TWI504628B - Hardened resin composition and hardened product thereof - Google Patents

Description

Curable resin composition and cured product thereof

The present invention relates to a curable resin composition suitable for use in electrical and electronic materials, particularly suitable for use in optical semiconductors, and cured products thereof.

As a sealing material for an optical semiconductor element such as an LED (Light Emitting Diode) product, an epoxy resin composition is used from the viewpoint of balance between performance and economy. In particular, a glycidyl ether type epoxy resin composition typified by a bisphenol A type epoxy resin excellent in heat resistance, transparency, and mechanical properties is widely used.

However, the industry has pointed out that the short-wavelength of the light-emitting wavelength of LED products (below 480 nm in LED products mainly emitting blue light) results in the coloring of the above-mentioned sealing materials on LED chips due to the influence of short-wavelength light. Finally, as an LED product, the illumination is reduced.

Therefore, an alicyclic epoxy resin represented by 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate and a glycidyl ether type epoxy resin composition having an aromatic ring In contrast, it is more excellent in transparency, and it is actively being studied as an LED sealing material (Patent Documents 1 and 2).

In general, an acid anhydride-based compound of the epoxy resin used in such a field is exemplified. In particular, an acid anhydride formed of a saturated hydrocarbon is used in many cases because it is excellent in light resistance of a cured product. The acid anhydride is usually an alicyclic acid anhydride such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride or tetrahydrophthalic anhydride, and in terms of ease of handling, it is mainly used at normal temperature. It is liquid methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride or the like.

However, when the above alicyclic acid anhydride is used as a hardener, the hardeners partially evaporate at the time of hardening due to a high vapor pressure, and thus are used as an hardener for an epoxy resin in an open system. In the case of thermal curing, not only the following problems occur, but also the characteristics thereof vary greatly depending on the hardening conditions, and it is difficult to stably obtain a cured product having a target property. The above problem means that the hardener itself volatilizes into the atmosphere, resulting in harmful substances toward Environmental pollution caused by the release of the atmosphere, adverse effects on the human body, and contamination of the production line, and poor curing of the epoxy resin composition caused by the absence of a specific amount of carboxylic anhydride (hardener) in the hardened material.

Moreover, the use of the hardened material of the prior hardener is more problematic when sealing the LED, especially the SMD (Surface Mount Device), and since the amount of the resin used is small, there is a problem that the depression occurs due to the problem of the previous volatilization. In the worst case, the line will be exposed. Further, cracks, peeling, and the like at the time of reflow soldering are insufficient due to insufficient hardening, so that it is difficult to withstand long-time lighting.

Further, as another problem, in recent years, LED products have been developed to have higher brightness for backlights such as lighting or TVs, and more heat is generated when lighting LEDs, so even if the alicyclic epoxy resin is used. The resin composition is also colored on the LED wafer, and eventually, as an LED product, the illuminance is lowered, and there is a problem in terms of durability (Patent Document 3).

Due to the problem of the durability of the above-mentioned epoxy resin, a oxoxane skeleton (specifically, Si-O) has been introduced, such as a polyoxyxylene resin or a polyfluorene-modified epoxy resin. The resin of the skeleton of the bond is used as a sealing material (Patent Document 3).

It is known that a resin which is usually introduced with a rhodium skeleton is more stable to light than an epoxy resin. Therefore, when it is used for the sealing material of the LED product, it can be said that the durability is superior to that of the epoxy resin from the viewpoint of coloring on the LED wafer. However, there are problems.

The resin into which the decane skeleton is introduced is more likely to exhibit friability significantly more than the usual epoxy resin. Therefore, the reflow resistance is poor, and the cracks during reflow are remarkable.

Further, the resin into which the decane skeleton is introduced is inferior in gas permeability resistance to a general epoxy resin. Therefore, when a polyfluorene oxide resin or a polyoxymethylene-modified epoxy resin is used as the LED sealing material, although coloring on the LED wafer is not a problem, there is a problem that deterioration and coloration of the internal constituent members are caused. . In particular, when used in a living environment, various compounds are suspended, and such a compound penetrates into the inside, thereby causing a problem. For example, when the above resin is used for lighting applications, there is a problem in that a gas such as an environment passes through a sealing material of an LED, thereby causing a silver component to be plated on a metal lead frame as a constituent member in the LED package. (Silver plating is performed in order to increase the reflectance) discoloration or blackening, and finally the performance as an LED product is lowered (Patent Documents 5 and 6).

In order to solve the problem of the gas permeation resistance, Patent Literatures 5 and 6 use a method of coating a gas permeation-protecting agent and coating a metal portion with an inorganic material. However, there are problems in that not only the steps are increased but also the productivity is changed. Poor, and the light extraction efficiency is deteriorated due to the difference in refractive index between the coating portion and the sealant.

[Patent Document 1] Japanese Patent Laid-Open No. 9-213997

[Patent Document 2] Japanese Patent Laid-Open No. 3618238

[Patent Document 3] International Publication No. 2005/100445

[Patent Document 5] Japanese Patent Laid-Open No. 2007-324256

[Patent Document 6] Japanese Patent Laid-Open No. 2000-174347

An object of the present invention is to obtain a cured product which has less volatilization during curing, is excellent in optical properties and corrosion-resistant gas properties of LEDs, and is excellent in toughness.

The present inventors conducted intensive studies in view of the actual situation as described above, and as a result, completed the present invention.

That is, the present invention is as follows.

(1) A curable resin composition containing an epoxy resin (A), a polyvalent carboxylic acid (B), and a zinc salt and/or a zinc complex (C) as essential components,

Wherein, the polycarboxylic acid (B), the zinc salt and/or the zinc complex (C) respectively satisfy the following conditions:

Polycarboxylic acid (B):

Polycarboxylic acid having at least two carboxyl groups and having a siloxane skeleton as a main skeleton

Zinc salt and / or zinc complex (C):

A zinc salt of a zinc carboxylate, a phosphate or a phosphoric acid, and/or a zinc complex having such an acid or ester as a ligand.

(2) The curable resin composition according to (1) above, wherein the polyvalent carboxylic acid (B) has a linear polyoxyalkylene structure and has a carboxylic acid at both ends.

(3) The curable resin composition according to (1) or (2) above, wherein the polyvalent carboxylic acid (B) is a methanol modified body and a cyclic saturated aliphatic acid anhydride having a linear polyoxyalkylene structure. The compound obtained by the reaction.

(4) The curable resin composition according to any one of the above (1) to (3), which comprises a hindered amine light stabilizer and a phosphorus-containing antioxidant.

(5) A cured product obtained by curing the curable resin composition according to any one of the above (1) to (4).

Since the curable resin composition of the present invention is excellent in corrosion resistance, it is extremely useful as an adhesive material or a sealing material for an optical semiconductor (such as an LED product) used in a living environment such as illumination, among optical materials.

Hereinafter, the curable resin composition of the present invention will be described.

The curable resin composition of the present invention contains an epoxy resin (A), a polyvalent carboxylic acid (B), a zinc salt, and/or a zinc complex (C) as essential components.

Examples of the epoxy resin (A) include a novolak type epoxy resin, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol aralkyl type epoxy resin, and the like. . Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, bismuth phenol, stilbene, 4,4′-biphenol, 2,2′-biphenol, 3,3′, 5, 5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc. ) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl) )-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 1,4-double ( a polycondensate of methoxymethyl)benzene or the like, a modified substance thereof, a halogenated bisphenol such as tetrabromobisphenol A, a glycidyl ether compound derived from an alcohol, an alicyclic epoxy resin, or a glycidol An amine-based epoxy resin, a glycidyl ester-based epoxy resin, or an organopolyoxyalkylene type epoxy resin (having a chain structure, a ring shape, a ladder shape, or a mixture structure of at least two or more of the above structures Epoxy Group and / or an epoxy structure of epoxy cyclohexane) and other solid or liquid epoxy resin, but is not limited to such. These may be used singly or in combination of two or more.

In particular, the main purpose of the curable resin composition of the present invention is for optical use. For use in optical applications, it is preferred to use an alicyclic epoxy resin or an organopolyoxyalkylene type epoxy resin. In the case of using an alicyclic epoxy resin, the resin is preferably a compound having an epoxycyclohexane structure in the skeleton, particularly preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure. .

The alicyclic epoxy resin may, for example, be an esterification reaction of a cyclohexene carboxylic acid with an alcohol or an esterification reaction of a cyclohexene methanol with a carboxylic acid (Tetrahedron vol. 36p. 2409 (1980), The method described in Tetrahedron Letters, p. 4475 (1980), or the like, or the method described in JP-A-2003-170059, JP-A-2004-262871, and the like. Furthermore, the compound produced by the transesterification reaction of the cyclohexene carboxylate (method described in the method described in JP-A-2006-052187, etc.) is oxidized and obtained.

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. , 5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopenta Glycols such as diol, tricyclodecane dimethanol, norbornene diol, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1 , a triol such as 4-butanediol, a tetraol such as neopentyl alcohol or 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 produced by a reaction of a cyclohexenal derivative with an acetal of an alcohol can be mentioned.

Further, examples thereof include oxidation of an alicyclic polyene oxide such as vinylcyclohexene or limonene, dicyclopentadiene, tricyclopentadiene, methyldicyclopentadiene, dicyclohexene or octadiene. And so on.

Specific examples of such epoxy resins include ERL-4221 and ERL-4299 (all of which are trade names, all manufactured by Dow Chemical), EPOLEAD GT401, EHPE3150, and EHPE3150CE (all of which are trade names, all manufactured by Daicel Chemical Industry). , and dicyclopentadiene dioxide, etc., but are not limited to these (Reference: General Description of Epoxy Resin, Basic Section I, p76-85).

These may be used singly or in combination of two or more.

The organic polyoxyalkylene type epoxy resin is not particularly limited as long as it is an organopolysiloxane having an epoxycyclohexane structure. In the present invention, an alkyl group having an epoxycyclohexyl group is particularly exemplified. Oxy decane is used for the compound obtained by the sol-gel reaction of the starting material.

Specifically, JP-A-2004-256609, JP-A-2004-346144, International Publication No. 2004/072150, JP-A-2006-8747, International Publication No. 2006/003990, Japan JP-A-2006-104248, International Publication No. 2007/135909, Japanese Laid-Open Patent Publication No. 2004-10849, Japanese Laid-Open Patent Publication No. 2004-359933, International Publication No. 2005/100445, and JP-A-2008-174640 A sesquiterpoxy-type organopolyoxane having a three-dimensionally expanded network structure as described above.

The structure of the organic polyoxyalkylene is not particularly limited. However, since the simple three-dimensional network structure of the siloxane compound is too hard, a structure in which the hardness is relaxed is expected.

In the present invention, a block structure having the above sesquiterpene oxide structure obtained by a sol-gel reaction in one molecule is particularly preferred. The production method and structure of such a compound are as described in International Publication No. 2010/026714.

Specifically, in the present invention, the structure is not particularly limited. However, since the structure of the organic polysiloxane having a simple three-dimensional network structure is too hard, a structure in which the hardness is relaxed is desired. In the present invention, a block structure having the above sesquiterpene oxide structure having a polyoxonium ion fragment and a coupling agent in one molecule (hereinafter referred to as a block type siloxane compound (A1)) is particularly preferred.

The block type siloxane compound (A1) is not a compound having a repeating unit in a straight chain like a usual block copolymer, but has a structure in which a three-dimensionally expanded network structure is used as a sesquioxane. The structure is the core, and the chain polyoxyl segment extends and is attached to the next sesquiterpene structure. This structure is effective in the sense that the cured product of the curable composition of the present invention is balanced in hardness and flexibility.

The block type oxoxane compound (A1) can be produced, for example, by using the alkoxydecane compound (a) represented by the formula (1) and the polyoxyxane oil (b) represented by the formula (2) as a raw material. The alkoxydecane compound (c) represented by the formula (3) can be used as a raw material, if necessary. The chain polyoxyxan moiety of the block type oxoxane compound (A1) is formed from polyoxyxane oil (b), and the three-dimensional network of sesquiterpene alkane is composed of alkoxy decane (a) (and It is formed by adding an alkoxydecane (c)) as needed. Hereinafter, each raw material will be described in detail.

The alkoxydecane (a) is represented by the following formula (1).

XSi(OR ₂ ) ₃ (1)

X in the general formula (1) is not particularly limited as long as it is an epoxy group-containing organic group. For example, an alkyl group having a carbon number of 1-4, such as a β-epoxypropylethyl group, a γ-glycidylpropyl group, or a γ-epoxypropyl butyl group, which is substituted with a propylene group, may be mentioned. Propyl, β-(3,4-epoxycyclohexyl)ethyl, γ-(3,4-epoxycyclohexyl)propyl, β-(3,4-epoxycyclopentyl)ethyl, β -(3,4-epoxycyclohexyl)propyl, β-(3,4-epoxycyclohexyl)butyl, β-(3,4-epoxycyclohexyl)pentyl, etc. having an epoxy group The cyclohexyl group having a carbon number of 5 to 8 is substituted with an alkyl group having 1 to 5 carbon atoms. Among these, an alkyl group having 1 to 3 carbon atoms substituted with a propylene group and having 1 to 3 carbon atoms substituted by a cyclohexyl group having 5 to 8 carbon atoms having an epoxy group is preferred. The base is, for example, preferably β-epoxypropylethyl, γ-glycidylpropyl, β-(3,4-epoxycyclohexyl)ethyl, particularly preferably β-(3,4-ring Oxycyclohexyl)ethyl.

In the general formula (1), a plurality of R _{2 's} may be the same or different, and each 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. These R ₂ are preferably a methyl group or an ethyl group from the viewpoint of reaction conditions such as compatibility and reactivity, and particularly preferably a methyl group.

Preferred examples of the alkoxydecane (a) include β-epoxypropylethyltrimethoxydecane, β-epoxypropylethyltriethoxydecane, and γ-epoxypropyl group. Propyltrimethoxydecane, γ-glycidylpropyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxy ring Hexyl)ethyltriethoxydecane, etc., particularly preferably β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. These alkoxydecanes (a) may be used singly or in combination of two or more kinds, and may be used in combination with the alkoxydecane (c) described below.

The polyoxygenated oil (b) has the following general formula (2)

The end of the structure shown contains a sterol-based chain polyoxyxide.

In the formula (2), a plurality of R ₃ may be the same or different, and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. .

Examples of the alkyl group having 1 to 10 carbon atoms include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group and an isopropyl group. , n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, anthracene Base, base, etc. Among these, in view of light resistance, a methyl group, an ethyl group, or a cyclohexyl group is preferable.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, and a xylyl group.

Examples of the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as a vinyl group, a 1-methylvinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.

From the viewpoint of light resistance and heat resistance, R _{3 is} preferably a methyl group, a phenyl group, a cyclohexyl group or a n-propyl group, and particularly preferably a methyl group or a phenyl group.

The m of the compound of the formula (2) is from 3 to 200, preferably from 3 to 100, more preferably from 3 to 50, on the average. When m is 3 or less, the cured product becomes too hard and the low elastic modulus characteristic is lowered. When m is 200 or more, the mechanical properties of the cured product tend to be deteriorated, which is not preferable.

The weight average molecular weight (Mw) of the polyoxygenated oil (b) is preferably in the range of 300 to 18,000 (GPC (measured value of gel permeation chromatography). In these, if the elastic modulus at a low temperature is considered, The molecular weight is preferably from 300 to 10,000, and more preferably from 300 to 5,000, particularly preferably from 500 to 3,000, in consideration of the compatibility at the time of compositional composition. When the weight average molecular weight is 300 or less, There is a characteristic that it is difficult to express a chain-like polyoxane moiety of a characteristic segment, and as a property of a block type, it is likely to be impaired, and if it exceeds 18,000, it has a steep layer separation structure, and when it is used for an optical material, permeability is deteriorated. In the present invention, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography) under the following conditions can be calculated as the polyoxygenated oil (b). Molecular weight.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

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

Flow rate: 1.0 ml/min.

Column temperature: 40 ° C

Solvent used: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

The dynamic viscosity of the polyoxygenated oil (b) is preferably a dynamic viscosity in the range of 10 to 200 cSt, more preferably a dynamic viscosity of 30 to 90 cSt. When it is 10 cSt or less, the viscosity of the block type siloxane compound (A1) becomes too low to be suitable as a photo-semiconductor sealant, and when it is 200 cSt or more, a block exists. The viscosity of the type siloxane compound (A1) is increased, which tends to adversely affect workability, and is therefore unsatisfactory.

As a preferable specific example of the polyoxygenated oil (b), the following product names are mentioned. For example, PRX413, BY16-873 manufactured by Dow Corning Toray Silicone Co., Ltd., X-21-5841, KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd., XC96-723, TSR160, YR3370, YF3800, XF3905, YF3057 manufactured by Momentive Co., Ltd. , YF3807, YF3802, YF3897, YF3804, XF3905, DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35 manufactured by Gelest , DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931, etc. In the above, from the viewpoints of molecular weight and dynamic viscosity, preferred are PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS. -S15, DMS-S21, PDS-1615. Among these, in order to have the characteristics of the flexibility of the polyoxynene fragment, from the viewpoint of molecular weight, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable. These polyoxygenated oils (b) may be used singly or in combination of two or more.

Next, the alkoxydecane (c) will be described in detail. The alkoxydecane (c) has a structure of the following formula (3).

R ₄ Si(OR ₅ ) ₃ (3)

R ₄ in the formula (3) represents a methyl group or a phenyl group.

In the general formula (3), a plurality of R _{5 's} may be the same or different, and each 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. From the viewpoint of reaction conditions such as compatibility and reactivity, R _{5 is} preferably a methyl group or an ethyl group.

Preferable specific examples of the alkoxydecane (c) include methyltrimethoxydecane, phenyltrimethoxydecane, methyltriethoxydecane, and phenyltriethoxydecane. Among the above, methyltrimethoxydecane and phenyltrimethoxydecane are preferred.

In the present invention, in order to adjust the molecular weight of the block type siloxane compound (A1), the compatibility at the time of formation of the composition, the heat resistance of the cured product, the light resistance, the low moisture permeability, the low gas permeability, and the like, the alkane The oxoxane (c) can be used in combination with the alkoxydecane (a).

When the alkoxydecane (c) is used in combination with the alkoxydecane (a), the alkoxydecane (c) is preferably a total of 5 to 70 moles of the alkoxydecane (a) and (c). It is used within the range of %, more preferably 5 to 50 mol%, and particularly preferably 10 to 40 mol%. If it is more than 70% by mole, the crosslinking density of the cured product is lowered, and the mechanical strength is lowered, which is not preferable.

With respect to the reaction ratio of the alkoxydecane (a), the polyoxyxane oil (b), and the alkoxydecane (c), it is preferred to carry out the reaction in the following ratio: relative to the polyoxyxane oil (b) 1 equivalent of the alcohol group, the alkoxy group in the alkoxydecane (a) (and the alkoxydecane (c) optionally added) is from 1.5 to 200, preferably from 2 to 200, in terms of equivalent weight. Very good between 2 and 100.

When the equivalent value exceeds 200, the cured product using the block type siloxane compound (A1) becomes too hard, and the low elastic modulus characteristic of the target is lowered.

Hereinafter, a preferred method for producing the block type siloxane compound (A1) will be specifically described.

As a method for producing the block type siloxane compound (A1), it is preferred to pass the production steps shown by the following (i) and (ii).

Manufacturing step (i): a step of performing a dealcoholization condensation of a sterol-terminated polyoxyl oil with a hydrazine compound having an alkoxy group

Manufacturing step (ii): a step of adding water to carry out hydrolysis condensation of the alkoxy groups of the alkoxy group-containing oxime compound

The production steps (i) and (ii) can be carried out in any order as long as the steps are passed.

As a preferable manufacturing method, the following three manufacturing methods are specifically mentioned.

<Manufacturing method (1)>

The production method (1) is a method of producing a block type siloxane compound (A1) by the following steps:

First, the following steps are carried out as the production step (i): a polyoxyxane oil having a sterol group at the end (b) and an alkoxy decane (a) having an alkoxy group (alkane added as needed) The dealcoholization condensation reaction of oxydecane (c)) is carried out by modifying the alkoxy decane at the end of the polyoxyxane oil, thereby obtaining an alkoxydecane modified body (d).

Then, the following steps are carried out as the production step (ii): alkoxydecane (a) which is an alkoxy group-containing compound (alkoxydecane (c) added as needed), and production step (i) Water is added to the alkoxydecane modified substance (d) of the obtained polyoxygenated oil to carry out a hydrolysis condensation reaction of the alkoxy groups.

<Manufacturing method (2)>

The production method (2) is a method of producing a block type siloxane compound (A1) by the following steps:

First, the following steps are carried out as the production step (ii): an alkane is carried out by adding water to an alkoxy oxime compound, that is, an alkoxydecane (a) (additional alkoxy decane (c)) The oxy groups are hydrolyzed and condensed with each other, whereby a sesquiterpene oxide (e) having an alkoxy group in the molecule is obtained.

Then, the following steps are carried out as the production step (i): the remaining in the sesquiterpene oxide structure is carried out by the reaction of the polyfluorene oxide (b) having a sterol group at the end with the sesquioxane (e) The dealcoholization condensation reaction of the alkoxy group with the decyl group.

<Manufacturing method (3)>

This production method (3) is a method of producing a block type siloxane compound (A1) by the following method:

First, as the production step (1), a polyoxyxane oil (b) having a decyl group at the terminal and an alkoxy decane (a) having an alkoxy group as an alkoxy group (additional alkoxy decane as needed) (c)) a dealcoholization condensation reaction, alkoxydecane modification of the polyxanthene oil end, thereby forming an alkoxydecane modified body (d), and then adding water to the system, and using a pot The One Pot is used as a manufacturing step in the hydrolysis and condensation reaction of the remaining alkoxydecane (a) (alkoxydecane (c)) and the alkoxy group of the alkoxydecane modified product (d). 2).

In the present invention, from the viewpoint of shortening the production steps, it is preferred to use the above-described production method (3) which is gradually reacted by a one-pot method.

Hereinafter, the manufacturing method (3) will be described more specifically.

When the reaction is carried out by the one-pot method, if the production step (i) is carried out in the reverse order of the above-mentioned production method (3), that is, after the production step (ii), the formation in the production step (ii) is carried out. The sesquiterpene oxide oligomer having an alkoxy group is incompatible with the polyoxyxane oil (b), and is not subjected to dealcohol condensation polymerization in the subsequent production step (i), and the possibility of residual polyoxyxene oil Higher. On the other hand, if the method of the production step (ii) is carried out by a one-pot method after the production step (i) as in the production method (3), the polyoxyxane oil (b) and the alkoxy decane (a) are used. Or the alkoxydecane (c) has a relatively high compatibility, so that the problem of being incompatible without performing the reaction as described above can be avoided. Further, since the unreacted low molecular alkoxydecane is present in a large amount with respect to the decyl alcohol group, it is also preferable from the viewpoint of reactivity. When the production step (i) in the case where the reaction is carried out by the one-pot method is the first-stage reaction, and the production step (ii) is the second-stage reaction, the first-stage reaction is first performed (the production step (i) In the case of performing a dealcoholization condensation of a polyoxyxanic oil (b) with an alkoxydecane (a) (optionally added alkoxydecane (c)), the terminal of the polyoxyxanic acid is subjected to an alkoxyalkyl group. The product was modified to obtain an alkoxydecane modified body (d). Since water is not added in the first-stage reaction, the alkoxy groups are not hydrolyzed and condensed, and when a reaction is carried out using 3 equivalents or more of an alkoxy group per equivalent of the decyl group, the alkoxy group is considered to be considered. The decane modified body (d) exists in a structure represented by the following formula (4).

In the formula (4), R ₃ and m have the same meanings as described above, and R ₆ represents the above X or R ₄ . R ₇ represents R ₂ when R ₆ is the above X, and R ₅ when R ₆ is the above R ₄ .

In the first-stage reaction, if the alkoxy group is reacted in an amount of less than 1.0 equivalent based on 1 equivalent of the sterol group, the alkoxy group is not present at the end of the first-stage reaction, so the second alkoxy group is not introduced. In the stage reaction, when the alkoxy group is reacted in an amount of from 1.0 to 1.5 equivalents, two or more of the alkoxydecane (a) (additional alkoxydecane (c)) may be added. The alkoxy group reacts with the sterol group of the polyoxyxane oil (b), and at the end of the first-stage reaction, it becomes a polymer and gelatinizes. Therefore, it is necessary to carry out the reaction of the alkoxy group in an amount of 1.5 equivalent or more with respect to 1 equivalent of the sterol group. From the viewpoint of controlling the reaction, it is preferably 2.0 equivalent or more.

After the completion of the first-stage reaction, the second-stage reaction (manufacturing step (ii)) is carried out by directly adding water to carry out hydrolysis condensation of the alkoxy groups. Further, in the second-stage reaction, the reactions (I) to (III) shown below are produced.

(I) The alkoxy groups of the alkoxydecane (a) (the alkoxydecane (c) added as needed) remaining in the system are condensed with each other.

(II) condensation of the alkoxydecane modified body (d) obtained in the first-stage reaction with the alkoxy group of the alkoxydecane (a) (optionally added alkoxydecane (c)) reaction.

(III) alkoxydecane modified body (d) obtained in the first-stage reaction and alkoxydecane (a) formed in (I) (addition of alkoxydecane (c) as required) The condensation reaction of the alkoxy groups of the partial condensates with each other.

In the second-stage reaction, the above reaction is produced in a composite manner, and the formation of the sesquiterpene alkane fragment and further the condensation with the chain-like polyoxane fragment derived from the polyoxygenated oil are carried out simultaneously.

The block type siloxane compound (A1) can also be produced without a catalyst, but if the catalyst is not used, the reaction proceeds slowly, and from the viewpoint of shortening the reaction time, it is preferably in the presence of a catalyst. get on. As the usable catalyst, it can be used as a compound which exhibits acidity or alkalinity. Examples of the acidic catalyst system 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, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate may be used. An inorganic base such as an alkali metal carbonate such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylamineethanol, triethanolamine or tetramethylammonium hydroxide. Among these, in particular, from the viewpoint of easily removing the catalyst from the product, an inorganic base is preferred, and sodium hydroxide or potassium hydroxide is particularly preferred. The amount of the catalyst added is usually 0.001 to 7.5% by weight, preferably 0.01 to the total weight of the alkoxydecane (a) (and the alkoxydecane (c) to be added as needed) in the reaction system. 5 wt%.

The method of adding the catalyst is directly added or used in a state of being dissolved in a solvent or the like which is soluble. Among them, it is preferred to add the catalyst in a state in which it is dissolved in an alcohol such as methanol, ethanol, propanol or butanol. In this case, as described above, the condensation of the alkoxydecane (a) (the alkoxydecane (c) added as needed) is carried out unilaterally as an aqueous solution using water or the like. The hemioxane oligomer and the polyoxygenated oil (b) may be incompatible to produce white turbidity.

The production of the block type siloxane compound (A1) can be carried out without a solvent or in a solvent. Further, a solvent may be added in the middle of the production step. The solvent used in the solvent is not dissolved in the solvent of the alkoxydecane (a), the alkoxydecane (c), the polyoxyxane (b), or the alkoxydecane modified product (d). Special restrictions. As such a solvent, for example, an aprotic polar solvent such as dimethylformamide, dimethylacetamide or tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone or cyclopentanone can be exemplified. Ketones, ethyl acetate, butyl acetate, ethyl lactate, isopropyl butyrate and other alcohols, alcohols such as methanol, ethanol, propanol, butanol, hexane, cyclohexane, toluene, Hydrocarbons such as xylene. In the present invention, from the viewpoint of controlling the reaction, a reaction in an alcohol is preferred, and methanol or ethanol is more preferred. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and the alkoxydecane (a) (and the alkoxydecane (c) added as needed) and the polyoxygenated oil (b) The total weight of the compound is 100 parts, and usually about 0 to 900 parts by weight is used. Although the reaction temperature depends on the amount of the catalyst, it is usually 20 to 160 ° C, preferably 40 to 140 ° C, and particularly preferably 50 to 150 ° C. Further, the reaction time is usually from 1 to 40 hours, preferably from 5 to 30 hours, in each production step.

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

The reaction can be carried out by washing only with water, but the reaction is carried out under any acidic or basic conditions. Therefore, it is preferably subjected to quenching by a neutralization reaction, followed by water washing or use. After the adsorbent adsorbs the catalyst, the adsorbent is removed by filtration.

If it is an acidic or basic compound, it can be used for the neutralization reaction. 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, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or hydrogencarbonate can be used. An alkali metal such as potassium, an inorganic base such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid or sodium tripolyphosphate, ammonia, triethylamine, and diammine An organic base such as ethylenetriamine, n-butylamine, dimethylamineethanol, 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 a phosphate or the like which is easier to adjust to a pH near neutral is more preferable.

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

For the activated clay, for example, active white clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168 manufactured by Toshinaga Chemical Co., Ltd., produced by Mizusawa Industrial Chemicals Co., Ltd. Galleon Earth, Mizuka Ace, etc. Examples of the activated carbon include CL-H, Y-10S, and Y-10SF manufactured by Ajinomoto Fine-Techno Co., Ltd., and S, Y, FC, DP, SA1000, K, A, KA, M, and CW130BR manufactured by Futamura Chemical Co., Ltd. , CW130AR, GM130A, etc. Examples of the zeolite include Molecular Sieve 3A, 4A, 5A, and 13X manufactured by Union Showa. Examples of the synthetic adsorbent include Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., or Amberlyst 15JWET, 15DRY, 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl manufactured by Rohm & Haas Company. , IRA404JCl, or Dowex 66, HCR-S, HCR-W2, MAC-3, etc. manufactured by Dow Chemical Company.

The adsorbent is added to the reaction liquid, and is subjected to a treatment such as stirring or heating. After the catalyst is adsorbed, 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, in addition to washing with water and filtration, purification may be carried out by a conventional separation and purification method. Examples of the purification method include column chromatography, concentration under reduced pressure, distillation, and extraction. These purification methods 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 remove the reaction solvent mixed with water from the system by distillation or concentration under reduced pressure after quenching, and then use a solvent separable from water. Washed with water.

After washing with water, the solvent is removed by concentration under reduced pressure or the like, whereby a block type siloxane compound (A1) can be obtained.

The block type siloxane compound (A1) obtained in the above manner is usually in the form of a liquid which is colorless and transparent and has fluidity at 25 °C. Further, the molecular weight thereof is preferably from 800 to 20,000, more preferably from 1,000 to 10,000, particularly preferably from 1,500 to 6,000, based on the weight average molecular weight measured by GPC. When the weight average molecular weight is 800 or less, the heat resistance may be lowered. When the weight average molecular weight is 20,000 or more, the viscosity is increased to adversely affect the workability.

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 used: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

Further, the epoxy equivalent of the block type siloxane compound (A1) (measured by the method described in JIS K-7236) is preferably 300 to 1,600 g/eq, more preferably 400 to 1,000 g/eq. Particularly preferred is 450 to 900 g/eq. When the epoxy equivalent is 300 g/eq or less, the cured product tends to be hard and the elastic modulus tends to be too high. When it is 1,600 g/eq or more, the mechanical properties of the cured product are deteriorated. The tendency is therefore not good.

The viscosity of the block type siloxane compound (A1) (E-type viscosity meter, measured at 25 ° C) is preferably from 50 to 20,000 mPa ‧ , more preferably from 500 to 10,000 mPa ‧ , particularly preferably from 800 to 5,000 mPa‧s. When the viscosity is 50 mPa·s or less, there is a possibility that the viscosity is too low and it is not suitable for use as an optical semiconductor sealing material. When the viscosity is 20,000 mPa·s or more, there is a case where the viscosity is too high and the workability is poor. .

The ratio of the cesium atom bonded to the three oxygen atoms derived from the sesquioxanes in the block type siloxane compound (A1) to the ruthenium atoms is preferably from 5 to 50 mol%, more preferably 8 ～30 mol%, especially preferably 10-20 mol%. If the ratio of the sulfenium atom bonded to the three oxygen atoms derived from the sesquiterpene is 5 mol% or less to all the ruthenium atoms, the hardened material becomes too soft as a characteristic of the chain polyoxynene fragment. The tendency is to worry about surface wrinkles or damage. Further, when it is 50 mol% or more, the cured product is too hard as a feature of the sesquioxane fragment, which is not preferable.

The ratio of the ruthenium atoms present can be determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, or the like of the block type siloxane compound (A1).

Hereinafter, the polyvalent carboxylic acid (B) will be described.

The polyvalent carboxylic acid (B) in the present invention is a polycarboxylic acid having at least two carboxyl groups and having a rhodium skeleton as a main skeleton, preferably having a linear polyoxyalkylene structure and having a carboxylic acid at both ends. The skeleton. More preferably, it is a compound obtained by the reaction of a methanol modified body having a linear polyoxyalkylene structure with an acid anhydride. By having a decane structure, it is easy to maintain the liquefaction of the hardener and adjust the viscosity, and when it is used as a sealing material, workability is improved.

The polyvalent carboxylic acid used in the present invention is preferably produced by a reaction of a polyfluorene oxide compound (f) with an acid anhydride (g) having one or more carboxylic acid anhydride groups in the molecule.

The polyoxygen compound (f) is preferably a compound represented by the following formula (5):

(In the formula (5), R ₉ represents an alkylene group having a total carbon number of 1 to 10, R ₈ represents a methyl group or a phenyl group, and p represents an average value of 1 to 100).

In the formula (5), specific examples of R ₉ 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. The alkyl group, the hexyl group, the ethyl group, the propoxy group, the propoxy group, the propoxy group, the propyl group, the propyl group, the propyl group and the like. Particularly preferred is a propoxy group of an ethyl group and an ethoxy group.

Further, R ₈ represents a methyl group or a phenyl group, and may be any one of the same kind or a heterogeneous group, which is obtained by addition reaction of the polyfluorene oxide compound (f) with the acid anhydride (g) (B) It is liquid at room temperature, and therefore is preferably a methyl group as compared with a phenyl group.

In the formula (5), p is from 1 to 100, preferably from 2 to 80, more preferably from 5 to 30, on the average.

The polyfluorene oxide compound (f) represented by the formula (5) is, for example, a polyfluorene-based compound having an alcoholic hydroxyl group at both terminals, and specific examples thereof include polyoxyxylene oil modified by methanol at both ends. X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, BY16-004, SF8427 (all manufactured by Dow Corning Toray), XF42-B0970, XF42 -C3294 (both manufactured by Momentive Performance Materials Japan LLC), etc., which are all available on the market. The modified polyoxygenated oil having an alcoholic hydroxyl group at both ends may be used alone or in combination of two or more. Among these, X-22-160AS, KF6001, KF6002, BY16-201, and XF42-B0970 are preferred.

The acid anhydride (g) may be a compound having one or more carboxylic acid anhydride groups in the molecule, and examples thereof include succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, and 2,3-butane dicarboxylic anhydride. a saturated aliphatic carboxylic anhydride such as 2,4-pentane dicarboxylic anhydride, 3,5-heptane dicarboxylic anhydride or 1,2,3,4-butane tetracarboxylic dianhydride, maleic anhydride, ten Unsaturated aliphatic carboxylic anhydride such as diyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, 1,3-cyclohexane dicarboxylic anhydride, norbornane-2,3- Dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, acid anhydride, methylic acid anhydride, bicyclo[2,2,2]octane-2,3-dicarboxylic anhydride, 1,2 , 4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, a cyclic saturated aliphatic carboxylic acid anhydride such as 1,2-4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, acid anhydride, methylamine Cycloalkane, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclic [2.2.2]-5-octene-2,3-dicarboxylic anhydride, etc. Group carboxylic anhydride, phthalic anhydride Examples of the aromatic carboxylic anhydride such as isophthalic anhydride, terephthalic anhydride, trimellitic anhydride, and pyromellitic anhydride, and 5-(2,5-dioxotetrahydrofuran)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2 a polycarboxylic acid compound having a saturated aliphatic carboxylic anhydride, a cyclic saturated carboxylic anhydride, or a cyclic unsaturated carboxylic anhydride in the same compound such as a dicarboxylic acid anhydride.

The acid anhydride (g) may be used alone or in combination of two or more. Among them, a cyclic saturated aliphatic acid anhydride and a cyclic saturated aliphatic acid anhydride are preferred, and hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, norbornane-2,3- are preferred. Dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3,4-butanetetracarboxylic acid Diacid anhydride. The preferred reason is that the polycarboxylic acid (B) obtained from the above is liquid at room temperature, and the transparency of the cured product obtained by hardening the polyvalent carboxylic acid (B) and the epoxy resin (A) Excellent.

Among them, methylhexahydrophthalic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are more preferred, and methylhexahydrophthalic anhydride is particularly preferred.

The reaction of the polyoxygen compound (f) with the acid anhydride (g) can be carried out in a solvent or in the absence of a solvent. The solvent is not particularly limited as long as it is a solvent which does not react with the polyoxosiloxane (f) represented by the formula (5) and the acid anhydride (g). Examples of the solvent that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl hydrazine, tetrahydrofuran, and acetonitrile, and methyl ethyl ketone and cyclopentanone. Examples of the ketones such as methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, and the like, are preferably aromatic hydrocarbons or ketones. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited, and it is usually preferably 0.1 to 300 parts by weight based on 100 parts by weight of the total of the polyfluorene oxide compound (f) and the acid anhydride (g).

In the reaction, a catalyst may also be used, and as a catalyst which can be used, for example, hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid, etc. may be mentioned. Acidic compounds, metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, amine compounds such as triethylamine, tripropylamine, and tributylamine, pyridine, dimethylaminopyridine , 1,8-diazabicyclo[5.4.0]undecyl-7-ene, heterocyclic compound such as imidazole, triazole or tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydrogen Tetrapropylammonium oxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethyl cetyl ammonium hydroxide, a tetra-ammonium salt such as trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate or trioctylmethylammonium acetate; These catalysts may be used alone or in combination of two or more. Among these, triethylamine, pyridine, and dimethylamine pyridine are preferred.

The amount of the catalyst to be used is not particularly limited, and it is usually preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the total weight of the polyoxonium compound (f) and the acid anhydride (g) represented by the formula (5). .

The reaction temperature in the reaction is usually from 80 to 180 ° C, preferably from 110 to 140 ° C. Further, the reaction time is usually from 1 to 12 hours. The Mw (weight average molecular weight) of the reaction product can be measured by GPC (gel permeation chromatography). When the reaction is completed, the heating is stopped, and when a solvent is used, the solvent can be removed under reduced pressure to obtain the desired polycarboxylic acid. The Mw (weight average molecular weight) of the obtained polycarboxylic acid can be similarly confirmed by GPC.

In the polyvalent carboxylic acid (B) of the present invention, in addition to the reactants of the polyfluorene oxide compound (f) and the acid anhydride (g), other polycarboxylic acids may be used in combination.

The other polyvalent carboxylic acid which can be used in combination is particularly preferably a 2- to 6-functional carboxylic acid, more preferably a compound obtained by a reaction of a 2 to 6-functional polyol having a carbon number of 5 or more and an acid anhydride. More preferably, the above acid anhydride is a polycarboxylic acid of a cyclic saturated aliphatic acid anhydride.

The 2 to 6-functional polyol is not particularly limited as long as it is an alcohol 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- Glycols such as 1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, and decylene glycol, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2 a triol such as hydroxymethyl-1,4-butanediol, a tetraol such as pentaerythritol or di-trimethylolpropane, or a hexaol such as dipentaerythritol.

Particularly preferred alcohols are alcohols having a carbon number of 5 or more, especially 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexane Preferred are compounds such as methanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, and the like. Among them, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, 2,4- are more preferable from the viewpoint of imparting heat resistance and light resistance and maintaining a high illuminance retention rate. An alcohol having a branched structure or a cyclic structure such as diethyl pentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol or norbornylene glycol.

Particularly preferred as the acid anhydride is methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, Bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,2,4- Among the tricarboxylic acid-1,2-anhydrides, methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride are preferred because of their high transparency.

The conditions of the addition reaction are not specifically specified, but one of the specific reaction conditions is that the acid anhydride and the polyol are reacted under a condition of no catalyst or solvent, and are heated at 40 to 150 ° C, and the reaction is directly after the reaction is completed. The method of taking out. However, it is not limited to this reaction condition.

The curable resin composition of the present invention preferably contains an acid anhydride. Specific examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and Physic anhydride, ceric anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylate An acid anhydride, an acid anhydride such as methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride or cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.

Particularly preferred are methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo [2 , 2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,2,4-tricarboxylic acid -1,2-anhydride, etc.

In particular, it is preferably represented by the following formula (6)

Hydrazine phthalic anhydride, methyl hexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, wherein methylhexahydrogen is preferred Phthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.

The curable resin composition of the present invention contains a zinc salt and/or a zinc complex (C).

The zinc salt and/or the zinc complex (C) is a salt and/or a complex compound containing zinc ions as a central element, and preferably a carboxylic acid such as zinc carboxylate, zinc phosphate or zinc phosphate. A compound of phosphate, phosphoric acid, etc. as a relative ion and/or a ligand.

Examples of the zinc carboxylate include zinc carboxylates having 1 to 30 carbon atoms, and examples thereof include 2-ethylhexanoic acid, octanoic acid, isodecanoic acid, stearic acid, isostearyl acid, and hydroxystearic acid. Carbenic acid, behenic acid, undecanoic acid, citric acid, and the like.

In the present invention, a carboxylic acid having 3 to 20 carbon atoms is preferred, and a carboxylic acid having 5 to 15 carbon atoms is more preferred.

As the zinc phosphate or zinc phosphate, a zinc salt and/or a zinc complex of phosphoric acid, a phosphate having a carbon number of 1 to 30 (monoester, diester, triester or a mixture thereof) is preferred. Examples of the alkyl group in the specific ester include a methyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, an octyl group, an isodecyl group, an isostearyl group, a decyl group, and a cetyl group.

In the present invention, a phosphate having a carbon number of 3 to 15 is particularly preferred, and the ester may be a single compound, and preferably the main component is a phosphate monoester. It is particularly preferred that the molar ratio of the monoester, diester, and triester in the phosphate contained is replaced by the purity measured by gas chromatography. However, since trimethylsulfonium alkylation is necessary Therefore, there is a difference in sensitivity. In the stage of performing the alkylation treatment of trimethyl hydrazine, the amount of the monoester body is preferably 50% by area or more.

Such a phosphate compound can be obtained by esterification using phosphorus pentoxide, phosphorus chlorochloride, phosphorus triphosphate or the like as a phosphorus oxidizing agent in an alcohol. Further, it can be obtained by reacting the phosphoric acid with, for example, zinc carbonate, zinc hydroxide or the like (Japanese Patent Publication No. EP699708).

Regarding the details of the zinc salt and/or the zinc complex of the phosphate, the ratio of the phosphorus atom to the zinc atom (P/Zn) is preferably from 1.2 to 2.3, more preferably from 1.3 to 2.0. Very good is 1.4 to 1.9. That is, the particularly preferable form is 2.0 mol or less with respect to the zinc ion 1 molar phosphate (or phosphoric acid), and it does not have a simple ion structure, and preferably has several molecules by an ionic bond (or a coordinate bond). And the associated structure.

Here, the ratio of the zinc salt and/or the zinc complex (C) is 0.01 to 8% by weight, more preferably 0.05 to 5% by weight, more preferably 0.05 to 5% by weight, based on the weight of the epoxy resin (A). It is 0.1 to 4% by weight. Further, it is particularly preferably 0.1 to 2% by weight.

As the curing agent, the polyvalent carboxylic acid (B) may be used alone or in combination with an acid anhydride, or may be used in combination with other curing agents. When it is used in combination, the ratio of the total amount of the polyvalent carboxylic acid compound (B) and the acid anhydride to the total amount of the curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Examples of the curing agent that can be used together include an amine compound, an acid anhydride compound, a guanamine compound, a phenol compound, and a carboxylic acid compound. Specific examples of the hardener which can be used include amines or polyamine compounds (by diaminodiphenylmethane, diethylenetriamine, triethylammonium diamine, diaminodiphenylphosphonium). , isophorone diamine, dicyanodiamine, dilinoleic acid dimer and polydiamine resin synthesized by stretching ethylene diamine, etc.; polyphenols (bisphenol A, bisphenol F) , bisphenol S, bismuth bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1'-linked Benzene]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxybenzene Ethylene, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde , o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4' a polycondensate of bis(methoxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene, 1,4'-bis(methoxymethyl)benzene or the like And such modified substances; halogenated bisphenol such as tetrabromobisphenol A Other compounds (imidazole, boron trifluoride-amine complex, anthracene derivative, etc.), etc.; but are not limited thereto.

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

In the curable resin composition of the present invention, it is preferable to use 0.7 to 1.2 equivalents of a curing agent per 1 equivalent of the epoxy group of the entire epoxy resin in terms of the ratio of the epoxy resin to the curing agent. When the amount is less than 0.7 equivalents per 1 equivalent of the epoxy group or more than 1.2 equivalents, there is a possibility that the hardening is incomplete and good hardened physical properties cannot be obtained.

In the curable resin composition of the present invention, a curing catalyst and a curing agent may be used in combination. Specific examples of the hardening accelerator which can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4-methylimidazole. , 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-all three 2,4-Diamino-6(2'-undecylimidazolium (1')) ethyl-all three 2,4-Diamino-6(2'-ethyl-4-methylimidazolium (1'))ethyl-all three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-all three - an isomeric cyanuric acid adduct, a 2:3 adduct of 2-methylimidazoisocyanuric acid, a 2-phenylimidazolium isocyanurate adduct, 2-phenyl-3,5 -Dimethylolidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Imidazoles, and such imidazoles and polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, etc. Salts, guanamines such as dicyanodiamine, diaza compounds such as 1,8-diaza-bicyclo(5.4.0) undecene-7, and tetraphenylborate, phenol novolac a salt such as varnish, a salt of the above polycarboxylic acid or phosphinic acid, an ammonium salt such as tetrabutylammonium bromide, cetyltrimethylammonium bromide or trioctylmethylammonium bromide, triphenylphosphine a phosphine or a phosphonium such as tris(toluene)phosphine, tetraphenylphosphine bromide or tetraphenylphosphine tetraphenylborate, or a phenol such as 2,4,6-triaminemethylphenol, or an amine addition a compound such as a metal compound such as tin octylate, and a microcapsule type hardened by forming the hardening accelerator into microcapsules Into the agent. Which of these hardening accelerators is used is suitably selected according to the characteristics required for the transparent resin composition obtained, for example, transparency, hardening speed, operation conditions, etc.. The curing catalyst is usually used in an amount of from 0.001 to 15 parts by weight based on 100 parts by weight of the epoxy resin.

The curable resin composition of the present invention may further contain a phosphorus-containing compound as a component imparting flame retardancy. The phosphorus-containing compound may be reactive or may be added. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, tolyl diphenyl phosphate, and tolyl phosphate. 2,6-di(xylenyl) ester, 1,3-phenylene bis(diphenylphosphonate), 1,4-phenylene bis(diphenylphosphonate), Phosphate such as 4,4'-biphenyl (di(xylenyl) phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5 a phosphine such as -dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with an active hydrogen of the above phosphine; red Phosphorus or the like; preferably a phosphate ester, a phosphine or a phosphorus-containing epoxy compound, particularly preferably 1,3-phenylene bis(diphenylphosphonate), 1,4-phenylene bis ( Di(xylenyl) phosphate, 4,4'-biphenyl (di(xylenyl) phosphate) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/epoxy resin = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, there is a possibility that the hygroscopic property and dielectric properties of the cured product are adversely affected.

Further, in the curable resin composition of the present invention, a binder resin may be blended as needed. Examples of the binder resin include a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamine resin, and a polyimine. It is a resin, a polyoxyl resin, etc., but it is not limited to these. The blending amount of the binder resin is preferably in the range of flame retardancy and heat resistance of the hardened curable material, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, per 100 parts by weight of the curable resin component. .

In the curable resin composition of the present invention, an inorganic filler may be added as needed. 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 dioxide or talc, or particles obtained by spheroidizing the particles, etc., 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 curable resin composition of the present invention. Further, in the curable resin composition of the present invention, a release agent such as a decane coupling agent, a stearic acid, a palmitic acid, a zinc stearate or a calcium stearate may be added, and various preparation agents such as a pigment may be added, and various thermosetting properties may be added. Resin.

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, transparency can be prevented without using a filler having a particle diameter of a nanometer level using the inorganic filler used above. And improve the mechanical strength and so on. The standard of the nano level is preferably a filler having an average particle diameter of 500 nm or less from the viewpoint of transparency, and particularly preferably a filler having an average particle diameter of 200 nm or less.

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, a phosphor may be added as needed. A fluorescent system, for example, has the effect of forming white light by absorbing a portion of the blue light emitted from the blue LED element and emitting wavelength-converted yellow light. After dispersing the phosphor in the curable resin composition in advance, 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, and a protoporate. More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, a prophthalate phosphor, a thiopentate phosphor, or a sulfide phosphor may be mentioned, and YAlO ₃ may also be mentioned: Ce, Y ₃ Al ₅ O ₁₂ :Ce, Y ₄ Al ₂ O ₉ :Ce, Y ₂ O ₂ S:Eu, Sr ₅ (PO ₄ ) ₃ Cl:Eu, (SrEu)O‧Al ₁₂ O ₃ or the like. The particle diameter of the above-mentioned phosphor is a particle diameter known in the art, and the average particle diameter is preferably from 1 to 250 μm, particularly preferably from 2 to 50 μm. In the case of using these phosphors, the amount thereof is from 1 to 80 parts by weight, preferably from 5 to 60 parts by weight, per 100 parts by weight of the above resin component.

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, in order to prevent precipitation of various phosphors upon hardening, a fine powder of cerium oxide (also referred to as AEROSIL or AEROSOL) is a representative of the shake imparting agent. As such a fine powder of cerium oxide, 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 AEROSIL, Japan).

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, an amine-based compound as a light stabilizer, a phosphorus-based compound as an antioxidant material, and a phenol may be contained in order to prevent coloration. a compound.

The amine-based compound may, for example, be tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)=1,2,3,4-butanetetracarboxylate or tetra(4) 2,2,6,6-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-tetraoxaspiro [5.5] Mixed esterified product of undecane, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-undecyloxy)- 2,2,6,6-tetramethylpiperidin-4-yl)ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, azelaic acid bis(2,2, 6,6-tetramethyl-4-piperidinyl), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4-benzylideneoxy -2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]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) malonate [[3,5-double (1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl ester, bis(2,2,6,6-tetramethyl-1(octyloxy)-4- phthalate Pyridyl)ester, reaction product of 1,1-dimethylethyl hydrogen peroxide with 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-diazanonane-1,10-diamine, dibutylamine-1,3,5-three -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexanediamine and N-(2,2,6,6-tetramethyl-4) Poly(condensate of piperidinyl)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-dodecyloxycarbonyl)ethyl-7-oxa-3,20-diazaspiro[5,1,11,2]octadecane-21- Ketone, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-ethylindolyl-3-dodecyl- 1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3, 20-diazaspiro[5,1,11,2]icosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo- [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), higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzene a hindered amine compound such as formamide, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), a diphenylketone compound such as octyl benzophenone, 2-(2H -benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2 -[2 -hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3-tert-butyl- 2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-third-pentylphenyl)benzotriazole, methyl 3-( Reaction product of 3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate with polyethylene glycol, 2-(2H-benzotriazole- a benzotriazole compound such as 2-yl)-6-dodecy-4-methylphenol, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4- Benzoate such as 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-based compound of the above-mentioned photostabilizing material, 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, LA-52, LA-57, LA- manufactured by Adeka. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87, and the like.

The phosphorus compound is not particularly limited, and examples thereof include 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl). Alkane, distearyl decyl neopentyl glycol diphosphite, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-third Butyl-4-methylphenyl)neopentitol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexyl neopentyl alcohol diphosphite, phosphorous tris(II) Ethyl phenyl) ester, tris(di-isopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-t-butylbenzene) phosphite Ester), tris(2,6-di-t-butylphenyl) phosphite, tris(2,6-di-t-butylphenyl) phosphite, 2,2'-methylene Bis(4,6-di-t-butylphenyl)(2,4-di-t-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di- Tributylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl) 2-tert-butyl-4-methylphenyl)phosphite, 2,2'-ethylenebis(4-methyl-6-t-butylphenyl) (2-tert-butyl- 4- Methylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-extended biphenyl diphosphite, tetrakis(2,4-di-third Phenyl)-4,3'-extended biphenyl diphosphite, tetrakis(2,4-di-t-butylphenyl)-3,3'-extended biphenyl diphosphite, four (2,6-di-t-butylphenyl)-4,4'-extended biphenyl diphosphite, tetrakis(2,6-di-t-butylphenyl)-4,3'- Stretched biphenyl diphosphite, tetrakis(2,6-di-t-butylphenyl)-3,3'-extended biphenyl diphosphite, bis(2,4-di-third Phenyl)-4-phenyl-phenylphosphite, bis(2,4-di-t-butylphenyl)-3-phenyl-phenylphosphite, bis(2,6-di -n-butylphenyl)-3-phenyl-phenylphosphite, bis(2,6-di-t-butylphenyl)-4-phenyl-phenylphosphite, bis (2, 6-di-t-butylphenyl)-3-phenyl-phenylphosphite, tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'- Biphenyl diphosphite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl toluene phosphate Base ester, phosphoric acid mono-phenylene Yl phosphate, tris butoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl ester.

A commercially available product can be used for the above phosphorus compound. Commercially available phosphorus-based compounds are not particularly limited, and examples thereof include: AdekaSTAB PEP-4C manufactured by Adeka, ADEKASTAB PEP-8, ADEKASTAB PEP-24G, ADEKASTAB PEP-36, ADEKASTAB HP-10, ADEKASTAB 2112, ADEKASTAB 260, ADEKASTAB 522A, ADEKASTAB 1178, ADEKASTAB 1500, ADEKASTAB C, ADEKASTAB 135A, ADEKASTAB 3010, ADEKASTAB TPP.

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 Heterospiro[5,5]undecane, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2'-Adenine Bis(4,6-di-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2,2'-methylene double (4 -methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2-tert-butyl-6-(3- Tributyl-2-hydroxy-5-methyl 4-methylphenol acrylate, 2-[1-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6-di-third amylphenyl Acrylate, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2 -T-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]-ethylene glycol ester, 2,4-di-tert-butylphenol, 2,4-di-third amyl phenol, 2-[1-(2-hydroxyl -3,5-di-p-pentylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate, bis-[3,3-bis-(4'-hydroxy-3' -T-butylphenyl)-butyric acid]-ethylene glycol ester or 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 1520L manufactured by Ciba Specialty Chemicals. AdekaSTAB AO-20, ADEKASTAB AO-30, ADEKASTAB AO-40, ADEKASTAB AO-50, ADEKASTAB AO-60, ADEKASTAB AO-70, ADEKASTAB AO-80, ADEKASTAB AO-90, ADEKASTAB AO-330, made by Adeka Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. manufactured by the chemical industry.

In addition to this, commercially available additive materials can be used as the colorant of the resin. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSO RB 2020 FDL, CHIMASSO RB FF, etc. 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 in the range of 0.005 to 5.0% by weight based on the curable resin composition of the present invention.

The curable resin composition of the present invention is obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily formed into a cured product by the same method as previously known. For example, an epoxy resin, a hardener, and optionally a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficiently used, such as an extruder, a kneader, a roller, a planetary mixer, etc., as needed. When it is mixed until it is uniform, a curable resin composition is obtained, and when the curable resin composition of the present invention obtained is in a liquid state, it is poured or cast, impregnated into a substrate, or composed of a curable resin. The material is poured into a mold for casting or the like, and then hardened by heating. In the case where the curable resin composition of the present invention obtained is in a solid form, a method of casting after melting, molding by a transfer molding machine or the like, and further curing by heating may be mentioned. The curing temperature and time are 80 to 200 ° C for 2 to 10 hours. As the hardening method, it can be rapidly solidified at a high temperature, but it is preferred to carry out a hardening reaction by gradually increasing the temperature. Specifically, initial hardening is performed between 80 and 150 ° C, and post-hardening is performed between 100 ° C and 200 ° C. As the stage of hardening, it is preferred to carry out the temperature increase in 2 to 8 stages, more preferably 2 to 4 stages.

Further, the curable resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethyl acetamide, N-A A curable resin composition varnish is formed in a solvent such as a pyrrolidone, and is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a pre-preparation. The molded body is subjected to hot press forming of the preform to form a cured product of the curable resin composition of the present invention. The solvent at this time is usually used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, based on the mixture of the curable resin composition of the present invention and the solvent. Further, the liquid composition may be obtained by directly obtaining a cured resin containing a carbon fiber by RTM.

Further, the curable resin composition of the present invention can also be used as a film-type sealing composition. When the film-type resin composition is obtained, the curable resin composition of the present invention is first applied onto a release film as the varnish, and after removing the solvent under heating, the film is subjected to the B-stage to form a sheet shape. Agent. The sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like, and a package of an optical semiconductor.

Next, the case where the curable resin composition of the present invention is used as a sealing material or a die-bonding material of a photo-semiconductor will be described in detail.

When the curable resin composition of the present invention is used as a sealing material or a die-bonding material for an optical semiconductor such as a high-brightness white LED, an epoxy resin, a hardener, a coupling material, an antioxidant, a light stabilizer, etc. are added. The composition is sufficiently mixed to prepare a curable resin composition, and is used as a sealing material or for both a die-bonding material and a sealing material. As a mixing method, a kneader, a three-roller, a universal mixer, a planetary mixer, a homomixer, a homodisperser, and a bead mill are used, which are mixed at normal temperature or under heating.

Optical semiconductor elements such as high-brightness white LEDs are usually laminated on GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, etc. on substrates such as sapphire, spinel, SiC, Si, ZnO, using an adhesive (a die-bonding material). A semiconductor wafer such as InN, AlN, or InGaN is formed on a lead frame, a heat release plate, and a package. Due to the flow of current, there is also a type in which a gold wire or the like is connected. In order to prevent the hot gas or moisture from damaging the semiconductor wafer to function as a lens, it is sealed with a sealing material such as an epoxy resin. The curable resin composition of the present invention can be used as the above-mentioned sealing material or die-bonding material. In terms of the step, it is preferred to use the curable resin composition of the present invention for both the die-bonding material and the sealing material.

As a method of adhering a semiconductor wafer to a substrate using the curable resin composition of the present invention, the curable resin composition of the present invention can be applied by a dispenser, infusion, or screen printing, and then the semiconductor wafer is placed and heat-hardened. And then the semiconductor wafer. For heating, hot air loop type, infrared light, high frequency, etc. 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 curing, for example, pre-curing may be carried out at 80 to 120 ° C for 30 minutes to 5 hours, and then subsequent curing may be carried out at 120 to 180 ° C for 30 minutes to 10 hours.

As a molding method of the sealing material, an injection method in which a sealing material is injected into a mold to which a semiconductor wafer is inserted and inserted into a mold to which a semiconductor wafer is inserted, and then heat-hardened and molded is formed; and a sealing material is injected into the mold in advance so that A semiconductor wafer to be fixed on a substrate is immersed therein and heat-hardened, and then subjected to a compression molding method such as demolding from a mold.

Examples of the injection method include a dispenser, transfer molding, and injection molding.

For heating, hot air loop type, infrared light, high frequency, etc. 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 curing, for example, pre-curing may be carried out at 80 to 120 ° C for 30 minutes to 5 hours, and then subsequent curing may be carried out at 120 to 180 ° C for 30 minutes to 10 hours.

Further, the curable resin composition of the present invention can be used for a general use of a curable resin such as an epoxy resin, for example, an adhesive, a coating, a coating agent, a molding material (including a sheet, a film, an FRP, etc.), and insulation. In addition to a material (including a printed circuit board, a wire coating, etc.) and a sealing material, other resins such as a sealing material, a cyanate resin composition for a substrate, and an acrylate resin which is a curing agent for a resist may be used. Additives, etc.

Examples of the adhesive agent include an adhesive for electronic materials other than civil engineering, construction, automotive, general-purpose, and medical adhesives. In the above, examples of the adhesive for electronic materials include an interlayer adhesive for a multilayer substrate such as a build-up substrate, a semiconductor adhesive such as an adhesive, an underfill, a BGA reinforcing underfill, and anisotropic conductive. An adhesive for mounting such as a film (ACF) or an anisotropic conductive paste (ACP).

Examples of the sealant include perfusion, impregnation, and transfer used for capacitors, transistors, diodes, light-emitting diodes, ICs (Integrated Circuits), LSIs (Large Scale Integration), and the like. Molded sealing, infusion sealing for IC or LSI COB, COF, TAB, etc., underfill for flip chip, etc., sealing for IC package such as QFP, BGA and CSP (including underfill for reinforcement) Wait.

The cured product obtained by the present invention can be used for various purposes represented by optical member materials. The material for optics generally refers to a material used for the purpose of passing visible light, infrared rays, ultraviolet rays, X-rays, and laser light through the material. More specifically, in addition to the sealing material for LEDs such as a lamp type and an SMD type, the following may be mentioned. The material of the liquid crystal display device such as a substrate material in the field of liquid crystal display, a light guide plate, a ruthenium sheet, a deflecting plate, a phase difference plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film may be mentioned. Further, examples thereof include a sealing material, an antireflection film, an optical correction film, an outer casing material, a front glass protective film, a front glass substitute material, and an adhesive which are expected to be color PDPs (plasma displays) for next-generation flat panel displays, and examples thereof The molding material of the LED used in the LED display device, the sealing material of the LED, the protective film of the front glass, the front glass replacement material, and the adhesive, and the substrate material and the light guide plate in the plasma-addressed liquid crystal (PALC) display, a ruthenium sheet, a deflecting plate, a phase difference plate, a viewing angle correction film, an adhesive, a polarizer protective film, and a protective film of the front glass in the organic EL (electroluminescence) display, a front glass substitute material, and an adhesive. Further, various film substrates in the field emission display (FED), a protective film for the front glass, a front glass substitute material, and an adhesive may be mentioned. In the field of optical recording, VD (disc) CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase change optical disc), optical disc substrate material, optical disc The machine reads the lens, protective film, sealing material, adhesive, and the like.

In the field of optical equipment, a lens material for a static camera, a viewfinder 稜鏡, a target 稜鏡, a viewfinder cover, and a light receiving sensor portion are exemplified. Further, a camera lens and a viewfinder of a camera can be cited. Further, a projection lens, a protective film, a sealing material, an adhesive, and the like of the projection television can be cited. Further, examples thereof include a material for a lens of a light sensing device, a sealing material, an adhesive, a film, and the like. Examples of the optical member field include a fiber material around a photo switch in an optical communication system, a lens, a waveguide, a sealing material for an element, an adhesive, and the like. Further, examples thereof include an optical fiber material around the optical connector, a ferrule, a sealing material, an adhesive, and the like. Examples of the light passive member and the optical circuit member include a lens, a waveguide, a sealing material for an LED, a sealing material for a CCD, an adhesive, and the like. Further, examples thereof include a substrate material around a photoelectron integrated circuit (OEIC), a fiber material, a sealing material for an element, and an adhesive. In the field of the optical fiber, for example, a lighting for decorative displays, a light guide tube, an industrial sensor, a display, a display, etc., and an optical fiber for digital connection of a communication infrastructure and a home. Examples of the material surrounding the semiconductor integrated circuit include a resist material for microetching technology for LSI and super LSI materials. In the field of automobiles and transport aircraft, there are listed lamp reflectors, bearing retainers, gear parts, corrosion resistant sleeves, switch parts, headlights, engine internals, electrical components, various interior and exterior parts, drive engines, brakes. Fuel tanks, anti-rust steel plates for automobiles, interior panels, interior materials, protection, end harnesses, fuel hoses, car lights, glass substitutes. Further, a multi-layer glass for a railway vehicle can be cited. Further, examples thereof include a toughness imparting agent for a structural material of an aircraft, an engine peripheral member, a protective ‧ end harness, and a corrosion resistant sleeve. In the field of construction, there are listed materials, processing materials, lampshades, film, glass interlayer film, glass substitutes, and solar cell peripheral materials. For agricultural use, a film for house coating can be cited. Examples of the next-generation optical ‧ electronic functional organic material include organic EL element peripheral materials, organic light refracting elements, optical amplification elements as optical-optical conversion devices, optical calculus elements, substrate materials around organic solar cells, fiber materials, and components. Sealing material, adhesive, and the like.

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 examples was measured by the following method.

(1) Molecular weight: The weight average molecular weight was calculated by a gel permeation chromatography (GPC) method under the following conditions and converted to polystyrene.

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 used: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

(2) Epoxy equivalent: It was measured by the method described in JIS K-7236.

(3) Viscosity: It was measured at 25 ° C using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. In the synthesis examples and examples, "parts" means parts by weight, and "%" means % by weight.

[Examples]

Synthesis Example 1 (20)

As step 1, 375 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and a benzyl alcohol-terminated oleic acid group having a weight average molecular weight of 1,700 (GPC measured value) 475 parts (the sterol group equivalent is 850, which is calculated to be one-half of the weight average molecular weight measured by GPC), and 0.5% of a potassium hydroxide (KOH) methanol solution is added to the reaction vessel, and the reaction is carried out under reflux. hour.

In the second step, after adding 655 parts of methanol, 144 parts of a 50% methanol solution of distilled water was added dropwise over 60 minutes, and the mixture was reacted under reflux for 8 hours. After the completion of the reaction, about 90% of the methanol was distilled and recovered by neutralizing with a 5% aqueous solution of sodium dihydrogen phosphate. Then, 750 parts of methyl isobutyl ketone (MIBK) was added and washed three times with water. 647 parts of the epoxy resin (A-1) used in the present invention was obtained by removing the solvent from the obtained organic phase under reduced pressure at 100 °C. The obtained compound had an epoxy equivalent of 541 g/eq and a weight average molecular weight of 2,100, which was a colorless transparent liquid resin.

Synthesis Example 2 (17)

As step 1, 263 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and a benzyl alcohol-terminated oleic acid having a weight average molecular weight of 1900 (GPC measured value) 475 parts (the sterol group equivalent is 950, which is calculated to be one-half of the weight average molecular weight measured by GPC), and 0.5% of potassium hydroxide (KOH) methanol solution is added to the reaction vessel, and the reaction is carried out under reflux. hour.

In the second step, after adding 655 parts of methanol, 115 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted under reflux for 8 hours. After the completion of the reaction, about 90% of the methanol was distilled and recovered by neutralizing with a 5% aqueous solution of sodium dihydrogen phosphate. Then, 750 parts of methyl isobutyl ketone (MIBK) was added and washed three times with water. 605 parts of the epoxy resin (A-2) used in the present invention was obtained by removing the solvent from the obtained organic phase at 100 ° C under reduced pressure. The obtained chemical compound had an epoxy equivalent of 636 g/eq and a weight average molecular weight of 2090, and its appearance was a colorless transparent liquid resin.

Synthesis Example 3 (18)

As step 1, 285 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and a methyl phenylpolyoxyl end oil having a weight average molecular weight of 1,700 (GPC measured value) 475 parts (the sterol group equivalent is 850, which is calculated to be one-half of the weight average molecular weight measured by GPC), and 0.5% of a potassium hydroxide (KOH) methanol solution is added to the reaction vessel, and the reaction is carried out under reflux. hour.

In the second step, after adding 655 parts of methanol, 123 parts of a 50% methanol solution of distilled water was added dropwise over 60 minutes, and the mixture was reacted under reflux for 8 hours. After the completion of the reaction, about 90% of the methanol was distilled and recovered by neutralizing with a 5% aqueous solution of sodium dihydrogen phosphate. Then, 750 parts of methyl isobutyl ketone (MIBK) was added and washed three times with water. 620 parts of the epoxy resin (A-3) used in the present invention was obtained by removing the solvent from the obtained organic phase at 100 ° C under reduced pressure. The obtained compound had an epoxy equivalent of 605 g/eq and a weight average molecular weight of 2,120, and its appearance was a colorless transparent liquid resin.

Synthesis Example 4

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, while adding a nitrogen hexahydrophthalic anhydride (Nippon Chemical & Chemical Co., Ltd., RIKACID MH, hereinafter referred to as an acid anhydride H-1), 84 parts were applied while performing a nitrogen purge. 239 parts of methanol-modified polyoxygenated oil (manufactured by Shin-Etsu Chemical Co., Ltd., X22-160AS), reacted at 60 ° C for 2 hours, and then heated and stirred at 90 ° C for 3 hours, thereby obtaining the following formula (7) 323 parts of the polycarboxylic acid (B-1) shown. The polycarboxylic acid obtained was a colorless liquid resin having a functional group equivalent of 646 g/eq.

Examples 1, 2, 3, 4, 5, Comparative Examples 1, 2

Using the epoxy resin (A-1) (A-2) (A-3) obtained in Synthesis Examples 1 to 3 as an epoxy resin, the polycarboxylic acid (B-1) obtained in Synthesis Example 4 was used as a hardener. An acid anhydride (H-1) was used as a hardener for the comparative example, and zinc 2-ethylhexylate (manufactured by Hope Chemical Co., Ltd., 18% of Octope Zn, hereinafter referred to as zinc salt C-1) was used as the zinc salt. A hardening accelerator (manufactured by Nippon Synthetic Chemical Co., Ltd., HISHICOLIN PX4MP, hereinafter referred to as Catalyst I-1) is used as a hardening accelerator, and a hindered amine (manufactured by Adeka, LA-81, hereinafter referred to as additive J-1) and phosphide (Adeka) are used. Manufactured, Adeka 260, hereinafter referred to as additive J-2) as an additive, formulated at a blending ratio (parts by weight) shown in Table 1 below, and defoamed for 20 minutes to obtain a curable resin composition of the present invention or comparatively used. Things.

(LED seal test)

The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes, and then filled in a syringe, and cast into a surface mount type in which a light-emitting element having an emission wavelength of 465 nm was mounted by a precision discharge device ( SMD type 5mmΦ) LED. Thereafter, the film was cured at 120 ° C for 1 hour, and further cured at 150 ° C for 3 hours under curing conditions, thereby obtaining a test LED.

Evaluation project

(a) Volatility: The surface of the cured product after sealing was visually evaluated for presence or absence of depression. In the table, ○: no depression was confirmed, △: less depression was confirmed, and ×: it was confirmed that there were many depressions.

(b) Wrinkles: ○ with no stickiness, viscous × (finger touch test)

(c) Reflow soldering test: After the obtained test LED was moisture-absorbed at 30 ° C, 70% × 72 hours, a high-temperature observation apparatus (SMT, Scope, SK-5000, manufactured by Sanyo Seiko Co., Ltd.) was used. It is confirmed whether the LED is cracked under the following reflow conditions. The test was carried out under the conditions of n = 3, and evaluated by (NG number) / (test number).

The temperature was raised from 25 ° C to 150 ° C at 2 ° C / sec, then held at 150 ° C for 2 minutes, and further raised to 260 ° C at 2 ° C / sec. After maintaining the temperature for 10 seconds, it was cooled to 1.3 ° C / sec. Room temperature.

(corrosion gas permeability test)

The curable resin composition obtained was filled in a syringe, and cast into a surface mount type LED package having an outer diameter of 5 mm square, which was mounted on a wafer having a center light wave of 465 nm, using a precision discharge device (inner diameter: 4.4 mm). , the outer wall height is 1.25mm). The cast molded product was placed in a heating furnace, hardened at 120 ° C for 1 hour, and further cured at 150 ° C for 3 hours to prepare an LED package. The LED package was placed in an etching gas under the following conditions, and the color change of the silver-plated lead frame portion inside the seal was observed. The results are shown in Table 1 below.

Measuring condition

Corrosive gas: 20% aqueous solution of ammonium sulfide (black when the sulfur component reacts with silver)

Contact method: the container of the ammonium sulfide aqueous solution and the LED package are simultaneously present in the wide-mouth glass bottle, and the cover of the wide-mouth glass bottle is covered, and the vulcanized ammonium sulfide gas is brought into contact with the LED package in a sealed state.

Determination of Corrosion: The time during which the lead frame inside the LED package became black (so-called blackening) was observed, and it was judged that the longer the discoloration time, the more excellent the corrosion-resistant gas property.

The observation system was performed once every 1 hour for 5 hours and evaluated. The evaluation evaluated the time before discoloration.

(LED lighting test)

The obtained curable resin composition was filled in a syringe, and cast on a surface mount type LED (SMD type 5 mm Φ, rated current: 30 mA) on which a light-emitting element having a wavelength of 465 nm was mounted by a precision discharge device. Thereafter, the film was cured at 120 ° C for 1 hour, and further cured at 150 ° C for 3 hours, thereby obtaining an LED for lighting test. The lighting test was performed at a current that greatly exceeded the rated current of 30 mA at 230 mA and 220 mA. The detailed conditions are as follows. As a measurement project, the illuminance before and after lighting for 40 hours was measured using an integrating sphere, and the retention of the illuminance of the test LED was calculated. The results are shown in Table 1.

Lighting detailed conditions

Central emission wavelength: 465 nm

Drive mode: fixed current mode, at the same time in 220 mA, 230 mA (light-emitting component rated current is 30 mA)

Drive environment: light at 85% wet heat engine at 85 ° C

Evaluation: illuminance retention after 40 hours

Comparative Example 3 uses at least an organic polyoxyalkylene (S-1) having at least two alkenyl groups bonded to a ruthenium atom and at least a bond to the ruthenium atom having addition polymerization to the alkenyl group. A polyanthracene resin obtained by addition polymerization of an organic hydrogenated polyoxyalkylene (S-2) of two hydrogen atoms.

The above polyoxyxylene resins S-1 and S-2 specifically have the following structure.

S-1: an organic hydrogenated polyoxyalkylene oxide having a phenyl group, a methyl group, and a vinyl group as an organic group in a molar ratio of 0.1% or less and containing a platinum catalyst and having a ratio of 0.4:1:1 in terms of moles.

S-2: an organic hydrogenated polyoxyalkylene having a phenyl group, a methyl group or a vinyl group as an organic group. The molar ratio of hydrogen atoms in a phenyl group, a methyl group, a vinyl group or a hydroquinone group is 2 in terms of moles. : 2:1:1 organic hydrogenated polyoxyalkylene.

Further, in Comparative Example 3, the blending ratio (quality ratio) was set to S-1: S-2 = 1:20, and the curing conditions were set to 150 ° C for 1 hour.

According to the above results, it is clear that the composition containing the curable resin composition of the present invention (epoxy resin (A), polycarboxylic acid (B) having a polyfluorene skeleton, and zinc salt and/or zinc complex (C) Compared with the curable resin composition of the comparative example, the silver plating of the lead frame is not discolored, and is excellent not only in corrosion resistance but also in crack resistance.

Further, even if the illuminance retention ratio is better than that of the polyoxynoxy resin in the high-current accelerated lighting test, it is known that the cured product is excellent in electrical reliability, light resistance, and heat resistance.

The present invention has been described in detail with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on Japanese Patent Application No. 2010-134465, filed on Jun. Moreover, all references cited are incorporated herein in their entirety.

Claims (7)

A curable resin composition comprising an epoxy resin (A), a polycarboxylic acid (B), and a zinc salt and/or a zinc complex (C) as essential components, wherein the polycarboxylic acid (B), zinc The salt and/or zinc complex (C) respectively satisfy the following conditions: polycarboxylic acid (B): a polycarboxylic acid having at least two carboxyl groups and having a rhodium skeleton as a main skeleton, by polyoxyl Manufactured by the reaction of a compound with methylhexahydrophthalic anhydride, zinc salt and/or zinc complex (C): zinc salt of zinc carboxylate, phosphate or phosphoric acid, and/or having such acid or ester A zinc complex as a ligand. The curable resin composition according to claim 1, wherein the epoxy resin (A) has a chain structure, a ring shape, a ladder shape, or a mixture structure of at least two or more of the above structures. An epoxy resin having a glycopropyl group and/or an epoxycyclohexane structure. The curable resin composition according to the first aspect of the invention, wherein the polyvalent carboxylic acid (B) has a linear polyoxyalkylene structure and has a carboxylic acid at both ends. The sclerosing resin composition of the first to third aspects of the patent application, wherein the polycarboxylic acid (B) is a methanol modified body and a cyclic saturated aliphatic acid anhydride having a linear polyoxyalkylene structure. The compound obtained by the reaction. Such as the sclerosing resin composition of the first to third items of the patent application scope A substance comprising a hindered amine light stabilizer and a phosphorus containing antioxidant. The curable resin composition of claim 4, which comprises a hindered amine light stabilizer and a phosphorus-containing antioxidant. A cured product obtained by hardening a curable resin composition according to any one of claims 1 to 6.