JP5768047B2 - Curable resin composition and cured product thereof - Google Patents

Description

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

Conventionally, an epoxy resin composition has been employed as a sealing material for optical semiconductor elements such as LED products in terms of a balance between performance and economy. In particular, glycidyl ether type epoxy resin compositions typified by bisphenol A type epoxy resins having excellent balance of heat resistance, transparency and mechanical properties have been widely used.
However, as a result of the shortening of the light emission wavelength of LED products (mainly 480 nm or less for LED products that emit blue light), the sealing material is colored on the LED chip under the influence of short wavelength light, and finally Has been pointed out that illuminance decreases as an LED product.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′epoxycyclohexylcarboxylate are more transparent than glycidyl ether type epoxy resin compositions having an aromatic ring. Since it is excellent, it has been actively studied as an LED sealing material. (Patent Documents 1 and 2)

In general, the epoxy resin curing agent used in such a field includes acid anhydride compounds. In particular, acid anhydrides formed with saturated hydrocarbons are often used because the cured product has excellent light resistance. As these acid anhydrides, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, etc. are common, and in particular, methylhexahydrophthalic anhydride, methyl which is liquid at room temperature. Tetrahydrophthalic anhydride and the like are mainly used because of easy handling.
However, when the above alicyclic acid anhydride is used as a curing agent, these curing agents have high vapor pressure and partly evaporate at the time of curing, so they are thermally cured in an open system using them as a curing agent for epoxy resin. In some cases, the product itself volatilizes in the atmosphere, causing not only environmental pollution and harmful effects on the human body due to the release of harmful substances to the atmosphere, but also contamination of the production line and a certain amount of carboxylic acid anhydride ( In addition to the problem of poor curing of the epoxy resin composition due to the absence of the curing agent), the properties of the epoxy resin composition may vary greatly depending on the curing conditions, and a cured product having stable and desired performance may be obtained. It is difficult to obtain.

  In addition, cured products using conventional curing agents are prominent when LEDs, especially SMD (Surface Mount Device) are sealed, and the amount of resin used is small. Causes a problem that the wire is exposed. Furthermore, there is a problem that it is difficult to withstand long-term lighting because cracking, peeling, and the like during solder reflow are further insufficiently cured.

  Another problem is that LED products in recent years have become increasingly brighter for lighting, TV backlights, and the like, and when the LEDs are turned on, they generate a lot of heat. Even the resin composition used causes coloration on the LED chip, and as a result, the illuminance is lowered as an LED product, leaving a problem in terms of durability. (Patent Document 3)

Because of the problem of durability of the epoxy resin, a resin having a siloxane skeleton (specifically, a skeleton having a Si—O bond) introduced as a silicone resin or a silicone-modified epoxy resin is used as a sealing material. Considerations are being made. (Patent Document 3)
In general, it is known that a resin having a siloxane skeleton introduced therein is more stable to heat and light than an epoxy resin. Therefore, when applied to the sealing material of LED products, it was said that it was superior to epoxy resin in terms of coloring on the LED chip.
But there are challenges.
A resin introduced with a siloxane skeleton is more likely to be brittle than a normal epoxy resin. Therefore, the reflow resistance is poor and cracks during reflow are conspicuous.
Furthermore, resins having a siloxane skeleton introduced are inferior in gas permeability resistance compared to ordinary epoxy resins. Therefore, when a silicone resin or a silicone-modified epoxy resin is used as the LED sealing material, coloring on the LED chip is not a problem, but there is a problem that internal components are deteriorated and coloring occurs. . In particular, when used in a living environment, various compounds are floating, and the penetration of such compounds into the interior triggers problems. For example, when the resin is used for lighting applications, the silver component (reflectance) plated on the metal lead frame, which is a constituent member in the LED package, by allowing gas in the environment to pass through the LED sealing material. In other words, the silver plating is applied to improve the color of the LED product, and the performance as an LED product is finally lowered. (Patent Documents 4 and 5).

  In order to clear this gas permeation resistance problem, Patent Documents 4 and 5 use techniques such as coating a gas permeation-resistant protective agent and coating a metal part with an inorganic material. In addition to an increase in productivity and productivity, there is a problem in that light extraction efficiency is deteriorated due to a difference in refractive index between the covering portion and the sealant.

Japanese Unexamined Patent Publication No. 9-213997 Japanese Patent No. 3618238 International Publication No. 2005/100445 Japanese Unexamined Patent Publication No. 2007-324256 Japanese Unexamined Patent Publication No. 2000-174347

  An object of this invention is to obtain the hardened | cured material which has little volatilization at the time of hardening, is excellent in the optical characteristic as LED, and a corrosion-resistant gas characteristic, and is excellent in toughness.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention is as follows.
(1) A curable resin composition comprising an epoxy resin (A), a polyvalent carboxylic acid (B), and a zinc salt and / or a zinc complex (C) as essential components.
However, the polyvalent carboxylic acid (B), the zinc salt and / or the zinc complex (C) each satisfy the following conditions.
Polyvalent carboxylic acid (B):
Polyvalent carboxylic acid zinc salt and / or zinc complex (C) having at least two or more carboxyl groups and having a siloxane skeleton as a main skeleton:
Zinc carboxylate, phosphoric acid ester or zinc salt of phosphoric acid, and / or zinc complex having these acids or esters as ligands (2) The polyvalent carboxylic acid (B) has a linear polysiloxane structure, Curable resin composition as described in said (1) which has carboxylic acid at the terminal.
(3) In the above (1) or (2), the polyvalent carboxylic acid (B) is a compound obtained by reacting a carbinol modified product having a linear polysiloxane structure with a cyclic saturated aliphatic acid anhydride. The curable resin composition described.
(4) The curable resin composition according to any one of (1) to (3) above, which contains 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 (1) to (4) above.

  Since the curable resin composition of the present invention is excellent in corrosion gas resistance, among optical materials, particularly as adhesives and sealing materials for optical semiconductors (LED products, etc.) used in living environments such as lighting. Very useful.

Hereinafter, it describes about the curable resin composition of this invention.
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 novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, -Hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis Polycondensates with (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, glycidyl ethers derived from alcohols, fats Cyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, organopolysiloxane type epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two kinds of glycidyl groups, and Epoxy tree having epoxy cyclohexane structure Examples thereof include, but are not limited to, solid or liquid epoxy resins such as (fat). These may be used alone or in combination of two or more.

In particular, the curable resin composition of the present invention is mainly used for optical applications. When used for optical applications, it is preferable to use an alicyclic epoxy resin or an organopolysiloxane type epoxy resin. In the case of an alicyclic epoxy resin, the resin is preferably a compound having an epoxycyclohexane structure in the skeleton, and particularly preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure.
Examples of alicyclic epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohol or esterification reaction of cyclohexene methanol and carboxylic acid (Tetrahedron vol.36p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) ), Or Tyschenko reaction of cyclohexene aldehyde (method described in Japanese Patent Laid-Open No. 2003-170059, Japanese Patent Laid-Open No. 2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester ( Examples thereof include a product obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Application Laid-Open No. 2006-052187.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

  Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned.

  Moreover, the thing etc. which oxidized cycloaliphatic polyolefin such as vinylcyclohexene, limonene, dicyclopentadiene, tricyclopentadiene, methyldicyclopentadiene, bicyclohexene, octadiene, etc. are mentioned.

Specific examples of these epoxy resins include ERL-4221, ERL-4299 (all trade names, all manufactured by Dow Chemical), Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries) and dicyclo Examples include, but are not limited to, pentadiene diepoxide (reference: review epoxy resin basic edition I p76-85).
These may be used alone or in combination of two or more.

The organopolysiloxane type epoxy resin is not particularly specified as long as it is an organopolysiloxane having an epoxycyclohexane structure, but in the present invention, a compound obtained by a sol-gel reaction using an alkoxysilane having an epoxycyclohexyl group as a raw material. Is mentioned.
Specifically, Japanese Unexamined Patent Publication No. 2004-256609, Japanese Unexamined Patent Publication No. 2004-346144, International Publication No. 2004/072150, Japanese Unexamined Patent Publication No. 2006-8747, International Publication No. 2006/003990, Japanese Unexamined Patent Publication No. 2006-104248, International Publication No. 2007/135909, Japanese Unexamined Patent Publication No. 2004-10849, Japanese Unexamined Patent Publication No. 2004-359933, International Publication No. 2005/100445, Japanese Unexamined Patent Publication. Examples thereof include silsesquioxane type organopolysiloxane having a three-dimensional network structure described in JP-A-2008-174640.
The structure of the organopolysiloxane is not particularly limited. However, since a siloxane compound having a simple three-dimensional network structure is too hard, a structure that relaxes the hardness is desired.
In the present invention, a block structure having a silicone segment and the aforementioned silsesquioxane structure obtained by a sol-gel reaction in one molecule is particularly preferable. Examples of a method for producing such a compound include a production method and a structure as described in WO2010 / 026714.
Specifically, in the present invention, the structure is not particularly limited, but the structure of the organopolysiloxane having a simple three-dimensional network structure is too hard, and thus a structure that reduces the hardness is desired. In the present invention, a block structure having a silicone segment and the above-mentioned silsesquioxane structure of a coupling agent in one molecule is particularly preferable (hereinafter referred to as a block-type siloxane compound (A1)).

  The block-type siloxane compound (A1) is not a compound having a repeating unit in a straight chain like a normal block copolymer, but has a three-dimensional network structure, with a silsesquioxane structure as a core. The chain-like silicone segment extends and leads to the next silsesquioxane structure. This structure is effective in the sense of giving a balance between hardness and flexibility to the cured product of the curable composition of the present invention.

  The block type siloxane compound (A1) can be produced using, for example, the alkoxysilane compound (a) represented by the general formula (1) and the silicone oil (b) represented by the general formula (2) as raw materials, If necessary, the alkoxysilane compound (c) represented by the general formula (3) can be used as a raw material. The chain-type silicone segment of the block-type siloxane compound (A1) is formed from the silicone oil (b), and the three-dimensional network-like silsesquioxane segment is the alkoxysilane (a) (and the alkoxy added if necessary) Silane (c)). Hereinafter, each raw material will be described in detail.

The alkoxysilane compound (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 organic group having an epoxy group. For example, β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl and other glycidoxy having 1 to 4 carbon atoms, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ -(3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group And an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as β- (3,4-epoxycyclohexyl) pentyl group. Among these, an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group, an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group, for example, β- A glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4-epoxycyclohexyl) ethyl group are preferable, and a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.

In the general formula (1), a plurality of R ₂ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₂ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of reaction conditions such as compatibility and reactivity.

  Specific preferred examples of the alkoxysilane (a) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxy. Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like, particularly β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane is preferred. These alkoxysilane compounds (a) may be used independently, may use 2 or more types, and can also be used together with the alkoxysilane (c) mentioned later.

  Silicone oil (b) has the following formula (2)

Is a chain silicone oil having a silanol group at the end having a structure represented by:
In the general formula (2), a plurality of R ₃ may be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl having 2 to 10 carbon atoms. Indicates a group.
Examples of the alkyl group having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like. Among these, considering light resistance, a methyl group, an ethyl group, and a cyclohexyl group are preferable.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, an 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 vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group, and hexenyl group.
R ₃ is preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group from the viewpoints of light resistance and heat resistance, and particularly preferably a methyl group or a phenyl group.

  M of the compound of General formula (2) shows 3-200 by an average value, Preferably it is 3-100, More preferably, it is 3-50. When m is less than 3, the cured product becomes too hard and the low elastic modulus characteristics are deteriorated. If m exceeds 200, the mechanical properties of the cured product tend to deteriorate, which is not preferable.

The weight average molecular weight (Mw) of the silicone oil (b) is preferably in the range of 300 to 18,000 (measured value by GPC (gel permeation chromatography)). Among these, those having a molecular weight of 300 to 10,000 are preferable in consideration of the elastic modulus at low temperature, and those having a molecular weight of 300 to 5,000 are more preferable in consideration of compatibility at the time of forming the composition. 1,000 is preferred. If the weight average molecular weight is less than 300, the properties of the chain silicone portion of the characteristic segment are difficult to be obtained, and the properties as a block type may be impaired. If it exceeds 18,000, a severe layer separation structure will be formed. When used as a material, the permeability becomes poor, making it difficult to use. In the present invention, as the molecular weight of the silicone oil (b), polystyrene conversion and weight average molecular weight (Mw) measured under the following conditions were calculated using GPC (gel permeation chromatography).
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The kinematic viscosity of the silicone oil (b) is preferably in the range of 10 to 200 cSt, more preferably 30 to 90 cSt. When the viscosity is less than 10 cSt, the viscosity of the block type siloxane compound (A1) becomes too low and may not be suitable as an optical semiconductor sealing agent. When the viscosity exceeds 200 cSt, the viscosity of the block type siloxane compound (A1) Is unfavorable because it tends to cause an adverse effect on workability.

  Specific examples of preferable silicone oil (b) include the following product names. For example, as manufactured by Toray Dow Corning Silicone, PRX413, BY16-873, as manufactured by Shin-Etsu Chemical Co., Ltd., X-21-5841, KF-9701, as manufactured by Momentive, XC96-723, TSR160, YR3370, YF3800 , XF3905, YF3057, YF3807, YF3802, YF3897, YF3804, XF3905, manufactured by Gelest, DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS -S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931 and the like. Among these, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 from the viewpoint of molecular weight and kinematic viscosity PDS-1615 is preferred. Among these, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight in order to give the silicone segment flexibility characteristics. These silicone oils (b) may be used alone or in combination of two or more.

Next, the alkoxysilane (c) will be described in detail. The alkoxysilane (c) has a structure of the following formula (3).
R ₄ (OR ₅ ) ₃ (3)
R ₄ in the general formula (3) represents a methyl group or a phenyl group.

In the general formula (3), a plurality of R ₅ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₅ is preferably a methyl group or an ethyl group from the viewpoint of reaction conditions such as compatibility and reactivity.

  Specific examples of preferred alkoxysilane (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Of these, methyltrimethoxysilane and phenyltrimethoxysilane are preferred.

  In the present invention, the alkoxysilane (c) adjusts the molecular weight of the block-type siloxane compound (A1), the compatibility with the composition, the heat resistance of the cured product, light resistance, low moisture permeability, low gas permeability, and the like. Therefore, it can be used in combination with alkoxysilane (a).

  When the alkoxysilane (c) is used in combination with the alkoxysilane (a), the alkoxysilane (c) is preferably used in the range of 5 to 70 mol% of the total of the alkoxysilanes (a) and (c). More preferred is mol%, and particularly preferred is 10 to 40 mol%. If it is larger than 70 mol%, the crosslink density of the cured product is lowered and the mechanical strength is lowered, which is not preferable.

As the reaction ratio of alkoxysilane (a), silicone oil (b), and alkoxysilane (c), alkoxysilane (a) (and added as needed) with respect to 1 equivalent of silanol group of silicone oil (b). It is preferable to carry out the reaction between 1.5 to 200, preferably 2 to 200, particularly preferably 2 to 100, with the alkoxy group in the alkoxysilane (c)) as an equivalent value.
When the equivalent value exceeds 200, the cured product using the block-type siloxane compound (A1) becomes too hard and the desired low elastic modulus characteristic is lowered.

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

As a manufacturing method of a block type siloxane compound (A1), it is preferable to pass through the manufacturing process shown by the following (i) and (ii).
Production step (i): Step of dealcoholization condensation of silanol-terminated silicone oil and silicon compound having alkoxy group Production step (ii): Hydrolysis condensation between alkoxy groups of silicon compound having alkoxy group by adding water In the process manufacturing process (i) (ii), the reaction may be performed in any order as long as it goes through each process.

Specific examples of preferred production methods include the following three production methods.
<Manufacturing method (I)>
First, as a production step (i), dehydration of a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) which is a silicon compound having an alkoxy group (alkoxysilane (c) added if necessary) A step of obtaining an alkoxysilane-modified product (d) by performing alkoxysilane modification on the terminal of the silicone oil by an alcohol condensation reaction is performed.
Next, alkoxysilane (a) which is a silicon compound having an alkoxy group as production step (ii) (alkoxysilane (c) added if necessary), and alkoxysilane of the silicone oil obtained in production step (i) A method of producing a block-type siloxane compound (A1) by passing through a step of adding water to the modified product (d) to perform a hydrolysis-condensation reaction between alkoxy groups.
<Manufacturing method (b)>
First, as a production step (ii), a hydrolytic condensation reaction between alkoxy groups is performed by adding water of alkoxysilane (a) (alkoxysilane (c) added as necessary) which is a silicon compound having an alkoxy group. Thus, a step of obtaining silsesquioxane (e) having an alkoxy group in the molecule is performed.
Next, as a production process (i), a reaction between the silanol group-containing silicone oil (b) and the silsesquioxane (e) causes a dealcoholization condensation reaction between the alkoxy group remaining in the silsesquioxane structure and the silanol group. A method for producing a block-type siloxane compound (A1) by passing through the steps.
<Manufacturing method (c)>
First, as a production step (i), dehydration of a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) which is a silicon compound having an alkoxy group (alkoxysilane (c) added if necessary) After the end of the silicone oil is modified with an alkoxysilane by an alcohol condensation reaction to obtain an alkoxysilane-modified product (d), water is added to the system, and the remaining alkoxysilane (a) (alkoxy) is produced as a production step (ii). A method for producing a block-type siloxane compound (A1) by carrying out hydrolysis condensation reaction between alkoxy groups of the silane (c)) and the alkoxysilane-modified product (d) in one pot.

In the present invention, from the viewpoint of shortening the production process, it is preferable to use the above production method (c) in which the reaction is sequentially carried out in one pot.
Hereinafter, the production method (c) will be described more specifically.
When the reaction is carried out in one pot, the silanol having an alkoxy group formed in the production step (ii) is performed in the reverse order of the production method (c) described above, that is, when the production step (ii) is performed after the production step (ii). There is a high possibility that the sesquioxane oligomer and the silicone oil (b) are not compatible with each other, the dealcoholization condensation polymerization does not proceed in the subsequent production step (i), and the silicone oil is left behind. On the other hand, if the method of performing manufacturing process (ii) in one pot after manufacturing process (i) like the manufacturing method (c) is used, silicone oil (b) and alkoxysilane (a) or alkoxysilane (c) Since the compatibility is relatively high, the problem that the reaction does not proceed without compatibility as described above can be avoided. Furthermore, since a large amount of unreacted low-molecular alkoxysilane is present with respect to the silanol group, it is preferable from the viewpoint of reactivity. Assuming that the production process (i) in the one pot is the first stage reaction and the production process (ii) is the second stage reaction, first, in the first stage reaction (production process (i)), the silicone oil (b) and alkoxy The dealcohol condensation of silane (a) (alkoxysilane (c) added if necessary) is carried out, and the terminal of the silicone oil is alkoxysilyl-modified to obtain an alkoxysilane-modified product (d). Since water is not added in the first stage reaction, hydrolysis condensation between alkoxy groups does not occur, and when the reaction is carried out using 3 equivalents or more of alkoxy groups per 1 equivalent of silanol groups, a modified alkoxysilane (D) is considered to exist in a structure as shown by the following formula (4).

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

  In the first stage reaction, if the alkoxy group is reacted in an amount less than 1.0 equivalent with respect to 1 equivalent of the silanol group, the alkoxy group does not exist at the end of the first stage reaction. Moreover, when an alkoxy group is made to react between 1.0-1.5 equivalent, two or more alkoxy groups in alkoxysilane (a) (alkoxysilane (c) added as needed) will become silicone oil (b). ), And becomes a polymer at the end of the first stage reaction, resulting in gelation. For this reason, it is necessary to make an alkoxy group react with 1.5 equivalent or more with respect to 1 equivalent of silanol groups. From the viewpoint of reaction control, 2.0 equivalents or more are preferable.

After completion of the first stage reaction, the second stage reaction (production process (ii)) in which water is added as it is to hydrolyze and condense alkoxy groups is performed. Further, in the second stage reaction, the following reactions (I) to (III) occur.
(I) Condensation reaction between alkoxy groups of alkoxysilane (a) remaining in the system (alkoxysilane (c) added if necessary).
(II) A condensation reaction between the alkoxy groups of the alkoxysilane-modified product (d) obtained in the first stage reaction and the alkoxysilane (a) (alkoxysilane (c) added as necessary).
(III) Alkoxy of partial condensate of alkoxysilane modified (d) obtained in the first stage reaction and alkoxysilane (a) (alkoxysilane (c) added if necessary) produced by (I) Condensation reaction between groups.
In the second stage reaction, the above reaction occurs in combination, and the formation of the silsesquioxane segment and the condensation with the silicone oil-derived chain silicone segment are simultaneously performed.

The production of the block type siloxane compound (A1) can be carried out without a catalyst, but if it is no catalyst, the reaction proceeds slowly, and it is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases such as alkali metal carbonates, and organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base is particularly preferable in terms of easy catalyst removal from the product, and sodium hydroxide and potassium hydroxide are particularly preferable. The amount of the catalyst added is usually 0.001 to 7.5% by weight, preferably 0, based on the total weight of the alkoxysilane (a) (and the alkoxysilane (c) added as necessary) in the reaction system. 0.01 to 5% by weight.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. At this time, as an aqueous solution using water or the like, as described above, the condensation of alkoxysilane (a) (alkoxysilane (c) added if necessary) is unilaterally advanced, There is a possibility that the silsesquioxane oligomer produced by the above and the silicone oil (b) are incompatible and become cloudy.

  The block type siloxane compound (A1) can be produced in the absence of a solvent or in a solvent. Moreover, a solvent can also be added in the middle of a manufacturing process. The solvent for use is not particularly limited as long as it is a solvent that dissolves alkoxysilane (a), alkoxysilane (c), silicone oil (b), and alkoxysilane-modified product (d). Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, and tetrahydrofuran, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and butanoic acid. Examples thereof include esters such as isopropyl, alcohols such as methanol, ethanol, propanol and butanol, hydrocarbons such as hexane, cyclohexane, toluene and xylene. In the present invention, reaction in alcohols is preferable from the viewpoint of reaction control, and methanol and ethanol are more preferable. The amount of solvent used is not particularly limited as long as the reaction proceeds smoothly, but alkoxysilane (a) (and alkoxysilane (c) added if necessary), a compound of silicone oil (b) Usually, about 0 to 900 parts by weight is used per 100 parts by weight. The reaction temperature is usually 20 to 160 ° C, preferably 40 to 140 ° C, particularly preferably 50 to 150 ° C, although it depends on the amount of catalyst. Moreover, reaction time is 1 to 40 hours normally in each manufacturing process, Preferably it is 5 to 30 hours.

  After completion of the reaction, the catalyst is removed by quenching and / or washing with water as necessary. When washing with water, depending on the type of solvent used, it is preferable to add a solvent that can be separated from water. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.

In this reaction, the catalyst may be removed only by washing with water, but the reaction is carried out under acidic or basic conditions. It is preferable to remove the adsorbent by filtration after adsorbing the catalyst using
Any compound that is acidic or basic can be used for the neutralization reaction. Examples of the compound exhibiting 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. Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphates, phosphates such as sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, Organic bases such as dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, in particular, inorganic bases or inorganic acids are preferable because they can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutral are more preferable.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
As the activated clay, for example, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168, manufactured by Mizusawa Chemical Industry, Galeon Earth, Mizuka Ace, etc. are listed. As the activated carbon, for example, CL-H, Y-10S, Y-10SF manufactured by Ajinomoto Fine-Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR are manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like. Examples of zeolite include, for example, molecular sieves 3A, 4A, 5A, and 13X, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, Dow Chemical Co., Dowex 66, HCR-S, HCR-W2, MAC-3 and the like can be mentioned.
The adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.

  After completion of the reaction or after quenching, it can be purified by conventional separation and purification means in addition to washing with water and filtration. Examples of the purification means include column chromatography, vacuum concentration, distillation, extraction and the like. These purification means may be performed singly or in combination.

  When the reaction is performed using a solvent mixed with water as a reaction solvent, the reaction solvent mixed with water is removed from the system by distillation or vacuum concentration after quenching, and then washed with a solvent that can be separated from water. It is preferable.

  After washing with water, the block siloxane compound (A1) can be obtained by removing the solvent by vacuum concentration or the like.

The appearance of the block-type siloxane compound (A1) thus obtained is usually colorless and transparent and is a liquid having fluidity at 25 ° C. The molecular weight is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,500 to 6,000 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the heat resistance may be lowered. When the weight average molecular weight is more than 20,000, the viscosity is increased and the workability is adversely affected.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The epoxy equivalent (measured by the method described in JISK-7236) of the block type siloxane compound (A1) is preferably 300 to 1,600 g / eq, more preferably 400 to 1,000 g / eq, particularly The thing of 450-900 g / eq is preferable. When the epoxy equivalent is less than 300 g / eq, the cured product is hard and the elastic modulus tends to be too high, and when it exceeds 1,600 g / eq, the mechanical properties of the cured product tend to deteriorate.

  The viscosity of the block-type siloxane compound (A1) (E-type viscometer, measured at 25 ° C.) is preferably 50 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, particularly 800 to 5 1,000 mPa · s is preferred. If the viscosity is less than 50 mPa · s, the viscosity may be too low to be suitable for use as an optical semiconductor encapsulant, and if it exceeds 20,000 mPa · s, the viscosity may be too high and workability may be poor. is there.

The proportion of silicon atoms bonded to three oxygens derived from silsesquioxane in the block-type siloxane compound (A1) with respect to all silicon atoms is preferably 5 to 50 mol%, more preferably 8 to 30 mol%, 10-20 mol% is especially preferable. When the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms is less than 5 mol%, the cured product tends to be too soft as a characteristic of the chain silicone segment, and surface tack There are concerns about injury. On the other hand, if it exceeds 50 mol%, the cured product becomes too hard as a feature of the silsesquioxane segment, which is not preferable.
The proportion of silicon atoms present can be determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of the block siloxane compound (A1).

Hereinafter, the polyvalent carboxylic acid (B) will be described.
The polyvalent carboxylic acid (B) in the present invention is a polyvalent carboxylic acid having at least two or more carboxyl groups and having a siloxane skeleton as a main skeleton, preferably having a linear polysiloxane structure, It is a skeleton having a carboxylic acid at the terminal. More preferably, it is a compound obtained by reacting a carbinol modified product having a linear polysiloxane structure with an acid anhydride. By having a siloxane structure, it is easy to maintain liquefaction of the curing agent and to adjust the viscosity, and the workability is improved when used as a sealing material.
The polyvalent carboxylic acid used in the present invention is preferably one produced by reacting the silicone compound (f) with an acid anhydride (g) having one or more carboxylic acid anhydride groups in the molecule.
As the silicone compound (f), the following formula (5)

（式（５）において、Ｒ_９は炭素総数１〜１０のアルキレン基を、Ｒ_８はメチル基又はフェニル基を、ｐは平均値で１〜１００をそれぞれ表す。）
に示される化合物が好ましい。

(In Formula (5), R ₉ represents an alkylene group having 1 to 10 carbon atoms, R ₈ represents a methyl group or a phenyl group, and p represents an average value of 1 to 100.)
The compound shown by these is preferable.

In formula (5), specific examples of R ₉ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, ethoxyethylene group, propoxyethylene group, Examples thereof include a propoxypropylene group and an ethoxypropylene group. Particularly preferred are propoxyethylene group and ethoxypropylene group.

Next, R ₈ represents a methyl group or a phenyl group, and may be the same or different, but the polyvalent carboxylic acid (B) obtained by addition reaction of the silicone compound (f) and the acid anhydride (g). Is liquid at room temperature, a methyl group is preferred compared to a phenyl group.

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

  Examples of the silicone compound (f) represented by the formula (5) include silicone compounds having alcoholic hydroxyl groups at both ends, and specific examples thereof include X-22-, which is a carbinol-modified silicone oil at both ends. 160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-201, BY16-004, SF8427 (all manufactured by Toray Dow Corning) XF42-B0970, XF42-C3294 (all manufactured by momentary)・ Performance Materials Japan Ltd.), etc. are all available from the market. These modified silicone oils having alcoholic hydroxyl groups at both ends can be used alone or in combination of two or more. Among these, X-22-160AS, KF6001, KF6002, BY16-201, and XF42-B0970 are preferable.

The acid anhydride (g) may be a compound having one or more carboxylic acid anhydride groups in the molecule. For example, succinic acid anhydride, methyl succinic acid anhydride, ethyl succinic acid anhydride, 2,3-butanedicarboxylic acid. Saturated aliphatic carboxylic acid anhydrides such as acid anhydrides, 2,4-pentanedicarboxylic acid anhydrides, 3,5-heptanedicarboxylic acid anhydrides, 1,2,3,4-butanetetracarboxylic acid dianhydrides, Unsaturated aliphatic carboxylic acid anhydrides such as acid anhydrides, dodecyl succinic acid anhydrides, hexahydrophthalic acid anhydrides, methylhexahydrophthalic acid anhydrides, 1,3-cyclohexanedicarboxylic acid anhydrides, norbornane-2,3 -Dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, nadic acid anhydride, methyl nadic 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 Cyclic cycloaliphatic carboxylic anhydrides such as 4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Nadic acid anhydride, methyl nadic acid anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid anhydride Cyclic unsaturated aliphatic carboxylic acid anhydride, phthalic acid anhydride, isophthalic acid anhydride, terephthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, etc. In addition, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 4- (2,5-dicarboxylic acid anhydride, etc. In the same compound such as oxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, saturated aliphatic carboxylic acid anhydride, cyclic saturated carboxylic acid anhydride, cyclic A polycarboxylic acid compound having a saturated carboxylic acid anhydride is also included.
The acid anhydride (g) can be used alone or in combination of two or more. Of these, cyclic saturated aliphatic acid anhydrides are preferable, and among them, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride. And 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and 1,2,3,4-butanetetracarboxylic dianhydride are preferred. The preferred reason is that the polyvalent carboxylic acid (B) obtained therefrom is liquid at room temperature, and the transparency of the cured product obtained by curing the polyvalent carboxylic acid (B) and the epoxy resin (A) is excellent. Because.
Among these, methylhexahydrophthalic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are more preferable, and methylhexahydrophthalic anhydride is particularly preferable.

  The reaction between the silicone compound (f) and the acid anhydride (g) can be performed in a solvent or without a solvent. As the solvent, any solvent that does not react with the silicone compound (f) represented by the formula (5) and the acid anhydride (g) can be used without particular limitation. Examples of solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, toluene and xylene. An aromatic hydrocarbon etc. are mentioned, Among these, an aromatic hydrocarbon and ketones are preferable. These solvents may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is preferable to use 0.1-300 weight part normally with respect to 100 weight part of total weights of the said silicone compound (f) and an acid anhydride (g).

  A catalyst may be used for the reaction. Examples of usable catalysts include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, water Metal hydroxides such as sodium oxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, amine compounds such as triethylamine, tripropylamine, tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4. 0] heterocyclic compounds such as undec-7-ene, imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tri Tylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium Examples include quaternary ammonium salts such as acetate and trioctylmethylammonium acetate. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

  Although there is no restriction | limiting in particular in the usage-amount of a catalyst, It is 0.1-100 weight normally with respect to 100 weight part of total weight of the silicone compound (f) represented by Formula (5) and an acid anhydride (g). It is preferably used if necessary.

The reaction temperature in the reaction is usually 80 to 180 ° C, preferably 110 to 140 ° C. The reaction time is usually 1 to 12 hours. 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 target polycarboxylic acid can be obtained by removing the solvent under reduced pressure. The Mw (weight average molecular weight) of the obtained polyvalent carboxylic acid can be confirmed by GPC as well.
The polyvalent carboxylic acid (B) in the present invention can be used in combination with other polyvalent carboxylic acid in addition to the reaction product with the silicone compound (f) and the acid anhydride (g).
Other polyvalent carboxylic acids that can be used in combination are particularly preferably bifunctional to hexafunctional carboxylic acids, and more preferably compounds obtained by reacting dihydric and polyfunctional alcohols having 5 or more carbon atoms with acid anhydrides. . Furthermore, the polycarboxylic acid whose said acid anhydride is a cyclic saturated aliphatic acid anhydride is preferable.
As the 2- to 6-functional polyhydric alcohol, the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, Diols such as tricyclodecane dimethanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, ditrimethylo Tetraols such as propane, and the like hexaol such as dipentaerythritol.
Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, Compounds such as 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol are preferred, and 2-ethyl-2-butyl-1. Alcohols having a branched chain structure or a cyclic structure such as 3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol are more preferable.
Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane- 2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and the like are preferable, Of these, methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride are preferable.
There are no particular restrictions on the conditions for the addition reaction, but one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted at 40 to 150 ° C. under non-catalytic and solvent-free conditions and heated to react. The method of taking out as it is after completion is mentioned.

The curable resin composition of the present invention may contain an acid anhydride. Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- And acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid An acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and the like are preferable.
Particularly preferably, the following formula (6)

Preferred are hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride represented by: methylhexahydrophthalic anhydride, cyclohexane-1,2, 4-tricarboxylic acid-1,2-anhydride is preferred.

The curable resin composition of the present invention contains a zinc salt and / or a zinc complex (C).
Zinc salt and / or zinc complex (C) is a salt and / or complex having zinc ion as a central element, preferably zinc carboxylate, zinc phosphate, zinc phosphate ester, etc., counter and / or ligand And compounds having ions such as carboxylic acid, phosphoric acid ester and phosphoric acid.
Examples of the zinc carboxylate include zinc carboxylates having 1 to 30 carbon atoms, such as 2-ethylhexylic acid, octylic acid, isodecylic acid, stearic acid, isostearic acid, hydroxystearic acid, undecylenic acid, behenic acid, undecanoic acid, and decanoic acid. Etc.
In the present invention, a carboxylic acid having 3 to 20 carbon atoms is particularly preferable, and 5 to 15 is more preferable.
As zinc phosphate and zinc phosphate ester, phosphoric acid and zinc salts and / or zinc complexes of phosphoric acid esters having 1 to 30 carbon atoms (monoester, diester, triester, or a mixture thereof) are preferable. Examples of such alkyl esters include methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decanyl, cetyl and the like.

In the present invention, a phosphoric ester having 3 to 15 carbon atoms is particularly preferred, and the ester may be mixed or single, but the main component is preferably a phosphoric monoester. In particular, the molar ratio of monoester, diester and triester in the phosphoric acid ester contained (substitute with the purity of gas chromatography. However, since it is necessary to carry out trimethylsilylation, there is a difference in sensitivity.) In the above, it is preferable that the abundance of the monoester is 50 area% or more at the stage of the trimethylsilylation treatment.
Such phosphoric acid ester compounds can be obtained by esterifying alcohol with phosphoric pentoxide, phosphorous oxychloride, phosphorous trichloride or the like as a phosphorylating agent. Moreover, these phosphoric acids are obtained by making it react with zinc carbonate, zinc hydroxide, etc., for example (patent document EP699708 gazette).

  As the details of the zinc salt and / or zinc complex of such phosphate ester, the ratio of phosphorus atom to zinc atom (P / Zn) is preferably 1.2 to 2.3, more preferably 1.3 to 2.0. . Especially preferably, it is 1.4-1.9. That is, in a particularly preferred form, the phosphate ester (or phosphoric acid) is 2.0 moles or less per mole of zinc ions, and not a simple ionic structure, but some molecules are involved by ionic bonds (or coordinate bonds). Those having a different structure are preferred.

  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, and more preferably 0.8% by weight with respect to the epoxy resin (A). 1 to 4% by weight. Further, it is particularly preferably 0.1 to 2% by weight.

As the curing agent, the polycarboxylic acid (B) can be used alone or in combination with an acid anhydride, and further in combination with other curing agents. When used in combination, the proportion of the total amount of the polyvalent carboxylic acid compound (B) and the acid anhydride in the total 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 in combination include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of curing agents that can be used include amines and polyamide compounds (such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and polyamide resins synthesized from linolenic acid dimer and ethylenediamine). Polyphenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, pheno (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, di Cyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) ) Polycondensates with benzene, 1,4′-bis (methoxymethyl) benzene, and their modified products, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols), and others (Imi Tetrazole, trifluoroborane - amine complex, guanidine derivatives, etc.) and the like, but is not limited thereto.
These may be used alone or in combination of two or more.

  In the curable resin composition of the present invention, the blending ratio of the epoxy resin and the curing agent is preferably 0.7 to 1.2 equivalents of the curing agent with respect to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the curable resin composition of the present invention, a curing catalyst can be used in combination with a curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'- Methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Various imidazoles such as imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid Acids, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as 7 and their tetrafes Salts such as ruborates and phenol novolacs, salts with the above polycarboxylic acids or phosphinic acids, ammonium salts such as tetrabutyl ammonium bromide, cetyltrimethyl ammonium bromide, trioctylmethyl ammonium bromide, triphenylphosphine, tri (tolyl) phosphine Phosphines and phosphonium compounds such as tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and curing thereof Examples thereof include a microcapsule-type curing accelerator having a microcapsule as an accelerator. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

  The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably 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 concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, binder resin can also be mix | blended with the curable resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

  An inorganic filler can be added to the curable resin composition of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable resin composition of the present invention. can do.

  When the curable resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, the particle size of the inorganic filler used is transparent by using a nano-order level filler. It is possible to supplement the mechanical strength and the like without hindering. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less.

When using the curable resin composition of this invention for an optical material, especially optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y _{4 Al 2 O 9: Ce,} Y 2 O 2 S: Eu, Sr5 (PO 4) 3 Cl: Eu, (SrEu) such as _O · _Al 2 O ₃ is exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably, 5-60 weight part is preferable.

  When the curable resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, for the purpose of preventing sedimentation of various phosphors upon curing, silica fine powder (also called Aerosil or Aerosol) is used. A thixotropic agent can be added. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

The curable resin composition of the present invention is an optical material, particularly an optical semiconductor encapsulant, containing an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant for the purpose of preventing coloring. be able to.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 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] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetramethyl -4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] buty Malonate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester decanedioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine- 2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], succinic acid Polymer of dimethyl and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa -3,20-diazadispiro [5,1,11,2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl Ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa -3,20-diazadispiro [5,1,11,2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2 ] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester 2,2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl ) And other hindered amine compounds, octabenzone and other benzophenone compounds, 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-tetrahydrophthalimide-methyl) -5-methyl Phenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl) Benzotriazole compounds such as -6-dodecyl-4-methylphenol, 2, -Benzoate type such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 Examples include triazine compounds such as-[(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited, and for example, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, and ADEKA, LA-52, LA-57, LA-, manufactured by Ciba Specialty Chemicals. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4 ′ -Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenyl Range phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis ( 2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butyl) Enyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl -Phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl Examples include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as an Adeka product, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, and Adekas tab 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-tert-butyl-4-hydroxyphenyl) propionate. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) 2), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis- [3 3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 2 -[1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4'-hydroxy- 3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114 IRGANOX 1098, Adekas 1520L AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, SUMITOMO CHEMICAL CO., LTD., Sumilizer GA-80, Sumizer MDP-S, Sumiliz er BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like are manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0.005 with respect to the curable resin composition of the present invention. It is in the range of -5.0% by weight.

  The curable resin composition of this invention is obtained by mixing each component uniformly. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin and a curing agent, and if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler and a compounding agent are uniformly used as necessary using an extruder, a kneader, a roll, a planetary mixer, etc. Mix well until it becomes a curable resin composition, and when the obtained curable resin composition of the present invention is liquid, potting and casting, impregnation into the substrate, curable resin composition in the mold Pour objects, cast, etc., and cure by heating. In addition, when the obtained curable resin composition of the present invention is solid, a method of molding by using a cast after casting or a transfer molding machine and further curing by heating can be mentioned. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, it can be hardened at a high temperature at a stretch, but it is preferable to raise the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 80 and 150 ° C., and post-curing is performed between 100 and 200 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

  Further, the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, glass fiber, A prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heat-dried is subjected to hot press molding to obtain a cured product of the curable resin composition of the present invention. can do. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

  Moreover, the curable resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, first, the curable resin composition of the present invention is applied as a varnish on a release film, and after removing the solvent under heating, by performing B-stage, It is formed as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.

  Next, the case where the curable resin composition of the present invention is used as an optical semiconductor sealing material or die bond material will be described in detail.

  When the curable resin composition of the present invention is used as a sealing material or die bond material for an optical semiconductor such as a high-intensity white LED, an epoxy resin, a curing agent, a coupling material, an antioxidant, a light stabilizer, etc. A curable resin composition is prepared by thoroughly mixing the additive, and is used as a sealing material or for both a die bond material and a sealing material. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

  Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens. The curable resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.

  As a method for adhering a semiconductor chip to a substrate using the curable resin composition of the present invention, the curable resin composition of the present invention is applied by dispenser, potting, or screen printing, and then heated by placing the semiconductor chip thereon. Curing can be performed to bond the semiconductor chip. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.

  The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

  Furthermore, the curable resin composition of the present invention can be used for general applications in which curable resins such as epoxy resins are used. For example, adhesives, paints, coating agents, molding materials (sheets, films, FRPs) Etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, acrylic ester resins as resist curing agents, etc. Examples include additives to resins and the like.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing used for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings used for COB, COF, TAB, etc. of ICs and LSIs, flip Examples include underfill used for chips and the like, and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

  The cured product obtained in the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wire harnesses, and corrosion resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical property value in an Example was measured with the following method.
(1) Molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by gel permeation chromatography (GPC) method.
-GPC conditions Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
(2) Epoxy equivalent: Measured by the method described in JISK-7236.
(3) Viscosity: 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 with reference to synthesis examples and examples. In the synthesis examples and examples, “part” means part by weight, and “%” means% by weight.

Synthesis Example 1 (20)
As Step 1, 375 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenylsilicone oil having a weight average molecular weight of 1700 (GPC measurement value) (weight measured using silanol equivalent 850, GPC) Calculated as half the average molecular weight.), 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel and reacted under reflux for 8 hours.
In Step 2, after adding 655 parts of methanol, 144 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase at 100 ° C. under reduced pressure, 647 parts of an epoxy resin (A-1) used in the present invention was obtained. The resulting compound was a liquid resin having an epoxy equivalent of 541 g / eq, a weight average molecular weight of 2,100, and an appearance having a colorless and transparent appearance.

Synthesis Example 2 (17)
As step 1, 263 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (measured by GPC) (weight measured using silanol equivalent 950, GPC) Calculated as half the average molecular weight.), 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel and reacted under reflux for 8 hours.
In Step 2, after adding 655 parts of methanol, 115 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. 605 parts of epoxy resin (A-2) used for this invention was obtained by removing a solvent at 100 degreeC under pressure reduction of the obtained organic phase. The resulting compound was a liquid resin having an epoxy equivalent of 636 g / eq, a weight average molecular weight of 2090, and a colorless and transparent appearance.

Synthesis Example 3 (18)
As step 1, 285 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured GPC value) (weight measured using silanol equivalent 850, GPC) Calculated as half the average molecular weight.), 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel and reacted under reflux for 8 hours.
As step 2, after adding 655 parts of methanol, 123 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase at 100 ° C. under reduced pressure, 620 parts of an epoxy resin (A-3) used in the present invention was obtained. The epoxy equivalent of the obtained compound was 605 g / eq, the weight average molecular weight was 2120, and the appearance was a colorless and transparent liquid resin.

Synthesis example 4
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH, hereinafter referred to as acid anhydride H-1) 84 And 239 parts of carbinol-modified silicone oil (X22-160AS manufactured by Shin-Etsu Chemical Co., Ltd.), reacted at 60 ° C. for 2 hours, and then heated and stirred at 90 ° C. for 3 hours to obtain a polyvalent carboxylic acid represented by the following formula (7) 323 parts of acid (B-1) was obtained. The resulting colorless liquid resin had a functional group equivalent of 646 g / eq. Met.
Formula (7)

Examples 1, 2, 3, 4, 5, Comparative Examples 1, 2
Epoxy resins (A-1) (A-2) (A-3) obtained in Synthesis Examples 1 to 3 as epoxy resins, polyvalent carboxylic acids (B-1) obtained in Synthesis Example 4 as curing agents, Acid anhydride (H-1) as a curing agent for comparative examples, zinc 2-ethylhexylate as a zinc salt (manufactured by Hope Pharmaceutical Co., Ltd., 18% octope Zn, hereinafter referred to as zinc salt C-1), curing accelerator As a curing accelerator (manufactured by Nippon Synthetic Chemical Co., Ltd., Hishicolin PX4MP, hereinafter referred to as catalyst I-1), as an additive, hindered amine (manufactured by ADEKA LA-81, hereinafter referred to as additive J-1), phosphorus compound (ADEKA) Manufactured by ADEKA 260, hereinafter referred to as additive J-2), blended at a blending ratio (parts by weight) shown in Table 1 below, defoamed for 20 minutes, and curable resin composition for the present invention or for comparison I got a thing.

(LED sealing test)
Surface mount type (SMD) in which the curable resin compositions obtained in the examples and comparative examples were vacuum degassed for 20 minutes, filled in a syringe and mounted with a light emitting element having an emission wavelength of 465 nm using a precision discharge device. Mold 5mmφ) LED was cast. Then, LED for a test was obtained by making it harden | cure on the hardening conditions of 120 degreeC for 1 hour, and also 150 degreeC for 3 hours.
Evaluation item (a) Volatility: The presence or absence of dents on the surface of the cured product after sealing was visually evaluated. In the table, ◯: no dents are observed, Δ: some dents are observed, x: many dents are observed.
(B) Tack: No stickiness ○ No stickiness × (finger touch test)
(C) Reflow test: After absorbing the obtained test LED at 30 ° C. and 70% × 72 hours, using a high-temperature observation apparatus (SMT Scope SK-5000 manufactured by Sanyo Seiko Co., Ltd.), the LED under the following reflow conditions was used. The presence or absence of cracks was confirmed. The test was performed with n = 3, and the evaluation was made by (number of NG) / (number of tests).
The temperature was raised from 25 ° C. to 150 ° C. at 2 ° C./second, then held at 150 ° C. for 2 minutes, further heated to 260 ° C. at 2 ° C./second, and maintained at 10 ° C. for 1.3 seconds / Cooling to room temperature in seconds.

(Corrosion gas permeability test)
Using the obtained curable resin composition, filling into a syringe and using a precision discharge device, an outer diameter 5 mm square surface-mount LED package (with an inner diameter of 4.4 mm and an outer wall height of 1) on which a chip having a central emission wave of 465 nm is mounted. .25 mm). The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours, and an LED package was prepared. The LED package was left in a corrosive gas under the following conditions, and the color change of the silver-plated lead frame part inside the seal was observed. The results are shown in Table 1.
・ Measurement condition Corrosion gas: 20% aqueous solution of ammonium sulfide (discolors black when sulfur component reacts with silver)
Contact method: A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
Judgment of corrosion: The time when the lead frame inside the LED package was discolored black (referred to as blackening) was observed, and it was determined that the longer the discoloration time, the better the corrosion gas resistance.
Observation was performed every hour, and evaluation was performed up to 5 hours. Evaluation evaluated time to discoloration.

(LED lighting test)
The obtained curable resin composition was filled in a syringe and cast into a surface-mounted LED (SMD type 5 mmφ, specified current 30 mA) equipped with a light emitting element having an emission wavelength of 465 nm using a precision discharge device. Then, LED for lighting test is obtained by making it harden | cure on the hardening conditions of 1 hour at 120 degreeC, and also 3 hours at 150 degreeC. In the lighting test, a lighting test was performed at currents of 230 mA and 220 mA, which greatly exceeded the specified current of 30 mA. Detailed conditions are shown below. As a measurement item, the illuminance before and after lighting for 40 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated. The results are shown in Table 1.
-Detailed lighting conditions Emission wavelength: Center emission wavelength, 465nm
Driving method: Constant current method, 220 mA, 230 mA (light emitting element stipulated current is 30 mA) 3 units are lit at the same time Driving environment: Lighting in 85 ° C, 85% wet heat machine Evaluation: Illuminance retention after 40 hours

As Comparative Example 3, an organopolysiloxane (S-1) having at least two alkenyl groups bonded to a silicon atom and an organohydrogen poly having at least two hydrogen atoms bonded to a silicon atom addition-polymerized to the alkenyl group A silicone resin obtained by addition polymerization of siloxane (S-2) was used.
The silicone resins S-1 and S-2 specifically have the following structure.
S-1: Organohydrogenpolysiloxane containing a platinum catalyst in a catalytic amount (0.1% or less) and having phenyl groups: methyl groups: vinyl groups in an amount of 0.4: 1: 1 in terms of moles as organo groups -2: An organohydrogenpolysiloxane having a phenyl group, a methyl group, or a vinyl group as an organo group, and the molar ratio of phenyl group: methyl group: vinyl group: hydrosilyl group is 2: 2: Organohydrogenpolysiloxane which is 1: 1.
In Comparative Example 3, the blending ratio (mass ratio) was S-1: S-2 = 1: 20, and the curing condition was 150 ° C. for 1 hour.

  From the above results, the curable resin composition of the present invention (a composition containing an epoxy resin (A), a polyvalent carboxylic acid (B) having a silicone skeleton, and a zinc salt and / or a zinc complex (C)) Compared to the curable resin composition of the comparative example, it becomes clear that the silver plating of the lead frame is not discolored, and not only has excellent corrosion gas resistance but also excellent crack resistance. Furthermore, it can be seen that the cured product is superior in electrical reliability, light resistance and heat resistance characteristics from the result that it shows a better illuminance retention rate in the high current accelerated lighting test than the silicone resin.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2010-134465) for which it applied on June 11, 2010, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

Claims (6)

A curable resin composition comprising an epoxy resin (A), a polyvalent carboxylic acid (B), and a zinc salt and / or a zinc complex (C) as essential components.
However, the polyvalent carboxylic acid (B), the zinc salt and / or the zinc complex (C) each satisfy the following conditions.
Polyvalent carboxylic acid (B):
A zinc salt and / or a zinc complex , which is a polyvalent carboxylic acid having at least two or more carboxyl groups and having a siloxane skeleton as a main skeleton, and produced by a reaction between a silicone compound and methylhexahydrophthalic anhydride (C):
Zinc carboxylate, phosphoric acid ester or zinc salt of phosphoric acid, and / or zinc complex having these acids or esters as ligands   The curable resin according to claim 1, wherein the epoxy resin is an epoxy resin having a glycidyl group and / or an epoxycyclohexane structure in a siloxane structure having a chain structure, a cyclic structure, a ladder structure, or a mixed structure of at least two of them. Composition. The curable resin composition according to claim 1 or 2 , wherein the polyvalent carboxylic acid (B) has a linear polysiloxane structure and has carboxylic acids at both ends. Claim 1-3 any one of a compound obtained by reaction of a carbinol modified product and cyclic saturated aliphatic acid anhydrides polycarboxylic acid (B) having a polysiloxane structure of the linear Curable resin composition. The curable resin composition according to any one of claims 1 to 4, comprising a hindered amine light stabilizer and a phosphorus-containing antioxidant. Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of Claims 1-5 .