KR20160100943A - Thermosetting resin composition, method for manufacturing reflective member for optical semiconductor device using same, and optical semiconductor device - Google Patents

Abstract

A thermosetting resin composition which suppresses the volatilization of the curing agent component during production and processing and suppresses discoloration due to heat and gives a cured product excellent in light reflectivity and reliability in a high temperature environment; And an optical semiconductor device having the reflective member. The thermosetting resin composition is a thermosetting resin composition comprising an epoxy resin, a curing agent, and a white pigment. The curing agent is an oligomer of a terminal carboxylic acid having a softening point of 50 ° C or higher.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting resin composition, a method of manufacturing a reflective member for an optical semiconductor device using the same,

The present invention relates to a thermosetting resin composition which suppresses volatilization of a curing agent during production and processing, suppresses discoloration due to heat, gives a cured product excellent in light reflectivity and reliability under a high temperature environment, and a reflective member A manufacturing method thereof, and a photosemiconductor device having the reflection member.

BACKGROUND ART Optical semiconductor devices such as LEDs (Light Emitting Didodes, light emitting diodes) are used in many electronic devices because of their low power consumption, long life, and small size. In recent years, according to the improvement of technology, it has been used in fields requiring high brightness such as head lamps for automobiles and lighting applications, and accordingly, a reflective member constituting the optical semiconductor is also provided with a UV Resistance and heat resistance.

BACKGROUND ART Polyphthalamide (PPA) resin is widely used as a material of a reflective member constituting an optical semiconductor.

In recent years, however, with the increase in the output of optical semiconductor devices, the junction temperature has increased, the light intensity has increased, or the light has been shortened in wavelength, and the reflection member using PPA resin has been severely deteriorated, There is a problem that a decrease or the like occurs. In addition, when the solder is bonded, it is discolored at a high temperature, and a high reflectance can not be maintained as a reflective member. In order to solve these problems, development of a thermosetting light-emitting resin composition excellent in light resistance and heat resistance has been demanded.

Patent Document 1 discloses a B-stage thermosetting light-sensitive resin composition containing an epoxy resin, a curing agent and a curing accelerator as thermosetting light-curing resin compositions having good light resistance and heat resistance. As the molding method of the thermosetting light-sensitive resin composition, after kneading sufficiently by a mixer, the mixture is melt-kneaded under a predetermined condition by a mixing roll, an extruder, a kneader, a roll, an extruder, And this composition is molded by transfer molding under the conditions of a mold temperature of 170 to 190 DEG C, a molding pressure of 2 to 8 MPa, and a molding time of 60 to 120 seconds. Thereafter, the mold is removed, It is described that the after-cure of the time is performed.

In this case, as the hardening agent, hexahydrophthalic anhydride is used, and in addition, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, It is described that acid anhydrides such as acid, anhydrous dimethylglutaric acid, anhydrous diethylglutaric acid, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride can be used. The epoxy resin composition for stage-shaped semiconductor encapsulation has a problem that the acid anhydride-based curing agent is volatilized when the temperature is applied during production by melt-kneading or during processing by transfer molding.

As well-known documents related to the present invention, there are the following Patent Documents 1 to 7.

Japanese Patent No. 5239688 Japanese Patent Application Laid-Open No. 2013-62519 Japanese Patent Application Laid-Open No. 2013-65899 Japanese Patent Application Laid-Open No. 2013-127068 Japanese Patent Application Laid-Open No. 2013-91809 Japanese Patent Application Laid-Open No. 2013-138221 Japanese Patent Application Laid-Open No. 2013-168684

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a thermosetting resin composition which suppresses the volatilization of the curing agent during production and processing, suppresses discoloration due to heat and is excellent in light reflectivity and reliability under a high temperature environment, A method of manufacturing a reflective member, and an optical semiconductor device having the reflective member.

That is, the present invention relates to the following (1) to (10).

(1) A thermosetting resin composition comprising an epoxy resin (A), a curing agent (B) and a white pigment (C), wherein the curing agent is an oligosester of a terminal carboxylic acid having a softening point of 50 ° C or higher,

(2) a thermosetting resin composition in which the oligomer of the terminal carboxylic acid has at least two or more carboxyl groups and has an aliphatic hydrocarbon group as a main skeleton,

(3) The thermosetting resin composition according to (1) or (2), wherein the white pigment (C) is a titanium dioxide powder,

(4) The thermosetting resin composition according to any one of (1) to (3), wherein the thermosetting resin composition has a light reflectance of 80% or more at a wavelength of 460 to 800 nm after thermosetting,

(5) The thermosetting resin composition according to any one of (1) to (4), wherein the content of the white pigment is 5 to 95% by weight based on the total amount of the thermosetting resin composition,

(6) The oligoester of the terminal carboxylic acid as set forth in (1) above, wherein the oligoester of the terminal carboxylic acid is a compound obtained by the reaction of a polyhydric alcohol having 2 to 6 carbon atoms with a carbon number of 6 or more and a saturated aliphatic cyclic acid anhydride, To (5), a thermosetting resin composition according to any one of

(7) The saturated aliphatic cyclic acid anhydride is at least one selected from the group consisting of hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2- A thermosetting resin composition according to any one of (1) to (6) above, which is a compound obtained by the reaction of an acid anhydride of

(8) The thermosetting resin composition according to any one of (1) to (7), which is used for forming the light reflection member constituting the optical semiconductor device,

(9) A reflective member for an optical semiconductor device obtained by curing the thermosetting resin composition according to any one of (1) to (8), wherein at least a part of the reflective member for the optical semiconductor device is any one of (1) A method for manufacturing a reflective member for an optical semiconductor device, comprising: forming a light-reflecting resin composition according to claim 1 by transfer molding;

(10) A light reflection member obtained by curing the thermosetting resin composition according to any one of (1) to (8), an optical semiconductor device having an optical semiconductor element,

.

(Effects of the Invention)

The thermosetting resin composition of the present invention containing the epoxy resin (A), the specific curing agent (B) and the white pigment (C) suppresses the volatilization of the curing agent during production and processing, suppresses discoloration due to heat, And is highly useful as a thermosetting resin composition excellent in reliability under a high temperature environment.

The present invention is characterized by containing an epoxy resin (A), a curing agent (B), and a white pigment (C).

The epoxy resin (A) in the present invention is not particularly limited and can be used as long as it is usually blended as a conventional thermosetting light-sensitive resin composition or an epoxy resin molding material. For example, phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, epoxidized novolak resins of aldehydes, and diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, and alkyl-substituted bisphenols Glycidylamine type epoxy resins obtained by the reaction of epichlorohydrin with polyamines such as cidyl ether, diaminodiphenylmethane and isocyanuric acid, alicyclic epoxy resins obtained by oxidizing olefinic bonds with peracid such as peracetic acid, Resins, silsesquioxane compounds and the like, and these may be used alone or in combination of two or more. Specific examples of these epoxy resins include epoxy resins, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate, triglycidyl isocyanurate, Silsesquioxane compounds.

Here, as the epoxy resin in the present invention, an epoxy resin having an alicyclic epoxy resin and triglycidylisocyanurate skeleton is preferably used alone or in combination, from the standpoint of excellent transparency and discoloration resistance.

Examples of the epoxy resin having a triglycidylisocyanurate skeleton include the following formula (A)

(Wherein the plurality of R _{4 s} present each independently represent an alkyl group having 1 to 6 carbon atoms which may have a direct bond, an oxygen atom or an ester bond,

(R ₅ represents an alkylene group having 1 to 6 carbon atoms which may have a direct bond, an oxygen atom or an ester bond). And at least one of R < ₄ > represents the formula (B)). Specific examples thereof include TEPIC-S (manufactured by Nissan Kagaku Kogyo Co., Ltd.) and the like.

Examples of preferred alicyclic epoxy resins include SEJ-01R (manufactured by Nippon Kayaku), Celloxide 2021 (manufactured by Daicel Chemical Industries Ltd.) and EHPE 3150 (manufactured by Daicel Chemical Industries, Ltd.). The compound is not particularly limited as long as it has an epoxycyclohexyl skeleton. Examples of the bifunctional functional group include an epoxy resin having two epoxycyclohexyl skeletons bonded with an oxygen atom or an alkylene group having 1 to 10 carbon atoms, which may have an ester bond. Examples of the monofunctional epoxy resin include an epoxy resin having an alkyl group having 1 to 10 carbon atoms or a hydroxyl group, which may have an oxygen atom as a substituent on the epoxycyclohexyl skeleton. Specific examples of preferable examples include 1,2-epoxy-4- ((2-hydroxypropyl) -1-butenyl) -1,3-cyclohexanecarboxylate of 3 ', 4'-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate and 2,2- 2-oxiranyl) cyclohexane adduct and the like.

The curing agent in the present invention is an oligomer of a terminal carboxylic acid having a softening point of 50 DEG C or higher.

Specific structural formulas include the following formula (1)

(Wherein the plurality of P's may contain an oxygen atom, a nitrogen atom, a hetero atom of a phosphorus atom having a content of 0 to 6, a residue of a polyhydric alcohol having 2 to 20 carbon atoms, and R denotes an aliphatic hydrocarbon having 2 to 20 carbon atoms N and k are independently present and represent an average of 1 to 6, and the total number of n is 2 or more and less than 12), and has an ester structure (preferably two esters Structure). And a plurality of carboxyl groups at the terminals.

Among them, it is preferable that the oligoester of the terminal carboxylic acid of the above formula (1) is a compound obtained by the esterification reaction of a polyhydric alcohol having 2 to 6 carbon atoms with a carbon number of 6 or more and a saturated aliphatic cyclic acid anhydride.

More specifically, in the oligosaccharide of the terminal carboxylic acid described in the above formula (1), the linking group R is preferably a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, and in the cycloalkane skeleton, An unsubstituted cyclohexane structure, particularly a methylcyclohexane structure having a methyl group is preferable from the optical properties of the cured product. The norbornane skeleton is preferably a norbornane or methylnorbornane structure.

The linking group P is preferably a residue of a polyhydric alcohol having 2 to 10 carbon atoms (a residue excluding a hydroxyl group from a polyhydric alcohol used in the reaction), but a branched chain crosslinking group or a cycloalkyl group is preferable, Is preferably a divalent crosslinking group defined by the following formula

(a) a straight chain alkyl chain having 6 to 20 carbon atoms, said straight chain alkyl chain having 3 to 12 carbon atoms and a straight chain main chain having 2 to 4 side chains, 10 bridges,

or,

(b) a divalent crosslinking group obtained by removing two hydroxyl groups from at least one crosslinked polycyclic diol selected from tricyclodecane dimethanol or pentacyclopentadecane dimethanol, which may have a methyl group on the cyclo ring, provided that P is (b), it is preferable that the substituent R ³ in the formula (2) to be described later represents a group other than a hydrogen atom when the linking group R is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton.

The softening point of the oligoester is usually 50 DEG C or higher, but is preferably 60 DEG C or higher, more preferably 80 DEG C or higher. The upper limit is not particularly limited, but is usually 500 ° C or lower, preferably 300 ° C or lower, and more preferably 200 ° C or lower.

The above-mentioned particularly preferred oligoester of a terminal carboxylic acid in the present invention can be obtained by addition reaction between a polyhydric alcohol having 6 to 6 carbon atoms and a saturated aliphatic cyclic acid anhydride.

The oligoester of the terminal carboxylic acid in the present invention may be a composition comprising two polyvalent carboxylic acids. As a method for obtaining an oligoester composition of a terminal carboxylic acid containing at least two oligoester of a terminal carboxylic acid, a method of mixing at least two oligoesters of a single terminal carboxylic acid obtained by the above method, In synthesizing an oligoester of a carboxylic acid, there is a method of using at least two kinds of mixtures as the hexahydrophthalic anhydride, or carrying out an addition reaction using two kinds of the polyhydric alcohols.

As the saturated aliphatic cyclic acid anhydride used in the synthesis of the oligoester of the terminal carboxylic acid, there may be mentioned an acid having a cyclohexane structure and having a methyl group substitution or a carboxyl group substitution on the cyclohexane ring or an unsubstituted cyclohexane ring, And a compound having at least one (preferably one) anhydride group in the molecule.

Specifically, there can be mentioned at least one acid anhydride selected from the group consisting of hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride .

Specific examples of the polyhydric alcohols having 2 to 6 carbon atoms and having 6 or more carbon atoms used in the synthesis of the oligoester of the terminal carboxylic acid in the present invention include a terminal carboxylic acid having a hydroxyl group at the terminal of the crosslinking group P in the formula (1) ≪ / RTI >

In the above formula (1), the crosslinking group represented by P is preferably a divalent crosslinking group defined by the above (a) or (b), and these will be specifically described below.

The divalent crosslinking group defined by the above (a) is a bivalent alcohol (diol) having a branching structure of 6 to 20 carbon atoms and a bivalent straight chain alkyl chain excluding the hydroxyl group, and the alkyl chain sandwiched by two alcoholic hydroxyl groups of the diol is the main chain , And an alkyl chain branched from the alkyl chain (referred to as a side chain). The side chain may be branched from any carbon atom constituting the main chain, and includes, for example, a case where it is branched from a carbon atom (terminal carbon atom of the main chain) bonded with an alcoholic hydroxyl group. Any crosslinking group having the above structure may be used. Specific examples of such a crosslinking group are shown in the following formula (a1).

In the above formula, an oxygen atom on both sides of P in the formula (1) is bonded to the * symbol.

The alkylene bridging group defined by the above (a) is not particularly limited as long as it has an alkyl branched chain (side chain) with respect to the main chain alkylene group, but it is preferably a main chain having 3 or more carbon atoms in the main chain and at least one alkyl side chain , And it is particularly preferable to have two or more alkyl side chains. More preferred examples thereof include a straight chain main chain having 3 to 12 carbon atoms and a crosslinking group having 2 to 4 side chains and at least one of the side chains having 2 to 10 carbon atoms. In this case, a crosslinking group in which at least two of the side chains have 2 to 10 carbon atoms is more preferable. And two to four side chains are preferably branched from other carbon atoms in the main chain.

More specific examples of the compound include a compound having a hydroxyl group bonded at the position marked with * in the crosslinking group described in the formula (a1).

Of polyhydric alcohols used as raw materials, polyhydric alcohols having at least two side chains and at least two of the side chains having a side chain of 2 to 4 carbon atoms are preferable.

Particularly preferred polyhydric alcohols among these skeletons are 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2- And 2,4-diethyl-1,5-pentanediol is particularly preferred.

The crosslinking group defined by the above-mentioned (b) includes a bivalent group represented by the following formula (b1).

The crosslinked polycyclic diol residue in the case of the crosslinking group defined in the above (b) is a diol residue having a tricyclodecane structure and a pentacyclopentadecane structure as main skeletons and is represented by the following formula (b2).

In the formulas, plural R ^{2 s} present each independently represent a hydrogen atom or a methyl group. Among them, a crosslinking group in which all of R ² are hydrogen atoms is preferable.

Specific examples thereof include tricyclodecane dimethanol, methyltricyclodecane dimethanol and pentacyclopentadecane dimethanol.

The reaction between the acid anhydride and the polyhydric alcohol is generally an addition reaction using an acid or a base as a catalyst, but in the present invention, a reaction without catalyst is particularly preferred.

When the catalyst is used, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, para toluenesulfonic acid, nitric acid, trifluoroacetic acid and trichloroacetic acid, , Metal hydroxides such as calcium hydroxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undeca-7- , Heterocyclic compounds such as imidazole, triazole and tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, Trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide And quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate and trioctylmethylammonium acetate. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferable.

The amount of the catalyst to be used is not particularly limited, but it is preferable to use 0.001 to 5 parts by weight, if necessary, with respect to 100 parts by weight of the total weight of the raw materials.

In this reaction, a reaction with a solvent is preferred, but an organic solvent may be used. The amount of the organic solvent to be used is 0.005 to 1 part by weight, preferably 0.005 to 0.7 part by weight, more preferably 0.005 to 0.5 part (that is, 50% by weight) based on 1 part by weight of the total amount of the acid anhydride and the polyhydric alcohol, Or less). When the amount of the organic solvent used is more than 1 part by weight based on 1 part by weight of the reaction substrate, the progress of the reaction is extremely slow, which is not preferable. Specific examples of the organic solvent that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and ananone, Ethers such as tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate can be used.

The reaction proceeds sufficiently at a temperature of about 20 ° C. From the problem of the reaction time, the reaction temperature is preferably 30 to 200 占 폚, more preferably 40 to 200 占 폚, particularly preferably 40 to 150 占 폚. Particularly, when the present reaction is carried out in the absence of a solvent, the reaction at 100 ° C or lower is preferable, and the reaction at 30-100 ° C or 40-100 ° C is particularly preferable because of the volatilization of the acid anhydride.

The reaction ratio between the acid anhydride and the polyhydric alcohol is theoretically equivalent to the reaction, but it can be changed as needed.

Specific examples of the charge ratio in the reaction include 0.001 to 2 equivalents, more preferably 0.01 to 1.5 equivalents, and still more preferably 0.1 to 2 equivalents, based on the hydroxyl group equivalent, of the polyhydric alcohol relative to 1 equivalent of the acid anhydride group in the functional group equivalent. It is preferable to add at a rate of 1.2 equivalents.

In the present invention, the oligoester of the terminal carboxylic acid to be obtained is preferably a solid. In order to obtain an oligoester of a solid resin-like terminal carboxylic acid, it is preferable to use a polyhydric alcohol having an equimolar equivalent or more. However, The fluidity becomes important because it is added, and in order to secure the fluidity, it is possible to break some balance in a range where the solidity is maintained from the viscosity balance (softening point is 50 ° C or more).

Specifically, the equivalent ratio of the alcoholic hydroxyl group to the acid anhydride equivalent is preferably 0.85 to 1.20 molar equivalents, particularly 0.90 to 1.1.0 molar equivalents.

The reaction time depends on the reaction temperature, the catalyst amount, and the like, but a long reaction time from the viewpoint of industrial production consumes enormous energy, which is not preferable. An excessively short reaction time means that the reaction is abrupt, and is not preferable from the viewpoint of safety. The preferred range is 1 to 48 hours, preferably 1 to 36 hours, more preferably 1 to 24 hours, and further preferably 2 to 10 hours.

After the completion of the reaction, when the catalyst is used, the catalyst is removed by neutralization, washing with water, adsorption, etc., and the solvent is distilled off to obtain the objective oligoester of the terminal carboxylic acid. On the other hand, when the reaction is carried out in the absence of a catalyst, the desired oligoester of a terminal carboxylic acid is obtained by distilling off the solvent if necessary. When a solvent is used, the desired oligosaccharide of the terminal carboxylic acid is obtained by removing the solvent. In the case of solvent-free or non-catalyst, the product can be obtained by drawing it as it is.

As a most preferred production method, the acid anhydride and the polyhydric alcohol are reacted at 40 to 150 캜 under the condition of no catalyst, and the solvent is removed and then withdrawn.

The composition containing the oligoester of the terminal carboxylic acid or the oligosester of the terminal carboxylic acid obtained as described above usually exhibits a colorless to pale yellow solid resin shape (it is crystallized in some cases). The oleic ester of the terminal carboxylic acid preferably has a softening point of 50 to 190 캜, more preferably 55 to 150 캜, and particularly preferably 60 to 120 캜. It is possible to provide a reflecting member which has a very high reflectance retention rate and is hardly deteriorated in reflectance even when it is subjected to the heat resistance test by mixing the oligoester of the terminal carboxylic acid having such softening point directly into the thermosetting resin composition without making it into a liquid phase.

Usually, when the crosslinking group is an alkylene group having a side chain defined by (a), it exhibits a colorless to light yellow solid resin form.

In the present invention, the oligoester of the terminal carboxylic acid is in the form of a solid resin in that the optimal method of using the thermosetting resin composition containing the terminal carboxylic acid oligosters is molding by transfer.

In the case of the crosslinking group defined as the crosslinking group (b), when the aliphatic hydrocarbon group is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, the oligosters of the terminal carboxylic acid in which the alicyclic substituents as a whole are hydrogen atoms, The coloration of the film is visible and is not particularly suitable for strict optical applications. When the aliphatic hydrocarbon group is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, the compound having a substituent group of methyl group or carboxyl group is less colored and its optical characteristics are improved.

Also in the compound of the crosslinking group defined in the above (a), when the aliphatic hydrocarbon group is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent is a methyl group or a carboxyl group, Do.

That is, when the oligosaccharide composition of the terminal carboxylic acid of the present invention is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, the substituent is preferably a methyl group or a carboxyl group, or a terminal carboxy group of the formula (1) Compositions comprising oligoesters of a carboxylic acid are preferred. In the case of the oligoester composition of the terminal carboxylic acid containing at least two oligoester of the terminal carboxylic acid, the oligosester of the terminal carboxylic acid of the formula (1) in which at least the substituent is not a hydrogen atom , Preferably a methyl group, or an oligoester of a terminal carboxylic acid of a carboxyl group) relative to the total amount of the oligoesters of the terminal carboxylic acid is preferably 50 mol% or more. More preferably an oligoester composition of a terminal carboxylic acid containing at least 70 mol%, and most preferably at least 90 mol%, of an oligoester of a terminal carboxylic acid of the formula (1) in which the substituent is not a hydrogen atom. And the remainder is an oligosaccharide of the terminal carboxylic acid of formula (1) wherein R is a hydrogen atom.

As the oligoester of the terminal carboxylic acid preferred in the present invention, an oligoester of a terminal carboxylic acid represented by the following formula (2) is used.

(Wherein P has the same meaning as defined above, and R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group.)

In the formula (2), an alkyl group or a carboxyl group having 1 to ³ carbon atoms can be suitably used for the reasons described above.

In the curable resin composition of the present invention, the oligoester of the terminal carboxylic acid may be used in combination with another curing agent. When used in combination, the proportion of the oligomer of the terminal carboxylic acid in the total curing agent is preferably 20% by weight or more, more preferably 30% by weight or more.

Examples of the curing agent that can be used in combination with the oligoester of the terminal carboxylic acid include an amine compound, an acid anhydride compound having an unsaturated ring structure, an acid anhydride having an organosiloxane skeleton, an amide compound, a phenol compound, Acid-based compounds and the like. Specific examples of the curing agent that can be used include a polyamide resin synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylene diamine , Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane Tetracarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclo Hexane-1,3,4-tricarboxylic acid-3,4-anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'- Phenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl (meth) acrylate, Dihydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclohexylcarbodiimide, dicyclohexylcarbodiimide, dicyclohexylcarbodiimide, Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4 ' - polycondensates of bis (chloromethyl) benzene and 1,4'-bis (methoxymethyl) benzene and their modifications, halogenated bisphenols such as tetrabromobisphenol A, imidazoles, trifluoroborane-amine Condensates of guanidine derivatives, terpenes and phenols, and the like, but are not limited thereto. These may be used alone, or two or more of them may be used.

The mixing ratio of the epoxy resin (A) and the curing agent (B) is preferably such that the ratio of the epoxy group (A) to the curing agent (B) in the total curing agent containing the curing agent (B), which is an oligosaccharide of a terminal carboxylic acid capable of reacting with the epoxy group (Acid anhydride group or hydroxyl group) is preferably 0.5 to 1.5 equivalents (carboxylic acid is one functional group, and acid anhydride is considered to be one functional group), particularly preferably 0.5 to 1.2 equivalents. When the amount is less than 0.5 equivalents or more than 1.5 equivalents based on 1 equivalent of the epoxy group, the curing becomes incomplete in either case, and there is a possibility that good curing properties may not be obtained.

The white pigment in the present invention is not particularly limited. For example, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, basic zinc carbonate, kaolin and calcium carbonate can be used. The white pigment may be hollow particles. The surface of the white pigment may be suitably treated with a silicon compound, an aluminum compound, an organic material, or the like. These may be used alone or in combination of two or more. The average particle diameter of the white pigment is preferably in the range of 0.01 to 50 mu m. When the thickness is less than 0.01 탆, the particles tend to agglomerate and the dispersibility tends to deteriorate. When the thickness exceeds 50 탆, the cured product tends not to be sufficiently obtained. The average particle size can be measured using, for example, a laser diffraction scattering particle size distribution meter. In the present invention, it is preferable to use a powder of titanium oxide, especially titanium dioxide. This is because it has high whiteness, light reflectivity, and hiding power, excellent dispersibility stability, and easy access. The crystal form of the titanium oxide is not particularly limited and may be a rutile type, an anatase type or a mixture of both. However, since the anatase type has a photocatalytic function, there is a possibility of deteriorating the resin, Do.

The content of the white pigment is preferably in the range of 10 wt% to 85 wt% with respect to the whole resin composition. When the total content is less than 10% by weight, the light reflection property of the cured product tends to be insufficient. When the content exceeds 85% by weight, the moldability of the resin composition is deteriorated and the production of the substrate tends to be difficult.

A curing accelerator may be added to the curable resin composition of the present invention if necessary. Examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl- Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole Sol (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4-methylimidazole (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, a 2: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenyl Imidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl- - phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and imidazoles thereof. Salts of oligo esters of terminal carboxylic acids such as acetic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid and oxalic acid, amides such as dicyandiamide, (5.4.0) undecene-7, and salts thereof such as tetraphenylborate and phenol novolac, oligoesters of the above-mentioned terminal carboxylic acids, salts of phosphinic acids, Tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, and hexadecyltrimethylammonium hydroxide (preferably C1 to C20 alkylammonium salts, triphenylphosphine, tri (toluyl) phosphine , Tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate and the like, phenols such as 2,4,6-trisaminomethylphenol and the like, amines , Metal compounds such as tin octylate, zinc octanoate, zinc stearate, copper naphthenate and cobalt naphthenate, and microcapsulated curing accelerators obtained by microcapsulating these curing accelerators. Is appropriately selected depending on the properties required for the obtained transparent resin composition, for example, transparency, curing rate, and working conditions. Preferable examples of the present invention include a phosphonium compound (more preferably, quaternary phosphonium) or zinc stearate.

The curing accelerator is used in an amount of usually 0.001 to 15 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the epoxy resin.

An inorganic filler may be added to the curable resin composition of the present invention as necessary in order to prepare the moldability. The inorganic filler may be the same as the white pigment. Examples of the inorganic filler include, but are not limited to, crystalline silica, fused silica, antimony oxide, titanium oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide and alumina. These may be used alone, or two or more of them may be used.

The blending amount of the inorganic filler is preferably 1 to 1000 parts by weight, more preferably 1 to 800 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B).

In addition, the curable resin composition of the present invention may contain an internal release agent such as a silane coupling agent, stearic acid, palmitic acid, zinc stearate, aluminum stearate and calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate Zinc stearate, zinc stearate, zinc stearate, zinc stearate, zinc stearate, zinc stearate, etc.), zinc stearate (zinc stearate, zinc stearate, etc.) , And various thermosetting resins may be added.

In addition to the components (A) to (C), additives such as known ionic supplements may be added to the curable resin composition of the present invention, if necessary.

Further, it is required that the light reflectance at a wavelength of 460 to 800 nm after thermosetting is 80% or more, more preferably 85% or more. If the optical reflectance is less than 80%, the optical semiconductor device tends not to contribute sufficiently to the improvement of the brightness.

The thermosetting resin composition of the present invention is obtained by uniformly dispersing and mixing the above-mentioned various components. Although the method is not particularly limited, a method of sufficiently mixing and mixing various components uniformly with a mixer or the like and then kneading or melt-kneading the mixture with a mixing roll, an extruder, a kneader, a roll or an extruder, . The conditions for kneading or melt-kneading may be determined depending on the kind and amount of the components, and are not particularly limited, and it is more preferable to knead for 5 to 40 minutes in the range of 20 to 100 占 폚. If the kneading temperature is less than 20 ° C, the dispersibility of each component is lowered, and it is difficult to sufficiently knead the resin composition. If the kneading temperature is higher than 100 ° C, the crosslinking reaction of the resin composition proceeds and the resin composition may be cured.

The thermosetting resin composition of the present invention is preferably capable of being pressed (tablet) at room temperature of 0 to 30 占 폚 before heat molding. The press molding may be carried out under the conditions of, for example, 0.01 to 10 MPa and 1 to 5 seconds. The mold used for pressurizing (tablet) molding is not particularly limited. For example, a mold made of a ceramic material or a fluorine-based resin material and composed of a round-bottomed mold (upper mold) and a mold half mold .

The thermosetting resin composition of the present invention is useful in applications such as optical semiconductor sealing materials and reflective materials for optical semiconductors which require high glass transition temperature and high transmittance.

In the case of using as a light-use medium, the production method is not particularly limited, but it is preferable to produce the thermosetting resin composition of the present invention by transfer molding, for example. The thermosetting resin composition of the present invention is poured into a mold and is cured for 60 to 800 seconds under the conditions of, for example, a mold temperature of 150 to 190 DEG C and a molding pressure of 2 to 20 MPa, Lt; 0 > C for 1 to 3 hours.

(Semiconductor device)

A semiconductor device according to the present invention includes a light reflection preventing member having a cylindrical hollow portion on a substrate, as described in International Publication No. 2012/124147, and a light reflection preventing member having a cylindrical hollow portion is disposed in the inner space of the cylindrical hollow portion And the optical semiconductor element is disposed on the substrate. Further, the sealing resin is sealed in the hollow portion by connecting one end of the optical semiconductor element and the substrate with a wire.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the following description. The measurement of the gel permeation chromatography (hereinafter referred to as " GPC ") in the synthesis examples is as follows. The column was a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the eluent was tetrahydrofuran and the flow rate was 1 ml / min. Column temperature was 40 占 폚 and detection was carried out using RI (Reflective index). Standard curve of polystyrene standard was Shodex. The functional group equivalent was calculated from the ratio calculated from GPC, and the value was determined by making one equivalent of each of carboxylic acid and acid anhydride. The softening point was measured at a heating rate of 2 DEG C / min using a softening point measuring device METTLER FP90 (manufactured by Metra Toredo K.K.).

Synthesis Example 1 (Oligoester B-1 of a terminal carboxylic acid)

In a flask equipped with a stirrer, a reflux condenser and a stirrer, 98.1 parts of tricyclodecane dimethanol was added while a nitrogen purge was carried out, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (manufactured by Shinnippon Pharmaceutical Co., Ltd., Ricasid MHT 59.4 parts of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Company) and 275.2 parts of MEK were added, and the mixture was stirred at 60 ° C for 1 hour After the reaction, the mixture was heated and stirred at 80 DEG C for 5 hours to obtain a curing agent. The obtained curing agent was represented by the following formula, and it was colorless and solid. The functional group equivalent was 225.2 g / eq. The softening point was 105.6 ° C.

TG-DTA of hardener

The volatility of the cured product was evaluated for each curing agent by the following test method. The results are shown in Table 1. The measurement method of TG / DTA is described.

(%) At each temperature of 150 DEG C, 180 DEG C, and 200 DEG C in the air at a temperature raising rate of 10 DEG C / minute by using a thermogravimetric analyzer (TG / DTA7200) manufactured by SII ANA NanoTechnology Co., Respectively.

The oligosters of the terminal carboxylic acid (B-1) obtained in Synthesis Example 1 and the hexahydrophthalic anhydride phthalic acid (Ricaside HH made by Shin-Nippon Rikagaku Co., Ltd.) It is apparent that the amount of volatilization is low and that it is clearly low in volatility as compared with ricaside HH. From these results, it is considered that the use of the oligoester of the terminal carboxylic acid of the present invention as a curing agent can solve the problem that the curing agent volatilizes during production and processing.

≪ Preparation of thermosetting light-sensitive resin composition (Example 1, Comparative Example 1)

Each component was compounded in accordance with the formulation table shown in Table 2, and sufficiently kneaded by a mixer. Then, the mixture was melt-kneaded under a predetermined condition by a mixing roll and cooled and pulverized to obtain a thermosetting light- A composition was prepared. In addition, the unit of the blending amount of each component in the table is parts by weight, and the blank indicates that the component is not used.

≪ Evaluation of thermosetting light-releasable resin composition >

The light reflectivities of the cured products were evaluated for the resin compositions of each of the examples and comparative examples by the following test methods. The results are shown in Table 2 (after 72 hours) and in Table 3 (after 144 hours).

<Light Reflectivity Test>

The resin compositions of each of the examples and comparative examples were transfer-molded under the conditions of a molding temperature of 150 캜, a molding pressure of 10.4 MPa and a cure time of 300 seconds, and then post-curing at 150 캜 for 3 hours to prepare test pieces having a thickness of 1.0 mm. Subsequently, the light reflectance at a wavelength of 460 nm was measured with an integral spherical spectrophotometer UV-3600 (manufactured by Shimadzu Corporation), and the light reflectivity of each test piece was evaluated according to the following evaluation criteria.

From the above results, it can be seen that the thermosetting resin composition of the present invention suppresses the volatilization of the curing agent component during production and processing, suppresses discoloration due to heat, and gives a cured product excellent in light reflectivity and reliability under a high temperature environment .

While the invention has been described in detail with reference to specific embodiments thereof, it is evident to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application (2013-260903) filed on December 18, 2013, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated in their entirety.

(Industrial availability)

The thermosetting resin composition of the present invention is an optically transparent thermosetting resin composition in that it suppresses volatilization of the curing agent component during production and processing, suppresses discoloration due to heat, and gives a cured product excellent in light reflectivity and reliability under a high temperature environment useful. Suppressing the volatilization of the curing agent component at the time of processing is important in improving the working environment and in manifesting the stable performance of the cured product. In addition, it is useful as a reflective member of an optical semiconductor for suppressing discoloration due to heat and obtaining a cured product excellent in light reflectivity and high temperature environment under high-temperature conditions.

Claims (10)

An epoxy resin, a curing agent, and a white pigment, wherein the curing agent is an oligosester of a terminal carboxylic acid having a softening point of 50 ° C or higher. The method according to claim 1,
Wherein the oligoester of the terminal carboxylic acid of the terminal carboxylic acid has at least two or more carboxyl groups and the aliphatic hydrocarbon group is the main skeleton. 3. The method according to claim 1 or 2,
Wherein the white pigment is a titanium dioxide powder. 4. The method according to any one of claims 1 to 3,
Wherein the thermosetting resin composition has a light reflectance of 80% or more at a wavelength of 460 to 800 nm after thermosetting. 5. The method according to any one of claims 1 to 4,
Wherein the content of the white pigment is 5 to 95% by weight based on the total amount of the thermosetting resin composition. 6. The method according to any one of claims 1 to 5,
The thermosetting resin composition according to claim 1, wherein the oligoester of the terminal carboxylic acid of the terminal carboxylic acid according to claim 1 is a compound obtained by reacting a polyfunctional polyhydric alcohol having 6 or more carbon atoms and a saturated aliphatic cyclic acid anhydride. 7. The method according to any one of claims 1 to 6,
Wherein the saturated aliphatic cyclic acid anhydride is at least one acid anhydride selected from the group consisting of hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2- Wherein the thermosetting resin composition is a thermosetting resin composition. 8. The method according to any one of claims 1 to 7,
A thermosetting resin composition for forming a light reflection member constituting an optical semiconductor device. A reflective member for an optical semiconductor device comprising a cured thermosetting resin composition according to any one of claims 1 to 8, wherein at least a part of the reflective member for the optical semiconductor device is in any one of claims 1 to 8 Wherein the light-use thermosetting resin composition described above is formed by transfer molding. A light semiconductor device comprising a light reflection member obtained by curing the thermosetting resin composition according to any one of claims 1 to 8 and an optical semiconductor element.