CN105637008A - Curable resin composition and cured product thereof - Google Patents

Abstract

An epoxy resin composition containing a cyclic siloxane compound (A) of a specific structure having two or more epoxy groups in-molecule, an epoxy resin curing agent (B), and an optional epoxy resin curing accelerator (C). The epoxy resin curing agent (B) is preferably a polycarboxylic acid resin or a polycarboxylic acid of a specific structure.

Description

Curable resin composition and cured product thereof

technical field

In particular, the present invention relates to a curable resin composition and a cured product thereof suitable for use in portions requiring high transparency, such as for sealing optical semiconductors.

Background technique

As resins for sealing optical semiconductors such as white light-emitting LEDs (Light Emitting Diodes, light-emitting diodes), dimethyl polysiloxanes containing unsaturated hydrocarbon groups have been used from the viewpoint of excellent light-resistant transparency and heat-resistant transparency. and organohydrogendimethylpolysiloxane silicone resin sealing material (see Patent Document 1).

In order to improve the efficiency of energization and light extraction for lighting LEDs, silver plating with high electrical conductivity and high light reflectance is widely used as a lead frame. The silver plating part is covered by the sealing material, but due to the high gas permeability of the silicone resin sealing material, the following problems have been found in recent years: sulfur-containing gases such as hydrogen sulfide in the air permeate and combine with the silver plating ( Silver sulfide) causes the surface of the lead frame to become black, and the light reflectivity decreases, resulting in a decrease in LED brightness.

Therefore, in order to reduce the permeability of sulfur-containing gases as an improvement in vulcanization resistance, polyphenylsiloxane resin sealing materials that introduce phenyl groups in polydimethylsiloxane resins to improve vulcanization resistance are gradually used (see Patent Document 2).

On the other hand, in order to reduce the thickness of liquid crystal displays and the like recently, LED packages are also being reduced in thickness. In order to reduce the thickness of the LED package, the resin sealing part is also thinned, and even a phenylpolysiloxane resin sealing material cannot obtain satisfactory vulcanization resistance.

In addition, in order to fix the surface-mount LED package to the substrate, it is necessary to go through a lead-free reflow process that temporarily exposes the entire package to high temperature. In this process, the sealing material may peel off from the package or cracks (cracks) may occur. question.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 4636242

Patent Document 2: Japanese Patent No. 4676735

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to provide an epoxy resin composition and its cured product. The epoxy resin composition can provide a cured product with excellent transparency, appropriate hardness, and excellent mechanical strength, and can provide It is an optical semiconductor sealing material that does not cause cracks during reflow soldering during semiconductor sealing, and is also excellent in sulfuration resistance and illuminance retention during long-term lighting.

means of solving problems

The present inventors have conducted intensive research in view of the above-mentioned actual situation, and found that a compound containing a cyclic siloxane compound having a specific structure having two or more epoxy groups in the molecule, an epoxy resin curing agent, and an optional curing accelerator The curable resin composition can solve the above-mentioned problems, and the present invention has been completed.

That is, the present invention relates to the following (1) to (13).

(1) An epoxy resin composition comprising a cyclic siloxane compound (A) having two or more epoxy groups in the molecule represented by the following formula (1), an epoxy resin curing agent (B ).

(In the formula, R ¹ represents a hydrocarbon group with 1 to 6 carbon atoms, X represents an organic group containing an epoxy group or a hydrocarbon group with 1 to 6 carbon atoms, and n represents an integer of 1 to 3. Multiple in the formula Each of R ¹ and X may be the same or different. Among the plurality of Xs present, at least two are epoxy group-containing organic groups.)

(2) The epoxy resin composition as described in (1) whose 90 mol% or more of X in formula (1) is an epoxy group-containing organic group.

(3) The epoxy resin composition as described in (1) or (2) whose epoxy resin curing agent (B) is polyvalent carboxylic acid resin.

(4) The epoxy resin composition as described in (3), wherein the polycarboxylic acid resin is obtained by at least making (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule and (b) containing one hydroxyl group in the molecule. An addition polymer obtained by reacting the above anhydride-based compounds.

(5) The epoxy resin composition as described in (4), wherein, (b) the compound containing more than one acid anhydride group in the molecule is selected from the group consisting of methyl hexahydrophthalic anhydride, glutaric anhydride and diethyl More than one compound in glutaric anhydride.

(6) The epoxy resin composition as described in (1) or (2) whose epoxy resin curing agent (B) is a polyhydric carboxylic acid represented by following formula (2).

(In the formula, multiple Qs that exist represent at least one of a hydrogen atom, a methyl group, and a carboxyl group, P represents an aliphatic group containing a chain and/or ring structure with 2 to 20 carbon atoms, and m represents 2 Integer of ~4.)

(7) The epoxy resin composition as described in (6), wherein the epoxy resin curing agent (B) represented by the formula (2) contains one or more compounds represented by the following formulas (3) to (6) compound.

(8) The epoxy resin composition as described in (1) or (2) whose epoxy resin curing agent (B) is a polyhydric carboxylic acid represented by following formula (8).

(In the formula, P and m represent the same meaning as the above-mentioned formula ( ² ), and R represents a hydrogen atom or an ethyl group.)

(9) The epoxy resin composition as described in (8), wherein the epoxy resin curing agent (B) represented by the formula (8) contains one or more compounds represented by the following formulas (9) to (12) compound.

(In the formulas (9) to (12), R ² represents the same meaning as the above-mentioned formula (8).)

(10) The epoxy resin composition according to any one of (1) to (9), further comprising an epoxy resin curing accelerator (C).

(11) The epoxy resin composition according to (10), wherein the epoxy resin curing accelerator (C) is a metal soap curing accelerator.

(12) A cured product obtained by curing the epoxy resin composition described in any one of (1) to (11).

(13) A resin composition for encapsulating an optical semiconductor, comprising the epoxy resin composition according to any one of (1) to (11).

(14) An optical semiconductor device obtained by sealing an optical semiconductor element with the resin composition for optical semiconductor sealing described in (13).

Invention effect

According to the present invention, a curable resin composition containing a cyclic siloxane compound having a specific structure having two or more epoxy groups in a molecule, an epoxy resin curing agent, and an optional curing accelerator can provide a highly transparent It is a cured product, and has excellent sulfuration resistance, illuminance retention during reflow soldering, and illuminance retention during long-term lighting, so it is extremely useful as a material requiring high transparency, especially as a sealing resin for optical semiconductors (LEDs, etc.) of.

detailed description

The curable resin composition of the present invention is characterized by containing a cyclic siloxane compound (A) having two or more epoxy groups in a molecule and an epoxy resin curing agent (B).

The cyclic siloxane compound (A) which has two or more epoxy groups in a molecule|numerator in this invention is a compound represented by following formula (1).

In formula (1), R ¹ represents a hydrocarbon group having 1 to 6 carbon atoms, X represents an epoxy group-containing organic group or a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3. A plurality of R ¹ and X present in the formula may be the same or different. Among the plurality of Xs present, at least two are epoxy group-containing organic groups.

Specific examples ^of R include methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl. From the viewpoint of heat-resistant transparency of the cured product, methyl and phenyl are preferred. From the viewpoint of ease of production, a methyl group is particularly preferred.

The organic group in X represents a compound containing C, H, N, and O atoms. Specific examples of organic groups containing epoxy groups include 2,3-epoxycyclohexylethyl, 3-epoxypropylene The oxypropyl group is preferably a 2,3-epoxycyclohexylethyl group from the viewpoint of heat-resistant transparency of a cured product. Here, the number of carbon atoms in the organic group is preferably 1-20, more preferably 3-15. In addition, a group in which a 2,3-epoxycyclohexylethyl group or a 3-glycidoxypropyl group was added via an alkylene group having 1 to 5 carbon atoms is preferred.

Specific examples of the hydrocarbon group having 1 to 6 carbon atoms in X include methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl, and from the viewpoint of heat-resistant transparency of the cured product, Methyl and phenyl are preferred, and methyl is particularly preferred from the viewpoint of ease of production.

Among the plurality of Xs present in the molecule, at least two are epoxy group-containing organic groups, and in the X of the compound represented by formula (1), an average of 90 mol% or more are epoxy group-containing organic groups When , the illuminance retention rate during long-term lighting is more excellent, so it is preferable, and it is particularly preferably 96 mol % or more.

From the viewpoint of the ease of production of the compound, n is preferably 2.

The cyclic siloxane compound (A) having two or more epoxy groups in the molecule represented by the formula (1) can pass through the hydrosilane compound of the cyclic hydrogen siloxane compound and the alkene compound having the epoxy group in the molecule. obtained by chemical reaction.

Specific examples of cyclic hydrogen siloxane compounds include: trimethylcyclotrisiloxane, triphenylcyclotrisiloxane, tetramethylcyclotetrasiloxane, tetraphenylcyclotetrasiloxane , pentamethylcyclopentasiloxane, pentaphenylcyclopentasiloxane, etc., and tetramethylcyclotetrasiloxane is preferable from the viewpoint of ease of manufacture.

Examples of olefin compounds having an epoxy group in the molecule include: 4-vinyl-1,2-epoxycyclohexane, 3-glycidoxy-1-propylene, etc., from the heat-resistant transparency of the cured product From the viewpoint of 4-vinyl-1,2-epoxycyclohexane is preferable.

For the hydrosilylation reaction, known metal complexes such as rhodium, palladium, and platinum can be used as catalysts. Specifically, tris(triphenylphosphine)rhodium chloride, hexachloroplatinic acid hexahydrate, divinyltetramethyldisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane Platinum complexes, dichlorobis(triphenylphosphine)platinum complexes, tetrakis(triphenylphosphine)platinum complexes, etc., FibreCat (trademark) 4001, FibreCat4003 (both manufactured by Wako Pure Chemical Industries, Ltd.), etc. , a commercially available platinum catalyst fixed on a solvent-insoluble carrier such as polyethylene, from the transparency of the obtained cyclic siloxane compound (A) having two or more epoxy groups in the molecule, the transparency of the cured product From the viewpoint of properties, hexachloroplatinic acid hexahydrate, divinyltetramethyldisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane platinum complex, dichlorobis( Triphenylphosphine) platinum complex, FibreCat4003.

From the viewpoint of workability, the catalyst used in the hydrosilylation reaction is preferably dissolved in a solvent and used as a solution. Usable solvents can be used as long as they dissolve the catalyst, and tetrahydrofuran and toluene are preferable from the viewpoint of solubility and handleability.

In the case of using as a solution, the catalyst may be added to the reaction liquid after being adjusted to 0.05 to 50% by weight.

When using a catalyst fixed to polyethylene or the like, it can be directly added to the reaction liquid.

The amount of the catalyst added is usually preferably added in the range of 0.1 ppm to 1000 ppm of the reaction substrate in terms of the amount of metal used in the catalyst. From the viewpoint of the transparency of the obtained cyclic siloxane compound (A) having two or more epoxy groups in the molecule and the transparency of its cured product, it is more preferably 1 ppm to 100 ppm, particularly preferably 2 ppm to 20ppm. When the added amount is less than 0.1 ppm, the addition reaction may slow down, and when the added amount exceeds 1000 ppm, the coloring of the silicone-modified epoxy resin may become severe.

After the hydrosilylation reaction, known methods such as washing with water, distillation, recrystallization, column chromatography, and adsorption (activated carbon, various minerals) can be used for purification.

The solvent used in the reaction and/or purification can be removed by distillation under reduced pressure or the like.

The epoxy equivalent (measured by the method described in JIS K7236) of the cyclic siloxane compound (A) having two or more epoxy groups in the molecule is preferably 180 to 400 g/eq, particularly preferably 190 to 250 g/eq.

The viscosity at 25°C of the cyclic siloxane compound (A) having two or more epoxy groups in the molecule is preferably 1,500 to 10,000 mPa·s, more preferably 2,000 to 8,000 mPa·s, and particularly preferably 3,000 to 7,000 mPa·s. s.

Specific examples of the cyclic siloxane compound (A) represented by formula (1) having two or more epoxy groups in the molecule are compounds represented by the following formulas (1-1) to (1-6).

In the epoxy resin composition of the present invention, epoxy resins other than the above-mentioned cyclic siloxane compound (A) having two or more epoxy groups in the molecule can be mixed and used.

Other epoxy resins that can be used include: epoxy resins that are glycidyl etherified products of phenolic compounds, epoxy resins that are glycidyl etherified products of various novolak resins, alicyclic epoxy resins, fatty Epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, epoxy resins with epoxy groups Copolymers of polymerizable unsaturated compounds and other polymerizable unsaturated compounds, condensates of silicon compounds having epoxy groups and other silicon compounds, silicone-modified epoxy resins, and the like.

Examples of epoxy resins that are glycidyl etherified phenolic compounds include: 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1 -bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-diphenol, tetra Methyl bisphenol A, Dimethyl bisphenol A, Tetramethyl bisphenol F, Dimethyl bisphenol F, Tetramethyl bisphenol S, Dimethyl bisphenol S, Tetramethyl-4,4'- Biphenol, Dimethyl-4,4'-biphenol, 1-(4-hydroxyphenyl)-2-[4-(1,1-bis(4-hydroxyphenyl)ethyl) Phenyl]propane, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), Trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, phenols having a diisopropylidene skeleton, 1,1-bis(4-hydroxyphenyl)fluorene Epoxy resins such as phenols having a fluorene skeleton, glycidyl etherified polyphenol compounds such as phenolized polybutadiene, etc.

Examples of epoxy resins that are glycidyl etherified products of various novolak resins include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F and bisphenols such as bisphenol S, novolac resins made of various phenols such as naphthols, phenol novolac resins containing a xylylene skeleton, phenol novolac resins containing a dicyclopentadiene skeleton, Glycidyl etherified products of various novolac resins such as biphenyl skeleton-containing phenol novolac resins and fluorene skeleton-containing phenol novolac resins.

Examples of the alicyclic epoxy resin include: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate Alicyclic epoxy resins having an aliphatic ring skeleton.

As said aliphatic epoxy resin, the epoxy resin containing glycidyl ether of polyalcohol, such as 1, 4- butanediol, 1, 6- hexanediol, polyethylene glycol, pentaerythritol, is mentioned, for example.

As said heterocyclic epoxy resin, the heterocyclic epoxy resin which has a heterocycle, such as an isocyanuric acid ring and a hydantoin ring, is mentioned, for example.

As said glycidyl ester type epoxy resin, the epoxy resin containing carboxylic acid esters, such as hexahydrophthalate diglycidyl ester, is mentioned, for example.

As said glycidylamine epoxy resin, the epoxy resin obtained by glycidylating amines, such as aniline and toluidine, is mentioned, for example.

Examples of epoxy resins obtained by glycidylating halogenated phenols include, for example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated methyl Epoxy resin obtained by glycidylation of halogenated phenols such as phenol novolac, chlorinated bisphenol S, and chlorinated bisphenol A.

As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, commercially available products include: MARPROOF (trade name) G-0115S, MARPROOF ( Brand name) G-0130S, MARPROOF (brand name) G-0250S, MARPROOF (brand name) G-1010S, MARPROOF (brand name) G-0150M, MARPROOF (brand name) G-2050M (manufactured by NOF Corporation), etc. , As the polymerizable unsaturated compound having an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, and the like can be cited. In addition, examples of copolymers of other polymerizable unsaturated compounds include methyl (meth)acrylate, ether (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, Styrene, vinylcyclohexane, etc.

The condensate of the above-mentioned silicon compound having an epoxy group and other silicon compounds is, for example: a hydrolytic condensate of an alkoxysilane compound having an epoxy group and an alkoxysilane compound having a methyl group or a phenyl group; Oxygen alkoxysilane compound and polydimethylsiloxane with silanol group, polydimethyldiphenylsiloxane with silanol group, polyphenylsiloxane with silanol group a condensate; or a condensed compound obtained by using them in combination. Examples of alkoxysilane compounds having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, Ethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like. Examples of alkoxysilane compounds having a methyl group or a phenyl group include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyl Dimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, etc. Examples of the polydimethylsiloxane having a silanol group and the polydimethyldiphenylsiloxane having a silanol group include: X-21-5841, KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.); BY16-873, PRX413 (manufactured by Toray Dow Corning Co., Ltd.); XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive High-Tech Materials Japan Co., Ltd.); DMS-S12 , DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, PDS-0338, PDS-1615 (manufactured by Gelest), etc.

Organosilicon-modified epoxy resin refers to a compound having two or more epoxy groups in the molecule and having an organosilicon (Si-O) bond as the main skeleton, for example, hydrogen siloxane represented by the following formula (13) It can be obtained by the hydrosilylation reaction of alkanes with 4-vinyl-1,2-epoxycyclohexane or 3-glycidoxy-1 propene.

In the formula (13), R ¹ represents the same meaning as the above-mentioned formula (1), and s is an average value, representing 1-100.

The above epoxy resins may be used alone or in combination of two or more.

Among the above-mentioned epoxy resins, from the viewpoint of transparency, heat-resistant transparency, and light-resistant transparency, it is preferable to use together alicyclic epoxy resins, condensates of silicon compounds having epoxy groups and other silicon compounds, Silicone modified epoxy resin. Among them, compounds having an epoxycyclohexane structure in the skeleton are preferable.

When the cyclic silicone compound (A) having two or more epoxy groups in the molecule is used in combination with other epoxy resins, the cyclic silicone compound (A) having two or more epoxy groups in the molecule The ratio of the oxane compound (A) is preferably 30 to 99 parts by weight, particularly preferably 60 to 97 parts by weight. When it is less than 30 parts by weight, there is a possibility that the illuminance retention rate at the time of the vulcanization resistance test and the crack resistance at the time of reflow soldering may deteriorate.

In the epoxy resin composition of the present invention, the compounding ratio of the entire epoxy resin containing the cyclic siloxane compound (A) having two or more epoxy groups in the molecule to the epoxy resin curing agent (B) , It is preferable to use 0.5-1.2 equivalents of curing agent with respect to 1 equivalent of epoxy groups of all epoxy resins. When less than 0.5 equivalents or more than 1.2 equivalents are used with respect to 1 equivalent of epoxy groups, there is a possibility that curing may not be complete and good cured properties may not be obtained.

Next, the epoxy resin curing agent (B) will be described. The epoxy resin curing agent (B) is a curing agent that cures the epoxy resin, for example: amine curing agent, phenol curing agent, acid anhydride curing agent, polycarboxylic acid resin, polycarboxylic acid curing agent, wherein Preferable are acid anhydride curing agents, polycarboxylic acid resins, and polycarboxylic acid curing agents. Examples of acid anhydride curing agents include: phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methyl Hexahydrophthalic anhydride, mixture of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic acid anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, 2,4-diethylglutaric anhydride, etc. Among these, hexahydrophthalic anhydride is preferred Formic anhydride and its derivatives.

Next, the polyvalent carboxylic acid resin will be described.

The polycarboxylic acid resin is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton. In the present invention, the polycarboxylic acid resin not only includes the polycarboxylic acid compound with a single structure, but also includes the mixture of multiple compounds with different positions or different substituents, that is, the polycarboxylic acid composition. In the present invention, These are collectively referred to as polyvalent carboxylic acid resins.

As the polycarboxylic acid resin, a difunctional to hexafunctional carboxylic acid is particularly preferred, and it is more preferred to use (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule and (b) a compound containing one or more acid anhydride groups in the molecule. The compound obtained by the reaction. Here, the reaction product of (a) and (b) above may be further reacted with another alcohol compound, or two or more compounds corresponding to the (a) or (b) component may be used.

(a) The polyol compound having two or more hydroxyl groups in the molecule is not particularly limited as long as it has two or more alcoholic hydroxyl groups in the molecule, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1, 3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentane Diol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol, norbornenediol, 2,2'-bis(4-hydroxycyclohexyl) Propane, 2-(1,1-dimethyl-2-hydroxyethyl)-5-ethyl-5-hydroxymethyl-1,3-di Alkanes and other diols, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol and other triols, pentaerythritol, ditrihydroxy Tetraols such as methylpropane, hexaols such as dipentaerythritol, etc., alcohol-terminated polyesters, alcohol-terminated polycarbonates, alcohol-terminated polyethers, polyols with a siloxane structure, trihydroxyethyl isocyanurate, iso Polyol compounds having an isocyanuric acid ring structure, such as trihydroxypropyl cyanurate, etc.

Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1 ,2-Cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol, norbornene Enediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 2-(1,1-dimethyl-2-hydroxyethyl)-5-ethyl-5-hydroxymethyl-1, 3-two Among them, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, Tricyclodecanedimethanol, norbornenediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 2-(1,1-dimethyl-2-hydroxyethyl)-5-ethyl -5-Hydroxymethyl-1,3-di Alcohols with branched or cyclic structures such as alkanes and other compounds. From the viewpoint of imparting high sulfur resistance, 2,4-diethylpentanediol, tricyclodecane dimethanol, 2,2'-bis(4-hydroxycyclohexyl)propane, 2-(1, 1-Dimethyl-2-hydroxyethyl)-5-ethyl-5-hydroxymethyl-1,3-di Alkanes and other compounds. Among them, especially in the branched structure, it is preferable to have two or more branches, and it is particularly preferable that the branches extend from different carbon atoms. Here, the alcohols having a branched chain structure or a cyclic structure preferably have 5 to 25 carbon atoms, particularly preferably 5 to 20 carbon atoms.

In addition, from the viewpoint of heat-resistant transparency, gas barrier properties, and mechanical strength of the cured product, those having an isocyanuric acid ring structure such as trishydroxyethyl isocyanurate and trishydroxypropyl isocyanurate are preferable. polyol compound.

The polyhydric alcohol which has a siloxane structure is not specifically limited, For example, the silicone oil represented by following formula (7) can be used.

(In formula (7), A ₁ represents the total number of carbon atoms that can be interrupted by ether bonds 1 to 10 alkylene groups, A ₂ represents methyl or phenyl. In addition, n is the number of repetitions, referring to the average value, which is 1 to 10 100.)

The above (a) polyol compound having two or more hydroxyl groups in its molecule may be used alone or in combination of two or more.

In order to use the obtained polyvalent carboxylic acid resin in a liquid state to impart high vulcanization resistance, it is preferable to mix the above-mentioned polyhydric alcohol having a siloxane structure with an alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms. Classes are mixed.

When a polyhydric alcohol having a siloxane structure is used in combination with alcohols having a branched chain structure or a cyclic structure with 5 to 25 carbon atoms, the amount used is the same as that of all alcohol compounds (having a siloxane structure) polyhydric alcohol)/(alcohols having a branched chain structure or cyclic structure with 5 to 25 carbon atoms) is preferably 1 to 20, from the heat-resistant transparency of the cured product and the appropriate viscosity of the polycarboxylic acid resin From a viewpoint, 5-15 are preferable, and 6-10 are especially preferable.

As (b) compounds containing one or more acid anhydride groups in the molecule, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, and methyl hexahydrophthalic anhydride are particularly preferred. Phthalic 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, glutaric anhydride, 2,4-diethylglutaric anhydride, succinic anhydride, etc. Among them, methylhexahydrophthalic anhydride, cyclohexane Alkane-1,3,4-tricarboxylic acid-3,4-anhydride, 2,4-diethylglutaric anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride , Cyclopentane tetracarboxylic dianhydride. Here, in order to increase the hardness, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferred, in order to increase the illuminance retention rate, methyl hexahydrophthalic anhydride is preferred, and in order to suppress the polycarboxylic acid resin The viscosity is too high, preferably 2,4-diethyl glutaric anhydride, glutaric anhydride.

The conditions for the addition reaction are not particularly specified, and the following methods can be cited: As one of the specific reaction conditions, an acid anhydride and a polyhydric alcohol are reacted at 40° C. to 150° C. Heating, after the reaction is over, take it out directly. However, it is not limited to these reaction conditions.

Next, the polyvalent carboxylic acid curing agent will be described.

As the polyvalent carboxylic acid, a compound represented by the following formula (2) is particularly preferable.

(In the formula (2), a plurality of Qs that exist represent at least one of a hydrogen atom, a methyl group, and a carboxyl group. P is derived from a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule with 2 to 20 carbon atoms. An aliphatic group containing a chain and/or a ring structure. m is an integer of 2 to 4.)

Among the compounds represented by the formula (2), dicarboxylic acid compounds represented by the following formulas (3) to (6) are particularly preferable from the viewpoint of the transparency of the cured product and high sulfuration resistance.

Moreover, the compound represented by following formula (8) is also especially preferable as polyhydric carboxylic acid resin.

(In the formula (8), P and m represent the same meaning as the above-mentioned formula (2), and R ² is a hydrogen atom or an ethyl group.)

Among the compounds represented by the formula (8), especially the dicarboxylic acid compounds represented by the following formulas (9) to (12) are excellent in transparency, high vulcanization resistance, low viscosity and workability of the cured product. Therefore preferred.

(In the formulas (9) to (12), R ² represents the same meaning as the above-mentioned formula (8).)

The compounding amount of the epoxy resin curing agent (B) is preferably a functional group reactive with the epoxy group (in the case of an acid anhydride curing agent, -CO-O-CO - represents an acid anhydride group) in an amount of 0.3 to 1.0 mol, more preferably in an amount of 0.4 to 0.8 mol. When the functional group reactive with the epoxy group is 0.3 mole or more, the heat resistance and transparency of the cured product are further improved. Therefore, it is preferable that the mechanical properties of the cured product be improved when the functional group reactive with the epoxy group is 1.0 mole or less. Further improvement is therefore preferred. Here, the "functional group reactive with epoxy groups" refers to the amino groups of amine curing agents, the phenolic hydroxyl groups of phenol curing agents, the acid anhydride groups of acid anhydride curing agents, polycarboxylic acid resins or The carboxyl group possessed by the polycarboxylic acid curing agent.

Next, the epoxy resin hardening accelerator (C) is demonstrated.

As the epoxy resin curing accelerator (C), there is a combination of the epoxy resin curing agent ( All curing accelerators capable of the curing reaction of B) can be used, and examples of the curing accelerator (C) that can be used include: ammonium salt-based curing accelerators, Salt curing accelerators, metal soap curing accelerators, imidazole curing accelerators, amine curing accelerators, phosphine curing accelerators, phosphite curing accelerators, Lewis acid curing accelerators, etc.

In the epoxy resin composition of this invention, it is preferable to use 0.001-15 weight part of hardening accelerators with respect to 100 weight part of epoxy resin compositions with respect to the compounding ratio of an epoxy resin hardening accelerator (C).

In the epoxy resin composition of the present invention, specific examples of the epoxy resin curing accelerator (C) that can be used include: 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole , 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6-(2'-methylimidazole ( 1')) ethyl-s-triazine, 2,4-diamino-6-(2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6- (2'-Ethyl, 4-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6-(2'-methylimidazole (1')) ethyl-s-triazine Azine·isocyanuric acid adducts, 2:3 adducts of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adducts, 2-phenyl-3,5-di Hydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Various imidazoles class, and these imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid and other polycarboxylic acid salts, bis Amides such as cyanamide, diaza compounds such as 1,8-diazabicyclo[5.4.0]undecene-7 and their salts such as tetraphenyl borate and novolak, and the above-mentioned polycarboxylic Salts of acids or phosphonic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri(cresyl) Phosphine, tetraphenyl bromide tetraphenyl borate other phosphines or Compounds, phenols such as 2,4,6-tris(aminomethyl)phenol, amine adducts, metal compounds such as tin octoate, etc., and microcapsule-type curing accelerators in which these curing accelerators are microcapsulated. Which of these curing accelerators to use is appropriately selected depending on properties required for a transparent resin composition to be obtained, such as transparency, curing speed, and operating conditions.

Among these, metal soap curing accelerators are excellent from the viewpoint of transparency and sulfidation resistance of cured products, and zinc carboxylate compounds are particularly preferable among metal soap curing accelerators.

Examples of metal soap curing accelerators include tin octoate, cobalt octoate, zinc octoate, manganese octoate, calcium octoate, sodium octoate, potassium octoate, calcium stearate, zinc stearate, magnesium stearate, stearate Aluminum stearate, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, 12-hydroxy Aluminum stearate, barium 12-hydroxystearate, lithium 12-hydroxystearate, sodium 12-hydroxystearate, calcium montanate, zinc montanate, magnesium montanate, aluminum montanate, lithium montanate, lignite sodium behenate, calcium behenate, zinc behenate, magnesium behenate, lithium behenate, sodium behenate, silver behenate, calcium laurate, zinc laurate, barium laurate, lithium laurate, Zinc monoenoate, zinc ricinoleate, barium ricinoleate, zinc myristate, zinc palmitate, etc. These catalysts may be used alone or in combination of two or more.

Zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, and zinc myristate can be used particularly preferably in order to obtain a cured product with excellent transparency and sulfuration resistance. Zinc salts of monocarboxylic acid compounds having 10 to 30 carbon atoms containing a hydroxyl group, such as zinc carboxylates having 10 to 30 carbon atoms such as zinc palmitate, and zinc 12-hydroxystearate. Among these, zinc stearate, zinc undecylenate and other zinc salts containing monocarboxylic acid compounds having 10 to 20 carbon atoms, 12- Zinc salts of monocarboxylic acid compounds containing 15 to 20 carbon atoms having hydroxyl groups such as zinc hydroxystearate, etc. Zinc stearate, zinc undecylenate, and zinc 12-hydroxystearate can be used more preferably, especially zinc stearate Zinc stearate, zinc 12-hydroxystearate can be used.

As the ammonium salt-based curing accelerator, for example: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylammonium hydroxide, Propyl Ammonium Hydroxide, Trimethyl Butyl Ammonium Hydroxide, Trimethyl Cetyl Ammonium Hydroxide, Trioctyl Methyl Ammonium Hydroxide, Tetramethyl Ammonium Chloride, Tetramethyl Ammonium Bromide, Tetramethyl Ammonium Hydroxide Ammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, etc. as Salt curing accelerators, for example: ethyl triphenyl bromide tetraphenyl borate methyl tributyl Dimethyl Phosphate Salt, Methyl Tributyl Diethyl phosphate salt, etc.

In other general uses, in addition to the above-mentioned ammonium salt curing accelerators, In addition to salt-based curing accelerators and metal soap-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, heterocyclic compound-based curing accelerators, phosphine-based curing accelerators, and phosphite-based curing accelerators can also be used , Lewis acid curing accelerator, etc.

As the above-mentioned epoxy resin curing accelerator (C), a compound that is solid at room temperature (25° C.) or a compound that is liquid at room temperature (25° C.) may be used. When using the epoxy resin composition of this invention for optical-semiconductor sealing use, when using the compound which is solid at room temperature (25 degreeC) as a hardening accelerator, you may melt|dissolve and use it in resin beforehand.

In the epoxy resin composition of the present invention, the viscosity of the composition can be adjusted and the hardness of the cured product can be enhanced by using a coupling agent as needed.

As a coupling agent that can be used, for example: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Propylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane , N-(2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyl Silane coupling agents such as dimethoxysilane and 3-chloropropyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearyl titanate , Di(dioctyl pyrophosphate) titanium oxyacetate, tetraisopropyl bis(dioctyl phosphite) titanate, neoalkoxy tris(p-N-(β-aminoethyl)aminobenzene Base) titanium coupling agents such as titanate; zirconium acetylacetonate, zirconium methacrylate, zirconium propionate, neoalkoxy zirconate, neoalkoxy trineodecanoyl zirconate, neoalkoxy tri (Lauryl)benzenesulfonyl zirconate, neoalkoxytris(ethylenediaminoethyl)zirconate, neoalkoxytris(m-aminophenyl)zirconate, ammonium zirconium carbonate, acetyl Aluminum acetone, aluminum methacrylate, aluminum propionate and other zirconium coupling agents or aluminum coupling agents, etc.

These coupling agents can be used alone or in combination of two or more.

A coupling agent is contained in the epoxy resin composition of this invention normally 0.05-20 weight part, Preferably it contains 0.1-10 weight part in the epoxy resin composition of this invention.

In the epoxy resin composition of the present invention, if necessary, an inorganic filler at a nanoscale level can be used to enhance mechanical strength and the like without hindering transparency. Based on the nanoscale level, it is preferable to use a filler having an average particle diameter of 500 nm or less, particularly an average particle diameter of 200 nm or less, from the viewpoint of transparency. Examples of inorganic fillers include: crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, bulk Powders of talc, spinel, titanium dioxide, talc, etc., or beads obtained by spheroidizing them, are not limited to these inorganic fillers. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is preferably used in an amount of 0 to 95% by weight in the epoxy resin composition of the present invention.

A phosphor can be added to the epoxy resin composition of this invention as needed. The phosphor has, for example, the role of absorbing part of the blue light emitted from the blue LED element and emitting yellow light after wavelength conversion, thereby forming white light. After dispersing the phosphor in the curable resin composition in advance, the optical semiconductor is sealed. The phosphor is not particularly limited, and conventionally known phosphors can be used, and examples thereof include aluminates, thiogallates, and orthosilicates of rare earth elements. More specifically, phosphors such as YAG phosphors, TAG phosphors, orthosilicate phosphors, thiogallate phosphors, and sulfide phosphors, YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu)O·Al ₂ O ₃ and the like. As the particle diameter of the phosphor, phosphors having a particle diameter known in this field can be used, but the average particle diameter is preferably 1 μm to 250 μm, particularly preferably 2 μm to 50 μm. When using these phosphors, the amount added is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.

For the purpose of preventing various phosphors from settling when they are cured, an activator represented by silica micropowder (also known as Aerosil (trade name) or aerosol (Aerosol)) can be added to the epoxy resin composition of the present invention. Denaturing agent.作为这样的二氧化硅微粉，可以列举例如：Aerosil(商品名)50、Aerosil90、Aerosil130、Aerosil200、Aerosil300、Aerosil380、AerosilOX50、AerosilTT600、AerosilR972、AerosilR974、AerosilR202、AerosilR812、AerosilR812S、AerosilR805、RY200、RX200(日本Aerosil Corporation), etc.

For the purpose of preventing coloration, the epoxy resin composition of the present invention may contain an amine compound as a light stabilizer, or a phosphorus-containing compound and a phenolic compound as an antioxidant.

Examples of the above-mentioned amine compounds include tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate, 1,2,3 , 4-butane tetracarboxylate (2,2,6,6-tetramethyl-4-piperidinyl) ester, 1,2,3,4-butane tetracarboxylate and 1,2,2,6, 6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane Mixed esters of sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-undecyloxy-2,2,6, 6-tetramethylpiperidin-4-yl) ester, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, sebacic acid bis(2,2,6,6-tetra Methyl-4-piperidinyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2, 6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylmethacrylic acid -4-piperidinyl ester, [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonic acid bis(1,2,2,6 ,6-pentamethyl-4-piperidinyl) ester, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) sebacate, 1, The reaction product of 1-dimethylethylhydroperoxide and octane, N,N',N",N"'-tetrakis(4,6-bis(butyl-(N-methyl-2,2, 6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5 -Triazine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6, Polycondensate of 6-tetramethyl-4-piperidinyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2 ,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl) Pyridyl)imino]], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl -20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazadispiro[5.1.11.2]eicosan-21-one, β-alanine, N -(2,2,6,6-Tetramethyl-4-piperidinyl)-dodecyl/tetradecyl ester, N-acetyl-3-dodecyl-1-(2, 2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20 -diazabispiro[5.1.11.2]eicodecan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo[5.1.11.2 ]dodecyl/tetradecyl propionate, malonic acid, [(4-methoxyphenyl)methylene]-bis(1,2,2,6 ,6-pentamethyl-4-piperidinyl) ester, higher fatty acid esters of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-phthalamide, N,N Hindered amine compounds such as '-bis(2,2,6,6-tetramethyl-4-piperidinyl), benzophenone compounds such as octylphenone, 2-(2H-benzotriazole-2 -yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3 -(3,4,5,6-Tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, 2-(3-tert-butyl-2-hydroxy-5 -Methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 3-(3-(2H-benzotriazole -2-yl)-5-tert-butyl-4-hydroxyphenyl)propionic acid methyl ester and polyethylene glycol reaction product, 2-(2H-benzotriazol-2-yl)-6-dodeca Benzotriazole compounds such as alkyl-4-methylphenol, benzoate compounds such as 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2- Triazine compounds such as (4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol are particularly preferably hindered amine compounds.

As an amine compound of the said light stabilizer, the following commercial item can be used.

The commercially available amine compound is not particularly limited, and examples thereof include TINUVIN (trade name) 765 manufactured by Ciba Specialty Chemicals, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB (trade name) 944, manufactured by ADEKA LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87, etc.

The phosphorus-containing compound is not particularly limited, and examples thereof include 1,1,3-tris(2-methyl-4-bis(tridecyl)phosphite-5-tert-butylphenyl)butyl alkane, pentaerythritol diphosphite distearyl, pentaerythritol diphosphite bis(2,4-di-tert-butylphenyl) ester, pentaerythritol diphosphite bis(2,6-di-tert-butyl-4- Methylphenyl) ester, phenyl bisphenol A pentaerythritol diphosphite, pentaerythritol diphosphite dicyclohexyl, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite ) ester, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, Tris(2,6-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl) Phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylene Bis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-ethylenebis(4-methyl-6 -tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 4,4'-biphenylene diphosphonite tetrakis(2,4-di-tert-butylphenyl) ) ester, 4,3'-biphenylene diphosphonite tetrakis(2,4-di-tert-butylphenyl) ester, 3,3'-biphenylene diphosphonite tetrakis(2,4- Di-tert-butylphenyl) ester, 4,4'-biphenylene diphosphonite tetrakis (2,6-di-tert-butylphenyl) ester, 4,3'-biphenylene diphosphonite Tetrakis(2,6-di-tert-butylphenyl) ester, 3,3'-biphenylene diphosphonite tetrakis(2,6-di-tert-butylphenyl) ester, 4-phenylphenylene Bis(2,4-di-tert-butylphenyl) phosphonate, bis(2,4-di-tert-butylphenyl) 3-phenylphenylphosphonite, 3-phenylphenylphosphonite Bis(2,6-di-n-butylphenyl) ester, 4-phenyl-phenylphosphonite bis(2,6-di-tert-butylphenyl)ester, 3-phenylphenylphosphonite bis (2,6-di-tert-butylphenyl) ester, 4,4'-biphenylene diphosphonite tetrakis (2,4-di-tert-butyl-5-methylphenyl) ester, tributyl phosphate Ester, Trimethyl Phosphate, Tricresyl Phosphate, Triphenyl Phosphate, Trichlorophenyl Phosphate, Triethyl Phosphate, Diphenyl Cresyl Phosphate, Diphenyl Mono-o-biphenyl Phosphate, Tributoxy Phosphate Ethyl ester, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc.

A commercial item can also be used for the said phosphorus-containing compound. The commercially available phosphorus-containing compound is not particularly limited, and examples thereof include ADKSTAB (trade name) PEP-4C, ADKSTABPEP-8, ADKSTABPEP-24G, ADKSTABPEP-36, ADKSTABHP-10, ADKSTAB2112, ADKSTAB260, ADKSTAB522A, ADKSTAB1178, ADKSTAB1500, ADKSTABC, ADKSTAB135A, etc.

The above-mentioned phenolic compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n- Octadecyl ester, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-tert-butyl-6-methylphenol , 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, pentaerythritol tetrakis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy ]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[3-(3-tert-butyl-5-methyl base-4-hydroxyphenyl)propionate], 2,2'-butylenebis(4,6-di-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) , 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenol acrylate, 2-[1-(2-hydroxy-3,5 -di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl ester, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4' -Butylene bis(3-methyl-6-tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-amylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), bis[3,3- Bis(4'-hydroxy-3'-tert-butylphenyl)butanoic acid]-ethylene glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-amylphenol, acrylic acid 2-[1 -(2-Hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-amylphenyl ester, bis[3,3-bis(4'-hydroxy-3'-tert Butylphenyl) butyrate] ethylene glycol ester, etc.

A commercial item can also be used for the said phenolic compound. The commercially available phenolic compound is not particularly limited, and examples thereof include IRGANOX (trade name) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, IRGANOX 1520L manufactured by Ciba Specialty Chemicals, Adeka Manufactured ADKSTAB (trade name) AO-20, ADKSTABAO-30, ADKSTABAO-40, ADKSTABAO-50, ADKSTABAO-60, ADKSTABAO-70, ADKSTABAO-80, ADKSTABAO-90, ADKSTABAO-330, Sumilizer manufactured by Sumitomo Chemical Industries (Trade name) GA-80, SumilizerMDP-S, SumilizerBBM-S, SumilizerGM, SumilizerGS(F), SumilizerGP, etc.

In addition to these, additives commercially available as anti-staining agents for resins can be used. Examples include THINUVIN (brand name) 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB (brand name) 2020FDL, and CHIMASSORB 119FL manufactured by Ciba Specialty Chemicals.

It is preferable to contain at least one or more of the above-mentioned phosphorus-containing compounds, amine compounds, and phenolic compounds, and the compounding amount thereof is not particularly limited, but is preferably 0.005 to 5.0 wt. % range.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components at normal temperature or under heating. For example, use extruder, kneader, three-roll machine, universal mixer, planetary mixer, homomixer, homodisperser, bead mill, etc. and so on for filtration treatment, thereby preparing.

The epoxy resin composition of the present invention can be obtained by combining the cyclic siloxane compound (A) (other epoxy resins as required), the epoxy resin curing agent (B) and It is prepared by sufficiently mixing additives such as a curing accelerator (C), an antioxidant, and a light stabilizer as optional components, and can be used as a sealing material. As a mixing method, normal temperature mixing or heating mixing such as a kneader, three-roll machine, universal mixer, planetary mixer, homomixer, homodisperser, bead mill, etc. can be used.

When the thus obtained epoxy resin composition of the present invention is used for encapsulation of optical semiconductors and is further required to be in a liquid state at room temperature (25° C.), the viscosity is preferably 100 to 20,000 mPa·s, More preferably, it is 2,000 to 12,000 mPa·s, and particularly preferably, it is 3,000 to 10,000 mPa·s.

Optical semiconductor elements such as high-brightness white LEDs are usually made of GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN laminated on substrates such as sapphire, spinel, SiC, Si, ZnO, etc. , AlN, InGaN and other semiconductor chips are glued on the lead frame, heat sink, and package. There is also a type in which metal wires such as gold wires are connected for the flow of electric current. In order to protect the semiconductor chip from heat and moisture and to function as a lens, it is sealed with a sealing material such as epoxy resin. The epoxy resin composition of this invention can be used as this sealing material.

As the molding method of the sealing material, it is possible to use: an injection method, in which the sealing material is injected into a template in which the substrate on which the optical semiconductor element is fixed, and then heated and cured to form; a compression molding method, in which the sealing material is injected into the mold in advance. The optical-semiconductor element fixed on the board|substrate is dipped in the said sealing material, heat-cured, and release|releases from a mold; etc.

A dispenser etc. are mentioned as an injecting method.

Heating can use methods such as hot air circulation, infrared rays, and high frequency. The heating conditions are, for example, preferably at 80°C to 230°C for about 1 minute to about 24 hours. For the purpose of reducing internal stress generated during heat curing, for example, pre-cure at 80°C to 120°C for 30 minutes to 5 hours, and then postcure at 120°C to 180°C for 30 minutes to 10 hours.

When using the hardened|cured material obtained by hardening the epoxy resin composition of this invention obtained by this for optical-semiconductor sealing, it is preferable that it is 40-80 by hardness meter A, and it is more preferable that it is 45-75. When the value of the durometer A is less than 40, the operability in the manufacturing process may be reduced due to stickiness (tackiness), and when the value of the durometer A exceeds 80, for example, cracks may occur during thermal cycles of cooling and heating. The reliability of the sealing material deteriorates.

In addition, the glass transition temperature (Tg) of the cured product is measured by DMA (Dynamic Mechanical Analysis), and is preferably 20°C to 60°C, particularly preferably 30°C to 50°C. When the temperature is lower than 20°C, there is a possibility of stickiness (tackiness), and when the temperature is higher than 60°C, for example, cracks may be generated during thermal cycles of cold and heat, which may deteriorate the reliability as a sealing material.

In addition, regarding the transmittance of the cured product, the transmittance at 400 nm is preferably 85% or more, particularly preferably 90% or more, for a cured product plate with a thickness of 0.8 mm. When it is less than 85%, the light extraction efficiency from an optical semiconductor element may fall.

In addition, the tensile elongation of the cured product is preferably 100% or more. If it is less than 100%, cracks may be generated during the reflow process when mounting the LED package, and the reliability as a sealing material may deteriorate.

In this specification, unless otherwise specified, ratios, percentages, parts, etc. are based on weight. In this specification, the expression "X-Y" represents the range from X to Y, and this range includes X and Y.

Example

Hereinafter, the present invention will be described in more detail through synthesis examples and examples. In addition, this invention is not limited to these synthesis examples and Examples. In addition, each physical property value in the synthesis example and the Example was measured by the following method. Here, parts represent parts by weight unless otherwise specified.

○Weight average molecular weight: The weight average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method under the following conditions was calculated.

Various conditions of GPC

Manufacturer: Shimadzu Corporation

Column: guard column SHODEXGPCLF-GLF-804 (3 pieces)

Flow rate: 1.0ml/min

Column temperature: 40°C

Solvent used: THF (tetrahydrofuran)

Detector: RI (Differential Refractive Index Detector)

○Epoxy equivalent: measured by the method described in JISK7236.

○Acid value: measured by the method described in JISK2501.

(circle) Viscosity: It measured at 25 degreeC using the Toki Sangyo Co., Ltd. E-type viscometer (TV-20).

○ ¹ H-NMR: JNM-ECS400 manufactured by JEOL Ltd. was used for measurement with a deuterated chloroform solvent.

Synthesis Example 1: Production Example of Cyclic Siloxane Compound Having Four Epoxy Groups in the Molecule

Put 33 parts of 4-vinyl-1,2-epoxycyclohexane and 0.03 parts of a tetrahydrofuran solution of 1% hexachloroplatinic acid hexahydrate into a 200 ml four-necked flask made of glass, set a Dairy condenser, and stir Apparatus, thermometer, and immerse the flask in an oil bath. The oil bath was heated and internal temperature was kept at 80 degreeC, 12 parts of 1,3,5,7- tetramethylcyclotetrasiloxanes were dripped there over 1 hour, and it was made to react for 1 hour in this state.

Nitrogen gas was blown into the obtained reaction solution, and at the same time, it was concentrated under reduced pressure at 110°C to remove tetrahydrofuran and excess 4-vinyl-1,2-epoxycyclohexane, thereby obtaining a compound having four epoxy groups in the molecule. 36 parts of cyclic siloxane compound (EP-1). The epoxy equivalent of the obtained compound was 190 g/eq, the viscosity was 2800 mPa·s, and the appearance was a colorless transparent liquid.

Synthesis example 2: Production example of a condensate of a silicon compound having an epoxy group and another silicon compound, that is, a condensate of an alkoxy silicon having an epoxycyclohexyl group and a silanol-terminated silicone oil

In a 2000ml four-neck flask made of glass, drop 394 parts of 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, polydimethyldiphenyl silicone oil (weight average molecular weight 1700, silicon alcohol) of silanol termination Alcohol equivalent 850, silanol-terminated silicone oil with 33% by weight of phenyl content) 475 parts, 4 parts of 5% by weight KOH methanol solution, 36 parts of isopropanol, set Dai's condenser, stirring device, thermometer, and immerse the flask in a water bath. The water bath was heated to keep the internal temperature at 72° C., and reacted for 10 hours.

Then, 656 parts of methanol were added, 173 parts of 50 weight% ion-exchange water methanol solutions were dripped over 60 minutes, and it was made to react at internal temperature 66 degreeC for 10 hours.

Then, after neutralizing by adding 17.5 parts of 5 weight% sodium dihydrogen phosphate aqueous solutions, distillation recovery of methanol was performed at 80 degreeC of water bath temperature. Then, for washing, 780 parts of methyl isobutyl ketone was added, and washing with water was repeated three times. Next, the solvent was removed from the organic layer at 100° C. under reduced pressure to obtain an epoxy group-containing polysiloxane (EP-2 ) 731 copies.

The epoxy equivalent of the obtained compound was 491 g/eq, the weight average molecular weight was 2090, the viscosity was 3328 mPa·s, and the appearance was a colorless transparent liquid.

Synthesis Example 3: Using silicone oil represented by the above formula (7) and a hydrogenated product of bisphenol A as (a) a polyol compound containing two or more hydroxyl groups in the molecule and using methylhexahydrophthalic anhydride as ( b) Production example of polyvalent carboxylic acid resin obtained by compound containing one or more acid anhydride groups in the molecule

X22-160AS (methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in which A1 is _a propoxyethylene group and A2 is a methyl group in the above _formula (7)) was charged into a 1000 ml glass-made flask) 294 Parts, 42 parts of hydrogenated bisphenol A, 164 parts of RIKACID (trade name) MH-T (manufactured by Shin Nippon Chemical Co., Ltd., methyl hexahydrophthalic anhydride), a Dairy condenser, a stirring device, a thermometer, and The flask was immersed in an oil bath. The oil bath was heated to keep the internal temperature at 80°C to 90°C, and reacted for 3 hours. Then, internal temperature was heated up to 100-110 degreeC, it was made to react for 4 hours, and 489 parts of polyvalent carboxylic acid resins (B-1) were obtained. The viscosity of the obtained polyvalent carboxylic acid resin was 19700 mPa·s, and the appearance was a colorless transparent liquid.

Synthesis Example 4: Using silicone oil represented by the above formula (7) and tricyclodecanedimethanol as (a) a polyol compound containing two or more hydroxyl groups in the molecule and methylhexahydrophthalic anhydride as ( b) Production example of polyvalent carboxylic acid resin obtained by compound containing one or more acid anhydride groups in the molecule

X22-160AS (methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in which A1 is _a propoxyethylene group and A2 is a methyl group in the above _formula (7)) 501 was put into a glass-made 2000 ml detachable flask. Parts, 63 parts of tricyclodecane dimethanol, 63 parts of RIKACIDMH-T286 parts, set up a Dairy condenser, a stirring device, a thermometer, and immerse the flask in an oil bath. The oil bath was heated to keep the internal temperature at 40°C to 50°C, and reacted for 4 hours. Then, internal temperature was heated up to 70 to 80 degreeC, it was made to react for 4 hours, and 833 parts of polyvalent carboxylic acid resins (B-2) were obtained. The viscosity of the obtained polyvalent carboxylic acid resin was 8450 mPa·s, the acid value was 111 mgKOH/g, and the appearance was a colorless transparent liquid.

Synthesis Example 5: Using the silicone oil represented by the above formula (7) and di Alkanediol as (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule and a polycarboxylic acid obtained by using methylhexahydrophthalic anhydride as (b) a compound containing one or more acid anhydride groups in the molecule Manufacturing example of resin

X22-160AS (methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in which A1 is _a propoxyethylene group and A2 is a methyl group in the above _formula (7)) was put into a glass-made 1000 ml detachable flask. copies, two 7.9 parts of alkanediol, 3.2 parts of RIKACIDMH-T3, set up a Dairy condenser, a stirring device, a thermometer, and immerse the flask in an oil bath. 98 parts of polyvalent carboxylic acid resins (B-3) were obtained by heating an oil bath, maintaining internal temperature at 70-80 degreeC, and making it react for 4 hours. The viscosity of the obtained polycarboxylic acid resin was 12390 mPa·s, the acid value was 113 mgKOH/g, and the appearance was a colorless transparent liquid.

Synthesis Example 6: Production example of a cyclic siloxane compound having four epoxy groups in the molecule using Fibrecat (trademark) 4003 (manufactured by Wako Pure Chemical Industries, Ltd.) as a platinum-immobilized catalyst as a hydrosilylation catalyst

Put 32.3 parts of 4-vinyl-1,2-epoxycyclohexane, 0.023 parts of Fibrecat4003 (platinum content 3.4% to 4.5%), and 50 parts of toluene into a 200 ml four-necked flask made of glass, and set a Dairy condenser, A stirring device, a thermometer, and the flask were immersed in an oil bath. The oil bath was heated and internal temperature was kept at 80 degreeC, 12 parts of 1,3,5,7- tetramethylcyclotetrasiloxanes were dripped there over 1 hour, and it was made to react in this state for 10 hours. ¹ H-NMR measurement was performed on the reaction solution, and as a result, the proton peak derived from hydrosiloxane disappeared.

Activated carbon (manufactured by Ajinomoto Finetechno Co., Ltd.) was added to the reaction solution, and stirred at room temperature (20°C to 30°C) for 3 hours, then the activated carbon and Fibrecat 4003 were removed by filtration, nitrogen was blown into the obtained filtrate, and at 60°C Concentrate under reduced pressure to remove toluene and excess 4-vinyl-1,2-epoxycyclohexane, thus obtaining a cyclic siloxane compound (EP-3) 36.7 with four epoxy groups in the molecule share. The epoxy equivalent of the obtained compound was 184.3 g/eq, the viscosity was 5601 mPa·s, and the external appearance was a colorless transparent liquid.

Synthesis Example 7: Production Example of a Cyclic Siloxane Compound Having Two or More Epoxy Groups in the Molecule with 91 Mole % of Organic Groups Containing Epoxy Groups in X of Formula (1) and 9 % of Hexyl Groups

Put 29.1 parts of 4-vinyl-1,2-epoxycyclohexane, 2.2 parts of 1-hexene, 0.047 parts of Fibrecat4003 (platinum content 3.4% to 4.5%), and 50 parts of toluene into a 200 ml glass four-necked flask , set up a Dairy condenser, a stirring device, a thermometer, and immerse the flask in an oil bath. Heat the oil bath to keep the internal temperature at 50°C to 58°C, add 12 parts of 1,3,5,7-tetramethylcyclotetrasiloxane dropwise over 1 hour, and react in this state for 10 hours . Then, the internal temperature was raised to 80° C. for further 6 hours of reaction. ¹ H-NMR measurement was performed on the reaction solution, and as a result, the proton peak derived from hydrosiloxane disappeared.

Activated carbon (manufactured by Ajinomoto Finetechno Co., Ltd.) was added to the reaction liquid, stirred at room temperature (20° C. to 30° C.) for 3 hours, then the activated carbon and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the obtained filtrate. Concentrate under reduced pressure at ℃ to remove toluene, excess 4-vinyl-1,2-epoxycyclohexane and 1-hexene, thereby obtaining a cyclic siloxane with two or more epoxy groups in the molecule Compound (EP-4) 35.9 parts. The epoxy equivalent of the obtained compound was 198.6 g/eq, the viscosity was 3799 mPa·s, and the appearance was a colorless transparent liquid. In addition, as a result of ¹ H-NMR analysis, X in formula (1) contained 91 mol% of epoxy group-containing organic groups and 9 mol% of hexyl groups.

Synthesis Example 8: Production Example of a Cyclic Siloxane Compound Having Two or More Epoxy Groups in the Molecule with 81 mol % of Organic Groups Containing Epoxy Groups in X of Formula (1) and 19 % of Hexyl Groups

Put 29.1 parts of 4-vinyl-1,2-epoxycyclohexane, 4.3 parts of 1-hexene, 0.047 parts of Fibrecat4003 (platinum content 3.4% to 4.5%), and 50 parts of toluene into a 200 ml glass four-necked flask , set up a Dairy condenser, a stirring device, a thermometer, and immerse the flask in an oil bath. Heat the oil bath to keep the internal temperature at 50°C to 58°C, add 12 parts of 1,3,5,7-tetramethylcyclotetrasiloxane dropwise over 1 hour, and react in this state for 37 hours . Then, the internal temperature was raised to 80° C. for further 4 hours of reaction. When ¹ H-NMR measurement was performed on the reaction solution, the proton peak derived from the hydrosiloxane disappeared.

Activated carbon (manufactured by Ajinomoto Finetechno Co., Ltd.) was added to the reaction liquid, stirred at room temperature (20° C. to 30° C.) for 3 hours, then the activated carbon and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the obtained filtrate. Concentrate under reduced pressure at ℃ to remove toluene, excess 4-vinyl-1,2-epoxycyclohexane and 1-hexene, thereby obtaining a cyclic siloxane with two or more epoxy groups in the molecule Compound (EP-5) 35.0 parts. The epoxy equivalent of the obtained compound was 213.5 g/eq, the viscosity was 1423 mPa·s, and the external appearance was a colorless transparent liquid. In addition, as a result of ¹ H-NMR analysis, X in formula (1) contained 81 mol% of epoxy group-containing organic groups and 19 mol% of hexyl groups.

Synthesis Example 9: Production Example of a Cyclic Siloxane Compound Having Two or More Epoxy Groups in the Molecule in X of Formula (1) with 76 mol % of Organic Groups Containing Epoxy Groups and 24 % of Hexyl Groups

Put 22.5 parts of 4-vinyl-1,2-epoxycyclohexane, 6.5 parts of 1-hexene, 0.047 parts of Fibrecat4003 (platinum content 3.4% to 4.5%), and 50 parts of toluene into a 200 ml four-necked glass flask , set up a Dairy condenser, a stirring device, a thermometer, and immerse the flask in an oil bath. Heat the oil bath to keep the internal temperature at 50°C to 58°C, add 12 parts of 1,3,5,7-tetramethylcyclotetrasiloxane dropwise over 1 hour, and react in this state for 24 hours . When ¹ H-NMR measurement was performed on the reaction solution, the proton peak derived from the hydrosiloxane disappeared.

Activated carbon (manufactured by Ajinomoto Finetechno Co., Ltd.) was added to the reaction liquid, stirred at room temperature (20° C. to 30° C.) for 3 hours, then the activated carbon and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the obtained filtrate. Concentrate under reduced pressure at ℃ to remove toluene, excess 4-vinyl-1,2-epoxycyclohexane and 1-hexene, thereby obtaining a cyclic siloxane with two or more epoxy groups in the molecule Compound (EP-6) 34.7 parts. The epoxy equivalent of the obtained compound was 229.9 g/eq, the viscosity was 840 mPa·s, and the external appearance was a colorless transparent liquid. In addition, as a result of ¹ H-NMR analysis, in X of the formula (1), the epoxy group-containing organic group was 76 mol%, and the hexyl group was 24 mol%.

Synthesis Example 10: Production Example of Silicone Modified Epoxy Resin

Put 32.3 parts of 4-vinyl-1,2-epoxycyclohexane, 0.023 parts of Fibrecat4003 (platinum content 3.4% to 4.5%), and 50 parts of toluene into a 200 ml four-necked flask made of glass, and set a Dairy condenser, A stirring device, a thermometer, and the flask were immersed in an oil bath. The oil bath was heated and internal temperature was kept at 80° C. to 85° C., 13.4 parts of 1,1,3,3-tetramethyldisiloxane was dripped there over 40 minutes, and it was made to react in this state for 5 hours. When ¹ H-NMR measurement was performed on the reaction solution, the proton peak derived from the hydrosiloxane disappeared.

Activated carbon (manufactured by Ajinomoto Finetechno Co., Ltd.) was added to the reaction liquid, stirred at room temperature (20° C. to 30° C.) for 3 hours, then the activated carbon and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the obtained filtrate. It concentrated under reduced pressure at °C and removed toluene and excess 4-vinyl-1,2-epoxycyclohexane to obtain 36.3 parts of (EP-7) having two epoxy groups in the molecule. The epoxy equivalent of the obtained compound was 193.8 g/eq, the viscosity was 840 mPa·s, and the external appearance was a colorless transparent liquid.

Synthesis Example 11: Production Example of a Condensate of a Silicon Compound Having an Epoxy Group and Other Silicon Compounds, That is, a Condensate of an Alkoxy Silicon Having an Epoxycyclohexyl Group and a Silanol-terminated Silicone Oil

111 parts of 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 100 parts of polydimethyldiphenylsiloxane with a silanol group having a molecular weight of 1700 (measured by GPC), 5 1 part of %KOH methanol solution and 8 parts of isopropanol were put into the reaction vessel, and the temperature was raised to 75°C. After heating up, the reaction was carried out under reflux for 10 hours. After the reaction, 120 parts of methanol was added, and then 48.6 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the reaction was continued for 10 hours under reflux. After completion of the reaction, neutralization was performed with a 5% sodium dihydrogen phosphate aqueous solution, and methanol was recovered by distillation at 80°C. Then, for washing, 174 parts of MIBK was added, and washing with water was repeated three times. Next, 174 parts of epoxy resins (EP-8) were obtained by removing a solvent from an organic phase at 100 degreeC under reduced pressure. The epoxy equivalent of the obtained compound was 411 g/eq, the weight average molecular weight was 3200, the viscosity was 15140 mPa·s, and the external appearance was colorless and transparent.

Synthesis Example 12: Using silicone oil represented by the above formula (7) and 2,2'-bis(4-hydroxycyclohexyl)propane as (a) a polyol compound containing two or more hydroxyl groups in the molecule and using methylhexa Synthesis example of polyvalent carboxylic acid resin obtained as (b) a compound containing one or more acid anhydride groups in the molecule of hydrophthalic anhydride and glutaric anhydride

18.2 g of RIKABINOLHB (2,2'-bis(4-hydroxycyclohexyl)propane, manufactured by Shin Nippon Chemical Co., Ltd.), 20.1 g of glutaric anhydride, and KF-6000 (Shin-Etsu Chemical Co., Ltd. Made by the company, methanol-modified silicone oil at both ends, methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in the above formula ( ₇ ) in which A1 is propoxyethylene, A2 is methyl, and _p is 7.5) 122.7 g , 39.0 g of RIKACI DMH-T (4-methylhexahydrophthalic anhydride, manufactured by Nippon Chemical Co., Ltd.), 200 g of toluene, a Dairy condenser, a stirring device, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated to 130° C., and the reaction was carried out for 8 hours while toluene was refluxed. When the reaction liquid was checked by GPC after completion of the reaction, the peaks of 4-methylhexahydrophthalic anhydride, glutaric anhydride, and 2,2'-bis(4-hydroxycyclohexyl)propane disappeared. Toluene was distilled off from the obtained reaction liquid under reduced pressure to obtain 195 g of polyvalent carboxylic acid resin (B-4). The polycarboxylic acid resin (B-4) had an acid value of 113.4 mgKOH/g, a viscosity of 2780 mPa·s, a polystyrene-equivalent weight average molecular weight of 1264 measured by GPC, and an appearance of a colorless transparent liquid.

Synthesis Example 13: Using silicone oil represented by the above formula (7) and tricyclodecane dimethanol as (a) a polyol compound containing two or more hydroxyl groups in the molecule and 2,4-diethylglutaric anhydride as (b) Production example of polyvalent carboxylic acid resin obtained by compound containing one or more acid anhydride groups in the molecule

X22-160AS (methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in which A1 is _a propoxyethylene group and A2 is a methyl group in the above _formula (7)) 91.8 Parts, 45.7 parts of tricyclodecane dimethanol, 112.5 parts of YH1120 (2,4-diethylglutaric anhydride, manufactured by Mitsubishi Chemical Corporation), a Dairy condenser, a stirring device, and a thermometer were installed, and the flask was immersed in an oil bath middle. The oil bath was heated to keep the internal temperature at 95°C to 105°C, and reacted for 6 hours. Then, internal temperature was heated up to 115 degreeC - 120 degreeC, it was made to react for 7 hours, and 248 parts of polyhydric carboxylic acid resins (B-5) were obtained. The viscosity of the obtained polyvalent carboxylic acid resin was 7219 mPa·s, the acid value was 146 mgKOH/g, and the appearance was a colorless transparent liquid.

Synthesis Example 14: Using silicone oil represented by the above formula (7) and 2,2'-bis(4-hydroxycyclohexyl)propane as (a) a polyol compound containing two or more hydroxyl groups in the molecule and using 2,4 - Production example of polyvalent carboxylic acid resin obtained by diethylglutaric anhydride as (b) a compound containing one or more acid anhydride groups in the molecule

Into a glass-made 1000 ml detachable flask, X22-160AS (methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in which A1 is _a propoxyethylene group and A2 is a methyl group in the above _formula (7)) 397.5 Parts, 149 parts of RIKABINOLHB (manufactured by Nippon Chemical Co., Ltd., 2,2'-bis(4-hydroxycyclohexyl)propane), 353.6 parts of YH1120 (2,4-diethylglutaric anhydride, manufactured by Mitsubishi Chemical Co., Ltd.), set Dairy condenser, stirring device, thermometer, and immerse the flask in an oil bath. The oil bath was heated to keep the internal temperature at 95°C to 105°C, and reacted for 4 hours. Then, internal temperature was heated up to 115 degreeC - 120 degreeC, it was made to react for 18 hours, and 895 parts of polyvalent carboxylic acid resins (B-6) were obtained. The viscosity of the obtained polyvalent carboxylic acid resin was 7859 mPa·s, the acid value was 123 mgKOH/g, and the appearance was a colorless transparent liquid.

Synthesis Example 15: Using silicone oil represented by the above formula (7) and 2,4-diethyl-1,5-pentanediol as (a) a polyol compound containing two or more hydroxyl groups in the molecule and using 2, Production example of polyvalent carboxylic acid resin obtained as (b) a compound containing one or more acid anhydride groups in the molecule of 4-diethylglutaric anhydride

X22-160AS (methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in which A1 is _a propoxyethylene group and A2 is a methyl group in the above _formula (7)) was put into a 500 ml glass-made flask) 36.8 Parts, PD-9 (manufactured by Kyowa Hakka Chemical Co., Ltd., 2,4-diethyl-1,5-pentanediol) 16.0 parts, YH1120 (2,4-diethylglutaric anhydride, manufactured by Mitsubishi Chemical Corporation) 47.2 parts Set up a Dairy condenser, a stirring device, a thermometer, and immerse the flask in an oil bath. The oil bath was heated, internal temperature was heated up to 115 to 120 degreeC, and it was made to react for 8 hours, and obtained 98 parts of polyvalent carboxylic acid resins (B-7). The viscosity of the obtained polyvalent carboxylic acid resin was 1797 mPa·s, the acid value was 155 mgKOH/g, and the appearance was a colorless transparent liquid.

Synthesis Example 16: Using silicone oil represented by the above formula (7) and tricyclodecane dimethanol as (a) a polyol compound containing two or more hydroxyl groups in the molecule and 2,4-diethylglutaric anhydride as (b) Production example of polyvalent carboxylic acid resin obtained by compound containing one or more acid anhydride groups in the molecule

In a 500 ml detachable glass flask, X22-160AS (methanol-terminated silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. in which A1 is _a propoxyethylene group and A2 is a methyl group in the above _formula (7)) 109.9 Parts, 36.6 parts of tricyclodecane dimethanol, 103.5 parts of YH1120 (2,4-diethylglutaric anhydride, manufactured by Mitsubishi Chemical Co., Ltd.), a Dairy condenser, a stirring device, and a thermometer were installed, and the flask was immersed in an oil bath middle. The oil bath was heated to keep the internal temperature at 95°C to 105°C, and reacted for 14 hours. Then, internal temperature was heated up to 115 degreeC - 120 degreeC, it was made to react for 1 hour, and 247 parts of polyhydric carboxylic acid resins (B-8) were obtained. The obtained polycarboxylic acid resin had a viscosity of 3077 mPa·s, an acid value of 136 mgKOH/g, and an appearance of a colorless transparent liquid.

Example 1: The cyclic siloxane compound (EP-1) with four epoxy groups in the molecule obtained in Synthesis Example 1 was used as 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxy ring ERL-4221 (manufactured by Dow Chemical Co., Ltd.) of hexyl methyl ester, polyvalent carboxylic acid resin (B-1) obtained in Synthesis Example 3, and zinc stearate as a curing accelerator were in the following Table 1. The epoxy resin composition of the present invention was obtained by adding to a polypropylene container, mixing, and defoaming for 5 minutes.

Examples 2 to 3: The cyclic siloxane compound (EP-1) having four epoxy groups in the molecule obtained in Synthesis Example 1, and the epoxy resin obtained in Synthesis Example 2 as other epoxy resins (EP-2), ERL-4221 (manufactured by Dow Chemical Co., Ltd.), which is 3,4-epoxycyclohexylcarboxylate 3,4-epoxycyclohexylmethyl ester, polyvalent carboxylic acid resin obtained in Synthesis Example 2 ( B-1), zinc stearate as a curing accelerator was added to a polypropylene container in the amount ratio described in the following Table 1, mixed, and defoamed for 5 minutes, thereby obtaining the epoxy resin composition of the present invention. things.

Example 4: The cyclic siloxane compound (EP-1) with four epoxy groups in the molecule obtained in Synthesis Example 1 was used as 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxy ring ERL-4221 (manufactured by Dow Chemical Co., Ltd.) of hexyl methyl ester, the polyvalent carboxylic acid resin (B-2) obtained in Synthesis Example 4, and zinc stearate as a curing accelerator were expressed in the following Table 1. The epoxy resin composition of the present invention was obtained by adding to a polypropylene container, mixing, and defoaming for 5 minutes.

Examples 5 to 6: The cyclic siloxane compound (EP-1) having four epoxy groups in the molecule obtained in Synthesis Example 1, and the epoxy resin obtained in Synthesis Example 2 as other epoxy resins (EP-2), the polyvalent carboxylic acid resin (B-2) obtained in Synthesis Example 4, and zinc stearate as a curing accelerator were added to a container made of polypropylene in the amount ratio described in the following Table 1, and carried out Mixing and defoaming for 5 minutes gave the epoxy resin composition of the present invention.

Example 7: Except having changed the polyhydric carboxylic acid resin of Example 4 into (B-3) obtained in the synthesis example 5, it carried out similarly to Example 1, and obtained the epoxy resin composition of this invention.

Examples 8 to 9: The epoxy resin composition of the present invention was obtained in the same manner as in Example 1 except that the polyvalent carboxylic acid resin of Examples 5 to 6 was changed to (B-3) obtained in Synthesis Example 5 .

Comparative Example 1: The epoxy resin (EP-2) obtained in Synthesis Example 2, ERL-4221 (Dow Chemical Co., Ltd. system), the polyvalent carboxylic acid resin (B-1) obtained in Synthesis Example 3, and zinc stearate as a curing accelerator were added to a container made of polypropylene in the amount ratio described in the following Table 1, and mixed, 5 minute defoaming, thereby obtaining the epoxy resin composition of the present invention.

Comparative example 2: the epoxy resin (EP-2) that obtains in the synthesis example 2, the multivalent carboxylic acid resin (B-2) that obtains in the synthesis example 4, as the zinc stearate of hardening accelerator in following table 1 The described quantitative ratio was put into a container made of polypropylene, mixed, and defoamed for 5 minutes to obtain the epoxy resin composition of the present invention.

Comparative example 3: the epoxy resin (EP-2) that obtains in the synthesis example 2, the multivalent carboxylic acid resin (B-3) that obtains in the synthesis example 5, the zinc stearate as hardening accelerator in following table 1 The described quantitative ratio was put into a container made of polypropylene, mixed, and defoamed for 5 minutes to obtain the epoxy resin composition of the present invention.

(evaluation test)

The compounding ratio and viscosity of the curable resin compositions for encapsulating optical semiconductors obtained in Examples 1 to 9 and Comparative Examples 1 to 3; the hardness, Tg, transmittance, and tensile elongation of the cured product were used as LED tests. Table 1 shows the results of cracking and sulfidation resistance after the reflow test. The tests in Table 1 were performed as follows.

(1) Viscosity

It measured at 25 degreeC using the Toki Sangyo Co., Ltd. E-type viscometer (TV-20).

(2) Hardness

The durometer A hardness was measured by the method described in JISK7215.

(3) Tg (glass transition temperature)

After the epoxy resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were vacuum degassed for 5 minutes, they were slowly cast into 30 mm × 20 mm on a glass substrate with a cofferdam made of heat-resistant adhesive tape. ×Height 0.8mm. The casting was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a test piece for transmittance with a thickness of 0.8 mm.

The obtained cured product was shaped into a width of 5 mm and a length of 25 mm, and DMA (Dynamic Mechanical Analysis) was measured under the following conditions, and Tg (glass transition temperature) was read.

<DMA measurement conditions>

Manufacturer: Seiko Instruments Co., Ltd.

Model: Viscoelasticity Analyzer EXSTARDMS6100

Measuring temperature: -50℃～150℃

Heating rate: 2°C/min

Frequency: 10Hz

Measurement Mode: Stretch Vibration

Glass transition temperature (Tg) measured by DMA method:

The temperature at the maximum point of the loss coefficient (tanδ = E"/E') represented by the quotient of the storage elastic modulus (E') and the loss elastic modulus (E") when measuring DMA was read.

(4) Cured product transmittance

After the epoxy resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were vacuum degassed for 5 minutes, they were slowly cast into 30 mm × 20 mm on a glass substrate with a cofferdam made of heat-resistant adhesive tape. ×Height 0.8mm. The casting was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a test piece for transmittance with a thickness of 0.8 mm. The light transmittance at 400 nm was measured on the obtained test piece under the following conditions.

<Spectrophotometer Measurement Conditions>

Manufacturer: Hitachi High-Tech Co., Ltd.

Model: U-3300

Slit width: 2.0nm

Scanning speed: 120nm/min

(5) Tensile elongation

The epoxy resin compositions for encapsulating optical semiconductors obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to vacuum defoaming for 5 minutes, and then slowly cast on a glass substrate with banks formed by heat-resistant tape. Into 50mm × 30mm × height 0.8mm. The casting was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a test piece having a thickness of 0.8 mm. The obtained test piece was processed into a width of 5 mm and a length of 50 mm, and for each cured product, tensile elongation was measured on each of five test pieces under the following conditions, and the average value was calculated.

<Tensile test measurement conditions>

Manufacturer: A&D Co., Ltd.

Model: Tensilon Universal Testing Machine RTG-1210

Distance between chucks: 15mm

Test speed: 5.0mm/min

The elongation was calculated from the movement distance of the chuck when the test piece was broken.

(6) Sulfur resistance test

The epoxy resin compositions for encapsulating optical semiconductors obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to vacuum defoaming for 5 minutes, filled in a syringe, and injected so that the opening was flat using a precision discharge device. As for the surface mount type LED, the surface mount type LED is mounted on a surface mount type LED package of 3.0mm×1.4mm×1.4mmt (sealing portion 0.6mmt) with silver-plated copper electrodes on the bottom surface There is a surface-mount type LED obtained by a light-emitting element having an emission wavelength of 450 nm. The surface mount type LED was sealed by pre-curing at 120° C. for 1 hour and then curing at 150° C. for 3 hours.

Measure the illuminance of the sealed surface-mount LED in advance, put it into a 170mm×170mm×50mmt glass container together with a 9cm diameter glass petri dish containing 2g of sulfur solid, and place it in a constant temperature bath at 80°C place. After standing for 3 hours, measure the illuminance again, and calculate the rate of change compared with the illuminance before the test.

In addition, the illuminance of LED was measured as follows.

The surface mount type LED package used for the test was installed on the wall surface of an integrating sphere (FOIS-1, manufactured by Ocean Optics) at 25° C. and 65% RH, and a constant current of 20 mA was passed through it, and the optical measurement device (Wavelength Calibration USB4000 series , OptoSirius Co., Ltd.) to measure the radiation beam (W).

(7) Reflow soldering test

The epoxy resin compositions for encapsulating optical semiconductors obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to vacuum defoaming for 5 minutes, filled in a syringe, and injected so that the opening was flat using a precision discharge device. As for the surface mount type LED, the surface mount type LED is mounted on a surface mount type LED package of 3.0mm×1.4mm×1.4mmt (sealing portion 0.6mmt) with silver-plated copper electrodes on the bottom surface There are surface-mount LEDs obtained from light-emitting elements having a light-emitting wavelength of 450 nm. The surface mount type LED was sealed by pre-curing at 120° C. for 1 hour and then curing at 150° C. for 3 hours.

Three samples of each of the obtained surface mount type LED packages were dried in an oven at 150°C for 24 hours, then placed in a constant temperature and humidity chamber at 30°C and 70% RH for 168 hours, and then reflowed by hot air circulation After welding the test device once, the external appearance was observed, and the number of cracks (cracks) confirmed in the cured sealing material was counted.

<Reflow Soldering Conditions>

Manufacturer: Tamura Manufacturing Co., Ltd.

Model: TNR15-225LH-M

Atmosphere: in the atmosphere

Temperature curve: From room temperature of 25°C to 180°C at 4°C/s, keep at 180°C-200°C for 120 seconds, then rise to 260°C at 4°C/s, keep at 260°C for 10 seconds, then cool naturally to Room temperature (25°C).

[Table 1]

From the results shown in Table 1, it is clear that for Comparative Examples (1) and (3) that did not use the cyclic siloxane compound (A) having two or more epoxy groups in the molecule, the sulfuration resistance test Among them, the illuminance decreased significantly, and in the comparative examples (2) and (3), cracks occurred in the reflow test. It can also be seen that Comparative Examples (1) to (3) have small tensile elongation and poor mechanical strength.

On the other hand, for Examples (1) to (9) using a cyclic siloxane compound (A) having two or more epoxy groups in the molecule, not only have appropriate viscosity, hardness, and Tg, but also In addition, the cured product has excellent transmittance and tensile elongation. In addition, the illuminance retention rate was high in the vulcanization resistance test, and cracks did not occur in the reflow test, so it is suitable as a resin composition for encapsulating optical semiconductors in fields requiring optical transparency.

Embodiment 10: with the cyclic siloxane compound (EP-3) that obtains in the synthesis example 6 with four epoxy groups in the molecule, the multivalent carboxylic acid resin (B-4) that obtains in the synthesis example 11, as Zinc stearate as a curing accelerator was put into a container made of polypropylene at the ratio described in the following Table 2, mixed, and defoamed for 5 minutes to obtain the epoxy resin composition of the present invention.

Embodiment 11: change the EP-3 of embodiment 10 into the cyclic siloxane compound (EP-4) that has two or more epoxy groups in the molecule obtained in synthesis example 7, and embodiment 10 except this Similarly, the epoxy resin composition of this invention was obtained.

Embodiment 12: Change the EP-3 of embodiment 10 into the cyclic siloxane compound (EP-5) that has two or more epoxy groups in the molecule obtained in synthesis example 8, and embodiment 10 except this Similarly, the epoxy resin composition of this invention was obtained.

Embodiment 13: change the EP-3 of embodiment 10 into the cyclic siloxane compound (EP-6) that has two or more epoxy groups in the molecule obtained in synthesis example 9, and embodiment 10 except this Similarly, the epoxy resin composition of this invention was obtained.

(evaluation test)

The compounding ratio and viscosity of the curable resin compositions for encapsulating optical semiconductors obtained in Examples 10 to 13; the hardness, transmittance, tensile elongation of the cured product, and cracks after the reflow test as an LED test Table 2 shows the results of the illuminance maintenance rate during the long-term lighting test. The tests in Table 2 were performed as described below.

(1) Viscosity

It measured at 25 degreeC using the Toki Sangyo Co., Ltd. E-type viscometer (TV-20).

(2) Hardness

The durometer A hardness was measured by the method described in JISK7215.

(3) Cured product transmittance

The epoxy resin compositions obtained in Examples 10 to 13 were subjected to vacuum degassing for 5 minutes, and then slowly cast to 30 mm×20 mm×height 0.8 mm on a glass substrate with a bank made of heat-resistant tape. The casting was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a test piece for transmittance with a thickness of 0.8 mm. The light transmittance at 400 nm was measured on the obtained test piece under the following conditions.

<Spectrophotometer Measurement Conditions>

Manufacturer: Hitachi High-Tech Co., Ltd.

Model: U-3300

Slit width: 2.0nm

Scanning speed: 120nm/min

(4) Tensile elongation

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 10 to 13 was subjected to vacuum degassing for 5 minutes, and then slowly cast to 50 mm × 30 mm × height on a glass substrate with a bank made of heat-resistant tape 0.8mm. The casting was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a test piece having a thickness of 0.8 mm. The obtained test piece was processed into a width of 5 mm and a length of 50 mm, and for each cured product, tensile elongation was measured on each of five test pieces under the following conditions, and the average value was calculated.

<Tensile test measurement conditions>

Manufacturer: A&D Co., Ltd.

Model: Tensilon Universal Testing Machine RTG-1210

Distance between chucks: 15mm

Test speed: 5.0mm/min

The elongation was calculated from the movement distance of the chuck when the test piece was broken.

(5) Reflow soldering test

The epoxy resin compositions for sealing optical semiconductors obtained in Examples 10 to 13 were subjected to vacuum defoaming for 5 minutes, filled in syringes, and injected onto surface-mount LEDs using a precision discharge device so that the openings were flat. In the above, the surface mount type LED is mounted on a surface mount type LED package with a silver-plated copper electrode 2.3mm x 0.4mm x 1.4mmt (0.4mmt in the sealing part) on the bottom surface. Surface-mount LEDs obtained from light-emitting elements. The surface mount type LED was sealed by pre-curing at 120° C. for 1 hour and then curing at 150° C. for 3 hours.

Three samples each of the obtained surface mount type LED packages were dried in an oven at 150°C for 24 hours, then placed in a constant temperature and humidity chamber at 30°C and 70% RH for 168 hours, and then passed through a hot air circulation system. The reflow test was performed once, and then the external appearance was observed, and the number of cracks (cracks) confirmed in the cured sealing material was counted.

<Reflow Soldering Conditions>

Manufacturer: Tamura Manufacturing Co., Ltd.

Model: TNR15-225LH-M

Atmosphere: in the atmosphere

Temperature curve: From room temperature of 25°C to 180°C at 4°C/sec, keep at 180°C-200°C for 120 seconds, then rise to 260°C at 4°C/s, keep at 260°C for 10 seconds, then cool naturally to Room temperature (25°C).

(6) Illuminance maintenance rate during long-term lighting test

The epoxy resin compositions for encapsulating optical semiconductors obtained in Examples 10 to 13 were subjected to vacuum defoaming for 5 minutes, filled in syringes, and injected onto surface-mount LEDs using a precision discharge device so that the openings were flat. Above, the above-mentioned surface mount type LED is a 2.3mm×0.4mm×1.4mmt (sealing portion 0.4mmt) surface mount type LED package with silver-plated copper electrodes on the bottom surface. Surface-mount LEDs obtained from light-emitting elements. The surface mount type LED was sealed by pre-curing at 120° C. for 1 hour and then curing at 150° C. for 3 hours.

The initial illuminance was measured for each two of the obtained surface mount type LED packages, and a constant current of 20 mA was flowed in an oven maintained at 100° C. to light it for 600 hours. Then, it was taken out from the oven, and the illuminance after the test was measured, and the retention rate compared with the initial illuminance was calculated, and the average value was used as the illuminance retention rate in the long-term lighting test.

In addition, the illuminance of LED was measured as follows.

The surface mount type LED package used for the test was installed on the wall surface of an integrating sphere (FOIS-1, manufactured by Ocean Optics) at 25° C. and 65% RH, and a constant current of 20 mA was passed through it, and the optical measurement device (Wavelength Calibration USB4000 series , OptoSirius Co., Ltd.) to measure the radiation beam (W).

[Table 2]

From the results shown in Table 2, it is clear that the viscosity is appropriate for the epoxy resin compositions of Examples 10 to 13 using the cyclic siloxane compound (A) having two or more epoxy groups in the molecule. , the hardness, transmittance and tensile elongation of the cured product are excellent. In addition, it does not generate cracks in a reflow test, has a high illuminance retention rate in a long-term lighting test, and is suitable as a resin composition for encapsulating optical semiconductors in fields requiring optical transparency. In particular, Examples 10 and 11 of EP-3 and EP-4 containing 91 mol% or more of the organic group containing an epoxy group in X of the formula (1) have excellent illuminance retention in the long-term lighting test, and the long-term Excellent reliability.

Embodiment 14: The cyclic siloxane compound (EP-3) with four epoxy groups in the molecule obtained in Synthesis Example 6, the organosilicon-modified epoxy resin (EP-7) obtained in Synthesis Example 10 ), the polyvalent carboxylic acid resin (B-5) obtained in Synthesis Example 13, and zinc stearate as a curing accelerator were added to a polypropylene container at the ratios listed in Table 3 below, and mixed for 5 minutes. Degassing, thereby obtaining the epoxy resin composition of the present invention.

Embodiment 15: Change polyhydric carboxylic acid resin (B-5) of embodiment 14 into polyhydric carboxylic acid resin (B-6) obtained in synthesis example 14, carry out similarly with embodiment 14 except this, obtain this Invented epoxy resin composition.

Embodiment 16; With the cyclic siloxane compound (EP-3) that obtains in the synthesis example 6 with four epoxy groups in the molecule, the multivalent carboxylic acid resin (B-7) that obtains in the synthesis example 15, as Zinc stearate as a curing accelerator was put into a container made of polypropylene at the ratio described in the following Table 3, mixed, and defoamed for 5 minutes to obtain the epoxy resin composition of the present invention.

Example 17: Change a part of the cyclic siloxane compound (EP-3) having four epoxy groups in the molecule of Example 16 into the organosilicon-modified epoxy resin (EP-3) obtained in Synthesis Example 10 7) Except that, it carried out similarly to Example 16, and obtained the epoxy resin composition of this invention.

Embodiment 18: Change polyhydric carboxylic acid resin (B-5) of embodiment 14 into polyhydric carboxylic acid resin (B-8) obtained in synthesis example 16, carry out similarly with embodiment 14 except this, obtain this Invented epoxy resin composition.

Comparative example 4: the epoxy resin (EP-2) that obtains in synthesis example 2, the epoxy resin (EP-8) that obtains in synthesis example 11, the multivalent carboxylic acid resin (B-5) that obtains in synthesis example 13 . Zinc stearate as a curing accelerator was put into a polypropylene container at the ratio described in the following Table 3, mixed, and defoamed for 5 minutes to obtain an epoxy resin composition of a comparative example.

Comparative Example 5: The polyhydric carboxylic acid resin (B-5) of Comparative Example 4 was changed to the polyhydric carboxylic acid resin (B-6) obtained in Synthesis Example 14, except that it was carried out in the same manner as Comparative Example 4, and a comparative result was obtained. Examples of epoxy resin compositions.

Comparative Example 6: The polyhydric carboxylic acid resin (B-5) of Comparative Example 4 was changed to the polyhydric carboxylic acid resin (B-7) obtained in Synthesis Example 15, except that it was carried out in the same manner as Comparative Example 4, and a comparative result was obtained. Examples of epoxy resin compositions.

Comparative Example 7: The polyvalent carboxylic acid resin (B-5) of Comparative Example 4 was changed to the polyvalent carboxylic acid resin (B-8) obtained in Synthesis Example 16, except that it was carried out in the same manner as Comparative Example 4, and a comparative result was obtained. Examples of epoxy resin compositions.

(evaluation test)

The compounding ratio and viscosity of the curable resin compositions for encapsulating optical semiconductors obtained in Examples 14 to 18 and Comparative Examples 4 to 7, the transmittance of the cured product, the tensile elongation, and the sulfuration resistance of the LED test Table 3 shows the results of cracks after the resistance and reflow soldering tests. The tests in Table 3 were performed as described below.

(1) Viscosity

It measured at 25 degreeC using the Toki Sangyo Co., Ltd. E-type viscometer (TV-20).

(2) Cured product transmittance

The epoxy resin compositions obtained in Examples 14 to 18 and Comparative Examples 4 to 7 were vacuum-degassed for 5 minutes, and slowly cast into 30 mm × 20 mm on a glass substrate with a cofferdam made of heat-resistant adhesive tape. ×Height 0.8mm. The casting was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a test piece for transmittance with a thickness of 0.8 mm. The light transmittance at 400 nm was measured on the obtained test piece under the following conditions.

<Spectrophotometer Measurement Conditions>

Manufacturer: Hitachi High-Tech Co., Ltd.

Model: U-3300

Slit width: 2.0nm

Scanning speed: 120nm/min

(3) Tensile elongation

The epoxy resin compositions for encapsulating optical semiconductors obtained in Examples 14 to 18 and Comparative Examples 4 to 7 were subjected to vacuum defoaming for 5 minutes, and then slowly cast on a glass substrate with banks made of heat-resistant tape. Into 50mm × 30mm × height 0.8mm. The casting was precured at 120° C. for 1 hour and then cured at 150° C. for 3 hours to obtain a test piece having a thickness of 0.8 mm. The obtained test piece was processed into a width of 5 mm and a length of 50 mm, and for each cured product, tensile elongation was measured on each of five test pieces under the following conditions, and the average value was calculated.

<Tensile test measurement conditions>

Manufacturer: A&D Co., Ltd.

Model: Tensilon Universal Testing Machine RTG-1210

Distance between chucks; 15mm

Test speed; 5.0mm/min

The elongation was calculated from the movement distance of the chuck when the test piece was broken.

(4) Sulfur resistance test

The epoxy resin compositions for encapsulating optical semiconductors obtained in Examples 14 to 18 and Comparative Examples 4 to 7 were subjected to vacuum defoaming for 5 minutes, filled in a syringe, and injected so that the opening was flat using a precision discharge device. In the surface mount type LED, the surface mount type LED is mounted on a surface mount type LED package with a silver-plated copper electrode 3.0 mm x 1.4 mm x 1.4 mmt (sealing portion 0.6 mmt) on the bottom surface There are surface-mount LEDs obtained from light-emitting elements having a light-emitting wavelength of 450 nm. The surface mount type LED was sealed by pre-curing at 120° C. for 1 hour and then curing at 150° C. for 3 hours.

Measure the illuminance of the sealed surface-mount LED in advance, put it into a 170mm×170mm×50mmt glass container together with a 9cm-diameter glass petri dish containing 2g of sulfur solid, and place it in a constant temperature bath at 80°C . After standing for 6 hours, measure the illuminance again, and calculate the rate of change compared with the illuminance before the test.

In addition, the illuminance of LED was measured as follows.

The surface mount type LED package used for the test was installed on the wall surface of an integrating sphere (FOIS-1, manufactured by Ocean Optics) at 25° C. and 65% RH, and a constant current of 20 mA was passed through it, and the optical measurement device (Wavelength Calibration USB4000 series , OptoSirius Co., Ltd.) to measure the radiation beam (W).

(5) Reflow soldering test

The epoxy resin compositions for encapsulating optical semiconductors obtained in Examples 14 to 18 and Comparative Examples 4 to 7 were subjected to vacuum defoaming for 5 minutes, filled in a syringe, and injected so that the opening was flat using a precision discharge device. In the surface mount type LED, the surface mount type LED is mounted on a surface mount type LED package with a silver-plated copper electrode 3.0 mm x 1.4 mm x 1.4 mmt (sealing portion 0.6 mmt) on the bottom surface There are surface-mount LEDs obtained from light-emitting elements having a light-emitting wavelength of 450 nm. The surface mount type LED was sealed by pre-curing at 120° C. for 1 hour and then curing at 150° C. for 3 hours.

Three samples each of the obtained surface mount type LED packages were dried in an oven at 150°C for 24 hours, then placed in a constant temperature and humidity chamber at 30°C and 70% RH for 168 hours, and then passed through a hot air circulation system. The reflow test was performed once, and then the external appearance was observed, and the number of cracks (cracks) confirmed in the cured sealing material was counted.

<Reflow Soldering Conditions>

Manufacturer: Tamura Manufacturing Co., Ltd.

Model: TNR15-225LH-M

Atmosphere: in the atmosphere

Temperature curve: From room temperature of 25°C to 180°C at 4°C/sec, keep at 180°C-200°C for 120 seconds, then rise to 260°C at 4°C/s, keep at 260°C for 10 seconds, then cool naturally to Room temperature (25°C).

[table 3]

From the results shown in Table 3, it is clear that for Comparative Examples (4) to (7) that did not use the cyclic siloxane compound (A) having two or more epoxy groups in the molecule, the sulfuration resistance test In this case, the illuminance was greatly reduced, and cracks occurred in the reflow test. It was also found that Comparative Examples (4) to (7) had low tensile elongation and poor mechanical strength.

On the other hand, Examples (14) to (18) using a cyclic siloxane compound (A) having two or more epoxy groups in the molecule were excellent in tensile elongation. In addition, the illuminance retention rate was high in the vulcanization resistance test, and cracks did not occur in the reflow test, so it is suitable as a resin composition for encapsulating optical semiconductors in fields requiring optical transparency.

Although this invention was demonstrated in detail with reference to the specific aspect, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

In addition, this application is based on the JP Patent application (2013-215442) of an application on October 16, 2013, The whole is taken in here by reference. In addition, all the references cited here are incorporated in this application in their entirety.

Industrial applicability

The curable resin composition of the present invention has an appropriate viscosity, and its cured product has an appropriate hardness and Tg, and is also excellent in light transmittance and tensile elongation. Therefore, it can be used in fields requiring optical transparency, especially It is used as a resin composition for optical semiconductor sealing.

Claims (14)

1. An epoxy resin composition comprising a cyclic siloxane compound (A) having two or more epoxy groups in the molecule represented by the following formula (1), an epoxy resin curing agent (B) , In the formula, R ¹ represents a hydrocarbon group with 1 to 6 carbon atoms, X represents an organic group containing an epoxy group or a hydrocarbon group with 1 to 6 carbon atoms, and n represents an integer of 1 to 3; multiple Rs present in the formula ^1. Each X may be the same or different; among the multiple Xs present, at least two are organic groups containing epoxy groups. 2. The epoxy resin composition according to claim 1, wherein 90 mol% or more of X in the formula (1) is an epoxy group-containing organic group. 3. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin curing agent (B) is a polyvalent carboxylic acid resin. 4. The epoxy resin composition as claimed in claim 3, wherein, the multivalent carboxylic acid resin is by at least making (a) polyhydric alcohol compound containing two or more hydroxyl groups in the molecule and (b) containing more than one in the molecule An addition polymer obtained by reacting an acid anhydride-based compound. 5. The epoxy resin composition as claimed in claim 4, wherein, (b) the compound containing more than one acid anhydride group in the molecule is selected from methyl hexahydrophthalic anhydride, glutaric anhydride and diethyl More than one compound in glutaric anhydride. 6. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin curing agent (B) is a polycarboxylic acid represented by the following formula (2), In the formula, multiple Qs that exist represent at least one of a hydrogen atom, a methyl group, and a carboxyl group, P represents an aliphatic group containing a chain and/or cyclic structure with 2 to 20 carbon atoms, and m represents 2 to 20 carbon atoms. Integer of 4. 7. The epoxy resin composition according to claim 6, wherein the epoxy resin curing agent (B) represented by formula (2) contains more than one compound represented by the following formulas (3) to (6) , 8. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin curing agent (B) is a polycarboxylic acid represented by the following formula (8), In the formula, P and m represent the same meaning as the formula (2), and R ² represents a hydrogen atom or an ethyl group. 9. The epoxy resin composition according to claim 8, wherein the epoxy resin curing agent (B) represented by the formula (8) contains more than one compound represented by the following formulas (9) to (12) , In formulas (9) to (12), R ² represents the same meaning as in formula (8). 10. The epoxy resin composition according to any one of claims 1 to 9, further comprising an epoxy resin curing accelerator (C). 11. The epoxy resin composition according to claim 10, wherein the epoxy resin curing accelerator (C) is a metal soap curing accelerator. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 11. The resin composition for optical semiconductor sealing containing the epoxy resin composition in any one of Claims 1-11. The optical-semiconductor device obtained by sealing an optical-semiconductor element with the resin composition for optical-semiconductor sealing of Claim 13.