TW201313772A - Curable resin composition for sealing optical semiconductor element and cured product thereof - Google Patents

Abstract

Provided is a resin composition that is extremely useful as a sealant for an optical semiconductor (such as an LED product) having excellent pot life and sulfur resistance. The curable resin composition for sealing an optical semiconductor comprises a curing catalyst having a melting point between 40 and 200 C and an epoxy resin and/or epoxy resin curing agent. Preferably the epoxy resin curing agent is, for instance, polyvalent carboxylic acid resin (A)obtained by addition reaction of a dual end-type carbinol-modified silicone oil represented by formula (1), a polyhydric alcohol compound having two or more hydroxyl groups per molecule, and a compound having one carboxylic anhydride group per molecule. (In formula (1), R1 is an alkylene group, and the like, R2 is an alkyl group, and the like, and m is an average value and is between 1 and 100.)

Description

Hardened resin composition for sealing optical semiconductor elements and cured product thereof

The present invention relates to a cured resin composition suitable for sealing an optical semiconductor element, and a cured product thereof.

As a resin for sealing an optical semiconductor element such as an LED (Light Emitting Diode), a bisphenol type epoxy resin or an alicyclic epoxy resin can be used in terms of excellent mechanical strength and adhesion. A liquid epoxy resin composition (see Patent Document 1). In recent years, LEDs are being used in fields requiring high brightness such as automotive headlamps or lighting applications. Accordingly, the resin for sealing optical semiconductor elements is particularly required to have UV resistance and heat resistance. However, it is difficult to say that the bisphenol type epoxy resin or the alicyclic epoxy resin as described above has sufficient UV resistance and heat resistance, and sometimes it cannot be used in a field having high brightness demand. Therefore, as a sealing material having high UV resistance, heat resistance and the like, a silicone resin sealing material (refer to Patent Document 2) using an organopolysiloxane containing an unsaturated hydrocarbon group can be used. It is made of organohydrogen polysiloxane. However, the sealing material using such a silicone resin is excellent in UV resistance and heat resistance, but has a problem that the sealing surface has a sticky feeling or a high gas permeability.

In the case of a problem of high gas permeability, in particular, the silver-plated surface for the LED is corroded and becomes silver sulfide due to the transmission of the sulfur-based gas, thereby causing blackening, causing a decrease in the illuminance of the LED. Therefore, it is urgent to take countermeasures (improvement of sulfidation resistance). The following countermeasures are made for this: Increasing the crosslink density of the cured epoxy resin or adding an aromatic organic group such as a phenyl group to the molecule; however, since the hardness of the cured product is inevitably increased, the thermal cycle resistance is poor, and cracks (fractures) or self-substrate are generated. There are concerns such as adverse effects such as peeling or deterioration of UV resistance due to an increase in aromatic organic groups. Moreover, it is still impossible to achieve a satisfactory sulfidation resistance.

In order to solve such problems, a condensate having an epoxy group or a phenyl group and a sealing material using an epoxy resin hardener have been studied, but it has not been satisfied. Further, since the viscosity rise (applicable period) after mixing the two liquids is fast, there is a problem that the workability is poor.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-277473

Patent Document 2: Japanese Patent No. 4636242

An object of the present invention is to provide a cured resin composition for sealing an optical semiconductor element which is excellent in pot life and excellent in vulcanization resistance, and a cured product thereof.

The inventors of the present invention conducted intensive studies in view of the above-described state of the art, and as a result, found that a hardened resin composition containing a curing catalyst having a melting point of 40 to 200 ° C and an epoxy resin and/or an epoxy resin hardener can solve the above problems. Thus, the present invention has been completed.

That is, the present invention is as follows:

(1) A cured resin composition for optical semiconductor sealing, which comprises a curing catalyst having a melting point of 40 to 200 ° C and an epoxy resin and/or an epoxy resin curing agent.

(2) The cured resin composition for optical semiconductor sealing according to (1) above, wherein the epoxy resin curing agent is a polyvalent carboxylic acid resin (A), and the polyvalent carboxylic acid resin (A) comprises the formula (1) An addition reaction of the methanol-modified oleic oil at both ends (a) with a compound (d) having a carboxylic anhydride group in the molecule, and a polyol compound (i) having two or more hydroxyl groups in the molecule and a carboxy group in the molecule Addition reactant of the acid anhydride group-containing compound (d):

(In the formula (1), R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms or an alkylene group having an ether bond having 1 to 10 carbon atoms, and R ₂ each independently represents an alkyl group having 1 to 3 carbon atoms or Phenyl group, m is an average value and represents 1 to 100).

(3) The hardened resin composition for optical semiconductor sealing according to the above (1), wherein the epoxy resin hardener is an eucalyptus oil (a) modified by the two-terminal methanol represented by the formula (1), and has an intramolecular A polyvalent carboxylic acid resin (A) obtained by subjecting a polyol compound (i) having two or more hydroxyl groups and a compound (d) having a carboxylic acid anhydride group in the molecule.

(In the formula (1), R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms or an alkylene group having an ether bond having 1 to 10 carbon atoms, and R ₂ each independently represents an alkyl group having 1 to 3 carbon atoms or Phenyl group, m is an average value and represents 1 to 100).

(4) The cured resin composition for optical semiconductor sealing according to the above (3), wherein the polyvalent carboxylic acid resin (A) further contains a compound (c) having two or more carboxylic acid anhydride groups in the molecule as a reaction raw material. The person who obtained the addition reaction.

(5) The cured resin composition for optical semiconductor sealing according to any one of the above (2), wherein the polyol compound (i) having two or more hydroxyl groups in the molecule is represented by the formula (2). Terminal alcohol polyester compound:

(In the formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and m is an average value and represents 1 to 100).

(6) The cured resin composition for optical semiconductor sealing according to any one of the above (1) to (5) wherein the epoxy resin is a silicone skeleton epoxy resin (B).

(7) The cured resin composition for sealing an optical semiconductor element according to the above (6), wherein the polyfluorene skeleton epoxy resin (B) is obtained by the following production steps (1) and (2) a decyl alcohol-terminated eucalyptus oil and an epoxy group-containing hydrazine compound represented by the formula (4), and an epoxy equivalent of 300 to 1500 g/eq as measured by the method described in JIS K-7236; Production step 1 a step of obtaining a modified eucalyptus oil by condensing a decyl alcohol group of a decyl alcohol terminal eucalyptus oil with an alkoxy group of an epoxy group-containing hydrazine compound; and a production step 2, after the production step 1, adding water to carry out residual alkoxylation a step of hydrolytic condensation of a base;

(In the formula (3), R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and p is an average value and represents 3 to 200; wherein, in the formula, R ₅ may be the same or different); XSi(R) ₆ ) _q (OR ₇ ) _r (4)

(In the formula (4), X represents an organic group containing an epoxy group, and R ₆ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, R ₇ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, q is an integer and represents 0 to 2, and r is an integer representing (3-q)).

(8) The cured resin composition for optical semiconductor sealing according to any one of the above (1) to (7), wherein the curing catalyst having a melting point of 40 to 200 ° C is a metal soap-based curing catalyst.

(9) The hardened resin composition for optical semiconductor sealing according to (8) above, wherein the metal soap is a zinc salt composed of a carboxylic acid compound.

(10) The cured resin composition for optical semiconductor sealing according to the above (9), wherein the zinc salt composed of the carboxylic acid compound is a zinc salt composed of a monocarboxylic acid compound having a hydroxyl group having 10 to 30 carbon atoms.

(11) The cured resin composition for optical semiconductor sealing according to (10) above, wherein the monocarboxylic acid compound having a hydroxyl group having 10 to 30 carbon atoms is 12-hydroxystearic acid.

(12) The cured resin composition for optical semiconductor sealing according to (10) above, wherein the monocarboxylic acid compound having a hydroxyl group having 10 to 30 carbon atoms is stearic acid.

(13) A cured product obtained by curing the cured resin composition for optical semiconductor sealing according to any one of the above (1) to (12).

(14) An LED comprising the cured product of the above (13).

According to the present invention, the cured resin composition containing a curing catalyst having a melting point of 40 to 200 ° C and an epoxy resin and/or an epoxy resin hardener is excellent in resistance to vulcanization and has a pot life, so that it is used as an optical semiconductor element (LED). Sealing materials are extremely useful.

The cured resin composition for an optical semiconductor element sealing material of the present invention comprises a curing catalyst having a melting point of 40 to 200 ° C and an epoxy resin and/or an epoxy resin curing agent.

The curing catalyst in the present invention is an epoxy group, an epoxy group and a carboxyl group, an epoxy group and a carboxylic anhydride group, an epoxy group and an amine group, an epoxy group and a thiol group, an epoxy group and an anthracene. A compound which initiates or promotes the hardening of an amine group or the like.

The resin composition for sealing an optical semiconductor of the present invention is the above hardening catalyst It also contains a hardening catalyst with a melting point of 40 to 200 °C.

In general, the resin composition for optical semiconductor sealing is liquid at room temperature, and as a molding method, a sealing material can be injected into a mold frame into which a substrate on which an optical semiconductor element is fixed, and then heat-hardened. In the compression molding method, a sealing material is injected into the mold in advance, and the optical semiconductor element fixed on the substrate is immersed therein, heat-hardened, and then released from the mold.

As the injection method, a dispenser or the like can be used.

The injected sealing resin is heated and hardened. The heating system used for hardening uses a hot air circulation type, an infrared ray, a high frequency, and the like. The heating conditions are, for example, preferably from 80 to 200 ° C for about 1 minute to 24 hours. In order to reduce the internal stress generated during heat curing, it is usually subjected to pre-hardening at, for example, 80 to 120 ° C for 30 minutes to 5 hours, and then subjected to subsequent hardening at 120 to 180 ° C for 30 minutes to 10 hours.

When the hardened resin composition for optical semiconductor sealing is a catalyst which is solid at room temperature (25 ° C), there is a problem that the illuminance of the LED is deteriorated due to white turbidity or the like of the cured product. Therefore, a liquid catalyst is usually selected. However, if it is a liquid hardening catalyst at room temperature (25 ° C), although the appearance of the cured product is excellent, it is a liquid epoxy resin and epoxy resin at room temperature (25 ° C). Since the hardeners are fused, they are combined as a curing catalyst even before being heated and hardened, causing an excessive increase in viscosity and a problem of deterioration in workability.

However, the catalyst which is solid at room temperature (25 ° C) is not fused at all at room temperature (25 ° C) to epoxy resin and epoxy resin hardener, so it is not Will cause excessive viscosity to rise. Further, at the time of heat curing, the solid catalyst is melted to express the catalyst energy and directly harden, so that the appearance of the cured product is not problematic.

The catalyst which is solid at room temperature (25 ° C) preferably has a melting point of 40 to 200 ° C from the viewpoint of processability and melting at the time of heat curing to exhibit catalyst energy. In such a case, it is more preferable to use a hardening catalyst having a melting point of 100 to 160 ° C from the viewpoint of suppressing excessive viscosity increase, and it is particularly preferable to use a curing catalyst having a melting point of 120 to 160 ° C.

In terms of excellent transparency, a catalyst having a melting point of 40 to 200 ° C is preferably an ammonium salt-based curing catalyst, a cerium salt-based curing catalyst, or a metal soap-based curing catalyst. Examples of the ammonium salt-based hardening catalyst include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylethylammonium hydroxide. , trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, tetramethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium Chloride), tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, and the like. Examples of the barium salt-based hardening catalyst include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethyl phosphate, and A. Tributylphosphonium diethylphosphate and the like. Examples of the metal soap-based hardening catalyst include calcium stearate, zinc stearate, and stearin. Magnesium, aluminum stearate, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, 12-hydroxystearic acid Magnesium, aluminum 12-hydroxystearic acid, bismuth 12-hydroxystearate, lithium 12-hydroxystearate, sodium 12-hydroxystearate, calcium montanate, zinc montanate, magnesium montanate, Aluminum montanate, lithium montanate, sodium montanate, calcium behenate, zinc behenate, magnesium phthalate, lithium dodecate, sodium dodecanoate, behenic acid Silver, calcium laurate, zinc laurate, barium laurate, lithium laurate, zinc undecylenate, zinc ricinoleate, ricinoleic acid, zinc myristate, Zinc palmitate. These catalysts may be used alone or in combination of two or more.

In order to obtain a cured product having a high melting point of a hardening catalyst and excellent transparency and sulfur resistance, it is particularly preferably used: zinc stearate, zinc montanate, zinc behenate, zinc laurate, undecene. a zinc carboxylic acid such as zinc cinnamate, zinc ricinoleate, zinc myristate or zinc palmitate, and a monocarboxylic acid compound having a carbon number of 10 to 30, such as zinc 12-hydroxystearic acid. The zinc salt is composed. Among these, zinc, which is composed of a monocarboxylic acid compound having 10 to 20 carbon atoms, such as zinc stearate or zinc undecylenate, can be preferably used from the viewpoint of excellent pot life and excellent sulfidation resistance. a zinc salt such as a salt or a monocarboxylic acid compound having a carbon number of 15 to 20, such as zinc, 12-hydroxystearic acid, or the like, and further preferably zinc stearate, zinc undecylenate or 12-hydroxyl hard. Zinc citrate, particularly preferably zinc stearate or zinc 12-hydroxystearate.

The curing catalyst having a melting point of 40 to 200 ° C is usually used in an amount of 0.001 to 15 parts by weight based on 100 parts by weight of the epoxy resin described below.

The hardening catalyst having a melting point of 40 to 200 ° C can also be pulverized and used. As the pulverization method, a jet mill, a planetary ball mill, a spiral mill or the like can be used.

An epoxy resin and/or an epoxy resin hardener is used in the cured resin composition of the present invention.

Hereinafter, the epoxy resin hardener will be described.

Examples of the epoxy resin curing agent include an amine compound, an acid anhydride compound, a guanamine compound, a phenol compound, and a polyvalent carboxylic acid.

In the present invention, the epoxy resin curing agent is preferably an acid anhydride or a polyvalent carboxylic acid from the viewpoint of hardness, workability (liquid at room temperature), and transparency of the cured product. An oil (a) modified with methanol at both ends, a polyol compound (i) having two or more hydroxyl groups in the molecule, a compound (d) having a carboxylic anhydride group in the molecule, and, if necessary, intramolecular The polyvalent carboxylic acid resin (A) obtained by subjecting the compound (c) having two or more carboxylic anhydride groups to an addition reaction.

Specific examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetrahydroortylene. Dimethyl anhydride, methyl nadic anhydride, ceric anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo [2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4- Anhydride such as tris-formic acid-3,4-anhydride.

In terms of light resistance, transparency, and processability, it is particularly preferred to be methyl. Tetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1 Heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4 - Anhydride, etc.

The polycarboxylic acid is a compound characterized by having at least two carboxyl groups.

The polyvalent carboxylic acid is preferably a carboxylic acid having 2 to 6 functional groups, and examples thereof include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, malic acid, and the like. Linear alkanoic acid, 1,3,5-pentane tricarboxylic acid, alkyl tricarboxylic acid such as citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrogen An aliphatic cyclic polycarboxylic acid such as phthalic acid, methyltetrahydrophthalic acid, cyclohexane tricarboxylic acid, nadic acid or methyl acid, sublinoleic acid or oleic acid A polymer obtained by reacting a polybasic acid of a saturated fatty acid and a dimer acid as a reducing substance thereof with a hydroxyl group of a 2-6 functional group and an acid anhydride, from the viewpoint of heat resistance and workability, It is preferably a compound obtained by the reaction of a 2-6 functional group polyol with an acid anhydride. Further, from the viewpoint of transparency, the above-mentioned acid anhydride is preferably a polyvalent carboxylic acid of a saturated aliphatic cyclic acid anhydride.

The polyol having a 2-6 functional group is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, and 1,2-butanediol. 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1 , diols such as 3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol, glycerin, trimethylolethane, trimethylolpropane, trishydroxyl Triols such as butylbutane and 2-hydroxymethyl-1,4-butanediol; tetraols such as pentaerythritol and di-trimethylolpropane; and hexaols such as dipentaerythritol.

Preferred polyols are alcohols having a carbon number of 5 or more, preferably 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexane. Alkane dimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Among them, from the viewpoint of heat resistance and transparency, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, and 1, An alcohol having a branched structure or a cyclic structure such as 4-cyclohexanedimethanol, tricyclodecane dimethanol or norbornylene glycol, and more preferably tricyclodecane dimethanol.

As an acid anhydride for reacting with a polyhydric alcohol, methyl tetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and butyl are preferable. Alkyltetracarboxylic 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, etc., among them, methylhexahydrophthalic anhydride and cyclohexane are preferable from the viewpoint of heat resistance, transparency, and processability. 1,3,4-tricarboxylic acid-3,4-anhydride.

The conditions of the addition reaction are not particularly limited as long as they are a known method. Specific reaction conditions include, for example, an acid anhydride or a polyhydric alcohol in a solvent-free or solvent-free condition. The reaction is carried out at 150 ° C and heated, and the method is directly taken out after the reaction is completed.

The epoxy resin curing agent used for the cured resin composition for optical semiconductor sealing of the present invention is preferably a polycarboxylic acid resin (A) which is an oil (a) which is modified at both ends of methanol, and has two or more hydroxyl groups in the molecule. Polyol The polyvalent carboxylic acid resin (A) obtained by subjecting the compound (i), the compound (d) having one acid anhydride group in the molecule, and the compound (c) having two or more acid anhydride groups in the molecule as needed.

In general, a polycarboxylic acid composed only of low molecular weight C, H, and O atoms is usually in a solid state at room temperature (25 ° C), and is difficult to be directly used as a hardening resin for optical semiconductor sealing composed of an epoxy resin. Hardener of matter. However, if the component contains a polyoxyalkylene compound having a repeating unit of a Si-O bond, it may exist in a liquid state at room temperature (25 ° C) depending on the amount of its intermolecular force. By using the methanol-modified eucalyptus oil (a) at both ends as a reaction raw material, the epoxy resin hardener used as the cured resin composition for optical semiconductor sealing of the present invention is preferably a polyvalent carboxylic acid resin (A). It is present in liquid form at room temperature (25 ° C).

The eucalyptus oil (a) modified with methanol at both ends, the polyol compound (i) having two or more hydroxyl groups in the molecule, and the compound (d) having an acid anhydride group in the molecule are subjected to an addition reaction, whereby the methanol at both ends is changed. The hydroxyl group of methanol of the eucalyptus oil (a) and the acid anhydride group of the compound (d) having an acid anhydride group in the molecule undergo a ring-opening addition reaction with the acid anhydride group, and the hydroxyl group of the polyol compound (i) has an acid anhydride. The acid anhydride group of the compound (d) is subjected to a ring-opening addition reaction with an acid anhydride group, and a polycarboxylic acid resin (A) having a carboxyl group at both terminals is obtained, that is, a polycarboxylic acid resin (A).

Further, a compound (c) having two or more acid anhydride groups in the molecule is used as a reaction raw material, whereby the eucalyptus oil (a) having both ends of methanol reformed and (or) a polyol compound having two or more hydroxyl groups in the molecule (i) 矽 ( (a) modified with methanol and methanol at both ends and/or both ends, and two or more hydroxy groups in the molecule The polyol compound (i) based on the polymerization is polymerized into the same molecule.

In particular, when the acid anhydride adduct of the two terminal methanol-modified oleic oils (a) is poorly miscible with the acid anhydride adduct of the polyol compound (i) having two or more hydroxyl groups in the molecule, it is used. a compound (c) having two or more acid anhydride groups in the molecule, whereby the eucalyptus oil (a) modified at both ends of the methanol and the polyol compound (i) having two or more hydroxyl groups in the molecule can be polymerized by the same molecule. It can be obtained as a homogeneous liquid substance at room temperature (25 ° C).

In the following, the eucalyptus oil (a) which is a two-terminal methanol reforming material which is a raw material of the polyvalent carboxylic acid resin (A), the polyol compound (i) having two or more hydroxyl groups in the molecule, and the compound having two or more acid anhydride groups in the molecule (c) and a compound (d) having an acid anhydride group in the molecule will be described.

First, the two-terminal methanol-modified eucalyptus oil (a) will be described.

An example of the eucalyptus oil (a) which is modified by the methanol at both ends is an anthracene compound having an alcoholic hydroxyl group at both terminals represented by the following formula (1).

(In the formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms, an alkylene group having an ether bond, R ₂ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and m is an average value and represents 1 ~100)

In the formula (1), specific examples of R ₁ include a methylene group, an exoethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and an isoamyl group. And an alkyl group having an ether bond such as an alkyl group, an ethoxy group, an ethyl group, a propoxy group, a propoxy group, an ethoxy group, a propyl group, and the like. Particularly preferred are propoxyethyl, ethoxypropyl.

Further, R ₂ represents an alkyl group having 1 to 3 carbon atoms such as a methyl group or a phenyl group, and may be any of the same or different types, in order to modify the both ends of the methanol (a), and have two molecules in the molecule. The polyhydric carboxylic acid resin obtained by the addition reaction of the above hydroxyl group polyol compound (i), the compound (d) having one acid anhydride group in the molecule, and the compound (c) having two or more acid anhydride groups in the molecule as necessary (A) is a liquid at room temperature, and is preferably a methyl group as compared with a phenyl group.

In the formula (1), m is an average value and is from 1 to 100, preferably from 2 to 80, more preferably from 5 to 30.

The two-terminal methanol-modified eucalyptus oil (a) represented by the formula (1) may, for example, be X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, BY16- 004, SF8427 (all manufactured by Toray Dow Corning Co., Ltd.), XF42-B0970, XF42-C3294 (all manufactured by Momentive Performance Materials Japan Co., Ltd.), and the like, and are available on the market. These two-terminal methanol-modified eucalyptus oils may be used alone or in combination of two or more. Among these, X-22-160AS, KF6001, KF6002, BY16-201, and XF42-B0970 are preferable.

Next, a polyol compound (i) having two or more hydroxyl groups in the molecule will be described.

As the polyol compound (i) having two or more hydroxyl groups in the molecule, For example, a terminal alcohol polyester compound (b), a hydrocarbon polyol compound (j), and a terminal alcohol polycarbonate compound are mentioned.

The terminal polyester compound (b) is not particularly limited, and examples thereof include a polyester compound having a hydroxyl group at the terminal represented by the following formula (2).

(In the formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and n is an average value and represents 1 to 100)

In the formula (2), specific examples of R ₃ include a methyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. a chain extending alkyl group, an extended isopropyl group, an ethyl butyl propyl group, an isobutyl group, an isoamyl group, a neopentyl group, a diethyl pentyl group, and the like a terminal alkyl group having a cyclic structure such as cyclopentane dimethylene or cyclohexane dimethylene. Among them, a branched alkyl group having a carbon number of 1 to 10 or a stretched alkyl group having a cyclic structure is preferred, and in particular, from the viewpoint of heat-resistant transparency of the cured product, ethylbutyl bromide is preferred. Base, isobutylene, neopentyl, diethyl pentyl, cyclohexane dimethylene.

In the formula (2), as a specific example of R ₄ , a carbon number of 1 to 10 such as an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an exooctyl group may be mentioned. Chain alkyl, isopropyl, ethyl butyl propyl, isobutyl, isopentyl, neopentylene, diethyl pentyl, etc., having a carbon number of 1 to 10 An alkyl group having a cyclic structure such as an alkyl group, a cyclopentane dimethylene group or a cyclohexane dimethylene group. Among them, a linear alkyl group having 1 to 10 carbon atoms is preferable, and from the viewpoint of adhesion of a cured product to a substrate or the like, a propyl group, a butyl group, a pentyl group and a hexyl group are particularly preferable.

In the formula (2), n is an average value and is from 1 to 100, preferably from 2 to 40, more preferably from 3 to 30.

The terminal alcohol polyester compound (b) has a weight average molecular weight (Mw) of from 500 to 20,000, preferably from 500 to 5,000, more preferably from 500 to 3,000. When the weight average molecular weight is less than 500, the cured product of the cured resin composition of the present invention has an excessively high hardness and is cracked in a heat cycle test or the like. If the weight average molecular weight is more than 20,000, the cured product is sticky. Feeling tired. In the present invention, the weight average molecular weight is a weight average molecular weight calculated by polystyrene conversion based on a value measured by GPC (gel permeation chromatography) under the following conditions ( Mw).

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min

Column temperature: 40 ° C

Solvent: THF (Tetrahydrofuran, tetrahydrofuran)

Detector: RI (differential refractive index detector)

The terminal alcohol polyester compound (b) represented by the formula (2) is, for example, a polyester polyol having an alcoholic hydroxyl group at its terminal. As a specific example, there are mentioned: Kyowapol 1000PA, Kyowapol 2000PA, Kyowapol 3000PA, Kyowapol 2000BA (all manufactured by Kyowa Hakko Chemical Co., Ltd.) as polyester polyol; Adeka Newace Y9-10, Adeka Newace YT-101 (all manufactured by ADEKA); Placcel 220EB, Placcel 220EC (all manufactured by Daicel Chemical Industries); Polylite OD-X-286, Polylite OD-X-102, Polylite OD-X-355, Polylite OD-X-2330, Polylite OD-X- 240, Polylite OD-X-668, Polylite OD-X-2554, Polylite OD-X-2108, Polylite OD-X-2376, Polylite OD-X-2044, Polylite OD-X-688, Polylite OD-X-2068 , Polylite OD-X-2547, Polylite OD-X-2420, Polylite OD-X-2523, Polylite OD-X-2555 (all manufactured by DIC); HS2H-201AP, HS2H-351A, HS2H-451A, HS2H-851A, HS2N-221A, HS2N-521A, HS2H-220S, HS2N-220S, HS2N-226P, HS2B-222A, HOKOKUOL HT-110, HOKOKUOL HT-210, HOKOKUOL HT-12, HOKOKUOL HT-250, HOKOKUOL HT -310, HOKOKUOL HT-40M (both manufactured by Fengguo Oil Co., Ltd.), etc., and are available on the market. These polyester compounds can be used singly or in combination of two or more. Among these, Kyowapol 1000PA, Adeka Newace Y9-10, and HS2N-221A are preferred.

Next, the hydrocarbon polyol compound (j) will be described.

The hydrocarbon polyol compound (j) is a hydrocarbon compound having two or more hydroxyl groups in the molecule, and examples thereof include ethylene glycol, propylene glycol, propanediol, butanediol, dimethyl alcohol, and pentanediol. ,new Pentanediol, hexanediol, dimethylbutanediol, heptanediol, dimethylpentanediol, diethylpropanediol, octanediol, dimethylhexanediol, diethylbutanediol, hydrazine Glycol, dimethyl heptanediol, diethyl pentanediol, decanediol, dimethyloctanediol, diethylhexanediol, ethylbutylpropanediol, 3-hydroxymethyl-1,5 a chain hydrocarbon polyol compound such as pentanediol, diglycerin, dipentaerythritol, trimethylolpropane or ditrimethylolpropane; or cyclopentanediol, cyclopentane dimethanol or cyclohexanediol a cyclic hydrocarbon polyol compound such as cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethanol, norbornane diol, norbornane dimethanol. These hydrocarbon polyol compounds (j) can be used singly or in combination of two or more. Among these, from the viewpoint of the strength of the cured product and the transparency of the cured product, tricyclodecane dimethanol, ditrimethylolpropane, and diglycerin are preferable.

Hereinafter, the terminal alcohol polycarbonate compound will be described.

The terminal alcohol polycarbonate compound is not particularly limited, and examples thereof include a polycarbonate compound having a hydroxyl group at the terminal represented by the following formula (7).

(In the formula (7), R ₈ represents an alkylene group having 1 to 10 carbon atoms, and s is an average value and represents 1 to 100)

In the formula (7), specific examples of R ₈ include a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. ~10 linear alkyl, isopropyl, ethyl butyl propyl, isobutyl, isoamyl, neopentyl, diethyl pentyl The alkyl group having a cyclic structure such as an alkyl group of a chain, a cyclopentane dimethylene group or a cyclohexane dimethylene group. Among them, in view of the fact that the viscosity of the terminal alcohol polycarbonate compound is not excessively high and workability, a linear extension of a carbon number of 4 to 7 such as a butyl group, a pentyl group, a hexyl group or a heptyl group is preferred. alkyl.

In the formula (7), R ₈ in the plural may be the same or different.

In the formula (7), s is an average value and is from 1 to 100, preferably from 2 to 40, more preferably from 3 to 30.

The weight average molecular weight (Mw) of the terminal alcohol polycarbonate compound is preferably from 500 to 20,000, more preferably from 500 to 5,000, still more preferably from 500 to 3,000. When the weight average molecular weight is 500 or more, the cured product of the optical resin sealing cured resin composition of the present invention is not excessively high in hardness, and is not required to be cracked in a heat cycle test or the like, which is preferable. Moreover, when the weight average molecular weight is 20,000 or less, there is no need to worry about the sticky feeling of the cured product, which is preferable. In the present invention, the weight average molecular weight is a weight average molecular weight (Mw) calculated based on polystyrene conversion based on a value measured by GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

The amount of the polyol compound (i) having two or more hydroxyl groups in the molecule is not particularly limited, and is preferably from 0.5 to 200 parts by weight, more preferably from 0.5 to 200 parts by weight, based on 100 parts by weight of the oleic oil (a) modified with methanol at both ends. 5 to 50 parts by weight, more preferably 10 to 30 parts by weight. When the amount is 0.5 parts by weight or more, the mechanical strength of the cured product is further improved, and when it is 200 parts by weight or less, the heat-resistant transparency of the cured product is further improved, or the viscosity of the obtained polyvalent carboxylic acid resin (A) is changed. It is more suitable, so it is better.

Hereinafter, the compound (c) having two or more carboxylic anhydride groups in the molecule will be described.

Examples of the compound (c) having two or more carboxylic acid anhydride groups in the molecule include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3 -5-(2,5-dioxotetrahydrofuryl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride), 4-(2,5 - Dihydrotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like.

The compound (c) having two or more carboxylic anhydride groups in the molecule may be used alone or in combination of two or more. In addition, since the cured product obtained by curing the polyvalent carboxylic acid resin (A) and the epoxy resin described below is excellent in transparency, it is preferably 1,2,3,4-butanetetracarboxylic dianhydride and 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, More preferably, it is 1,2,3,4-butane tetracarboxylic dianhydride.

Hereinafter, the compound (d) having a carboxylic anhydride group in the molecule is subjected to Description.

The compound (d) having a carboxylic anhydride group in the molecule may, for example, be succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, 2,3-butane dicarboxylic anhydride, 2,4-pentane dicarboxylic anhydride, 3, a saturated aliphatic carboxylic acid anhydride such as 5-heptane dicarboxylic anhydride, an unsaturated aliphatic carboxylic anhydride such as maleic anhydride or dodecyl succinic anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic acid Anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, ceric anhydride, methylic acid anhydride, two a cyclic saturated aliphatic carboxylic anhydride such as cyclo[2,2,2]octane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, tetrahydroortylene Formic anhydride, methyltetrahydrophthalic anhydride, ceric acid anhydride, methyl benzoic anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2, a cyclic unsaturated aliphatic carboxylic acid anhydride such as 2,2]-5-octene-2,3-dicarboxylic acid anhydride, phthalic anhydride, isophthalic anhydride, terephthalic anhydride, trimellitic anhydride, etc. Aromatic carboxylic anhydride and the like.

The compound (d) having a carboxylic anhydride group in the molecule may be used singly or in combination of two or more. Among them, since the cured product obtained by curing the polyvalent carboxylic acid resin (A) and the epoxy resin is excellent in transparency, it is preferably hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or tetrahydrogen. Phthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride. More preferred is methylhexahydrophthalic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and particularly preferably methylhexahydrophthalic anhydride.

In the case of use, it has a combination of two carboxylic anhydride groups in the molecule with respect to 100 parts by weight of the compound (d) having one carboxylic anhydride group in the molecule. The amount of the substance (c) to be used is usually 5 to 1000 parts by weight, preferably 10 to 500 parts by weight, more preferably 15 to 300 parts by weight. When it is more than 300 parts by weight, the polyvalent carboxylic acid resin (A) may be excessively polymerized and the workability may be deteriorated.

The eucalyptus oil (a) having two-terminal methanol reforming, the polyol compound (i) having two or more hydroxyl groups in the molecule, the compound (c) having two or more carboxylic anhydride groups in the molecule, and one carboxylic anhydride group in the molecule The compound (d) is used in an amount of 1 equivalent to the total alcoholic hydroxyl group of the oleic oil (a) modified with methanol at both ends and the polyol compound (i) having two or more hydroxyl groups in the molecule, preferably having one in the molecule. The compound (d) of the carboxylic anhydride group and the total carboxylic anhydride group of the compound (c) having two or more carboxylic anhydride groups in the molecule at the time of use are from 0.5 to 2.0 equivalents, more preferably from 0.8 to 1.5 equivalents. When the amount is 0.5 equivalent or more, the mechanical strength of the cured product is good, and when it is 2.0 equivalents or less, a large amount of the carboxylic acid anhydride group does not remain, and storage stability is good, which is preferable.

The production of the polyvalent carboxylic acid resin (A) can be carried out in a solvent or in the absence of a solvent. The solvent is not limited to the eucalyptus oil (a) which is not modified with methanol at both ends, the polyol compound (i) having two or more hydroxyl groups in the molecule, the compound (d) having one carboxylic anhydride group in the molecule, and the intramolecular use during use. A solvent which reacts with the compound (c) having two or more carboxylic anhydride groups can be used without particular limitation. As a solvent which can be used, for example, an aprotic polar solvent such as dimethylformamide, dimethylacetamide, dimethyl hydrazine, tetrahydrofuran or acetonitrile such as methyl b. Ketones of ketone, cyclopentanone, and methyl isobutyl ketone, such as toluene and xylene Among the aromatic hydrocarbons and the like, among these, aromatic hydrocarbons or ketones are preferred. These solvents may be used alone or in combination of two or more. In the case of using a solvent, the amount of the oleic oil (a) modified with methanol at both ends, the polyol compound (i) having two or more hydroxyl groups in the molecule, and the compound having a carboxylic anhydride group in the molecule (d) In the case of use, the total amount of the compound (c) having two or more carboxylic acid anhydride groups in the molecule is preferably from 0.5 to 300 parts by weight.

The polyvalent carboxylic acid resin (A) can be produced without a catalyst or can be produced using a catalyst. In the case of using a catalyst, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, and hydrogen peroxide. Metal hydroxides such as sodium, potassium hydroxide, calcium hydroxide, magnesium hydroxide, amine compounds such as triethylamine, tripropylamine, and tributylamine, pyridine, dimethylaminopyridine, 1,8-dioxinbicyclo[5 , 4,0] undecene-7, imidazole, triazole, tetrazole and other heterocyclic compounds, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutyl hydroxide Ammonium, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecyl ammonium hydroxide, trioctylmethylammonium hydroxide, tetramethyl 4-grade ammonium salt such as ammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, etc., tetraethyl orthotitanate, tetra-ortho-titanate Metal soaps such as tert-acids such as esters, tin octoate, cobalt octoate, zinc octoate, manganese octoate, calcium octylate, sodium octoate and potassium octylate.

In the case of using a catalyst, one type or a mixture of two or more types may be used.

In the case of using a catalyst, the amount of the oleic oil (a) modified with methanol at both ends, the polyol compound (i) having two or more hydroxyl groups in the molecule, and the compound having a carboxylic anhydride group in the molecule (d) In the case of use, the total amount of the compound (c) having two or more carboxylic anhydride groups in the molecule is preferably 100 parts by weight, preferably 0.05 to 10 parts by weight.

The method of adding the catalyst may be directly added or used in a state of being dissolved in a soluble solvent or the like. In this case, since the compound (c) having two or more carboxylic acid anhydride groups in the unreacted molecule or the compound (d) having one carboxylic acid anhydride group in the molecule is reacted, it is preferred to avoid the use of an alcoholic solvent such as methanol or ethanol. Or water.

The reaction temperature at the time of producing the polyvalent carboxylic acid resin (A) depends on the amount of the catalyst and the solvent to be used, and is usually 20 to 160 ° C, preferably 50 to 150 ° C, and particularly preferably 60 to 145 ° C. Further, the total reaction time is usually from 1 to 20 hours, preferably from 3 to 12 hours. The reaction can be carried out in two or more stages. For example, it can be reacted at 20 to 100 ° C for 1 to 8 hours, and then reacted at 100 to 160 ° C for 1 to 12 hours. In the above case, the volatilization can be suppressed by the following means: in particular, the compound (d) having a carboxylic anhydride group in the molecule is mostly volatile, and when the volatility is higher, the reaction is carried out in advance at 20 to 100 ° C. After that, the reaction was carried out at 100 to 160 °C. Thereby, not only the harmful substance can be suppressed from diffusing into the atmosphere, but also the polyvalent carboxylic acid resin (A) can be obtained as needed.

In the case of production using a catalyst, the catalyst may be removed by quenching and/or washing as needed, or may be directly used as a hardening accelerator for the cured resin composition of the present invention. .

In the case of performing the water washing step, it is preferably according to the solvent used. A solvent which can be separated from water is added in the kind. As preferred solvents, for example, methyl ethyl ketone, methyl isobutyl ketone, ketone of cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, isopropyl butyrate and the like can be exemplified. For example, hydrocarbons such as hexane, cyclohexane, toluene, and xylene.

When the solvent is used for the reaction or water washing, it can be removed by concentration under reduced pressure or the like.

The polycarboxylic acid resin (A) obtained in the above manner is usually a liquid having a fluidity at 25 °C. Further, the molecular weight thereof is preferably from 800 to 80,000, more preferably from 1,000 to 10,000, still more preferably from 1,500 to 8,000, as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, there is a case where the fluidity at 25 ° C is lowered, and when it is higher than 80,000, there is a phase of the epoxy resin which is used in the case of using the cured resin composition. Poor solubility.

The weight average molecular weight is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

Acid value of the produced polycarboxylic acid resin (A) (using JIS K-2501 The measured method is preferably from 35 to 200 mgKOH/g, more preferably from 50 to 180 mgKOH/g, still more preferably from 60 to 150 mgKOH/g. When the functional group equivalent is less than 35 mgKOH/g, the mechanical properties of the cured product tend to deteriorate, and when it exceeds 150 mgKOH/g, the cured product tends to be too hard and the modulus of elasticity is too high.

The viscosity of the polycarboxylic acid resin (A) (E-type viscometer, measured at 25 ° C) is preferably from 50 to 800,000 mPa ‧ , more preferably from 500 to 100,000 mPa ‧ , and particularly preferably from 800 to 30,000 mPa ‧ s . When the viscosity is lower than 50 mPa‧s, there is a case where the viscosity is too low and it is not suitable for the use of the optical semiconductor sealing material. When the viscosity is higher than 800,000 mPa·s, there is a case where the viscosity is too high and the workability is poor.

In the cured resin composition of the present invention, two or more kinds of acid anhydrides, polycarboxylic acids, and polycarboxylic acid resins (A) may be used in combination. In particular, when a solid polycarboxylic acid is used in a liquid semiconductor or the like which is required to be liquid at room temperature (25 ° C), it is preferred to use a liquid acid anhydride and/or a polycarboxylic acid resin in combination ( A) and used as a liquid mixture. When used in combination, the acid anhydride and/or polycarboxylic acid resin (A) can be used in a ratio of from 0.5 to 99.5% by weight based on the total of the epoxy resin hardener.

An acid anhydride and/or a polycarboxylic acid and/or a polycarboxylic acid resin (A) when used as an epoxy resin hardener in combination with a curing agent other than the above-mentioned acid anhydride and/or polycarboxylic acid and/or polycarboxylic acid resin (A) The ratio of the total amount to the total amount of the hardener is preferably 30% by weight or more, and particularly preferably 40% by weight or more.

Examples of the curing agent that can be used together include an amine compound, a guanamine compound, and a phenol compound. As a specific example of a hardener that can be used, Mention may be made of amines or polyamine compounds (diaminodiphenylmethane, diethylidene triamine, triethylidene tetramine, diaminodiphenylsulfone, isophor a polyphenol (bisphenol A, bisphenol F, bisphenol S, etc.) of ketone diamine (isophoronediamine), dicyandiamide, dilinoleic acid dimer and ethylenediamine. Bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4, 4'-diphenol (3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol), hydroquinone, resorcinol, naphthalenediol ), tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, transalkane) Substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentane Alkene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4' - bis(chloromethyl)benzene, 1,4'-bis (methoxy a polycondensate of benzyl or the like, and the like, a halogenated bisphenol such as tetrabromobisphenol A, a condensate of a terpene and a phenol, and the like (imidazole, boron trifluoride-amine complex) However, it is not limited to these, and these may be used alone or in combination of two or more.

Hereinafter, the epoxy resin contained in the cured resin composition for optical semiconductor sealing of the present invention will be described. Examples of the epoxy resin include an epoxy resin which is a glycidyl ether compound of a phenol compound, an epoxy resin which is a glycidyl etherate of various novolak resins, an alicyclic epoxy resin, and an aliphatic system. Epoxy resin, heterocyclic epoxy resin, shrinkage a glyceride-based epoxy resin, a glycidylamine-based epoxy resin, an epoxy resin obtained by glycidylating a halogenated phenol, a condensate having an epoxy group and a condensate of a hydrazine compound, and a ring A copolymer of a polymerizable unsaturated compound of an oxy group and a polymerizable unsaturated compound other than the above. Among them, from the viewpoint of the transparency of the cured product and the heat-resistant transparency, it is preferably one of the condensate of the epoxy group and the condensate of the other, that is, the polyoxyl skeleton epoxy resin. (B).

Hereinafter, the polyfluorene skeleton epoxy resin (B) will be described.

The polyfluorene skeleton epoxy resin (B) of the present invention is a resin having an epoxy group having a oxime bond (Si-O bond) as a main skeleton, and can be obtained, for example, by using an epoxy group-containing oxime compound. Further, obtained by polymerization of a hydrazine compound, a hydrolyzed polycondensate of an alkoxy decane compound having an epoxy group and an alkoxy decane having a methyl group or a phenyl group, or an alkoxy decane compound having an epoxy group and decane may be mentioned. a polycondensate of an alcohol-based terminal eucalyptus oil or the like. Further, an addition polymer of an anthracene resin having a hydroquinone group (SiH group) and an epoxy compound having an unsaturated hydrocarbon group such as a vinyl group or the like can also be exemplified.

With regard to the polyfluorene skeleton epoxy resin (B) in the present invention, among them, a decyl alcohol-terminated eucalyptus oil (e) and an epoxy group-containing hydrazine compound (f) (and an alkoxylate as necessary) are preferred. (g) A polyfluorene skeleton epoxy resin obtained as a raw material through the following two-stage production step.

Hereinafter, the stanol-based terminal eucalyptus oil (e), the epoxy group-containing hydrazine compound (f), and the alkoxy sulfonium compound (g) will be described.

First, the stanol-based terminal eucalyptus oil (e) will be described.

The stanol-based terminal eucalyptus oil (e) is a terminal having the following formula (3) A decyl alcohol-based oxime resin.

In the formula (3), R ₅ represents an alkyl group having 1 to 3 carbon atoms such as a methyl group or a phenyl group. R ₅ which is present in plural may be the same or different, and it is preferable to contain a phenyl group from the viewpoint of compatibility with other resins, high refractive index, and sulfurization resistance.

From the viewpoint of viscosity adjustment of the polyoxymethylene skeleton epoxy resin (B), it is preferred to contain a methyl group.

The ratio of the phenyl group contained is preferably 0.05 to 2.0 moles, more preferably 0.1 to 1.0 moles, still more preferably 0.15 to 0.3 moles, and even more preferably 0.15 to 0.2, based on the substituted methyl group 1 mole. Moor. If it is less than 0.05 mol, there is a case where the compatibility with other raw materials in the composition is poor, the refractive index of the cured product is low, the light extraction efficiency of the LED is deteriorated, or the sulfurization resistance is poor, and if it is higher than 2.0, In the case of Mohr, there is a case where the light resistance (UV resistance) of the cured product is poor or the thermal cycle resistance is poor.

In the formula (3), p is an average value and represents 3 to 200, preferably 3 to 100, more preferably 3 to 50. When p is less than 3, the cured product is too hard and the thermal cycle resistance is lowered. If p is more than 200, there is a case where the mechanical strength of the cured product is lowered.

The weight average molecular weight (Mw) of the stanol-based terminal eucalyptus (e) is preferably It is in the range of 400~3000 (GPC). When the weight average molecular weight is less than 400, it is difficult to express the characteristics of the oxygen-containing portion, and the heat resistance and the light resistance are poor. If it exceeds 3,000, it is used for the optical semiconductor because of the relatively clear layer separation structure. The permeability is reduced when the component is sealed.

In the present invention, the molecular weight of the stanol-based terminal eucalyptus oil (e) is a weight calculated based on a value measured by GPC (gel permeation chromatography) under the following conditions. Average molecular weight (Mw).

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

The stanol-based terminal eucalyptus oil (e) can be produced, for example, by hydrolyzing and condensing: dimethyldioxane, tolyldichlorodecane, diphenylalkane, dimethyldichlorodecane, toluene Dichlorodecane, diphenyl dichlorodecane.

Preferred examples of the stanol-based terminal eucalyptus oil (e) include the following product names. For example, PRX413 and BY16-873 manufactured by Toray Dow Corning, X-21-5841 and KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd., XC96-723, TSR160, YR3370, YF3800, XF3905, and YF3057 manufactured by Momentive Co., Ltd. YF3807, YF3802, YF3897, YF3804, XF3905, manufactured by Gelest DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS- 0332, PDS-1615, PDS-9931, etc. Among the above, from the viewpoints of molecular weight and dynamic viscosity, it is preferably PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-. S15, DMS-S21, PDS-1615. Among these, from the viewpoint of molecular weight, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable. These stanol-based terminal eucalyptus oils (e) may be used singly or in combination of two or more.

Next, the epoxy group-containing telluride (f) will be described.

The epoxy group-containing telluride (f) in the present invention is an alkoxyhalide compound represented by the formula (4).

XSi(R ₆ ) _q (OR ₇ ) _r    (4)

In the formula (4), X is not particularly limited as long as it is an organic group having an epoxy group.

For example, β-glycidoxy ethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, and the like have a carbon number of 1 to 4 substituted by a glycidoxy group. Alkyl, glycidyl, β-(3,4-epoxycyclohexyl)ethyl, γ-(3,4-epoxycyclohexyl)propyl, β-(3,4-epoxycycloheptane Ethyl group, 4-(3,4-epoxycyclohexyl)butyl, 5-(3,4-epoxycyclohexyl)pentyl, etc. A cycloalkyl group of 5 to 8 is substituted with an alkyl group having 1 to 5 carbon atoms. In the above, an alkyl group having 1 to 3 carbon atoms substituted with a glycidyloxy group and an alkyl group having 1 to 3 carbon atoms substituted by a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group is preferably used. It is β-glycidoxyethyl, γ-glycidoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, and especially in terms of coloring inhibition, preferably β -(3,4-Epoxycyclohexyl)ethyl.

In the formula (4), R ₆ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl Wait. Among these R ₆ , a methyl group or a phenyl group is preferred from the viewpoint of compatibility and heat-resistant transparency of the cured product.

R ₇ in the formula (4) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Among these R ₇ , a methyl group or an ethyl group is preferred from the viewpoint of reaction conditions such as compatibility and reactivity, and a methyl group is particularly preferable.

q in the formula (4) is an integer and represents 0, 1, 2, and r represents (3-q). q is preferably 0 or 1 from the viewpoint of the viscosity of the polyoxymethylene skeleton epoxy resin (B) and the mechanical strength of the cured product.

Preferred examples of the epoxy group-containing telluride (f) include β-glycidoxy ethyltrimethoxysilane and β-glycidoxyethyltriethoxysilane. Baseline, γ-glycidoxypropyltrimethoxydecane, γ-glycidyloxy Propyltriethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropylphenyldimethoxydecane, γ-glycidoxypropylcyclohexyl Dimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2-( 3,4-Epoxycyclohexyl)ethylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethylphenyldimethoxydecane, 2-(3,4- Ethoxycyclohexyl)ethylcyclohexyldimethoxydecane, etc., more preferably 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. These epoxy group-containing tellurides (f) may be used singly or in combination of two or more kinds, and may be used in combination with the alkoxy sulfonate (g) shown below.

In the polyoxymethylene skeleton epoxy resin (B), an alkoxy ruthenium compound (g) represented by the following formula (5) can be used together with the epoxy group-containing telluride (f). The viscosity, refractive index, and the like of the polyfluorene skeleton epoxy resin can be adjusted by using the alkoxylate (g) in combination.

Si(R ₆ ) _s (OR ₇ ) _t    (5)

R ₆ and R ₇ in the formula (5) represent the same contents as the above, and s is an integer and represents 0, 1, 2, and 3, and t represents (4-s).

Preferable specific examples of the alkoxyhalide compound (g) which can be used together include methyltrimethoxydecane, phenyltrimethoxydecane, cyclohexyltrimethoxydecane, methyltriethoxydecane, and phenyl. Triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, and the like. Among the above, preferred are methyltrimethoxydecane, phenyltrimethoxydecane, dimethyldimethoxydecane, and diphenyl. Dimethoxy decane.

In the present invention, from the viewpoint of an increase in refractive index and a decrease in sulfidation resistance, a decyl alcohol-terminated eucalyptus oil (e) and an epoxy group-containing hydrazine compound (f) (and an optional alkane) are preferably used. At least one of the oxonides (g)) uses a compound having an aromatic skeleton, and it is particularly preferred to use a compound having a phenyl group. In particular, the stanol-based terminal eucalyptus oil (e) preferably has a phenyl group. The reason for this is that the excessive viscosity increase of the polyfluorene skeleton epoxy resin (B) can be suppressed by using the decyl alcohol-based terminal eucalyptus oil (e) introduced with a phenyl group, and on the other hand, if a phenyl group is used The epoxy group-containing telluride (f) (and, if necessary, the alkoxylate (g)) may have a large increase in viscosity and poor workability.

In the production of the polyoxyl skeleton epoxy resin (B), the epoxy group-containing telluride (f) is used in an amount of less than 1.5 equivalents per equivalent of the stanol group of the decyl alcohol end oxime (e). And (or optionally alkoxylate (g)) alkoxy group, then two or more of the epoxy group-containing telluride (f) (and optionally alkoxylate (g)) The oxy group reacts with the stanol group at the terminal end of the decyl alcohol-terminated eucalyptus oil (e), and is excessively polymerized at the end of the production step 1 described below to cause gelation. Therefore, it is necessary to react an alkoxy group in an amount of 1.5 equivalent or more with respect to 1 equivalent of the stanol group. From the viewpoint of controlling the reaction, it is preferably 2.0 equivalent or more.

Next, the manufacturing steps 1 and 2 will be described.

(manufacturing step 1)

Condensation of a decyl alcohol group of a decyl alcohol end oxime oil (e) with an alkoxy group of an epoxy group-containing oxime compound (f) (and optionally an alkoxylate (g)) And the step of obtaining the modified oyster sauce (h).

(manufacturing step 2)

After the production step 1, a step of hydrolyzing and condensing the remaining alkoxy group is carried out by adding water.

The present invention is characterized in that the polymerization of the modified emu oil (h) and the epoxy group-containing telluride (f) (and optionally the alkoxylate (g)) is carried out via the above-mentioned production steps 1 and 2.

By dividing the manufacturing step into two stages, the stanol group of the decyl alcohol end eucalyptus oil (e) and the oxo group containing the epoxy group (f) (and optionally the alkoxylate (g)) After the alkoxy group is reacted to obtain the modified eucalyptus oil (h), the residual alkoxy group is subjected to dealcoholization condensation to obtain a uniform stable product.

If the manufacturing step is set to one stage and water is added at the beginning of the production, the condensation reaction of the stanol group with the alkoxy group and the polymerization reaction of the alkoxydecane with each other may become a competitive reaction due to the mutual reaction rate. The difference in the compatibility of the product results in the acquisition of a heterogeneous compound, or the adverse effect on the product due to the residual large amount of stanol-based terminal eucalyptus oil (e) having no epoxy group.

The production step 1 is preferably carried out in the presence of a solvent, and in terms of controlling the reaction, an alcohol is particularly preferred in the solvent. Examples of the alcohol which can be used include alcohols having 1 to 10 carbon atoms, and specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, octanol, and decyl alcohol. , decyl alcohol, cyclohexanol, cyclopentanol and the like. In the present invention, a primary alcohol or a secondary alcohol is preferred, and it is particularly preferred to use a primary alcohol or a primary alcohol and a secondary alcohol. Examples of the primary alcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, decyl alcohol, decyl alcohol, and propylene glycol. Further, as an example of the secondary alcohol, isopropyl alcohol or cyclohexane may be mentioned. Alcohol, propylene glycol, and the like. Further, in view of the subsequent removal performance, a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol or t-butanol is preferred. These alcohols may be used in combination, and when they are mixed, they are preferably two or more selected from the group consisting of primary alcohols and secondary alcohols, and at least one kind is preferable in terms of excellent solubility of the following catalysts. The composition contains a primary alcohol. The amount of the preferred primary alcohol is 5% by weight or more, more preferably 10% by weight or more based on the total amount of the alcohol.

In the present reaction, a secondary alcohol is used, whereby the amount of change in the weight average molecular weight per unit time of the reaction system of the production step 1 is smaller than that in which only the primary alcohol is used, so that the control of the reaction is easier. In general, in the case of large-scale reaction such as industrial production, strict control of reaction time and reaction temperature becomes difficult, and therefore, in terms of controlling the reaction, the combination of secondary alcohols is useful for large-scale reactions such as industrial production.

In the production step 1, the amount of the alcohol used is preferably based on the total weight of the decyl alcohol-terminated oxime (e) and the epoxy group-containing oxime (f) (and optionally the alkoxylate (g)). It is contained in an amount of 2% by weight or more. More preferably, it is 2 to 100% by weight, further preferably 3 to 50% by weight, and particularly preferably 4 to 40% by weight.

When the amount is more than 100% by weight, the progress of the reaction is extremely slow. When the amount is less than 2% by weight, the reaction other than the target reaction is carried out to cause a high molecular weight, which causes gelation, an increase in viscosity, and elasticity of the cured product. The increase in modulus.

In the present reaction, other solvents may be used in combination as needed.

As a solvent which can be used together, for example, esters such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butyrate can be exemplified. Classes, such as hydrocarbons of hexane, cyclohexane, toluene, xylene, and the like.

The reaction in the production step 1 can also be carried out without a catalyst, but if the catalyst is not used, the reaction proceeds slowly, so from the viewpoint of shortening the reaction time, it is preferably carried out in the presence of a catalyst. . As the usable catalyst, any compound which exhibits acidity or alkalinity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid, acetic acid, and oxalic acid. Further, as an example of the alkaline catalyst, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide or barium hydroxide such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate can be used. An inorganic base such as an alkali metal carbonate, an organic base such as ammonia, triethylamine, di-ethyltriamine, n-butylamine, dimethylaminoethanol, triethanolamine or tetramethylammonium hydroxide.

Among these, an alkaline base is preferred, and an inorganic base is preferred because it is easy to remove the catalyst from the product. Specifically, an alkali metal salt such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or an alkaline earth metal salt is preferred, and a hydroxide is particularly preferred.

The amount of the catalyst added is usually 0.001 to 5% by weight based on the total weight of the decyl alcohol-terminated oxime (e) and the epoxy group-containing oxime (f) (and optionally the alkoxylate (g)). Preferably, it is 0.01 to 2% by weight.

The catalyst may be added directly or dissolved in a soluble solution. It is used in the state of the agent or the like. Among them, it is preferred to add the catalyst in a state in which the catalyst is dissolved in an alcohol such as methanol, ethanol, propanol or butanol. At this time, since the sol-gel reaction other than the target reaction competes, the alkoxy group of the epoxy group-containing telluride (f) (and optionally the alkoxylate (g)) is condensed. On the other hand, the reaction product formed by this is incompatible with the stanol-based terminal eucalyptus oil (e), and it is likely to be white turbid. Therefore, it is necessary to add it as an aqueous solution using water or the like.

The allowable range of moisture at this time is usually 0.5 by weight relative to the total weight of the decyl alcohol-terminated oxime (e) and the epoxy-containing oxime (f) (and optionally the alkoxylate (g)). % or less, more preferably 0.3% by weight or less, and even more preferably no moisture as much as possible.

The reaction temperature in the production step 1 depends on the amount of the catalyst and the solvent to be used, and is usually 20 to 160 ° C, preferably 40 to 100 ° C, and particularly preferably 50 to 95 ° C. Further, the reaction time is usually from 1 to 20 hours, preferably from 3 to 12 hours.

It is considered that the modified eucalyptus oil (h) obtained in the above-described manner in the production step 1 has a structure represented by the following formula (6) as a main component (confirmation of the structure is difficult and cannot be correctly identified).

In the formula (6), R ₅ and p have the same meanings as described above. R ₈ represents any of X, R ₆ and -OR ₇ described above, and R ₉ represents R ₆ and/or -OR ₇ .

Next, the manufacturing step 2 will be described in detail.

After completion of the reaction in the production step 1, water is added to carry out polymerization of the alkoxy groups remaining in the obtained modified eucalyptus oil (h) (sol-gel reaction). In this case, the above-mentioned epoxy group-containing telluride (f) (and optionally alkoxylate (g)) and a catalyst may be added as needed within the above range. The reaction is based on (1) upgrading the eucalyptus oil (h) to each other, and/or (1) upgrading the eucalyptus oil (h) and (2) the epoxy group-containing hydrazine compound (f) (and alkoxylation in the case of use) Between the substances (g)), and/or (3) the oxime containing the epoxy group (f) (and the alkoxy saccharide (g) in the case of use) and (4) the oxime containing the epoxy group ( f) (and in the case of use, a step of carrying out a polymerization reaction between a part of the polymer of the alkoxylate (g)) and the modified eucalyptus oil (h). It is considered that the polymerization reactions of the above (1) to (4) are simultaneously carried out in parallel.

In particular, in the production step 2, as in the prior art, as the catalyst, an alkaline inorganic catalyst is also preferable, and the necessary amount can be added in advance at the stage of the production step 1. However, it should not exceed the range described in the manufacturing step 1 as a preferred aspect.

In the production step 2, it is preferred to add a solvent.

As the solvent in the production step 2, it is preferred to use an alcohol in the same manner as in the production step 1. Examples of the alcohol that can be used include alcohols having 1 to 10 carbon atoms, and specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, octanol, and decyl alcohol. Sterol, cyclohexanol, cyclopentanol, and the like. In the present invention, a primary alcohol, a secondary alcohol, and particularly preferably a primary alcohol are particularly preferred. Further, in view of the subsequent removal performance, a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol or t-butanol is preferred. These alcohols can be used in combination. The presence of such alcohols contributes to molecular weight control and stability.

The amount of the alcohol added is relative to the total weight of the decyl alcohol-terminated eucalyptus oil (e) added in the production step 1 and the epoxy group-containing hydrazine compound (f) (and optionally the alkoxylate (g)). 20 to 200% by weight, preferably 20 to 150% by weight, particularly preferably 30 to 120% by weight.

Water is added to the production step 2 (any of ion-exchanged water, distilled water, and purified water can be used). The amount of water used is usually from 0.5 to 8.0 equivalents, more preferably from 0.6 to 5.0 equivalents, still more preferably from 0.65 to 2.0 equivalents, based on the amount of the alkoxy group remaining.

When the amount of water is less than 0.5 equivalent, there is a possibility that the progress of the reaction proceeds slowly, and the epoxy group-containing telluride (f) (and optionally the alkoxylate (g)) does not react. Problems such as residualness, or the inability to form a sufficient mesh, cause hardening failure after hardening of the cured resin composition described below. Further, when it exceeds 8.0 equivalents, the molecular weight cannot be controlled, and a high molecular weight of more than necessary is required. Further, there is a possibility of hindering the stability of the polyoxymethylene skeleton epoxy resin (B).

The reaction temperature in the production step 2 depends on the amount of the catalyst and the solvent to be used, and is usually 20 to 160 ° C, preferably 40 to 100 ° C, and particularly preferably 50 to 95 ° C. Further, the reaction time is usually from 1 to 20 hours, preferably from 3 to 12 hours.

After the reaction is completed, the catalyst is removed by quenching and/or washing with water as needed. In the case of performing water washing, it is preferred to add a solvent which can be separated from water depending on the kind of the solvent to be used. As preferred solvents, for example, methyl ethyl ketone, methyl isobutyl ketone, ketone of cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, isopropyl butyrate and the like can be exemplified. , such as hexane, cyclohexane Hydrocarbons of alkane, toluene and xylene.

In the present reaction, the catalyst can be removed by washing only with water, and in the case of performing the reaction under any of acidic and basic conditions, it is preferably subjected to rapid cooling by a neutralization reaction and then washed with water. Alternatively, the adsorbent may be removed by filtration after adsorbing the catalyst with an adsorbent.

The neutralization reaction can be used as long as it is a compound which exhibits acidity or basicity. Examples of the compound which exhibits acidity include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid, acetic acid, and oxalic acid. Further, as an example of a compound showing basicity, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide or barium hydroxide such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate or hydrogencarbonate can be used. Potassium alkali metal carbonate, such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid, sodium phosphate triphosphate, etc., inorganic base, ammonia, triethylamine, diethyl ether An organic base such as an amine, n-butylamine, dimethylaminoethanol, triethanolamine or tetramethylammonium hydroxide. Among these, in particular, from the viewpoint of easy removal from the product, an inorganic base or an inorganic acid is preferred, and further preferably a phosphate which is more easily adjusted to a pH near neutral.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic/organic synthetic adsorbent, ion exchange resin, and the like. Specific examples thereof include the following products.

Examples of the activated clay include: activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, and G-168 manufactured by Toshinaga Chemical Co., Ltd., Galleon Earth, Mizuka Ace, manufactured by Mizusawa Chemical Industry Co., Ltd. Wait. Examples of the activated carbon include those manufactured by Ajinomoto Fine-Techno Co., Ltd. CL-H, Y-10S, Y-10SF, S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR, CW130AR, GM130A, etc. manufactured by Futamura Chemical Co., Ltd. Examples of the zeolite include Molecular Sieve 3A, 4A, 5A, and 13X manufactured by Union Showa. Examples of the synthetic adsorbent include Kyoword 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., or Amberlyst 15JWET, 15DRY, 16WET, 31WET, A21 manufactured by Rohm and Hass. Amberlite IRA400JCI, IRA403BLCI, IRA404JCI, Dowex 66, HCR-S, HCR-W2, MAC-3, etc. manufactured by Dow Chemical Company.

After the adsorbent is added to the reaction liquid and subjected to a treatment such as stirring or heating to adsorb the catalyst, the adsorbent is filtered, and the residue is washed with water, whereby the catalyst and the adsorbent can be removed.

After completion of the reaction or after quenching, it may be purified by washing and filtration by other conventional separation and purification means. Examples of the purification means include column chromatography, concentration under reduced pressure, distillation, and extraction. These purification means may be carried out singly or in combination of plural kinds.

When the reaction is carried out using a solvent mixed with water as a reaction solvent, it is preferred to use a solvent which can be separated from water after the reaction solvent mixed with water is removed from the system by distillation or concentration under reduced pressure after quenching. Washed with water.

After washing with water, the polyfluorene skeleton epoxy resin (B) of the present invention can be obtained by removing the solvent by concentration under reduced pressure or the like.

The polyfluorene skeleton skeleton epoxy resin (B) obtained in the above manner is usually colorless and transparent, and is liquid in a fluidity at 25 °C. Again, its The molecular weight is preferably from 800 to 3,000, more preferably from 1,000 to 3,000, still more preferably from 1,500 to 2,800, based on the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, there is a case where the heat resistance is lowered. When the weight average molecular weight is higher than 3,000, there is a case where the sealing material is peeled off from the substrate during reflow using the sealed LED element.

The weight average molecular weight is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

The epoxy equivalent of the polyoxymethylene skeleton epoxy resin (B) (measured by the method described in JIS K-7236) is preferably from 300 to 1,500 g/eq, more preferably from 320 to 1400 g/eq, and further preferably. It is 350~1200 g/eq, especially 350~1000 g/eq. When the epoxy equivalent is less than 300 g/eq, the cured product tends to be too hard, and when it is higher than 1500 g/eq, the mechanical properties of the cured product tend to deteriorate.

The polyoxyl skeleton epoxy resin (B) may be a single polyfluorene skeleton epoxy resin (B), or a mixture of two or more polyfluorene skeleton epoxy resins (B). Here, as far as the moderate mechanical strength of the hardened material is concerned, In the case of a single polyoxyl skeleton epoxy resin (B), the epoxy resin is preferably from 300 to 1500 g/eq, particularly preferably from 350 to 1000 g/eq; in the case of two or more polyfluorene skeletons In the case of a mixture of epoxy resins (B), the epoxy equivalent of the specific polyoxyl skeleton epoxy resin (B) × (the content of the specific polyoxyl skeleton epoxy resin (B) / polyoxyn skeleton The epoxy equivalent of the sum of the total amount of the epoxy resins (B) is preferably from 300 to 1,500 g/eq, particularly preferably from 350 to 1000 g/eq.

The viscosity of the polyoxyl skeleton epoxy resin (B) (measured by an E-type viscometer at 25 ° C) is preferably 50 to 20,000 mPa ‧ , more preferably 500 to 10,000 mPa ‧ , and particularly preferably 800 5,000 mPa‧s. When the viscosity is less than 50 mPa ‧ s, there is a case where the viscosity is too low and it is not suitable for the use of the optical semiconductor sealing material, and when it is higher than 20,000 mPa ‧ s, the viscosity is too high and the workability is lowered.

In the polyfluorene skeleton epoxy resin (B), the ratio of the ruthenium atom having three oxygen atoms bonded to the entire ruthenium atom is preferably from 3 to 50 mol%, more preferably from 5 to 30 mol%, It is especially good for 6~15 moles. If the ratio of the ruthenium atom bonded to the three oxygen atoms derived from the sesquisestam atom to all the ruthenium atoms is less than 3 mol%, the cured product tends to be too soft, and surface wrinkles or damage may occur. The situation. Moreover, if it exceeds 50 mol%, there exists a case where a hardened|cured material becomes hard.

The ratio of the ruthenium atoms present can be determined by ¹ H NMR (nuclear magnetic resonance), ²⁹ Si NMR, elemental analysis, or the like of the polyfluorene skeleton epoxy resin (B).

The above is preferred for the polyoxyl skeleton epoxy resin (B) of the present invention. Illustratively, that is, a condensate of a decyl alcohol-terminated oleic oil (e) obtained by the production steps 1 and 2 and an alkyl group-containing oxime compound (f) (and optionally an alkoxylate (g)) .

As the polyoxyl skeleton epoxy resin (B), an epoxy group-containing telluride (f) (and optionally an alkoxylate (g)) which does not use the above stanol-based terminal eucalyptus oil (e) can also be exemplified. Polycondensate.

In this case, the epoxy group-containing telluride (f) (and the alkoxy group represented by the above formula (5) represented by the above formula (4) can be produced by a reaction of one stage. The telluride (g) is obtained by adding water in the presence of a catalyst or a solvent as described above, and condensing under the conditions of a reaction temperature of 40 to 100 ° C and a reaction time of 1 to 24 hours.

After the condensation, the condensate of the epoxy group-containing telluride (f) (and optionally the alkoxylate (g)) can be obtained by quenching, removing, washing with water and concentration as described above.

The embodiment of the polyfluorene skeleton epoxy resin (B) which is particularly preferable in view of having excellent sulfur resistance and excellent pot life is as follows.

(i) A polyfluorene skeleton epoxy resin (B) wherein the ratio of the phenyl group in the substituent bonded to the fluorene is 0.05 to 2.0 moles with respect to the substituted methyl group 1 mole.

(ii) A polyfluorene skeleton epoxy resin (B) wherein the ratio of the phenyl group in the substituent bonded to the oxime is 0.15 to 0.2 mol per mol of the substituted methyl group.

(iii) a polyfluorene skeleton epoxy resin (B) as described in (i) or (ii) above, The ratio of the ruthenium atom having 3 oxygen atoms bonded to the total ruthenium atom is 3 to 50 mol%.

(iv) a polyfluorene skeleton epoxy resin (B) according to the above (i) or (ii), wherein a ratio of ruthenium atoms having 3 oxygen atoms bonded to all ruthenium atoms is 6 to 15 mol% .

(v) The polyfluorene skeleton epoxy resin (B) according to any one of the above (i) to (iv), wherein the epoxy equivalent is from 350 to 1000 g/eq.

(vi) The polyxanylene skeleton epoxy resin (B) mixture according to any one of the above (i) to (iv), wherein when it is a mixture of two or more polyfluorene skeleton epoxy resins (B), The epoxy equivalent of the specific polyoxyl skeleton epoxy resin × (the content of the specific polyoxyl skeleton epoxy resin (B) / the total amount of the polyoxyl skeleton epoxy resin (B)) The equivalent weight is 350~1000 g/eq.

In the resin composition for optical semiconductor sealing of the present invention, an epoxy resin other than the above-mentioned polyoxymethylene skeleton epoxy resin (B) may be used singly or in combination.

Examples of other epoxy resins that can be used include epoxy resins which are glycidyl ether compounds of phenol compounds, epoxy resins which are glycidyl ether compounds of various novolak resins, alicyclic epoxy resins, and fats. Family epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, epoxy resin obtained by glycidylating halogenated phenols, polymerization with epoxy groups A copolymer of an unsaturated compound and a polymerizable unsaturated compound other than the above.

As a ring of glycidyl etherate which can be used as the above phenolic compound Examples of the oxygen resin include epoxy resins such as 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-double [ 4-(2,3-hydroxy)phenyl]ethyl]phenyl]propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethylbisphenol 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'-methylene Base-bis(4-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, isophthalic acid Diphenols, hydroquinones, pyrogallols, phloroglucinol, phenols having a diisopropylidene skeleton, 1,1-di-4-hydroxyphenylhydrazine and the like, phenols having an anthracene skeleton, phenol A glycidyl etherate of a polyphenol compound such as polybutadiene.

Examples of the epoxy resin which can be used as the glycidyl etherate of the various novolak resins include phenol, cresol, phenol, butanol, octylphenol, bisphenol A, and bisphenol F. A phenol novolak resin containing various phenols such as bisphenols and naphthols, a phenolic novolac resin containing a xylene skeleton, a phenolic novolac resin containing a dicyclopentadiene skeleton, and a biphenyl skeleton The phenolic novolac resin, the glycidyl etherified product of various novolak resins, such as a phenolic novolak resin containing an anthracene skeleton.

Examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-(3,4-epoxy)carboxylic acid cyclohexyl ester and bis(3,4-epoxycyclohexyl). An alicyclic epoxy resin having an aliphatic ring skeleton such as methyl) adipate.

Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.

Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric acid ring or an intramethylene urea ring.

The glycidyl ester-based epoxy resin may, for example, be an epoxy resin composed of a carboxylic acid ester such as hexahydrophthalic acid diglycidyl ester.

Examples of the glycidylamine-based epoxy resin include an epoxy resin obtained by glycidylating an amine such as aniline or toluidine.

Examples of the epoxy resin obtained by glycidylating a halogenated phenol include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, and brominated cresol novolac. An epoxy resin obtained by glycidylating a halogenated phenol such as chlorinated bisphenol S or chlorinated bisphenol A.

As a copolymer of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound other than the above, commercially available products include Marproof G-0115S, Marproof G-0130S, and Marproof. G-0250S, Marproof G-1010S, Marproof G-0150M, Marproof G-2050M (manufactured by Nippon Oil Co., Ltd.), etc., as the polymerizable unsaturated compound having an epoxy group, for example, glycidyl acrylate and methyl group are mentioned. Glycidyl acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, and the like. Moreover, examples of the copolymer of the other polymerizable unsaturated compound include methyl (meth)acrylate, (meth)acrylate, (benzyl) methacrylate, cyclohexyl (meth)acrylate, and benzene. Ethylene, ethylene cyclohexane, and the like.

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

Among the above epoxy resins, from the viewpoint of transparency, heat-resistant transparency, and light-resistant transparency, an alicyclic epoxy resin is preferably used in combination. In the case of an alicyclic epoxy resin, it is preferred to have an epoxycyclohexane in the skeleton. The compound of the structure is particularly preferably an epoxy resin obtained by an acidification reaction of a compound having a cyclohexene structure.

Examples of the epoxy resin include those obtained by oxidizing a compound which can be produced by the following method (all of which are incorporated herein by reference): esterification of cyclohexenecarboxylic acid with an alcohol Or an esterification reaction of cyclohexene methanol with a carboxylic acid (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc.), or a cyclohexaaldehyde quaternary reaction (tishchenko) The method described in Japanese Patent Laid-Open No. Hei. No. 2003-262871, and the like, and the transesterification reaction of cyclohexene carboxylate (Japanese Patent Laid-Open No. 2006-052187) The method described in the bulletin and the like).

The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, new a glycol such as pentanediol, tricyclodecane dimethanol or norbornene, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1, Triols such as 4-butanediol, tetraols such as neopentyl alcohol and di-trimethylolpropane. Further, examples of the carboxylic acid include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid, but are not limited thereto.

Further, an acetal compound obtained by a reaction of a cyclohexenal derivative with an acetal of an alcohol may be mentioned.

Specific examples of the epoxy resins include: ERL-4221 UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celloxide 2021P, Epolead GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries), and dicyclopentadiene Epoxides and the like, but are not limited thereto (Reference: Epoxy Resin General Basics, p. 76-85, the entire contents of which are incorporated herein by reference).

In the case where the polyfluorene skeleton epoxy resin (B) and other epoxy resins are used in combination, the ratio of the polyoxymethylene skeleton epoxy resin (B) is preferably 60 to 99 parts by weight with respect to the entire epoxy resin composition. It is especially suitable for 90 to 97 parts by weight. When it is less than 60 parts by weight, the light resistance (UV resistance) of the cured product may be lowered.

In the hardened resin composition of the present invention, the blending ratio of all the epoxy resin and the epoxy resin hardener containing the polyfluorene skeleton epoxy resin (B) is preferably 1 equivalent to the epoxy group of the entire epoxy resin. To use 0.5 to 1.2 equivalents of hardener. When it is less than 0.5 equivalents or more than 1.2 equivalents with respect to 1 equivalent of the epoxy group, there is a case where hardening is incomplete and good hardened physical properties cannot be obtained.

In the hardened resin composition of the present invention, a hardening catalyst which is liquid at room temperature (25 ° C) and a hardened contact having a melting point of 40 to 200 ° C can be used without impairing the pot life characteristics of the cured resin composition. Use together with the media. As a curing catalyst which is liquid at room temperature (25 ° C), zinc octoate is mentioned in terms of transparency and sulfidation resistance.

When mixing a liquid hardening catalyst at room temperature (25 ° C) with a catalyst having a melting point of 40 to 200 ° C, the melting point of all the hardening catalysts The hardening catalyst for 40 to 20 ° C is preferably 60 to 99 parts by weight. If it is less than 60 parts by weight, there is a case where the pot life is lowered. Further, all of the curing catalyst is usually used in the range of 0.001 to 15 parts by weight based on 100 parts by weight of the total epoxy resin.

By using a coupling agent as needed in the cured resin composition of the present invention, the viscosity of the composition and the hardness of the cured product can be adjusted.

Examples of the coupling agent which can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxydecane, and 3-glycidoxypropylmethyldimethacrylate. Oxane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-(2-aminoethyl)3-aminopropylmethyldimethoxydecane, N-(2- Aminoethyl) 3-aminopropylmethyltrimethoxy decane, 3-aminopropyltriethoxy decane, 3-mercaptopropyltrimethoxy decane, vinyltrimethoxy decane, N-(2-(ethylene) N-(2-(vinylbenzylamino)ethyl) 3-aminopropyl trimethoxysilane hydrochloride, 3-methylpropenyloxypropyl trimethyl a decane coupling agent such as oxoxane, 3-chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxyoxane; (N-ethylaminoethylamino) isopropyl titanate, tristearyl Isopropyl triisostearoyl titanate, bis(dioctyl pyrophosphate) oxyacetate, bis(dioctyl phosphite) tetraisopropyl titanate, neoalkoxy tris(p-N-( a titanium-based coupling agent such as β-aminoethyl)aminophenyl) titanate; Ethylene zirconium pyruvate, zirconium methacrylate, zirconium propionate, neoalkoxy zirconate, neo-alkoxy neosyl zirconate, tris(dodecyl) benzenesulfonyl zirconate Neoalkoxy ester, neoalkoxy ester of tris(ethylenediamineethyl)zirconate, neoalkoxylate of tris(m-aminophenyl)zirconate, ammonium zirconium carbonate, acetoacetate A zirconium or aluminum coupling agent such as aluminum, aluminum methacrylate or aluminum propionate.

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

The coupling agent is usually contained in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on the hardening resin composition of the present invention.

In the cured resin composition of the present invention, by using an inorganic filler of a nanometer level as needed, mechanical strength and the like can be supplemented without impairing transparency. From the viewpoint of transparency, the standard of the nano level is preferably a filler having an average particle diameter of 500 nm or less, and particularly preferably an average particle diameter of 200 nm or less. Examples of the inorganic filler include crystalline vermiculite, molten vermiculite, alumina, zircon, calcium silicate, calcium carbonate, tantalum carbide, tantalum nitride, boron nitride, zirconium oxide, forsterite, and talc. A powder such as spinel, titanium oxide or talc, or a bead formed by spheroidizing or the like, but is not limited thereto. These filler materials may be used singly or in combination of two or more. The content of the inorganic filler is from 0 to 95% by weight based on the cured resin composition of the present invention.

In the cured resin composition of the present invention, a phosphor may be added as needed. The phosphor has, for example, a function of forming white light by absorbing a portion of the blue light emitted from the blue LED element and emitting wavelength-converted yellow light. The phosphor is previously dispersed in the cured resin composition, and thereafter the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include an aluminate of a rare earth element, a thiogallate, an orthosilicate, and the like. More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, a prophthalate phosphor, a thiogallate phosphor, or a sulfide phosphor can be exemplified, and YAlO ₃ :Ce can be exemplified. 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 or the like. As the particle diameter of the phosphor, the particle diameter known in the art can be used as the average particle diameter, and is usually from 1 to 250 μm, particularly preferably from 2 to 50 μm. In the case of using such a phosphor, the amount thereof is usually 1 to 80 parts by weight, preferably 5 to 60 parts by weight, per 100 parts by weight of the resin component.

In order to prevent sedimentation of various phosphors upon hardening, a thixotropes imparting agent typified by a fine powder of vermiculite (also referred to as aerosil or aerosol) may be added to the cured resin composition of the present invention. As such fine powder of vermiculite, for example, Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, RY200, RX200 (manufactured by Japan Aerosil Co., Ltd.).

In order to prevent coloring, the cured resin composition of the present invention may contain an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant.

As the above amine compound, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, tetrakis (2) can be mentioned. , 2,6,6-tetramethyl-4-piperidinyl-1,2,3,4-butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2, 2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxy Mixed ester of spiro[5,5]undecane, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-undecyloxy) Base-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, bis (2,2 ,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 4-benzene Methoxyoxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy] Ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]-2,2,6,6-tetramethylpiperidine, 1,2 , 2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5- Bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-1-(xin) Reaction product of oxy)-4-piperidinyl)ester, 1,1-dimethylethylhydroperoxide and octane, N,N',N",N"'-tetra-(4,6 - bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-three -2-yl)-4,7-dioxane-1,10-diamine, dibutylamine-1,3,5-three -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl) Polycondensate of phenyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imido]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 2, 2, 4, 4 -tetramethyl-20-(β-lauroyloxycarbonyl)ethyl-7-oxa-3,20-dioxaspiro[5,1,11,2]icosane-21-one, β - N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl acetate, N-ethyl decyl-3-dodecyl- 1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3, 20-dioxaspiro[5,1,11,2]icosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-dioxinbicyclo- [5,1,11,2]-docosane-20-propionic acid lauryl ester/tetradecyl ester, malonic acid [(4-methoxyphenyl)-methylene]- Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, N,N Hindered amines such as '-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-benzenedimethylamine, benzophenone-based compounds such as benzophenone, 2- (2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriene Oxazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3 -T-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-third-pentylphenyl)benzotriazole , the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propanoate and polyethylene glycol, 2-(2H- Benzotriazole-based compound such as benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2,4-di-t-butylphenyl-3,5-di- Benzoate such as tributyl-4-hydroxybenzoate, 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[(hexyl)oxy]phenol, etc. A compound or the like is particularly preferably a hindered amine compound.

As the amine compound which can be used as the above-mentioned light stabilizer, a commercially available product as shown below can be used.

The commercially available amine-based compound is not particularly limited, and examples thereof include TINUVIN 765, TINUVIN 770 DF, TINUVIN 144, TINUVIN 123, TINUVIN 622 LD, TINUVIN 152, CHIMASSO RB 944 manufactured by Ciba Specialty Chemicals, and LA-52, LA-57, LA-62 manufactured by ADEKA. , LA-63P, LA-77Y, LA-81, LA-82, LA-87, etc.

The phosphorus compound is not particularly limited, and examples thereof include 1,1,3-tris(2-methyl-4-di-phosphite tridecyl-5-t-butylphenyl)butane. (1,1,3-tris(2-methyl-4-ditridecylphosphite-5-t-butylphenyl)butane), distearyl pentaerythritol diphosphite, bis(2,4-di-t-butyl Phenyl) pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methyl Phenyl) pentaerythritol diphosphite, phenyl bisphenol A neopentyl alcohol diphosphite, dicyclohexyl neopentyl alcohol diphosphite, tris(diethylphenyl) phosphite, Tris(di-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(2) ,6-di-t-butylphenyl)phosphite, tris(2,6-di-t-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di -T-butylphenyl)(2,4-di-t-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl) ( 2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-t-butylphenyl) (2-tert-butyl- 4-methylphenyl)phosphite, 2,2'-ethylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) Phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-extended biphenylphosphonate, tetrakis(2,4-di-t-butylphenyl)- 4,3'-Extended biphenyl diphosphinate, tetrakis(2,4-di-t-butylphenyl)-3,3'-extended biphenylphosphonate, tetrakis (2,6- Di-t-butylphenyl)-4,4'-extended biphenylphosphonate, tetra ( 2,6-di-t-butylphenyl)-4,3'-extended biphenylphosphonate, tetrakis(2,6-di-t-butylphenyl)-3,3'- Biphenyl diphosphinate, bis(2,4-di-t-butylphenyl)-4-phenyl-phenylphosphinate, bis(2,4-di-t-butylphenyl) )-3-phenyl-phenylphosphinate, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di- Tributylphenyl)-4-phenyl-phenylphosphinate, bis(2,6-di-t-butylphenyl)-3-phenyl-phenylphosphinate, tetra(2) ,4-di-t-butyl-5-methylphenyl)-4,4'-extended biphenylphosphonate, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate Ester, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxyl phosphate, tributyl phosphate Ethyl ethyl ester, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like.

Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus-based compound is not particularly limited, and examples thereof include Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, and Adekastab 260 manufactured by ADEKA. Adekastab 522A, Adekastab 1778, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, and the like.

The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-third Butyl-6-methylphenol, 1,6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], three (3,5) -di-t-butyl-4-hydroxybenzyl)-isocyanate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl -4-hydroxybenzyl)benzene, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis-[2- [3-(3-Tertibutyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxy Spiro[5,5]undecane, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2'-butylene Bis(4,6-di-tert-butylphenol), 4,4'-butylene bis(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-third Butyl-2-hydroxy-5-methylbenzyl)-4-methylphenol acrylate, 2-[1-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl]- 4,6-di-third amyl phenyl acrylate, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-甲Base-6-tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-p-pentylphenol, 4, 4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), bis-[3,3 - bis-(4'-hydroxy-3'-tert-butylphenyl)-butyric acid]-glycol ester, 2,4-di-tert-butylphenol, 2,4-di-third pentyl Phenol, 2-[1-(2-hydroxy-3,5-di-third-pentylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate, bis-[3,3 -bis-(4'-hydroxy-3 '-Tertiary butylphenyl)-butyric acid]-diol ester and the like.

Commercially available products can also be used as the phenolic compound. The commercially available phenolic compound is not particularly limited, and examples thereof include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, IRGANOX 1520 L, manufactured by Ciba Specialty Chemicals, and Adekastab AO-20 manufactured by ADEKA. Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-330, SumiliZer GA-80, manufactured by Sumitomo Chemical Industries, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc.

Among them, commercially available additive materials can be used as the coloring preventive agent for the resin. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSO RB 2020 FDL, CHIMASSO RB FF, and the like manufactured by Ciba Specialty Chemicals can be cited.

At least one or more of the phosphorus compound, the amine compound, and the phenol compound are preferably contained, and the amount thereof is not particularly limited, and is 0.005 to 5.0% by weight based on the total weight of the cured resin composition of the present invention. .

The hardened resin composition of the present invention can be prepared by sufficiently mixing an additive such as a hardening catalyst having a melting point of 40 to 200 ° C, an epoxy resin, an epoxy resin hardener, a coupling agent, an antioxidant, and a light stabilizer. The composition is used as a sealing material. As the mixing method, a kneader, a three-roll mill, a universal mixer, a planetary mixer, a homomixer, a homodisperser, a bead mill, or the like can be used, and it can be mixed at normal temperature or under heating conditions.

Optical semiconductor elements such as high-brightness white LEDs are usually laminated on GaAs, GaP, GaAlAs, GaAsP, AIGa, InP, GaN, etc. on a substrate such as sapphire, spinel, SiC, Si, or ZnO using an adhesive (wafer bonding material). A semiconductor wafer such as InN, AlN, or InGaN is formed on a lead frame, a heat release plate, or a package. In order to circulate current, there is also a type in which a lead wire such as a gold wire is connected. In order to prevent the semiconductor wafer from being damaged by heat or moisture and functioning as a lens, it is sealed with a sealing material such as an epoxy resin. The hardened resin composition of the present invention can be used for the sealing material.

As a method of forming the sealing material, an injection method in which a sealing material is injected into a mold frame in which a substrate on which an optical semiconductor element is fixed is inserted and then heat-hardened and formed is formed; a sealing material is preliminarily injected onto the mold to be fixed on the substrate. A compression molding method in which an optical semiconductor element is immersed therein and heat-hardened, and then released from a mold.

As the injection method, a dispensing method or the like can be cited.

For heating, a hot air circulation type, an infrared ray, a high frequency, or the like can be used. The heating conditions are, for example, preferably from 80 to 230 ° C for about 1 minute to 24 hours. In order to reduce the internal stress generated during heat hardening, for example, pre-hardening may be carried out at 80 to 120 ° C for 30 minutes to 5 hours, and then subsequent hardening may be carried out at 120 to 180 ° C for 30 minutes to 10 hours.

In the present specification, the ratio, the percentage, the portion, and the like are based on the weight unless otherwise specified. In the present specification, the expression "X~Y" means a range from X to Y, and the range includes X and Y.

Example

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. Furthermore, the present invention is not limited to the above-described synthesis examples and examples. Further, each physical property value in the synthesis example was measured by the following method.

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

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 roots)

Flow rate: 1.0 ml/min

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refractive index detector)

○ Epoxy equivalent: measured by the method described in JIS K-7236.

○ Acid value: It was measured by the method described in JIS K-2501.

○ Viscosity: Measured at 25 ° C using an E-type viscometer.

Synthesis Example 1 (Synthesis Example of Polyaroxy Oxide Skeleton Epoxy Resin (B) Producing Cerium Alkenyl Terminal Emu Oil (e) and Epoxy Group Containing Telluride (f) via a Two-Step Manufacturing Process)

(manufacturing step 1)

394 parts of 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane and a dimethylol diphenyl decane having a stanol group having a molecular weight of 1,700 (GPC measured value) were added to the reaction vessel. There were 475 parts of 0.18 moles of phenyl group, 4 parts of a 0.5% KOH methanol solution, and 36 parts of isopropyl alcohol with respect to methyl 1 molar, and the temperature was raised to 75 °C. After the temperature was raised, the reaction was carried out under reflux for 10 hours.

(manufacturing step 2)

After adding 656 parts of methanol, 172.8 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and further reacted under reflux for 10 hours.

After completion of the reaction, it was neutralized by a 5% aqueous solution of sodium hydrogen monophosphate, and then methanol was recovered by distillation at 80 °C. Thereafter, 780 parts of MIBK was added for washing, and then washed with water three times. Then, 731 parts of the polyfluorene skeleton epoxy resin (B-1) was obtained by removing the solvent of the organic phase at 100 ° C under reduced pressure. The obtained resin had an epoxy equivalent of 491 g/eq, a weight average molecular weight of 2090, a viscosity of 3530 mPa·s, and a colorless transparent liquid.

Synthesis Example 2 (Synthesis example of a polyfluorene skeleton epoxy resin (B) which produces a decyl alcohol group-terminated eucalyptus oil (e) and an epoxy group-containing hydrazine compound (f) via a two-stage production step)

(manufacturing step 1)

Add 2-(3,4-epoxycyclohexyl)ethyltrimethoxine to the reaction vessel 444 parts of alkane having a molecular weight of 1700 (GPC measured value) of dimethylol diphenyl decane having a decyl alcohol group (having 0.18 moles of phenyl groups relative to methyl 1 molar) 400 parts, 0.5% KOH methanol The solution was 3.6 parts, 32.4 parts of isopropyl alcohol, and the temperature was raised to 75 °C. After the temperature was raised, the reaction was carried out under reflux for 10 hours.

(manufacturing step 2)

After adding 480 parts of methanol, 194.4 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and further reacted under reflux for 10 hours.

After completion of the reaction, it was neutralized by a 5% aqueous solution of sodium hydrogen monophosphate, and then methanol was recovered by distillation at 80 °C. Thereafter, 724 parts of MIBK was added for washing, and then washed three times with water. Then, 658 parts of the polyfluorene skeleton epoxy resin (B-2) was obtained by removing the solvent of the organic phase at 100 ° C under reduced pressure. The obtained resin had an epoxy equivalent of 410 g/eq, a weight average molecular weight of 2713, a viscosity of 15680 mPa·s, and a colorless transparent liquid.

Synthesis Example 3 (an oil (a) modified with both ends of methanol, a terminal alcohol polyester compound (b), a compound (c) having two or more carboxylic acid anhydride groups in the molecule, and a carboxylic anhydride group in the molecule Synthesis Example of Polycarboxylic Acid Resin (A) Obtained by Addition Reaction of Compound (d)

Adding 47.1 parts of Xenon X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), which is modified with methanol at both ends, to a glass separation flask equipped with a stirring device, a Dairy condenser, and a thermometer, ADEKA as a polyester polyol. NEWACE Y9-10 (ADEKA (shares) manufactured by the above formula (2) wherein R ₃ is a neopentyl group extending and R ₄ is butyl extension of the polyester polyol) 11.8 parts, RIKACID BT-100 (1,2,3 , 4-butane tetracarboxylic dianhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.) 2.5 parts, RIKACID MH (methylhexahydrophthalic anhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.), 16.6 parts, reacted at 140 ° C 77.5 parts of the polycarboxylic acid resin (A-1) was obtained in 10 hours. At this time, the peaks of RIKACID BT-100 and RIKACID MH disappeared in the GPC measurement. The polycarboxylic acid resin is a colorless and transparent liquid at the end of the reaction, but becomes a cloudy liquid as the temperature of the reaction liquid drops. The obtained compound had an acid value of 88.8 mgKOH/g, a weight average molecular weight of 3452, a viscosity of 5730 mPa·s, and a white liquid appearance.

Synthesis Example 4

(Polycarboxylic acid resin obtained by addition reaction of eucalyptus oil (a) having a two-terminal methanol modification, a hydrocarbon polyol compound (j), and a compound (c) having two or more carboxylic acid anhydride groups in the molecule (A) Synthesis example)

Adding 589 parts of Xenon X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), which is modified with methanol at both ends, to a glass separation flask equipped with a stirring device, a Dairy condenser, and a thermometer, as a hydrocarbon polyol compound 74 parts of cyclodecane dimethanol, 337 parts of RIKACID MH (methylhexahydrophthalic anhydride, manufactured by Nippon Chemical and Chemical Co., Ltd.), and reacted at 90 ° C for 10 hours to obtain a polycarboxylic acid resin (A-2) Share. At this time, the peak of RIKACID MH disappeared in the GPC measurement. The obtained compound had an acid value of 111.1 mgKOH/g, a weight average molecular weight of 1216, a viscosity of 7,870 mPa·s, and a colorless transparent liquid.

Example 1

40 parts of the polyfluorene skeleton epoxy resin (B-1) obtained in Synthesis Example 1 and the polyfluorene skeleton skeleton epoxy resin (B-2) 60 obtained in Synthesis Example 2 were added. Part, ERL-4221 (3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexylcarboxylate, manufactured by Dow Chemical) 5 parts, Synthesis Example 3 as an epoxy resin hardener 72.4 parts of the polycarboxylic acid resin (A-1) obtained in the above, 1.1 parts of zinc stearate (melting point: 120 to 126 ° C) as a curing catalyst, and these were mixed and defoamed for 5 minutes to obtain the present invention. A cured resin composition for optical semiconductor sealing.

Example 2

40 parts of the polyfluorene skeleton epoxy resin (B-1) obtained in Synthesis Example 1 and 60 parts of the polyfluorene skeleton epoxy resin (B-2) obtained in Synthesis Example 2 were added, and ERL-4221 (3) was added. , 4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexylcarboxylate (manufactured by Dow Chemical) 5 parts, a polycarboxylic acid obtained in Synthesis Example 3 as an epoxy resin hardener 72.4 parts of the resin (A-1) and 1.1 parts of zinc undecylenate (melting point: 115 to 125 ° C) as a curing catalyst, and these were mixed and defoamed for 5 minutes to obtain the hardening of the optical semiconductor sealing of the present invention. Resin composition.

Example 3

40 parts of the polyfluorene skeleton epoxy resin (B-1) obtained in Synthesis Example 1 and 60 parts of the polyfluorene skeleton epoxy resin (B-2) obtained in Synthesis Example 2 were added, and ERL-4221 (3) was added. , 4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexylcarboxylate (manufactured by Dow Chemical) 5 parts, a polycarboxylic acid obtained in Synthesis Example 3 as an epoxy resin hardener 72.4 parts of the resin (A-1) and 1.6 parts of zinc 12-hydroxystearate (melting point 145 to 155 ° C) as a curing catalyst, and these were mixed and defoamed for 5 minutes to obtain the optical semiconductor sealing of the present invention. Hardened resin composition.

Example 4

40 parts of the polyfluorene skeleton epoxy resin (B-1) obtained in Synthesis Example 1 and 60 parts of the polyfluorene skeleton epoxy resin (B-2) obtained in Synthesis Example 2 were added, and ERL-4221 (3) was added. , 4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexylcarboxylate (manufactured by Dow Chemical) 5 parts, a polycarboxylic acid obtained in Synthesis Example 3 as an epoxy resin hardener 72.4 parts of the resin (A-1) and 1.1 parts of zinc 12-hydroxystearate (melting point: 145 to 155 ° C) as a curing catalyst, and these were mixed and defoamed for 5 minutes to obtain the optical semiconductor sealing of the present invention. Hardened resin composition.

Example 5

60 parts of the polyfluorene skeleton epoxy resin (B-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexyl group was added. 5 parts of the polycarboxylic acid resin (A-2) obtained in Synthesis Example 4 as an epoxy resin hardener, 5 parts by weight of the carboxylic acid ester (manufactured by Dow Chemical), zinc stearate as a curing catalyst (melting point 120~) 1.1 parts of 126 ° C), and these were mixed and defoamed for 5 minutes to obtain a cured resin composition for optical semiconductor sealing of the present invention.

Comparative example 1

40 parts of the polyfluorene skeleton epoxy resin (B-1) obtained in Synthesis Example 1 and 60 parts of the polyfluorene skeleton epoxy resin (B-2) obtained in Synthesis Example 2 were added, and ERL-4221 (3) was added. , 4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexylcarboxylate (manufactured by Dow Chemical) 5 parts, a polycarboxylic acid obtained in Synthesis Example 3 as an epoxy resin hardener 72.4 parts of the resin (A-1), 0.5 parts of zinc octoate (liquid at room temperature (25 ° C)) as a curing catalyst, These were mixed and defoamed for 5 minutes to obtain a cured resin composition for optical semiconductor sealing.

Comparative example 2

60 parts of the polyfluorene skeleton epoxy resin (B-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexyl group was added. 5 parts of a polycarboxylic acid resin (A-2) obtained in Synthesis Example 4 as an epoxy resin hardener, 5 parts by weight of carboxylic acid ester (manufactured by Dow Chemical), zinc octoate as a hardening catalyst (at room temperature (25) 1.1 parts in a liquid form at ° C), and the mixture was mixed and defoamed for 5 minutes to obtain a cured resin composition for optical semiconductor sealing.

Evaluation test

The blending ratio of the cured resin composition for optical semiconductor sealing obtained in Examples 1 to 5 and Comparative Examples 1 and 2, and the pot life test of the cured product, the sulfurization resistance test, the hardness of the durometer, and the cured product transmittance The results are shown in Table 1. The tests in Table 1 were carried out in the following manner.

(1) Applicable period test:

The cured semiconductor composition for optical semiconductor sealing obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was filled in a 10 cc syringe made of polypropylene, vacuum degassed for 2 minutes, and placed at 25 ° C, 65%. The viscosity at 25 ° C was measured using an E-type viscometer at 0 hours, 8 hours, and 24 hours in an RH environment. The increase rate of the viscosity at each set time from the initial viscosity was calculated.

(2) Vulcanization resistance test:

The optical semiconductor seals obtained in Examples 1 to 5 and Comparative Examples 1 and 2 After the vacuum defoaming was performed for 5 minutes with the hardened resin composition, it was filled in a syringe, and cast on a surface-mount type LED equipped with a light-emitting element having an emission wavelength of 450 nm by using a precision discharge device so that the opening was flat. forming. After pre-curing at 120 ° C for 1 hour, it was cured at 150 ° C for 3 hours to seal the surface-mount LED. The surface-encapsulated LED was placed in a closed container of about 3.2 liters of polypropylene together with two polyethylene containers (opened) having an opening diameter of 2 cm and a height of 1.5 cm, which were filled with 6 ml of a 20% ammonium sulfide aqueous solution. Place at room temperature (20 ~ 27 ° C). After standing, the discoloration of the silver-plated portion of the bottom surface was visually confirmed. In the table, ◎ is completely discolored without being placed for 6 hours; ○ is completely discolored without being placed for 4 hours; Δ is slightly discolored when placed for 4 hours; and × is discolored if placed for 4 hours.

(3) Hardness tester hardness:

The cured resin composition for optical semiconductor sealing obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was subjected to vacuum degassing for 5 minutes, and then used to have an aluminum foil so as to have a diameter of 30 mm and a height of 70 mm. Casting in the mold. The cast molded product was pre-cured at 120 ° C for 1 hour, and then cured at 150 ° C for 3 hours to obtain a test piece for hardness tester having a thickness of 7 mm. The hardness of the obtained test piece (type A) was measured by the method described in JIS K-6253.

(4) Hardened material transmittance:

The epoxy resin composition obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was subjected to vacuum defoaming for 5 minutes, and then formed into a heat-resistant adhesive tape to have a size of 30 mm × 20 mm × a height of 0.8 mm. Slowly on the glass substrate of the barrier Cast molding. The cast molded product was pre-cured at 120 ° C for 1 hour, and then cured at 150 ° C for 3 hours to obtain a test piece for transmittance of 0.8 mm in thickness. The obtained test piece was measured for light transmittance at 400 nm under the following conditions.

Spectrophotometer measurement conditions

Manufacturer: Hitachi High-Technologies Co., Ltd.

Model: U-3300

Slit width: 2.0 nm

Scanning speed: 300 nm/min

From the results shown in Table 1, it is clear that Comparative Examples 1 to 2 which are liquid-based hardening catalyst zinc octoate at room temperature (25 ° C) are excellent in sulfidation resistance, but are placed in the pot life test for 8 hours. After the initial viscosity increased by 1.7 times to 2.0 times, the processability is poor. On the other hand, Examples 1 to 5 using a curing catalyst having a melting point of 40 to 200 ° C which is solid at room temperature (25 ° C) are excellent not only in vulcanization resistance but also in the pot life test. After the hour, the initial viscosity is increased by 1.2 to 1.4 times, so the workability is excellent. Further, the hardness of the durometer is moderate hardness, and the cured product has excellent transmittance, and can be preferably used as a resin composition for optical semiconductor sealing.

In addition, the present application is based on a Japanese patent application filed on Sep. 9, 2011 (Japanese Patent Application No. 2011-196936). Moreover, all references cited are incorporated herein in their entirety.

[Industrial availability]

The cured resin composition of the present invention is extremely useful as an optical semiconductor element (LED) sealing material because it has excellent sulfur resistance and long pot life.

Claims (14)

A cured resin composition for optical semiconductor sealing, comprising a curing catalyst having a melting point of 40 to 200 ° C, and an epoxy resin and/or an epoxy resin curing agent. The cured resin composition for optical semiconductor sealing according to the first aspect of the invention, wherein the epoxy resin curing agent is a polyvalent carboxylic acid resin (A), and the polycarboxylic acid resin (A) comprises: represented by the formula (1) An addition reaction of the methanol-modified oleic oil at both ends (a) with a compound (d) having a carboxylic anhydride group in the molecule, and a polyol compound (i) having two or more hydroxyl groups in the molecule and a carboxy group in the molecule Addition reactant of the acid anhydride group-containing compound (d): (In the formula (1), R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms or an alkylene group having an ether bond having 1 to 10 carbon atoms, and R ₂ each independently represents an alkyl group having 1 to 3 carbon atoms or Phenyl group, m is an average value and represents 1 to 100). The hardened resin composition for optical semiconductor sealing according to the first aspect of the invention, wherein the epoxy resin hardener is an oil (a) modified by the two-terminal methanol represented by the formula (1), and has two molecules in the molecule. A polyvalent carboxylic acid resin (A) obtained by subjecting a polyol compound (i) having a hydroxyl group or more and a compound (d) having a carboxylic anhydride group in the molecule to an addition reaction: (In the formula (1), R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms or an alkylene group having an ether bond having 1 to 10 carbon atoms, and R ₂ each independently represents an alkyl group having 1 to 3 carbon atoms or Phenyl group, m is an average value and represents 1 to 100). The hardened resin composition for optical semiconductor sealing according to the third aspect of the invention, wherein the polyvalent carboxylic acid resin (A) is further composed of a compound (c) having two or more carboxylic acid anhydride groups in the molecule as a reaction raw material. The winner of the addition reaction. The hardened resin composition for optical semiconductor sealing according to any one of claims 2 to 4, wherein the polyol compound (i) having two or more hydroxyl groups in the molecule is an end represented by the formula (2) Alcohol polyester compound: (In the formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and m is an average value and represents 1 to 100). The hardened resin composition for optical semiconductor sealing according to any one of the items 1 to 5, wherein the epoxy resin is a polyfluorene skeleton epoxy resin (B). The hardened resin composition for sealing an optical semiconductor element according to the sixth aspect of the invention, wherein the polyfluorene skeleton epoxy resin (B) is represented by the formula (3) obtained by the following production steps 1 and 2. A polymer of a decyl alcohol-terminated eucalyptus oil and an epoxy group-containing hydrazine compound represented by the formula (4), and an epoxy equivalent of 300 to 1500 g/eq as measured by the method described in JIS K-7236: Step 1: a step of condensing a decyl alcohol group of a decyl alcohol terminal sulfonate with an alkoxy group of an epoxy group-containing hydrazine compound to obtain a modified eucalyptus oil; and a production step 2, after the production step 1, adding water to carry out residual alkoxylation a step of hydrolytic condensation of a base; (In the formula (3), R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and p is an average value and represents 3 to 200; wherein, in the formula, R ₅ may be the same or different); XSi(R) ₆ ) _q (OR ₇ ) _r (4) (In the formula (4), X represents an organic group containing an epoxy group, and R ₆ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or An aromatic hydrocarbon group having 6 to 10 carbon atoms, R ₇ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, q is an integer and represents 0 to 2, and r is an integer, indicating (3-q) )). The hardened resin composition for optical semiconductor sealing according to any one of the above-mentioned items, wherein the curing catalyst having a melting point of 40 to 200 ° C is a metal soap-based curing catalyst. The hardened resin composition for optical semiconductor sealing according to the eighth aspect of the invention, wherein the metal soap is a zinc salt composed of a carboxylic acid compound. The hardened resin composition for optical semiconductor sealing according to the ninth aspect of the invention, wherein the zinc salt composed of a carboxylic acid compound is a zinc salt composed of a monocarboxylic acid compound having a hydroxyl group having 10 to 30 carbon atoms. The hardened resin composition for optical semiconductor sealing according to claim 10, wherein the monocarboxylic acid compound having a hydroxyl group having 10 to 30 carbon atoms is 12-hydroxystearic acid. The hardened resin composition for optical semiconductor sealing according to claim 10, wherein the monocarboxylic acid compound having a hydroxyl group having 10 to 30 carbon atoms is stearic acid. A cured product obtained by curing the cured resin composition for optical semiconductor sealing according to any one of claims 1 to 12. An LED having a cured product of claim 13 of the patent application.