JP6239587B2 - Polyvalent carboxylic acid composition, curing agent composition for epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a polyvalent carboxylic acid composition used as a curing agent for an epoxy resin composition suitable for electrical and electronic material applications, a curing agent composition for epoxy resin containing the same, and an epoxy resin composition containing the same.

Polyvalent carboxylic acid has excellent performance as a crosslinking agent, condensing agent, etc., such as high thermal stability, good electrical properties, chemical resistance, etc., as well as formation of condensates and good reactivity. As a molecular manufacturing raw material, it has attracted much attention and is widely used.
It is also known that polyvalent carboxylic acids can be used as curing agents for epoxy resins.

A curable resin composition containing an epoxy resin is used as a resin having excellent heat resistance in the fields of architecture, civil engineering, automobiles, aircraft, and the like. In recent years, especially in the field of semiconductor-related materials, electronic devices such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become key to light, thin, short, and small. Very high characteristics have been demanded for packaging materials represented by resins.
In addition, with the recent advancement of advanced information technology, in order to smoothly transmit and process a huge amount of information, instead of conventional signal transmission using electric wiring, technology utilizing optical signals is being developed. In the field of optical components such as blue LEDs and optical semiconductors, development of a resin composition that gives a cured product excellent in transparency is desired.

In general, the epoxy resin curing agent used in such a field includes acid anhydride compounds. In particular, an acid anhydride formed with a saturated hydrocarbon is often used because a cured product of an epoxy resin composition using the anhydride is excellent in 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 thermally cured in an open system as a curing agent for an epoxy resin, a part of these curing agents evaporate during curing because of high vapor pressure. This volatilized curing agent is released into the atmosphere, causing environmental pollution and adverse effects on the human body. Furthermore, such as contamination of the production line, poor curing of the epoxy resin composition due to the absence of a predetermined amount of carboxylic acid anhydride (curing agent) in the cured product, changes in cured product characteristics and production stability associated therewith, etc. A problem occurs.

  In addition, a cured product using a conventional acid anhydride as a curing agent is conspicuous when an LED, particularly SMD (Surface Mount Device) is sealed, and because the amount of resin used is small, If dents occur and are severe, the problem arises 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.

Japanese Unexamined Patent Publication No. 2003-277473 Japanese Laid-Open Patent Publication No. 2008-066333 International Publication No. 2011/043400 Pamphlet Japanese Unexamined Patent Publication No. 2005-185521

In order to solve such a problem, a method of using a polyvalent carboxylic acid as a curing agent can be considered. However, ordinary polyvalent carboxylic acids are often solidified, particularly crystallized due to their hydrogen bonds, and are very difficult to use as a liquid composition. In order to solve such problems, the use of silicone-based polyvalent carboxylic acid as a curing agent was studied. However, although the volatility problem was solved, the characteristics were improved in terms of adhesion and corrosion gas permeability. It was bad and difficult to use.
Furthermore, in order to improve adhesion and corrosion gas permeability, we tried to solve the problem by using polyvalent carboxylic acid and silicone polyvalent carboxylic acid together, but the viscosity of the epoxy resin composition increased, and workability was improved. Problems such as deterioration and difficulty in casting into narrow packages have occurred.

  The present invention reduces the volatilization of the curing agent during curing, and further provides a cured product containing a polyvalent carboxylic acid that gives a cured product having excellent heat resistance, optical properties, adhesion, stretchability, and corrosion gas permeability, And it aims at providing the epoxy resin composition containing this hardening | curing agent composition.

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

(1)
A carboxylic acid compound (J) obtained by addition reaction of a silicone oil (a) represented by the following formula (1) and a compound (b) having one or more carboxylic anhydride groups in the molecule; Addition reaction of an alcohol compound (c) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyhydric phenol compound are hydrogenated with a compound (d) having one or more carboxylic anhydride groups in the molecule A polycarboxylic acid composition containing the polycarboxylic acid compound (K) obtained by

(In Formula (1), R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms which may be via an ether bond, and R ₂ each independently represents a methyl group, a phenyl group or a cyclohexyl group. n is the number of repetitions, which means an average value and is 1 to 100.)

(2)
The polyvalent carboxylic acid composition according to (1) above, wherein the compounds (b) and (d) having one or more carboxylic anhydride groups in the molecule are acid anhydrides having a cyclic saturated hydrocarbon as a mother skeleton. object,
(3)
Compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule are methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid anhydride and bicyclo [ 2,2,1] polyvalent carboxylic acid composition according to (1) or (2) above, which is at least one acid anhydride selected from heptane-2,3-dicarboxylic acid anhydride,
(4)
The alcohol compound (c) in which at least one aromatic ring having a hydroxyl group of the polycyclic polyphenol compound is hydrogenated is a hydrogenated bisphenol, a hydrogenated trisphenol or a hydrogenated tetraphenol (1) To (3), the polyvalent carboxylic acid composition according to any one of
(5)
When the ratio (weight ratio) between the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) is expressed as (J) / (K), the ratio (1) is 99.7 / 0.3 to 50/50. ) To (4), the polyvalent carboxylic acid composition according to any one of

(6)
A mixture of silicone oil (a) and an alcohol compound (c) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyphenol compound are hydrogenated has one or more carboxylic anhydride groups in the molecule. The method for producing a polyvalent carboxylic acid composition according to any one of the above (1) to (5), wherein the compounds (b) and (d) having the same are added and reacted simultaneously,
(7)
The method for producing a polyvalent carboxylic acid composition according to (6), wherein the following step (A) and step (B) are sequentially reacted in one pot,
Step (A): Step of reacting silicone oil (a) with compound (b) having one or more carboxylic anhydride groups in the molecule Step (B): One having a hydroxyl group of a polycyclic polyhydric phenol compound A step of reacting the alcohol compound (c) in which the aromatic ring is hydrogenated with a compound (d) having one or more carboxylic anhydride groups in the molecule;
(8)
The method for producing a polyvalent carboxylic acid according to (6) or (7), wherein the reaction is performed at 40 to 150 ° C. in a solvent-free or 50 wt% or less organic solvent with respect to the raw material to be used,
(9)
With respect to the polyvalent carboxylic acid composition according to any one of (1) to (5), a compound (e) having one or more carboxylic acid anhydride groups in the molecule is added at a weight ratio of 0.1. Curing agent composition for epoxy resin mixed with ˜50% by weight,
(10)
The polyhydric carboxylic acid composition according to any one of (1) to (5), or the epoxy resin composition containing the epoxy resin curing agent composition and the epoxy resin according to (9),
(11)
The epoxy resin composition according to (10), wherein the epoxy resin is an alicyclic epoxy resin and / or an epoxy group-containing silicone resin,
(12)
The epoxy resin composition according to (10), which contains an epoxy group-containing silicone resin as an epoxy resin,
(13)
A cured product obtained by curing the epoxy resin composition according to any one of (10) to (12),
About.

  The polyvalent carboxylic acid composition of the present invention is useful as a curing agent for an epoxy resin, and in particular, the curing agent composition containing the polyvalent carboxylic acid is volatile in a temperature range usually employed for curing the epoxy resin. The cured product of the epoxy resin composition using it is excellent in heat resistance, optical properties, adhesion, corrosion gas permeability and stretchability. The epoxy resin composition using the polyvalent carboxylic acid composition of the present invention is a raw material such as a paint, an adhesive, a molded article, a semiconductor, a resin for an optical semiconductor encapsulant, a resin for an optical semiconductor die bond material, a polyimide resin, It is useful as a modifier, plasticizer, lubricant oil raw material, medical and agrochemical intermediate, paint resin raw material, and toner resin. In particular, since this polyvalent carboxylic acid composition is excellent in curing ability for epoxy resin and transparency of the cured product obtained therefrom, it is optimal for use in sealing an optical semiconductor typified by a high-intensity white LED, etc. In addition, excellent solder reflow resistance can be obtained.

  The polyvalent carboxylic acid composition of the present invention is an addition reaction between a silicone oil (a) represented by the following formula (1) and a compound (b) having one or more carboxylic anhydride groups in the molecule. And an alcohol compound (c) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyhydric phenol compound are hydrogenated. And a polyvalent carboxylic acid compound (K) (hereinafter also simply referred to as carboxylic acid (K)) obtained by addition reaction of the compound (d) having one or more carboxylic acid anhydride groups in the molecule with It is essential to contain.

(In Formula (1), R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms which may be via an ether bond, and R ₂ each independently represents a methyl group, a phenyl group or a cyclohexyl group. n is the number of repetitions, which means an average value, and is 1 to 100.)

The silicone oil (a) is represented by the formula (1). In the formula (1), specific examples of R ₁ include alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene, —C ₃ H ₆ —O—. A group having a structure of C ₂ H ₄ —, a group having a structure of —C ₂ H ₄ —O—C ₂ H ₄ —, a group having a structure of —C ₃ H ₆ —O—C ₃ H ₆ —, etc. A C1-C10 ether bond containing alkylene group is mentioned. Particularly preferably a propylene _{group, -C 3 H 6 -O-C} 2 H 4 - is.

In the silicone oil represented by the above formula (1), 2 to 80 is preferable, and 3 to 60 is particularly preferable as the repeating number n.
Moreover, 300-10000 are preferable as a weight average molecular weight, and 500-5000 are especially preferable.

Polycyclic polyhydric phenol compound (polycyclic polyphenol compound used in the present invention means a compound having two or more six-membered rings and having two or more phenolic hydroxyl groups. As the alcohol compound (c) in which one or more aromatic rings having a hydroxyl group are hydrogenated, 2,2-bis (4-hydroxycyclohexyl) propane (= hydrogenated bisphenol A), 1,1-bis (4-hydroxycyclohexyl) ethane (= hydrogenated bisphenol E), 4,4′-bicyclohexanol (= hydrogenated biphenol), 3,3 ′, 5,5′-tetramethyl-4,4′-bicyclohexanol, Methylene biscyclohexanol (= hydrogenated bisphenol F), 4,4 ′, 4 ″ -methylidenetriscyclohexanol, 4,4 ′-[(4-hydroxy Cyclohexyl) methylene] bis (2-methylhexanol), 4,4 ′-(1- {4- [1- (4-hydroxycyclohexyl) -1-methylethyl] phenyl} ethylidene) biscyclohexanol, 4,4 ′ -[4- (4-hydroxycyclohexyl) cyclohexylidene] bisphenol, 4,4 '-[4- (4-hydroxycyclohexyl) cyclohexylidene] bis (2-methylphenol), 4,4'-[4- (4-hydroxycyclohexyl) cyclohexylidene] bis (2,6-dimethylphenol, dihydroxydecahydronaphthalene (= hydrogenated dihydroxynaphthalene), dihydroxytetradecahydroanthracene, 1,4-cyclohexylenebis (methylethanol), 5,5 ′-(1-methylethylidene) bis [1, 1 ′-(bicyclohexyl) -2-ol], 5,5 ′-(1,1′-cyclohexylidene) bis [1,1 ′-(bicyclohexyl) -2-ol], 5,5′- (Cyclohexylmethylene) bis [1,1 ′-(bicyclohexyl) -2-ol], 1,1,2,2, -tetrakis (4-hydroxycyclohexyl) ethane, 1,1,2,2, -tetrakis ( 3,5-dimethyl-4-hydroxycyclohexyl) ethane. However, the present invention is not limited to these, and one kind or a mixture of two or more kinds may be used.
Among these, hydrogenated bisphenol such as hydrogenated bisphenol A, hydrogenated biphenol, and hydrogenated dihydroxynaphthalene are preferable.

The compounds (b) and (d) (b and d may be the same) having one or more carboxylic anhydride groups in the molecule used in the present invention include one or two compounds in the molecule. Those having a carboxylic anhydride group are preferred, and compounds having a saturated hydrocarbon structure are particularly preferred. Further, those having a cyclic structure are particularly preferred. Specifically, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic anhydride, bicyclo [2,2,1] heptane- Examples include 2,3-dicarboxylic acid anhydride, cyclobutanetetracarboxylic acid dihydrate, butanetetracarboxylic acid dianhydride, and the like, but are not limited thereto, and one kind or a mixture of two or more kinds may be used. .
In the present invention, those having one carboxylic anhydride group are particularly preferred, and methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic anhydride, bicyclo [2,2, 1] Heptane-2,3-dicarboxylic anhydride is preferable, and methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic anhydride are particularly preferable.

Silicone oil (a) and a compound (b) having a carboxylic anhydride group and / or an alcohol compound (c) and a carboxylic acid in which one or more aromatic rings having a hydroxyl group of a polycyclic polyphenol compound are hydrogenated The reaction between an alcohol and an acid anhydride that causes an addition reaction between the compound (d) having an acid anhydride group and an acid anhydride is generally an addition reaction catalyzed by an acid or a base. Reaction is preferred.
When a catalyst is used, examples of the catalyst that can be used include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, hydroxide Metal hydroxides such as potassium, calcium hydroxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7 -Heterocyclic compounds such as ene, imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethyl Ammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, A quaternary ammonium salt such as trioctylmethylammonium acetate is exemplified. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferred.
The amount of the catalyst used is not particularly limited, but is preferably 0.001 to 5 parts by weight based on the total weight of the raw material of 100 parts by weight.

  In this reaction, a reaction without a solvent is preferable, but an organic solvent may be used. The amount of the organic solvent used is 0.005 to 1, preferably 0.005 to 0.7, more preferably 0.005 to 0.5 (ie 50 % By weight or less). When the weight ratio exceeds 1, the progress of the reaction may be extremely slow. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, diethyl ether , Ethers such as tetrahydrofuran and dioxane, and ester compounds such as ethyl acetate, butyl acetate and methyl formate can be used.

The reaction temperature is preferably 40 to 200 ° C, particularly preferably 40 to 150 ° C. In particular, when this reaction is carried out in the absence of a solvent, the reaction at 100 ° C. or lower is preferred, and the reaction at 40 to 100 ° C., particularly 40 to 80 ° C. is preferred because of the volatilization of the acid anhydride.
When a compound having high crystallinity at room temperature, such as cyclohexane-1,2,4-tricarboxylic acid anhydride, is used, it is preferable to perform the reaction at 100 to 150 ° C. in order to sufficiently dissolve the crystal.
When an acid anhydride that easily volatilizes and an acid anhydride with high crystallinity are used in combination, it is possible to prevent volatilization of the acid anhydride by increasing the temperature stepwise.

The reaction ratio of (a) and (b), (c) and (d) in the reaction for obtaining the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) is theoretically equivalent to the reaction in an equimolar amount. Although preferable, it can be changed as required. That is, as will be described later, in the curing agent composition for epoxy resin of the present invention, when the acid anhydride used and the acid anhydride used here are the same, the reaction is carried out in an excess of acid anhydride at the time of production. When the reaction for obtaining the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) is completed, a mixture (curing agent composition) of the acid anhydride and the polyvalent carboxylic acid of the present invention can be obtained.
As a specific reaction ratio, the functional group equivalent is compared, and when (b) (or (d)) is 1, (a) (or (c)) is 0.001 to 1. It is 0, More preferably, it is 0.01-1.0, More preferably, it is 0.1-1.0. When manufacturing a hardening | curing agent composition as mentioned above, it is preferable to use in the range of 0.01-0.7, More preferably, 0.01-0.4.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a large amount of energy. An excessively short reaction time means that the reaction is abrupt and is not preferable from the viewpoint of safety. A preferable range is 1 to 48 hours, more preferably 1 to 36 hours, and further preferably 1 to 24 hours.

  When a catalyst is used after completion of the reaction, the catalyst is removed by neutralization, water washing, adsorption, etc., and the solvent is distilled off to obtain the desired polyvalent carboxylic acid. In the reaction without a catalyst, if necessary, the solvent is distilled off, and in the case of no solvent and without a catalyst, the polycarboxylic acid (J) and the polyvalent carboxylic acid (K) can be obtained by removing the solvent as it is. .

  The most preferable production method is a method in which the reaction is carried out at 40 to 150 ° C. under the conditions of no catalyst and no solvent, and is taken out as it is after the reaction is completed.

The target polyvalent carboxylic acid composition can be obtained by mixing the polyvalent carboxylic acid (J) and polyvalent carboxylic acid (K) thus obtained. The ratio (weight ratio) is (J) / (K) = 99.7 / 0.3 to 50/50, more preferably 99.7 / 3 to 60/40. When the amount of the polyvalent carboxylic acid (J) is too large, problems occur in the gas permeation resistance and reflow resistance of the cured product. When the amount of the polyvalent carboxylic acid (K) is too large, the solidified or highly viscous product is handled. It becomes difficult.
Here, the ratio (weight ratio) of (J) / (K) is preferably 99/1 to 70/30, more preferably 99/1 to 80/20, and particularly preferably 99/1 to 85/15. By mixing 1 or more by weight ratio (K), the corrosion gas permeability is particularly improved, and by mixing 70 or more by weight ratio (J), the light resistance is excellent, This is because cracks are unlikely to occur and illuminance deterioration is less likely to occur when used as an LED sealing material. In particular, by mixing (J) in a weight ratio of 80 or more (particularly preferably 85 or more), the above characteristics can be achieved in a balanced manner.

In the present invention, the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) can also be produced simultaneously. Specific methods include (i)
A mixture of silicone oil (a) and an alcohol compound (c) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyphenol compound are hydrogenated has one or more carboxylic anhydride groups in the molecule. The compounds (b) and (d) having them are charged and reacted at the same time.
(Ii)
The following steps (A) and (B) are sequentially reacted in one pot.
Step (A): Step of reacting silicone oil (a) with compound (b) having one or more carboxylic anhydride groups in the molecule Step (B): One having a hydroxyl group of a polycyclic polyhydric phenol compound Process step (A) (or process (B)) in which the alcohol compound (c) having the hydrogenated aromatic ring and the compound (d) having one or more carboxylic anhydride groups in the molecule are reacted. After performing, the compound used for a process (B) (or process (A)) is injected | thrown-in sequentially, and reaction and mixing are performed in a system.
(Iii)
When compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule are the same, silicone oil (a) (or one or more aromatic rings having a hydroxyl group of a polycyclic polyhydric phenol compound) A hydrogenated alcohol compound (c)) and compounds (b) and (d) having one or more carboxylic anhydride groups in the molecule, and after reacting, a polycyclic polyhydric phenol An alcohol compound (c) (or silicone oil (a)) in which one or more aromatic rings having a hydroxyl group of the compound are hydrogenated is charged and reacted.

The polycarboxylic acid composition of the present invention thus obtained is usually a colorless liquid to semi-solid substance.
The polycarboxylic acid composition of the present invention has excellent transparency, epoxy resin curing agent, paint, adhesive, molded article, semiconductor, optical semiconductor encapsulant resin, optical semiconductor die bond material resin, polyamide resin , Useful as raw materials and modifiers for polyimide resins, plasticizers and lubricating oil raw materials, medical and agrochemical intermediates, raw materials for resin for paints, resin for toners, especially when used as a curing agent for epoxy resins Since the cured product has excellent transparency, it is extremely useful as a curing agent for epoxy resin used for high-intensity white LED and other optical semiconductor encapsulation.

Hereinafter, it describes about the hardening | curing agent composition for epoxy resins of this invention containing the polyhydric carboxylic acid composition of this invention.
When the polyvalent carboxylic acid composition of the present invention is used as a curing agent for an epoxy resin, particularly as a liquid composition, a curing agent composition obtained by mixing the polyvalent carboxylic acid composition of the present invention and another acid anhydride is used. Can be used as a form.
As other acid anhydrides that can be used, compounds having one or more carboxylic acid anhydride groups in the molecule are preferred, and acid anhydrides having no aromatic ring in their structure are particularly preferred. Specifically, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1 And heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and the like.
When used as a curing agent composition in a mixture with an acid anhydride, the proportion of the polycarboxylic acid composition of the present invention is preferably 0.1 to the total weight of the acid anhydride and the polycarboxylic acid. 50% by weight, more preferably 0.1 to 30% by weight. By using together in such a range, there are effects in terms of fluidity of the composition, heat resistance of the cured product, and mechanical strength.

Hereinafter, the polyvalent carboxylic acid composition of the present invention, preferably the epoxy resin composition of the present invention (hereinafter also referred to as a curable resin composition) including the epoxy resin curing agent composition of the present invention will be described.
The curable resin composition of the present invention contains an epoxy resin as an essential component.

  Examples of the epoxy resin that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. 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-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) It has a glycidyl group and / or an epoxycyclohexane structure Epoxy resins) include solid or liquid epoxy resins such as, but not limited thereto.

In particular, when the curable resin composition of the present invention is used for optical applications, an alicyclic epoxy resin and / or an epoxy group-containing silicone resin is preferable, and an epoxy resin having a silsesquioxane structure is more preferable. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These alicyclic epoxy resins include esterification reaction of cyclohexene carboxylic acid with alcohols or esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) ), 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 The thing etc. which oxidized the compound which can be manufactured by reaction (The method as described in Unexamined-Japanese-Patent No. 2006-052187 etc.) are mentioned.
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- Diols such as pentanediol, 1,6-hexanediol, cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol And tetraols. 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, as an alicyclic epoxy resin other than the above, an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the reaction mixture and the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), reaction A method using an organic solvent as a medium (Japanese Patent Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

In the curable resin composition of the present invention, the polyvalent carboxylic acid (or the curing agent composition) of the present invention may be used in combination with other curing agents. When used in combination, the proportion of the polyvalent carboxylic acid of the present invention in the total curing agent is preferably 20% by weight or more, particularly preferably 30% by weight or more.
Examples of other curing agents that can be used in combination include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, 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-1,3,4-tricarboxylic acid- 3, -Anhydride, 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, phenols ( Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4 Polycondensates with '-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine Examples include, but are not limited to, complexes, guanidine derivatives, and condensates of terpenes and phenols. These may be used alone or in combination of two or more.

  In the curable resin composition of the present invention, the ratio of the curing agent to the epoxy resin is 0.5 to 1.5 equivalents (note that the acid anhydride group is monofunctional) with respect to 1 equivalent of the epoxy groups of all epoxy resins. The amount is preferably 0.5 to 1.2 equivalents. When less than 0.5 equivalent or more than 1.5 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 accelerator may be used in combination with the 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 ruborate and phenol novolac, salts with the above polycarboxylic acids, or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium 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.

The curable resin composition of the present invention preferably contains a zinc salt and / or a zinc complex. In the curable resin composition of the present invention, the zinc salt and / or the zinc complex contributes as a curing accelerator between the epoxy resin and the curing agent.
The zinc salt and / or zinc complex is a salt and / or complex having a zinc ion as a central element, preferably a carboxylic acid having an alkyl group having 1 to 30 carbon atoms as a counter ion and / or a ligand. , Phosphoric acid ester, and phosphoric acid. Examples of the alkyl group having 1 to 30 carbon atoms include methyl group, isopropyl group, butyl group, 2-ethylhexyl group, octyl group, isodecyl group, isostearyl group, decanyl group, and cetyl group.
In the present invention, a zinc carboxylate and a zinc phosphate ester are particularly preferable. By using a zinc carboxylate body or a zinc phosphate ester body, corrosion resistance and gas permeability can be improved.
As the particularly preferred zinc carboxylate in the present invention, an alkyl group having a chain-branched structure or an alkyl group having a functional group such as an olefin is preferably included in the compound, and those having 3 to 30 carbon atoms are particularly preferable. Particularly preferred is 5-20. These are preferable in terms of compatibility, and if the number of carbons is too large (when the number of carbons exceeds 30), or there is no structure such as a branched structure or a functional group, the compatibility with the resin may be low. Examples include 2-ethylhexyl zinc, zinc isostearate, zinc undecylenate, and zinc behenate.

In the present invention, a particularly preferable phosphoric acid ester is preferably a zinc salt and / or zinc complex of phosphoric acid or phosphoric acid ester (monoalkyl ester, dialkyl ester, trialkyl ester, or a mixture thereof). It may contain the body. Specifically, the molar ratio of monoalkyl ester, dialkyl ester, and trialkyl ester in the phosphoric acid ester contained (substitute with the purity of gas chromatography. However, since trimethylsilylation is required, there is a difference in sensitivity. In this case, it is preferable that the amount of the monoalkyl ester compound is 50 area% or more at the stage of the trimethylsilyl treatment.
Such zinc salt and / or zinc complex of zinc phosphate ester can be obtained by reacting phosphate ester with, for example, zinc carbonate, zinc hydroxide, etc. (Patent Document EP 699708).
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. preferable.
Especially preferably, it is 1.4-1.9. That is, in a particularly preferable form, the amount of phosphate ester (or phosphate derived from phosphate ester) is 2.0 mol or less per mol of zinc ion, and not a simple ionic structure, but some molecules are ion-bonded (or coordinated). Those having a structure related by bonding) are preferred. Such a zinc salt and / or zinc complex can also be obtained, for example, by the technique described in Japanese National Publication No. 2003-51495.
As such a compound, as a commercial product, zinc carboxylate, Zn-St, Zn-St 602, Zn-St NZ, ZS-3, ZS-6, ZS-8, ZS-7, ZS-10, ZS -5, ZS-14, ZS-16 (manufactured by Nitto Kasei Kogyo), XK-614 (manufactured by King Industry), 18% Octop Zn (Hope Pharmaceutical), SCI-ZNB (manufactured by San Ace), phosphate ester and / or zinc phosphate LBT-200B (manufactured by SC Organic Chemistry), XC-9206 (manufactured by King Industry).
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 0.001-15 weight part normally with respect to 100 weight part of epoxy resins, More preferably, it is 0.01-5 weight part, Especially preferably, it is used in 0.01-3 weight part. In this reaction, curing is possible without using a curing accelerator, but addition of a curing accelerator is preferred from the viewpoint of coloring during curing. In particular, use of a zinc salt and / or a zinc complex is preferable in order to prevent coloring and obtain corrosion resistance gas permeability.

  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 / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

  Furthermore, you may add antioxidant to the curable resin composition of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part of resin components in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part.

  Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) ethyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

Specific examples of phosphorus antioxidants include 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2 , 4-Di-tert-butyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexyl Pentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, Tris (2,6- -Tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4 , 6-Di-tert-butylphenyl) (2-tert-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-) Methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert- Butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphe Nylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenedi Phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6 -Di-n-butylphenyl) -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 ′ -Biphenylene diphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcridyl phosphate, diphenyl monoorthoxenyl phosphate, tolubutoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate.
A commercial item can also be used for the said phosphorus antioxidant.
For example, Adeka Stub PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB C, 135A, ADK STAB 3010, and ADK STAB TPP.

In the present invention, the amount of phosphorus antioxidant used is preferably 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and still more preferably 0.1 to 4% by weight with respect to the epoxy resin. 2% by weight.
These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the curable resin composition of this invention as needed.
As a light stabilizer, it is preferable to contain a hindered amine compound especially, and it is preferable to contain a phosphorus compound as needed. 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-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) 6-tetramethyl-4-piperidyl) sebacate, bis (1-oudecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6-tetra Til-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-1,1-dimethylethyl hydroperoxide and octane reactive product of decanedioic acid, 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]], dimethyl succinate and 4 -Hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa-3, 20-diazaspiro [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, 2 0-diazaspiro [5,1,11,2] heneicosane-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 Hindered amines such as 1,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) Compounds and the like.
The following commercially available products can be used as the amine compound as the light stabilizer.
For example, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, and ADEKA manufactured by Ciba Specialty Chemicals, LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like can be mentioned.
In the present invention, the light stabilizer is used in a weight ratio with respect to the epoxy resin, preferably 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and particularly preferably 0.1 to 2. % By weight. When the amount is less than 0.005% by weight, the effect is insufficient, and when the amount exceeds 5% by weight, an influence on the heat-resistant coloring property may appear.

  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 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, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.

When using the curable resin composition of this invention for an 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, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are 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 these phosphors are used, the amount added is preferably 1 to 80 parts by weight and more preferably 5 to 60 parts by weight with respect to 100 parts by weight of the resin component.
When the curable resin composition of the present invention is used as an optical material, particularly an optical semiconductor encapsulant, silica fine powder (also called aerosil or aerosol) is used for the purpose of preventing sedimentation during curing of various phosphors. 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 R974Rero12R, Aerosil R202, AerosilR202, AerosilR202 , RY200, RX200 (manufactured by Nippon Aerosil Co., Ltd.) and the like.

  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, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are thoroughly mixed using an extruder, kneader, roll, etc. as necessary until uniform. If the curable resin composition is in liquid form, potting or casting, impregnating the base material, pouring the curable resin composition into a mold, casting, curing by heating, or solid In this case, there is a method of molding by using a casting after melting or a transfer molding machine and further curing by heating. 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 increase 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 or paper and drying by heating 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 be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is formed by applying the curable resin composition of the present invention on the release film as the curable resin composition varnish, removing the solvent under heating, and then performing B-stage. To obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

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

  When the epoxy resin composition of the present invention is used as a sealing material for an optical semiconductor such as a high-intensity white LED, or a die bond material, a curing agent (curing agent composition) containing the polyvalent carboxylic acid composition of the present invention. In addition to the epoxy resin, an epoxy resin composition is prepared by thoroughly mixing additives such as a curing accelerator, a coupling material, an antioxidant, a light stabilizer, etc., and as a sealing material or a die bond material Used for both encapsulants. As a mixing method, a kneader, a three-roller, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, or the like may be used at room temperature or with heating.

  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 epoxy 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 of 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 the curable resin composition of the present invention is used. There is a method in which a semiconductor chip is placed on top and heat-cured. By this method, the semiconductor chip can be bonded to the substrate. 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 thermosetting resins such as epoxy resins are used. Specifically, adhesives, paints, coating agents, molding materials (sheets) , Film, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, and acrylate esters as resist curing agents Examples thereof include additives to other 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 for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

  The cured product of the present invention obtained by curing the curable resin composition of 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 polarizing 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 plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. 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 wireness, 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.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.

Synthesis Example 1 (Synthesis of a condensate between a silicon compound having an epoxy group and another silicon compound)
394 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of polydimethyldiphenylsiloxane having a silanol group with a molecular weight of 1700 (measured by GPC), 4 parts of 0.5% KOH methanol solution, and 36 parts of isopropyl alcohol The reaction vessel was charged and heated to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours. After the reaction, after adding 656 parts of methanol, 172.8 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 780 parts of methyl isobutyl ketone (MIBK) was added for washing, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 731 parts of an epoxy group-containing siloxane compound (EP-1). The obtained compound had an epoxy equivalent of 491 g / eq and the appearance was colorless and transparent.

Synthesis Example 2 (Synthesis of a condensate between a silicon compound having an epoxy group and another silicon compound)
492 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 444 parts of polydimethyldiphenylsiloxane having a silanol group with a molecular weight of 1700 (measured by GPC), 4 parts of 0.5% KOH methanol solution, and 36 parts of isopropyl alcohol The reaction vessel was charged and heated to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours. After the reaction, after adding 533 parts of methanol, 216 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 660 parts of MIBK was added for washing, and washing with water was repeated three times. Subsequently, the organic phase was removed under reduced pressure at 100 ° C. to obtain 783 parts of an epoxy group-containing siloxane compound (EP-2). The epoxy equivalent of the obtained compound was 411 g / eq, and the appearance was colorless and transparent.

Example 1
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 8.3 parts of 2,2-bis (4-hydroxycyclohexyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.), both ends carbinol-modified silicone X22-160AS Add 58.9 parts (manufactured by Shin-Etsu Chemical Co., Ltd.) and 32.8 parts MH-T (methylcyclohexanedicarboxylic acid anhydride, manufactured by Shin Nippon Rika Co., Ltd.). When the reaction was carried out at 120 ° C. for 3 hours, 99 parts of a polyvalent carboxylic acid composition (MA-1) was obtained as a colorless transparent liquid. The obtained polyvalent carboxylic acid composition (MA-1) had a viscosity of 17562 mPa · s and a transmittance of 97.6% at 400 nm.

Example 2
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 7.4 parts of 4,4′-bicyclohexanol (manufactured by Tokyo Chemical Industry Co., Ltd.), both ends carbinol-modified silicone X22-160AS (Shin-Etsu Chemical ( Co., Ltd.) 58.9 parts, MH-T (methylcyclohexanedicarboxylic anhydride, Shin Nippon Rika Co., Ltd.) 33.7 parts was added and reacted at 80 ° C. for 3 hours and at 100 ° C. for 3 hours while purging with nitrogen. As a result, 99 parts of a polyvalent carboxylic acid composition (MA-2) was obtained as a cloudy liquid. The viscosity of the obtained polyvalent carboxylic acid composition (MA-2) was 13645 mPa · s.

Comparative Example 1
In a flask equipped with a stirrer, reflux condenser, and stirrer, 7.4 parts of tricyclodecane dimethanol (manufactured by TCD Alcohol DM OXEA), both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) 58.9 parts, 33.7 parts of MH-T (methylcyclohexanedicarboxylic acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd.) were added, and the reaction was performed at 50 ° C. for 2 hours and at 80 ° C. for 3 hours while purging with nitrogen. As a colorless transparent liquid, 98 parts of a polyvalent carboxylic acid composition (MC-1) was obtained. The obtained polyvalent carboxylic acid composition (MC-1) had a viscosity of 8448 mPa · s and a transmittance at 96 nm of 96%.

Comparative Example 2
In a flask equipped with a stirrer, a condenser and a thermometer, 47.1 parts of both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), polyester polyol (Adeka New Ace) having the following formula (2) Y9-10 ADEKA Co., Ltd.) 11.8 parts, Ricacid BT-100 (butanetetracarboxylic dianhydride Shin Nippon Rika Co., Ltd.) 2.5 parts, methylhexahydrophthalic anhydride (Ricacid MH New) 16.6 parts of Nippon Rika Co., Ltd.) were charged and reacted at 80 ° C. for 2 hours and at 140 ° C. for 16 hours to obtain 77.5 parts of a polyvalent carboxylic acid composition (MC-2). This polycarboxylic acid composition was a colorless and transparent liquid at the end of the reaction, but the appearance became a cloudy liquid as the temperature of the reaction liquid decreased. The acid value of the obtained compound was 77 mgKOH / g, and the viscosity was 5730 mPa · s.

(In the formula, k represents the number of repeating units, R ₃ represents neopentylene, and R 4 represents butylene.)

Example 3, Comparative Examples 3-4
The polyvalent carboxylic acid composition (MA-1) of the present invention obtained in Example 1 and, as a comparative example, the polyvalent carboxylic acid composition (MC-1) (MC-2) produced in Comparative Examples 1 and 2 As a curing agent, epoxy resin (EP-1) (EP-2) obtained in Synthesis Examples 1 and 2 as an epoxy resin, and zinc behenate (SCI-ZNB manufactured by Sanace Co., Ltd.) 1), a light stabilizer (LA-81 manufactured by ADEKA, hereinafter referred to as additive AD-1) and an antioxidant (ADEKA 260 manufactured by ADEKA, hereinafter referred to as additive AD-2) are shown in Table 1 below. It mix | blended by the mixture ratio (weight part), defoamed for 20 minutes, and obtained the curable resin composition for this invention and a comparison.
The following evaluation was performed about the obtained curable resin composition and its hardened | cured material. The results are shown in Table 1.

<Maximum point elongation>
Measurement conditions Tensile test Conforms to JIS K 6911 Sample Thickness 0.9 ± 0.05mm Cross-sectional area 4.5 ± 0.2mm ²
Speed 5mm / min Chuck distance 15mm
Analysis conditions (Distance between chucks at break -15 mm) / 15 mm × 100

<Glass transition temperature, elastic modulus>
Measurement conditions Dynamic viscoelasticity measuring device: DMS6100 (Seiko Instruments Inc.)
Measurement temperature range: -50 ° C to 150 ° C
Temperature increase rate: 2 ° C / min
Specimen size: 5mm x 7mm
Analysis conditions Glass transition temperature (Tg): The temperature at the maximum point of the Tan-δ peak was defined as Tg.
Elastic modulus: Storage elastic modulus at 0 ° C

<Reflow test>
The obtained curable resin composition was vacuum degassed for 20 minutes, then filled into a syringe, and using a precision discharge device, a copper electrode (reflector) with silver plating on the bottom surface was provided (1) 5 mm × 5 mm × Two types of surface-mount LED packages of 1.4 mmt (sealing part 0.6 mmt) and (2) 3.2 mm × 2.8 mm × 1.3 mmt (sealing part 0.6 mmt) emit light having an emission wavelength of 450 nm. Casting was carried out on the element mounted so that the opening was flat. After pre-curing at 120 ° C. for 1 hour, it was cured at 150 ° C. for 3 hours to seal the surface-mounted LED. The obtained test LED was heated at 30 ° C. 60% × 96 Hr, and then heated using a lead-free N2 reflow system (TNR15-225LH-M, Tamura Seisakusho Co., Ltd.) at 260 ° C. × 10 seconds, (1) The package No. 2 was evaluated for the presence or absence of cracks, and the package (2) was evaluated for the presence or absence or degree of peeling between the reflector portion and the resin in four stages of A, B, C, and D, respectively. The results are shown in Table 1.

<Corrosion gas permeability test>
The LED package having the size (1) was sealed in the same manner, and left in a corrosive gas under the following conditions, and the change in the color of the silver-plated reflector inside the seal was observed.
Corrosive gas: 20 ppm hydrogen sulfide
Exposure conditions: 25 ° C, humidity 75%, 4 days Post-exposure treatment: heating at 85 ° C for 6 hours Corrosion judgment: Evaluation of the degree of discoloration of the reflector inside the LED package in four stages: A, B, C, D did. The results are shown in Table 1.

  As is clear from the above results, the cured product of the curable resin composition of the present invention has a practical glass transition temperature and elastic modulus as a structure. Therefore, the curable resin composition of the present invention is used as an LED sealing material. Since it has stretchability and is not too high in elasticity, a cured product having excellent solder reflow resistance can be obtained.

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 Japan patent application (Japanese Patent Application No. 2013-042973) for which it applied on March 5, 2013, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

  The epoxy resin composition using the polyvalent carboxylic acid composition of the present invention is suitably used for electrical and electronic materials.

Claims (11)

Polyhydric carboxylic acid compound (J) obtained by addition reaction of silicone oil (a) represented by the following formula (1) and compound (b) having one or more carboxylic anhydride groups in the molecule An alcohol compound (c) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyphenol compound are hydrogenated and a compound (d) having one or more carboxylic anhydride groups in the molecule A method for producing a polyvalent carboxylic acid composition containing a polyvalent carboxylic acid compound (K) obtained by addition reaction , wherein the silicone oil (a) and a polycyclic polyhydric phenol compound have a hydroxyl group Polyhydric carboxylic acid in which compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule are charged and reacted in a mixture with the alcohol compound (c) in which the aromatic ring is hydrogenated set Method of manufacturing a thing.

(In Formula (1), R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms which may be via an ether bond, and R ₂ each independently represents a methyl group, a phenyl group or a cyclohexyl group. n is the number of repetitions, which means an average value and is 1 to 100.) 2. The polyvalent carboxylic acid composition according to claim 1, wherein the compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule are acid anhydrides having a cyclic saturated hydrocarbon as a mother skeleton. Manufacturing method . Compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule are methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid anhydride and bicyclo [ The method for producing a polyvalent carboxylic acid composition according to claim 1 or 2, which is at least one acid anhydride selected from 2,2,1] heptane-2,3-dicarboxylic acid anhydride. The alcohol compound (c) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyphenol compound are hydrogenated is a hydrogenated bisphenol, a hydrogenated trisphenol or a hydrogenated tetraphenol. 4. The method for producing a polyvalent carboxylic acid composition according to any one of 3 above. The ratio (weight ratio) between the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) is 99.7 / 0.3 to 50/50 when expressed in (J) / (K). The manufacturing method of the polyhydric carboxylic acid composition as described in any one of -4 . The manufacturing method of the polyhydric carboxylic acid composition as described in any one of Claims 1-5 which makes the following process (A) and the process (B) react sequentially by 1 pot.
Step (A): A step of reacting a silicone oil (a) with a compound (b) having one or more carboxylic anhydride groups in the molecule,
Step (B): an alcohol compound (c) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyhydric phenol compound are hydrogenated and a compound having one or more carboxylic anhydride groups in the molecule (d ). The production of the polyvalent carboxylic acid composition according to any one of claims 1 to 6 , wherein the reaction is carried out at 40 to 150 ° C in an organic solvent of 50% by weight or less with respect to the raw material to be used without solvent. Method. The compound (e) having one or more carboxylic anhydride groups in the molecule is added to the polyvalent carboxylic acid composition produced by the method according to any one of claims 1 to 7 in a weight ratio of 0. method for producing an epoxy resin curing agent composition mixed 1 to 50% by weight. Epoxy mixed claimed polycarboxylic acid composition was prepared by the method according to any one of claims 1-7, or an epoxy resin curing agent compositions were prepared by the method of claim 8 and an epoxy resin A method for producing a resin composition. The method for producing an epoxy resin composition according to claim 9 , wherein the epoxy resin is at least one selected from an alicyclic epoxy resin and an epoxy group-containing silicone resin. The manufacturing method of the epoxy resin composition of Claim 9 which contains an epoxy group containing silicone resin as an epoxy resin.