and used. Further, the LED of the present invention may be protected by applying the composition of the present invention to an LED mounted on a matrix substrate by a printing method, transfer molding, injection molding, compression molding or the like. When the light-emitting semiconductor device such as an LED is coated by potting, injection, or the like, the resin composition of the present invention is preferably liquid. The viscosity of the resin composition is preferably from 10 mPa ‧ to 1,000,000 mPa ‧ at a measurement value of a rotational viscometer at 25 ° C, particularly preferably from about 100 mPa ‧ to 1,000,000 mPa ‧ s. On the other hand, when a light-emitting semiconductor device is manufactured by transfer molding or the like, it can be formed not only by using the liquid resin but also by solidifying (liquidifying) the liquid resin. The particles are shaped.

In the present invention, the curing conditions of the coating protective material can be appropriately selected in the range of 72 minutes at 200 ° C to 200 ° C for 3 minutes in consideration of the balance between the productivity and the heat resistance of the light-emitting element or the casing in accordance with the working conditions. When transfer molding or injection molding is employed, the light-emitting semiconductor device can be easily fabricated by molding at a temperature of 150 ° C to 180 ° C and a pressure of 20 kgf / cm ² to 50 kgf / cm ² for 1 minute to 5 minutes. Further, post-hardening (secondary hardening or post-curing) may be carried out at 150 ° C to 200 ° C for 1 hour to 4 hours.

[Example]

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

[Example 1]

1-0.0-allyl-3,5-diglycidyl isocyanurate 200.0 g (0.71 mol), and the following formula

N≒3, dispersion is 1.02

131.7 g (0.37 mol) of hydroquinone (hydrogen oxane A) was placed in a 0.5 liter separable flask, and a 2% octanol solution of chloroplatinic acid (platinum (Pt) amount of 20 ppm) was added. After reacting at 80 ° C to 100 ° C for 6 hours, the unreacted product was distilled off under reduced pressure to obtain 312 g of a colorless transparent liquid (referred to as "Compound I"). The yield was 94%.

The physical properties of Compound 1 are as follows.

Epoxy equivalent (using automatic titrator GT-100 manufactured by Mitsubishi Chemical Corporation): 245 g/mol

Refractive index (25 ° C, using digital refractometer RX5000 manufactured by ATAGO): 1.47577

Elemental analysis values C: 0.432 (0.442), Si: 0.1517 (0.1528), O: 0.2555 (0.2437), N: 0.0888 (0.0914), H: 0.0720 (0.0680), where ( ) is the theoretical value.

Specific gravity (23 ° C): 1.11

Viscosity (60 ° C): 5.02 Pa‧ s

Dispersion: 1.02 (using HLC-8220GPC manufactured by Tosoh Corporation, tetrahydrofuran (THF) solvent)

[Example 2]

200.0 g (1.61 mol) of ethylene oxide cyclohexene (ie 1,2-epoxy-4-vinylcyclohexane) and 259.8 g of hydroquinone (hydrogen oxane A) of the formula (0.73 mol) was placed in a 0.5 liter separable flask, and a 2% octanol solution of chloroplatinic acid (20 ppm of Pt) was added, and the mixture was reacted at 80 ° C to 100 ° C for 7 hours, and then distilled under reduced pressure. Unreacted material, 423 g of a colorless transparent liquid (referred to as "Compound II") was obtained. The yield was 92%.

The physical properties of Compound II are as follows.

Epoxy equivalent (using automatic titrator GT-100 manufactured by Mitsubishi Chemical Corporation): 245 g/mol

Refractive index (25 ° C, using digital refractometer RX5000 manufactured by ATAGO): 1.47577

Elemental analysis values C: 0.4965 (0.5070), Si: 0.2490 (0.2541), O: 0.1550 (0.1447), H: 0.0995 (0.0942), wherein ( ) is a theoretical value.

Specific gravity (23 ° C): 1.10

Viscosity (60 ° C): 2.03Pa‧s

Dispersion: 1.02 (using HLC-8220GPC manufactured by Tosoh Corporation, THF solvent)

[Example 3 and Example 4]

The compound III and the compound IV were respectively obtained in the same manner as in Example 1 except that the hydroquinone A was used instead of the hydroquinone A in the amounts shown in the following Table 1.

Hydroquinone B

n≒4, the dispersion is 1.08

Hydroquinone C

n≒8, the dispersion is 1.06

[Example 5 to Example 15, Comparative Example 1 to Comparative Example 7]

Preparation of the composition

The compound I to the compound IV, the curing agent, and the like were sufficiently mixed with a composition (parts by mass) shown in the following Table 2, Table 3, and Table 4 using a planetary mixer to prepare a cured resin composition. The components in these tables are as follows.

Epoxy I: In the same manner as in Example 1, 1-allyl-3,5-diglycidyl isocyanurate and dimethylfluorenone having a hydroquinone at both ends (160HDM; average molecular weight) An anthrone-modified epoxy compound obtained by an addition reaction of 160, a dispersion of 1.35 (manufactured by Shin-Etsu Chemical Co., Ltd.) (dispersion degree: 1.35)

Epoxy II: Triglycidyl isocyanurate (TEPIC-S: manufactured by Nissan Chemical Industry Co., Ltd.)

Hardener: 4-methylhexahydrophthalic anhydride (Rikacid MH: manufactured by New Japan Physical and Chemical Co., Ltd.)

Hardening catalyst: quaternary phosphonium salt (U-CAT 5003: manufactured by San-Apro Co., Ltd.)

Antioxidant I: Tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate]pentaerythritol ester

Antioxidant II: Triphenyl phosphite

UV absorber: 2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazabispiro[5.1.11.2]-docosane-20-propionic acid Tetradecyl ester

Phosphor: 钇 ‧ aluminum ‧ garnet (YAG)

Tackifier: γ-mercaptopropyltrimethoxydecane (KBM803) (manufactured by Shin-Etsu Chemical Co., Ltd.)

Inorganic filler: cerium oxide

Characterization of hardened materials of examples and comparative examples

The viscosity of the composition and the properties of the cured product were evaluated by the following methods. The resin composition was heated at 100 ° C for 1 hour and then heated at 150 ° C for 4 hours to be hardened. The results are shown in Tables 2 to 4.

(1) Appearance of hardened material

The appearance of the cured product was visually observed, and the presence or absence of discoloration and transparency was visually evaluated.

(2) hardness

The rod-shaped cured product was measured (D hardness) in accordance with JIS K6301.

(3) Viscosity

The measurement was carried out using a BM type rotational viscometer manufactured by Toki Sangyo Co., Ltd.

(4) Glass transition point and expansion coefficient

A test piece having a width of 5 mm, a thickness of 4 mm, and a length of 15 mm was cut out from the cured product, and a thermal analysis device EXSTAR6000TMA (manufactured by SII NanoTechnology Co., Ltd.) was used to heat the temperature from -100 ° C to 300 ° C at a heating rate of 5 ° C / min. The inflection point acts as a glass transition point (Tg). Further, the average expansion coefficient was determined from the elongation of the sample before and after the glass transition point.

(5) Bending strength, flexural modulus

A test piece having a width of 5 mm, a thickness of 4 mm, and a length of 100 mm was cut out from the cured product, and measured by an automatic drawing measurement apparatus AGS-50 (manufactured by Shimadzu Corporation) in accordance with JIS K6911.

(6) Light penetration

The light transmittance (T ₀ ) of a cured product having a thickness of 1 mm at a wavelength of 800 nm to 300 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Further, the light transmittance (T ₁ ) of the cured product after heating at 150 ° C for 400 hours was measured in the same manner to obtain T ₁ /T ₀ (%).

LED device production and evaluation

The bottom side of the silver-plated LED preform (3 mm × 3 mm × 1 mm, the diameter of the opening was 2.6 mm) was fixed to the InGaN-based blue light-emitting device using a silver paste. Then, the light-emitting element is connected to the external electrode with a metal wire. Thereafter, each composition was filled in the opening of the package, cured at 100 ° C for 1 hour, and then cured at 150 ° C for 2 hours to seal the opening. Twenty packages were produced using each composition.

(8) Temperature cycle test, high temperature and high humidity lighting test

Ten of the LEDs obtained by the above method were used for the temperature cycle test (-40 ° C to 125 ° C, 2000 cycles and 3000 cycles), and the appearance was observed. In addition, another 10 LEDs were used to illuminate the LEDs at 50 mA under high temperature and high humidity (65 ° C, 950% RH) for 500 hours, and then the package interface was observed for adhesion, cracking, and discoloration. The results are shown in Tables 5 and 6.

As shown in the respective tables, the epoxy resin composition of the present invention containing an anthrone-modified epoxy compound having a controlled molecular weight distribution was superior in crack resistance in a temperature cycle test as compared with the resin composition of the comparative example. Moreover, it is also excellent in the lighting test under high temperature and high humidity, and is excellent in heat resistance.

[Industrial availability]

The resin composition for optical semiconductor sealing of the present invention is excellent in heat resistance and crack resistance, and is suitable for sealing an optical semiconductor element.

The above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Although the present invention has been described above by way of a preferred example, it is not intended to limit the invention, and any one skilled in the art. In the scope of the technical solutions of the present invention, some modifications or modifications may be made to the equivalents of equivalent changes, but the contents of the technical solutions of the present invention are not deviated from the present invention. It is still within the scope of the technical solution of the present invention to make any simple modifications, equivalent changes and modifications to the above examples.

Claims (12)

A resin composition for sealing a photo-semiconductor comprising the following components (A), (B), and (C): (A) having two or more epoxy groups in one molecule, and having the following formula (1) And 100 parts by weight of an anthrone-modified epoxy compound having a degree of dispersion of 1.0 to 1.2 R ^{1 is} independent of each other and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² is a group represented by the following formula (2) or (3), and a is an integer of 0 to 10, b is an integer from 0 to 10. (B) The amount of the curing agent is from 0.05 parts by mass to 3 parts by mass per 100 parts by mass of the total amount of the component (A) and the component (B). The resin composition for optical-semiconductor sealing according to the above-mentioned item (1), which contains the following (D) in terms of 100 parts by mass of the total amount of the component (A) and the component (B); Component to component (I): (D) Epoxy resin having two or more epoxy groups in one molecule 0.1 parts by mass to 90 parts by mass (E) Antioxidant 0.01 parts by mass to 1.0 part by mass (F) Ultraviolet absorber 0.01 Parts by mass to 1.0 parts by mass (G) 0.1 parts by mass to 100 parts by mass of the phosphor (H) 0.01 parts by mass to 1.0 part by mass of the tackifier (I) 0.01 parts by mass to 100 parts by mass of the inorganic filler. The resin composition for optical semiconductor sealing according to claim 1, wherein the (B) curing agent is an acid anhydride. The resin composition for optical semiconductor sealing according to the first aspect of the invention, wherein the (C) hardening catalyst is a phosphonium salt. The resin composition for optical semiconductor sealing according to claim 2, wherein the epoxy resin having two or more epoxy groups in the molecule (D) is an alicyclic epoxy resin or contains isocyanuric acid. Epoxy resin of the acid ester ring. The resin composition for optical semiconductor sealing according to the second aspect of the invention, wherein the (E) antioxidant is a hindered phenol-based antioxidant. The resin composition for optical semiconductor sealing according to the second aspect of the invention, wherein the (E) antioxidant is a phosphorus-based antioxidant. The optical semiconductor sealing resin as described in claim 2 A composition wherein the (F) ultraviolet absorber is a hindered amine-based ultraviolet absorber. The resin composition for optical semiconductor sealing according to the second aspect of the invention, wherein the (H) tackifier is a mercapto-based decane coupling agent. The resin composition for optical semiconductor sealing according to any one of the above-mentioned items, wherein a is an integer of 0 to 10, and b is an integer of 0 to 10. The resin composition for optical semiconductor sealing according to any one of the above-mentioned items, wherein b is 0. The resin composition for optical-semiconductor sealing according to any one of the preceding claims, wherein: R ^{1 is} selected from an alkyl group, a cycloalkyl group, an aryl group or a partial hydrogen atom of such a group. At least one of groups substituted by a halogen atom, an amine group or a hydroxyl group.