TW201538612A - Thermosetting resin composition, method for manufacturing reflective member for optical semiconductor device using same, and optical semiconductor device - Google Patents

Abstract

Provided are: a thermosetting resin composition yielding a cured product having excellent reflectivity of light and reliability in high-temperature environments, and in which volatilization of curing agent components during manufacturing and processing is suppressed and discoloration due to heat is suppressed; a method for manufacturing a reflective member for an optical semiconductor device using the thermosetting resin composition; and an optical semiconductor device having the reflective member. The thermosetting resin composition of the present invention is a thermosetting resin composition for light reflection, comprising an epoxy resin, a curing agent, and a white pigment, the curing agent being an oligoester of a terminal carboxylic acid having a softening point of at least 50 DEG C.

Description

Thermosetting resin composition, method for producing reflective member for optical semiconductor device using the same, and optical semiconductor device

The present invention relates to a thermosetting resin composition, a method for producing a reflective member for an optical semiconductor device using the same, and an optical semiconductor device having the same, which is capable of suppressing production and processing. The volatilization of the curing agent suppresses discoloration caused by heat, and is excellent in light reflectivity and reliability in a high-temperature environment.

Optical semiconductor elements such as LEDs (Light Emitting Diodes) are used in most electronic devices because of their low power consumption, long life, and small size. It has been used in electronic devices with low brightness. However, in recent years, due to advances in technology, it has been used in areas requiring high brightness such as automotive headlamps or lighting applications. With this, the industry has also reflected components that constitute optical semiconductors. UV resistance and heat resistance are required.

As a material constituting a reflective member of an optical semiconductor, polyphthalamide (PPA) resin is widely used at present.

However, in recent years, due to the high output of the optical semiconductor device, the junction temperature rises, the light intensity increases, or the short wavelength of light develops, causing a problem that the deterioration is severe in the reflective member using the PPA resin. Uneven color or peeling, mechanical strength reduction, etc. condition. Further, there has been a problem that discoloration occurs at a high temperature during solder bonding, and it is impossible to maintain a high reflectance as a reflection member. In order to solve such problems, the industry is expected to develop a thermosetting light-reflecting resin composition excellent in light resistance and heat resistance.

Patent Document 1 is a thermosetting light-reducing light which is excellent in light resistance and heat resistance. In the resin composition for injection, a B-stage thermosetting light-reflecting resin composition containing an epoxy resin, a curing agent, and a curing accelerator as a constituent component is disclosed. As a method of molding the thermosetting light-reflecting resin composition, there is described a method in which, after kneading sufficiently by a mixer, melting is performed by a mixing roll, an extruder, a kneader, a roll, and an extruder under specific conditions. The resin composition for thermosetting light reflection is prepared by kneading, cooling, and pulverization, and the composition is subjected to transfer molding at a metal mold temperature of 170 to 190 ° C, a molding pressure of 2 to 8 MPa, and a molding time of 60 to 120 seconds. After the molding was carried out under the conditions, the metal mold was removed and hardened at 120 to 180 ° C for 1 to 3 hours.

In this case, hexahydrophthalic anhydride is used as the hardener, and in addition, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, tetrahydroortho Phthalic anhydride, methylic acid anhydride, ceric anhydride, glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrogen An acid anhydride such as phthalic anhydride, the epoxy resin composition for B-stage semiconductor sealing has the following problems: when it is produced by melt-kneading or when it is processed by transfer molding, according to studies by the inventors of the present invention. The acid-based hardener evaporates due to an increase in temperature.

Further, as a known document related to the present invention, the following Patent Documents 1 to 7 can be cited.

Patent Document 1: Japanese Patent No. 5239688

Patent Document 2: Japanese Laid-Open Patent Publication No. 2013-62519

Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-65899

Patent Document 4: Japanese Laid-Open Patent Publication No. 2013-127068

Patent Document 5: Japanese Laid-Open Patent Publication No. 2013-91809

Patent Document 6: Japanese Laid-Open Patent Publication No. 2013-138221

Patent Document 7: Japanese Laid-Open Patent Publication No. 2013-168684

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermosetting property which suppresses volatilization of a curing agent during production and processing, suppresses discoloration due to heat, and is excellent in light reflectivity and reliability in a high-temperature environment. A resin composition, a method for producing a reflective member for an optical semiconductor device using the same, and an optical semiconductor device having the reflective member.

That is, the invention of the present application 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 oligomer of a terminal carboxylic acid having a softening point of 50 ° C or higher. (2) The thermosetting resin composition according to (1), wherein the oligoester of the terminal carboxylic acid has at least two or more carboxyl groups, and the aliphatic hydrocarbon group is a main skeleton; (3) (1) The thermosetting resin composition according to any one of (1) to (3), wherein the white pigment (C) is a titanium oxide powder, and the thermosetting resin composition according to any one of (1) to (3), wherein In the above thermosetting resin composition, the light reflectance at a wavelength of 460 to 800 nm after heat curing is 80%. (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 thermosetting resin composition according to any one of the above (1), wherein the oligoester of the terminal carboxylic acid of (1) is a 2 to 6 functional polyol having a carbon number of 6 or more and is saturated. The thermosetting resin composition of any one of the above-mentioned (1) to (6), wherein the saturated aliphatic cyclic acid anhydride is selected and selected At least one acid anhydride of a group consisting of free hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (8) The thermosetting resin composition according to any one of (1) to (7) for forming a light reflecting member constituting the optical semiconductor device; (9) a reflecting member for an optical semiconductor device In the manufacturing method of the optical semiconductor device, the thermosetting resin composition according to any one of (1) to (8) is cured by a reflection member, and the manufacturing method is carried out by (1) to (8) Light of any one (a) an optical semiconductor device having a thermosetting resin composition according to any one of (1) to (8), wherein the reflective thermosetting resin composition is subjected to transfer molding to form at least a part of a reflective member for an optical semiconductor device; A light reflecting member formed by hardening a material and an optical semiconductor element.

The thermosetting resin composition of the present invention containing the epoxy resin (A), the specific curing agent (B), and the white pigment (C) suppresses volatilization of the curing agent during production and processing, and suppresses heat generation. A thermosetting resin composition excellent in discoloration, light reflectivity, and high-temperature environment is extremely useful.

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

In the present invention, the epoxy resin (A) is not particularly limited as long as it is blended as a resin composition for thermosetting light reflection or an epoxy resin molding material. For example, a phenolic phenolic-type epoxy resin or an o-cresol novolak-type epoxy resin represented by phenol and an aldehyde novolak resin can be epoxidized, and bisphenol A or bisphenol F, bisphenol S, alkyl substituted bisphenol and other diglycidyl ether, glycidylamine ring obtained by reaction of polyamines such as diaminodiphenylmethane and iso-cyanuric acid with epichlorohydrin The oxy-resin may be an alicyclic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid, a sesquiterpene oxide compound or the like, and these may be used singly or in combination of two or more. Among these epoxy resins, coloring is preferably small, and specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and isocyanuric acid epoxide. A propyl ester, a tri-epoxypropyl isocyanurate, a sesquiterpoxy compound.

Here, as the epoxy resin in the present invention, it is preferred to use an alicyclic epoxy resin or a triepoxypropyl isocyanurate skeleton alone or in combination in terms of transparency and discoloration resistance. Epoxy resin.

Further, as the epoxy resin having a triglycidyl isocyanurate skeleton, for example, an epoxy resin having a structure of the following formula (A) can be suitably used.

(wherein, a plurality of R ₄ independently represent an alkyl group having 1 to 6 carbon atoms which may have a direct bond, an oxygen atom or an ester bond, and the following formula (B)

(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 a formula (B)). Specifically, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.

In addition, examples of the preferred alicyclic epoxy resin include SEJ-01R (manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021 (manufactured by Daicel Co., Ltd.), and EHPE 3150 (manufactured by Daicel Co., Ltd.). The compound name is not particularly limited as long as it has an epoxycyclohexyl skeleton, and examples of the bifunctional ones include two epoxycyclohexyl skeletons and a carbon number of 1 to 10 which may have an oxygen atom or an ester bond. An epoxy resin in which an alkyl group is bonded, as an example of a monofunctional one, may be an alkyl group having an oxygen atom and having an oxygen atom of 1 to 10 on an epoxycyclohexyl skeleton. An epoxy resin having a base or a hydroxyl group as a substituent. Specific preferred examples thereof include 3,4-epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexylmethyl ester and 2,2-bis(hydroxymethyl)-1-butanol. 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct and the like.

The term "hardener" as used in the present invention means a terminal carboxylic acid having a softening point of 50 ° C or higher. Oligoester.

The specific structural formula has a structure of the following formula (1) and is a compound having an ester structure (preferably two ester structures) in the molecule. Further, it is a compound having a plurality of carboxyl groups at its terminal.

(In the formula, P is a residue of a polyhydric alcohol having 2 to 20 carbon atoms which may contain a hetero atom having a content of 0 to 6, an oxygen atom, a nitrogen atom or a phosphorus atom, and R represents a carbon number of 2 to 20. An aliphatic hydrocarbon group; a plurality of n, k exist independently, and represent 1 to 6 in terms of an average value; further, a total of n is 2 or more and less than 12)

Among them, the oligoester of the terminal carboxylic acid of the above formula (1) is preferably a compound obtained by esterification reaction of a hexavalent 6-membered polyol having a carbon number of 6 or more and a saturated aliphatic cyclic acid anhydride.

More specifically, in the oligoester of the terminal carboxylic acid described in the above formula (1), the linking group R is preferably a cycloalkane skeleton having a carbon number of 4 to 10, or a lowering The alkane skeleton preferably has a substituted or unsubstituted cyclohexane structure, particularly a methylcyclohexane structure having a methyl group, in the cycloalkane skeleton in terms of optical properties of the cured product. Again, as a drop a norbomane skeleton, preferably a lower Alkane, methyl drop Alkane structure.

The linking group P is a residue of a polyol having 2 to 10 carbon atoms (a residue obtained by removing a hydroxyl group from a polyol used for the reaction), preferably a branched crosslinking group or a cycloalkyl group, especially P is preferably a divalent crosslinking group defined by the following (a) or (b).

(a) is a chain alkyl chain having a branched structure of 6 to 20 carbon atoms, the chain alkyl chain having a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and at least a cross-linking group having a carbon number of 2 to 10 in a side chain; or (b) at least one cross-linking selected from tricyclodecane dimethanol or pentacyclopentadecane dimethanol having a methyl group on the ring A bivalent crosslinking group obtained by removing two hydroxyl groups from a polycyclic diol; wherein, when P is (b), preferably, the linking group R is a cycloalkane skeleton having a carbon number of 4 to 10 or a lowering In the case of the alkane skeleton, the substituent R ³ in the following formula (2) represents a group other than a hydrogen atom.

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

In the present invention, the above-mentioned oligoester of the terminal carboxylic acid is preferably obtained by subjecting a hexa- or higher-functional polyol having 6 or more carbon atoms to a saturated aliphatic cyclic acid anhydride.

The oligoester of the terminal carboxylic acid in the present invention may also be a composition containing two kinds of polycarboxylic acids. As a method of obtaining an oligoester composition of a terminal carboxylic acid containing an oligoester of at least two terminal carboxylic acids, there is a method of mixing at least two oligoesters of a single terminal carboxylic acid obtained by the above method. Or a method of performing an addition reaction using a mixture of at least two kinds of the above-mentioned hexahydrophthalic anhydride or two kinds of the above-mentioned polyhydric alcohols when synthesizing the oligoester of the terminal carboxylic acid.

a saturated aliphatic cyclic acid used as a synthesis of an oligoester of a terminal carboxylic acid The anhydride may, for example, have a cyclohexane structure in which one or more (preferably one) and a cyclohexane ring bond are contained in the molecule by a methyl group or a carboxyl group or an unsubstituted group. An anhydride group-based compound.

Specifically, it is selected from the group consisting of hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. At least one acid anhydride.

6 or more carbons used as a synthesis of an oligoester of a terminal carboxylic acid in the present invention Specific examples of the 2-6-functional polyol include an oligoester of a terminal carboxylic acid having a hydroxyl group at the terminal of the crosslinking group P in the above formula (1).

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

The divalent cross-linking group defined by the above (a) is a divalent chain alkyl chain obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure of 6 to 20 carbon atoms, and its structure is sandwiched. The alkyl chain between the two alcoholic hydroxyl groups of the diol serves as a main chain and has a structure of an alkyl chain (referred to as a side chain) branched from the alkyl chain. The side chain may be branched from any of the carbon atoms constituting the main chain, and may also include a branch of a carbon atom (the terminal carbon atom of the main chain) bonded by, for example, an alcoholic hydroxyl group. Any crosslinkable group having such a structure may be any, and specific examples of such a crosslinkable group are shown in the following formula (a1).

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

The alkylene crosslinking group defined by the above (a) is as long as it is an alkyl group for the main chain. The structure having an alkyl branch (side chain) is not particularly limited, and preferably has a carbon number of 3 or more in the main chain, has at least one alkyl side chain, and particularly preferably has 2 or more alkyl groups. Base side chain. More preferably, a linear chain having a carbon number of 3 to 12 and 2 to 4 side chains, and at least one side chain having a carbon number of 2 to 10 may be mentioned. In this case, a crosslinking group in which at least two of the side chains have a carbon number of 2 to 10 is further preferable. Further, it is preferred to branch on different carbon atoms of 2 to 4 side chain autonomous chains.

The more specific compound is a compound in which a hydroxyl group is bonded to the position of the * symbol in the crosslinking group described in the above formula (a1).

The polyol used as a raw material is preferably a polyol having at least two side chains, and at least two of the side chains are side chains having 2 to 4 carbon atoms.

Among such a skeleton, as a preferred polyhydric alcohol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl -1,3-hexanediol or the like, and particularly preferably 2,4-diethyl-1,5-pentanediol.

The crosslinking group defined in the above (b) is represented by the following formula (b1) The 2 price base.

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

In the formula, a plurality of R ² each independently represent a hydrogen atom or a methyl group. Among these, R ² is preferably a crosslinking group of a hydrogen atom.

Specific examples thereof include tricyclodecane dimethanol, methyl tricyclodecane dimethanol, pentacyclopentadecaned dimethanol, and the like.

As a reaction between an acid anhydride and a polyhydric alcohol, it is usually an addition of an acid or a base as a catalyst. Preferably, but in the present invention, the reaction is carried out without a catalyst.

In the case of using a catalyst, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid. , metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-di Diazabicyclo [5.4.0] eleven carbon-7-ene, imidazole, triazole, tetrazole and other heterocyclic compounds, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl hydroxide Ammonium, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethyl cetyl ammonium hydroxide, hydroxide a quaternary ammonium salt such as octylmethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate or trioctylmethylammonium acetate. These catalysts can be used alone or in combination of two or more. Among these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

The amount of the catalyst used is not particularly limited, and is usually 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of the raw materials, and is preferably used as needed.

In the present reaction, it is preferred to carry out the reaction without a solvent, but it is also possible to use an organic solvent. The amount of the organic solvent to be used is 0.005 to 1 part by weight, preferably 0.005 to 0.7 part, more preferably 0.005 to 0.5 part by weight based on 1 part by weight of the total amount of the above-mentioned acid anhydride as the reaction substrate. (ie 50% by weight 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 above reaction substrate, the progress of the reaction becomes extremely slow, which is not preferable. Specific examples of the organic solvent that can be used include an alkane such as hexane, cyclohexane or heptane, an aromatic hydrocarbon compound such as toluene or xylene, methyl ethyl ketone, methyl isobutyl ketone or cyclopentane. Ketones such as ketone and cyclohexanone, diethyl ether, tetrahydrofuran, and An ether such as an alkyl group; an ester compound such as ethyl acetate, butyl acetate or methyl formate.

Regarding this reaction, even at a temperature of about 20 ° C, the reaction will fully advance. Row. In terms of the reaction time, the reaction temperature is preferably from 30 to 200 ° C, more preferably from 40 to 200 ° C, and particularly preferably from 40 to 150 ° C. In particular, when the reaction is carried out under the conditions of no solvent, the reaction of the temperature of 100 ° C or lower is preferable because of the volatilization of the acid anhydride, and it is particularly preferably a reaction of 30 to 100 ° C or 40 to 100 ° C.

The reaction ratio of the above acid anhydride to the above polyol is theoretically preferably a reaction under the molar conditions, but may be changed as needed.

The specific addition ratio of the two at the time of the reaction is preferably 0.001 to 2 equivalents, more preferably 0.01 to 1.5 equivalents, more preferably 0.01 to 1.5 equivalents, based on the equivalent of the functional group, based on 1 equivalent of the acid anhydride group. The polyol is added in a ratio of 0.1 to 1.2 equivalents.

Preferably, the oligoester of the terminal carboxylic acid obtained in the present invention is solid. In order to obtain an oligoester of a solid resin-like terminal carboxylic acid, it is preferred to use a polyol having a molar equivalent or more, but by adding a filler. The fluidity becomes important, and in order to ensure the fluidity, the balance of the viscosity can be slightly broken within the range of maintaining the solid state (softening point of 50 ° C or more).

Specifically, the equivalent of the alcoholic hydroxyl group is preferably from 0.85 to 1.20 mol equivalents, more preferably from 0.90 to 1.10 mol equivalents, based on the anhydride equivalent.

Although the reaction time also depends on the reaction temperature, the amount of the catalyst, etc., from the viewpoint of industrial production, a long-term reaction consumes a large amount of energy, which is not preferable. Moreover, too short a reaction time means that the reaction is impatient and poor in terms of safety. The preferred range is preferably from 1 to 48 hours, preferably from 1 to 36 hours, more preferably from 1 to 24 hours, and still more preferably from 2 to 10 hours.

After the completion of the reaction, when a catalyst is used, the catalyst is removed by neutralization, water washing, adsorption, or the like, respectively, and the solvent is distilled off, whereby an oligoester of the desired terminal carboxylic acid is obtained. On the other hand, in the case where the reaction is carried out under the conditions of no catalyst, the solvent is distilled off as needed, whereby an oligoester of the desired terminal carboxylic acid is obtained. Further, in the case of using a solvent, an oligoester of a terminal carboxylic acid of a target is obtained by removing a solvent. Further, in the case of no solvent or no catalyst, the product is produced by directly taking out.

As an optimum manufacturing method, the above acid anhydride and the above polyol are used in the absence of a catalyst. The reaction was carried out at 40 to 150 ° C under the conditions, and the solvent was removed and taken out.

The oligoester of the above terminal carboxylic acid or the oligomer containing the terminal carboxylic acid thus obtained The composition of the ester is usually in the form of a colorless to pale yellow solid resin (sometimes crystallized). The softening point of the oligoester of the terminal carboxylic acid is preferably from 50 to 190 ° C, more preferably from 55 to 150 ° C, still more preferably from 60 to 120 ° C. By directly mixing the oligoester having a terminal carboxylic acid having such a softening point into a liquid form, it is directly mixed into the thermosetting resin composition, and has an extremely high reflectance retention ratio, and becomes available even if A reflective member whose reflectance is not easily lowered when a heat resistance test is applied.

In general, in the case where the crosslinking group is an alkylene group having a side chain defined by (a), it is in the form of a colorless to pale yellow solid resin.

In the present invention, the most preferred method of using a thermosetting resin composition containing an oligoester of a terminal carboxylic acid is transfer molding, and thus the oligoester of the terminal carboxylic acid is in the form of a solid resin.

In the case where the crosslinking group is a crosslinking group defined by (b), the aliphatic hydrocarbon group is a cycloalkane skeleton having a carbon number of 4 to 10 or a lowering In the case of an alkane skeleton, the alicyclic substituents are all colored at the end of the carboxylic acid of the hydrogen atom, and are not suitable for optical applications requiring particularly stringent requirements. The aliphatic hydrocarbon group is a cycloalkane skeleton having a carbon number of 4 to 10 or In the case of an alkane skeleton, such a coloring of a compound in which a substituent is a methyl group or a carboxyl group is small, and optical properties are improved.

In the compound of the crosslinking group defined in the above (a), the aliphatic hydrocarbon group is a cycloalkane skeleton having a carbon number of 4 to 10 or a lowering In the case of an alkane skeleton, a compound having a substituent of a methyl group or a carboxyl group is preferred because it has an optical property.

That is, as the oligoester composition of the terminal carboxylic acid of the present invention, it is a naphthene skeleton having a carbon number of 4 to 10 or a lower In the case of an alkane skeleton, a composition containing an oligoester of a terminal carboxylic acid of the formula (1), and a substituent of the composition of the terminal carboxylic acid of the formula (1) is preferably a methyl group or a carboxyl group. Or have both. In the case of an oligoester composition of a terminal carboxylic acid containing two or more kinds of the terminal carboxylic acid oligoester, it is preferably a composition having a content of 50 mol with respect to the total amount of the oligoester of the terminal carboxylic acid. An oligoester of a terminal carboxylic acid of the formula (1) wherein at least the substituent is not a hydrogen atom or more (the substituent is an oligoester of the terminal carboxylic acid of the above alkyl group, preferably a methyl group or a carboxyl group). More preferably, it is an oligoester composition of a terminal carboxylic acid containing 70 mol% or more of the terminal carboxylic acid of the terminal carboxylic acid of the formula (1) in which the substituent is not a hydrogen atom, and preferably contains 90 mol% or more. An oligoester composition of a terminal carboxylic acid of an oligoester of a terminal carboxylic acid of the formula (1) which is not a hydrogen atom. The remainder is an oligoester of a terminal carboxylic acid of the formula (1) which is an R-based hydrogen atom.

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

(In the above formula, P represents the same meaning as described above, and R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a carboxyl group)

Here, in the above formula (2), for the reason as described above, R ³ may suitably use an alkyl group or a carboxyl group having 1 to 3 carbon atoms.

In the curable resin composition of the present invention, the oligoester of the terminal carboxylic acid can also be used He used the hardener together. In the case of use in combination, the ratio of the terminal carboxylic acid oligoester to all the hardeners is preferably 20% by weight or more, and more preferably 30% by weight or more.

Examples of the curing agent which 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 organic siloxane skeleton, a guanamine compound, and a phenol compound. A carboxylic acid compound or the like. Specific examples of the hardener which can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophoronediamine, and dicyano group. Diamine, polyamine resin synthesized from dimer of linoleic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, four Hydrogen phthalic anhydride, methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride Bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4 -tricarboxylic acid-3,4-anhydride, bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3 ',5,5'-Tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris(4-hydroxyphenyl) Methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) With formaldehyde, acetaldehyde, benzaldehyde , p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl , 4,4'-bis(methoxymethyl)-1.1'-biphenyl, 1,4'-bis(chloromethyl)benzene, 1,4'-bis(methoxymethyl)benzene, etc. a polycondensate, such a modified substance, a halogenated bisphenol such as tetrabromobisphenol A, an imidazole, a boron trifluoride-amine complex, an anthracene derivative, a condensate of a terpene and a phenol, etc., but are not limited In these. These may be used alone or in combination of two or more.

Further, regarding the blend ratio of the epoxy resin (A) and the hardener (B), 1 equivalent of the epoxy group in the epoxy resin (A), containing an active group (an acid anhydride group or a hydroxyl group) in all the hardeners of the hardener (B) which is an oligoester of a terminal carboxylic acid which can react with the epoxy group It is preferably 0.5 to 1.5 equivalents (the carboxylic acid is regarded as a monofunctional group, and the acid anhydride is regarded as a monofunctional group), and particularly preferably 0.5 to 1.2 equivalents. When the amount is less than 0.5 equivalents per equivalent of the epoxy group or exceeds 1.5 equivalents, the hardening becomes incomplete and good hardenability is not obtained.

The white pigment in the present invention is not particularly limited, and for example, alumina or oxygen can be used. Magnesium, cerium oxide, titanium oxide, zirconium oxide, zinc oxide, basic zinc carbonate, kaolin, calcium carbonate, and the like. Further, the white pigment may also be a hollow particle. Further, the white pigment may be appropriately surface-treated with a ruthenium compound, an aluminum compound, an organic substance or the like. These may be used alone or in combination of two or more. Further, the average particle diameter of the white pigment is preferably in the range of 0.01 to 50 μm. When it is less than 0.01 μm, the particles tend to aggregate and the dispersibility tends to be deteriorated. When the thickness exceeds 50 μm, the reflection characteristics of the cured product tend not to be sufficiently obtained. The above average particle diameter can be measured, for example, by a laser diffraction scattering type particle size distribution meter. In the present invention, a powder of titanium oxide is preferably used, and a powder of titanium dioxide is particularly preferably used. The reason for this is that whiteness, light reflectivity, and concealing power are high, dispersion stability is excellent, and it is easy to acquire. The crystal form of the titanium oxide is not particularly limited, and may be a rutile type or an anatase type, or a mixture of the two, but the anatase type may have a photocatalytic function and may cause deterioration of the resin. In the case of the invention, it is preferably a rutile type.

Further, the content of the white pigment is preferably in the range of 10% by weight to 85% by weight based on the total amount of the resin composition. When the total content is less than 10% by weight, the light reflection property of the cured product tends to be insufficiently obtained. When the total content is more than 85% by weight, the moldability of the resin composition is deteriorated, and the substrate is deteriorated. The production becomes difficult.

A hardening accelerator may be added to the curable resin composition of the present invention as needed. Examples of the hardening accelerator include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzylidene. 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2 -undecyl imidazole, 2,4-diamino-6-(2'-methylimidazolium (1')) ethyl-symmetric three , 2,4-diamino-6-(2'-undecylimidazolium (1')) ethyl-symmetric three 2,4-Diamino-6-(2'-ethyl, 4-methylimidazolium (1')) ethyl-symmetric three , 2,4-diamino-6-(2'-methylimidazolium (1')) ethyl-symmetric three - an isomeric cyanuric acid adduct, a 2:3 adduct of 2-methylimidazoisocyanuric acid, a 2-phenylimidazolium isocyanurate adduct, 2-phenyl-3,5 -Dimethylolidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Imidazoles, and terminal carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyroic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, etc. a salt of an oligoester, a guanamine such as dicyandiamide, a diazepine compound such as 1,8-diazabicyclo (5.4.0) undec-7-ene, and a tetraphenylborate thereof. a salt such as a phenol novolak, an oligoester of the above terminal carboxylic acid or a salt of a phosphonic acid, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, a quaternary ammonium salt such as cetyltrimethylammonium hydroxide (preferably a C1 to C20 alkylammonium salt, triphenylphosphine, tris(tolylmethyl)phosphine, tetraphenylphosphonium bromide, tetraphenylene a phosphine or a ruthenium compound such as tetraphenylborate, a phenol such as 2,4,6-triaminomethylphenol, or an amine adduct, a metal compound such as tin hydride, zinc octoate, zinc stearate, copper naphthenate or cobalt naphthenate, and a microcapsule-type hardening accelerator which is a microcapsule of the hardening accelerator. The hardening accelerator is appropriately selected depending on the properties required for the obtained transparent resin composition, for example, transparency, curing rate, working conditions, etc. Preferred examples of the present invention include an anthracene compound (more preferably Grade 4 鏻) 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.

In the curable resin composition of the present invention, in order to adjust the formability, it may be necessary Add an inorganic filler. Further, the inorganic filler may be the same as the white pigment. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, cerium oxide, titanium oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, and aluminum oxide, but are not limited thereto. These may be used alone or in combination of two or more.

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

Further, a decane coupling agent may be added to the curable resin composition of the present invention. Internal mold release agent such as stearic acid, palmitic acid, zinc stearate, aluminum stearate, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, Zinc compound (metal soap) such as zinc myristate or zinc phosphate (zinc octyl phosphate, zinc stearyl phosphate, etc.), light stabilizer such as surfactant, hindered amine, antioxidant, coupling agent, etc. Admixture, various thermosetting resins.

Further, in the curable resin composition of the present invention, in addition to the above components (A) to (C), an additive such as a known ion trapping agent may be added as needed.

Further, it is preferable that the light reflectance of the wavelength of 460 to 800 nm after the heat curing is 80% or more, and more preferably the light reflectance is 85% or more. If the light reflectance is less than 80%, the brightness of the optical semiconductor device may not be sufficiently promoted.

The thermosetting resin composition of the present invention can be obtained by uniformly mixing the above various components Obtained by dispersing and mixing. The method is not particularly limited, and a method in which various components are sufficiently uniformly stirred and mixed by a mixer or the like, and then kneaded or melted by a mixing roll, an extruder, a kneader, a roll, an extruder, or the like. Mix and cool and smash. The conditions of the kneading or the melt kneading may be determined depending on the type of the component or the blending amount, and are not particularly limited, and it is more preferably 5 to 40 minutes in the range of 20 to 100 ° C. When the kneading temperature is less than 20 ° C, the dispersibility of each component is lowered, and it is difficult to sufficiently knead. When the temperature is higher than 100 ° C, the crosslinking reaction of the resin composition proceeds, and the resin composition is hardened.

The thermosetting resin composition of the present invention is preferably at 0 before heat forming. Pressurization (pressing plate) molding at room temperature of ~30 °C. The press molding can be carried out, for example, under the conditions of 0.01 to 10 MPa and 1 to 5 seconds. Further, the metal mold used for press molding (pressing plate) molding is not particularly limited, and it is preferably composed of a dies (upper metal mold) and a dies (lower metal mold), for example, a ceramic system. It is composed of a material or a fluorine resin material.

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

In the case of use for light reflection, the manufacturing method is not particularly limited, for example, The thermosetting resin composition of the present invention is preferably produced by transfer molding. The thermosetting resin composition of the present invention is injected into a metal mold, and is cured from a metal mold after being cured for 60 to 800 seconds under the conditions of a mold temperature of 150 to 190 ° C and a molding pressure of 2 to 20 MPa, for example. Hardening temperature 150 ° C ~ 180 ° C thermal hardening 1 ~ 3 hours.

(semiconductor device)

In the semiconductor device of the present invention, a specific example is exemplified for a representative structure, such as international As described in Japanese Laid-Open Patent Publication No. 2012/124147, a light-reflecting member having a cylindrical hollow portion is disposed on a substrate, and an optical semiconductor element is disposed on the substrate in an internal space of the cylindrical hollow portion. Further, the end portion of the optical semiconductor element is connected to the substrate by a wire, and the sealing resin is sealed in the hollow portion.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited. Further, in the synthesis example, the measurement of the gel permeation chromatography (hereinafter referred to as "GPC") is as follows. The column was made of Shodex SYSTEM-21 (KF-803L, KF-802.5 (×2), K-802), and the eluent was used to connect the eluent to tetrahydrofuran at a flow rate of 1 ml/min. The column temperature was 40 °C. The detection was performed by RI (Reflective Index) using a standard polystyrene manufactured by Shodex. Further, the functional group equivalent was calculated from the ratio calculated by GPC, and the value was determined by setting the carboxylic acid and the acid anhydride to 1 equivalent. Further, the softening point was measured using a softening point measuring device METTLER FP90 (manufactured by Mettler Toledo Co., Ltd.) at a temperature rising rate of 2 ° C/min.

Synthesis Example 1 (oligoester B-1 of terminal carboxylic acid)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 98.1 parts of tricyclodecane dimethanol, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride were added while performing nitrogen purge. Manufactured by Nippon Chemical Co., Ltd., Rikacid MHT, ratio 7:3), 117.6 parts, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 59.4 parts, 275.2 parts of MEK was reacted at 60 ° C for 1 hour and then heated and stirred at 80 ° C for 5 hours to obtain a hardener. The hardener obtained is represented by the following formula and is colorless and solid. Further, the functional group equivalent was 225.2 g/eq. The softening point is 105.6 °C.

Hardener TG-DTA (Thermogravimetric-Differential Thermal Analysis)

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

Using a thermogravimetric analyzer (TG/DTA7200) manufactured by SII Nano Technology Co., Ltd., the reduction at each temperature of 150 ° C, 180 ° C, and 200 ° C was measured in air at a heating rate of 10 ° C / min (%) ).

The oligoester (B-1) of the terminal carboxylic acid obtained in Synthesis Example 1 was compared with hexahydrophthalic anhydride (Rikacid HH manufactured by Nippon Chemical Co., Ltd.) to find an oligoester of a terminal carboxylic acid. The almost non-volatile content below 200 ° C is significantly lower than that of Rikacid HH. Based on the results, it is considered that the problem of volatilization of the curing agent at the time of production and processing can be solved by using the oligoester of the terminal carboxylic acid of the present invention as a curing agent.

<Preparation of Resin Composition for Thermosetting Light Reflection (Example 1, Comparative Example 1)>

Each component was blended according to the blending table shown in Table 2, and kneaded thoroughly by a mixer, and then melt-kneaded under a specific condition by a mixing roll, and cooled and pulverized to prepare Example 1 and Comparative Example 1. A resin composition for thermosetting light reflection. Further, the unit of the blending amount of each component in the table is a part by weight, and the blank column indicates that the component is not used.

<Evaluation of Resin Composition for Thermosetting Light Reflection>

The light reflectance of the cured product was evaluated by the following test methods for the resin compositions of the respective examples and the comparative examples. The results are shown in Table 2 (after 72 hours) and Table 3 (after 144 hours).

<Light Reflectivity Test>

The resin compositions of the respective examples and the comparative examples were subjected to transfer molding at a molding temperature of 150 ° C, a molding pressure of 10.4 MPa, and a curing time of 300 seconds, and then subjected to a post-hardening treatment at 150 ° C for 3 hours to thereby produce a thickness of 1.0. Mm test piece. Then, the light reflectance at a wavelength of 460 nm was measured by an integrating sphere type spectrophotometer UV-3600 (manufactured by Shimadzu Corporation), and the light reflectance of each test piece was evaluated based on the following evaluation criteria.

Based on the above results, it is known that the thermosetting resin composition of the present invention can provide suppression The volatilization of the hardener component at the time of manufacture and processing, suppresses discoloration by heat, and is excellent in light reflectivity and reliability in a high-temperature environment.

Hereinabove, the present invention has been described in detail with reference to specific aspects, but it is clear to the Various changes and modifications can be made without departing from the spirit and scope of the invention.

Further, the present application is based on a Japanese patent application (2013-260903) filed on Dec. Also, all of the reference frames cited herein are incorporated herein in their entirety.

[Industrial availability]

The thermosetting resin composition of the present invention can provide a cured product which suppresses volatilization of a curing agent component during production and processing, suppresses discoloration due to heat, and is excellent in light reflectivity and reliability in a high-temperature environment. A thermosetting resin composition for reflection is useful. It is important to suppress the volatilization of the hardener component at the time of processing in order to improve the work environment and the performance of the cured product. In addition, it is possible to obtain a cured product which is excellent in the reliability of the light-reducing light due to heat and the high-temperature environment, and is useful for a reflecting member of a high-output optical semiconductor.

Claims (10)

A thermosetting resin composition comprising a thermosetting resin composition for light reflection comprising an epoxy resin, a curing agent, and a white pigment, wherein the curing agent is an oligoester of a terminal carboxylic acid having a softening point of 50 ° C or higher ( Oligoester). The thermosetting resin composition according to claim 1, wherein the terminal carboxylic acid oligoester has at least two or more carboxyl groups, and the aliphatic hydrocarbon group is a main skeleton. The thermosetting resin composition according to claim 1 or 2, wherein the white pigment is titanium dioxide powder. The thermosetting resin composition 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. The thermosetting resin composition 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. The thermosetting resin composition according to any one of claims 1 to 5, wherein the oligoester of the terminal carboxylic acid of claim 1 is a 2-6 functional polyol having a carbon number of 6 or more. A compound obtained by reaction with a saturated aliphatic cyclic acid anhydride. The thermosetting resin composition according to any one of claims 1 to 6, wherein the saturated aliphatic cyclic acid anhydride is selected from the group consisting of hexahydrophthalic anhydride and methylhexahydrophthalic acid A compound obtained by reacting at least one acid anhydride of a group consisting of acetic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. The thermosetting resin composition according to any one of claims 1 to 7, which is used for forming a light reflecting member constituting the optical semiconductor device. A method for producing a reflection member for an optical semiconductor device, wherein the thermosetting resin composition according to any one of claims 1 to 8 is cured by a reflection member, wherein the manufacturing method is The thermo-reflective resin composition for light reflection according to any one of the first to eighth aspects of the invention is subjected to transfer molding to form at least a part of a reflection member for an optical semiconductor device. An optical semiconductor device comprising a light-reflecting member and an optical semiconductor element obtained by curing the thermosetting resin composition according to any one of claims 1 to 8.