WO2011043400A1 - Polycarboxylic acid composition, process for preparation thereof, and curable resin compositions containing the polycarboxylic acid composition - Google Patents

Abstract

Provided is a polycarboxylic acid composition which ensures reduction in the volatilization of a curing agent in curing and which can provide cured products that exhibit excellent heat resistance, light resistance, resistance to corrosive gas permeation, tight adhesion, and toughness. The polycarboxylic acid composition is characterized by comprising both (J) a carboxylic acid compound obtained by addition reaction of (a) a silicone oil represented by general formula (1) with (b) a compound that contains at least one carboxylic anhydride group in the molecule and (K) a polycarboxylic acid compound obtained by addition reaction of (c) a saturated aliphatic polyhydric alcohol that has two or more alcoholic hydroxyl groups with (d) a compound that has at least one carboxylic anhydride group in the molecule. In general formula (1), R₁ is an alkylene group that contains 1 to 10 carbon atoms in total and may be interrupted by an ether linkage; R₂ is methyl or phenyl; and n represents the number of repeating units, with the weight-average molecular weight of the compound of general formula (1) being 500 to 5000.

Description

Polyvalent carboxylic acid composition and method for producing the same, and curable resin composition containing the polyvalent carboxylic acid composition

The present invention relates to a polyvalent carboxylic acid composition suitable for use in electrical and electronic materials and a method for producing the same. Furthermore, the present invention relates to a curable resin composition containing the polyvalent carboxylic acid composition as a curable component.

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.
Further, in recent years, the use in the optoelectronics related field has attracted attention. In particular, with the advancement of advanced information technology in recent years, in order to smoothly transmit and process a huge amount of information, a technique utilizing an optical signal has been developed instead of the conventional signal transmission using electric wiring. Accordingly, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of a resin composition that gives a cured product having excellent transparency is desired.

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 cured products have excellent light resistance (see, for example, Patent Documents 1 and 2). As these acid anhydrides, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride are generally used. Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. are mainly used.
However, when the above alicyclic acid anhydride is used as a curing agent, these curing agents have a high vapor pressure and tend to partially evaporate during curing. For this reason, when these alicyclic acid anhydrides are used as a curing agent for epoxy resins and thermally cured in an open system, the alicyclic acid anhydrides volatilize in the atmosphere, causing harmful substances to the atmosphere. There are concerns about environmental pollution and harmful effects on humans. In addition, there is a problem that the epoxy resin composition is poorly cured due to contamination of the production line and the absence of a predetermined amount of carboxylic acid anhydride (curing agent) in the cured product. The characteristics vary greatly depending on the curing conditions, and it is difficult to stably obtain a cured product having the intended performance.

The effect of the above volatilization on the cured product is prominent when an LED, particularly an LED used for a SMD (Surface Mount Device) is sealed with a cured product using a conventional acid anhydride as a curing agent. Since LED sealing uses a small amount of resin, there is a problem that dents are generated when acid anhydrides volatilize, and in severe cases, the wires are exposed. Furthermore, since cracks and peeling occur during solder reflow, or curing becomes insufficient, the obtained cured product has a problem that it is difficult to withstand long-term lighting.

Japanese Unexamined Patent Publication No. 2003-277473 Japanese Laid-Open Patent Publication No. 2008-066333

For such a problem, a method using 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 inventors of the present invention have studied using a silicone-based polyvalent carboxylic acid as a curing agent. Although the above problem was solved, desired properties were not obtained in terms of adhesion and corrosion gas permeability, and it was difficult to use as a cured product such as a sealing material.
Furthermore, in the curing with an organosiloxane type epoxy resin, the resulting cured product tends to be brittle, and there is a problem in toughness.

The present invention provides a polyvalent carboxylic acid composition that suppresses volatilization of a curing agent during curing, and further provides a cured product excellent in heat resistance, light resistance, corrosion resistance gas permeability, adhesion, toughness, and the like. It aims at providing the manufacturing method. Another object of the present invention is to provide a curable resin composition containing the polyvalent carboxylic acid 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) The following formula (1)

 
 

(In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, R ₂ represents a methyl group or a phenyl group, n represents a repeating unit, and Formula (1) The weight average molecular weight of the compound represented by) is 500 to 5,000.)
A carboxylic acid compound (J) obtained by subjecting a silicone oil (a) represented by the formula (b) to a compound (b) having one or more carboxylic anhydride groups in the molecule;
Polyvalent carboxylic acid obtained by addition reaction of saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher alcoholic hydroxyl group and compound (d) having one or more carboxylic anhydride groups in the molecule Compound (K),
Containing a polyvalent carboxylic acid composition,
(2)
The polyvalent carboxylic acid composition according to item (1), wherein the compounds (b) and (d) are acid anhydrides having a cyclic saturated hydrocarbon as a mother skeleton,
(3)
The compounds (b) and (d) are methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and bicyclo [2,2,1] heptane- The polyvalent carboxylic acid composition as described in (1) or (2) above, which is at least one acid anhydride selected from the group consisting of 2,3-dicarboxylic acid anhydrides,
(4)
The polyvalent carboxylic acid composition according to item (3), wherein the compounds (b) and (d) essentially comprise methylhexahydrophthalic anhydride,
(5)
Any one of (1) to (4) above, wherein the compound (c) is a polyhydric alcohol having 2 to 6 functional groups, and the total number of carbon atoms in one molecule is 5 to 20. The polyvalent carboxylic acid composition as described,
(6)
A method for producing the polyvalent carboxylic acid composition according to any one of (1) to (5) above,
Compounds (b) and (d) having one or more carboxylic anhydride groups in the molecule are added to a mixture containing silicone oil (a) and a saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher functional alcoholic hydroxyl group. And the addition reaction between the silicone oil (a) and the compound (b) and the addition reaction between the compound (c) and the compound (d) are performed simultaneously. Production method,
(7)
A method for producing the polyvalent carboxylic acid composition according to any one of (1) to (5) above,
A method for producing a polyvalent carboxylic acid composition, wherein the following step (A) and step (B) are sequentially reacted in one pot,
Step (A): Step of addition reaction of silicone oil (a) and compound (b) having one or more carboxylic anhydride groups in the molecule Step (B): Saturated fat having a bifunctional or higher functional alcoholic hydroxyl group Step (8) of reacting an aromatic polyhydric alcohol (c) with a compound (d) having one or more carboxylic anhydride groups in the molecule
(6) or (7) above, wherein the addition reaction is carried out at 40 to 150 ° C. in an organic solvent of 50% by weight or less based on the total amount of reaction substrate in the raw material to be used without solvent. Method for producing polyvalent carboxylic acid composition,
(9)
A curable resin composition comprising the polyvalent carboxylic acid composition according to any one of (1) to (5) above and an epoxy resin;
(10)
The curable resin composition as described in (9) above, wherein the epoxy resin is an alicyclic epoxy resin and / or an epoxy group-containing silicone resin,
(11)
The curable resin composition as described in (9) above, wherein the epoxy resin is an epoxy group-containing silicone resin,
(12)
A cured product obtained by curing the curable resin composition according to any one of (9) to (11),
About.

The polyvalent carboxylic acid composition of the present invention is useful as a curing agent for an epoxy resin. In particular, the curable resin composition of the present invention is used as a curing agent in a temperature range usually employed for curing an epoxy resin. In addition to extremely low volatility of the polyvalent carboxylic acid component, it is excellent in heat resistance, light resistance, adhesion, corrosion resistance gas permeability, toughness and the like. The polyvalent carboxylic acid composition of the present invention includes paints, adhesives, molded articles, semiconductors, optical semiconductor encapsulant resins, optical semiconductor die bond material resins, polyimide resins and other raw materials and modifiers, plasticizers, It is useful as a raw material for lubricating oils, intermediates for pharmaceuticals and agricultural chemicals, resin for paints, and resin for toners. Especially, it has excellent curing ability for epoxy resins and transparency of cured products obtained from it. It is extremely useful as a curing agent for an epoxy resin for sealing a representative optical semiconductor.

The polyvalent carboxylic acid composition of the present invention has the following formula (1)

 


 

(In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, R ₂ represents a methyl group or a phenyl group, n represents a repeating unit, and Formula (1) The weight average molecular weight of the compound represented by) is 500 to 5,000.)
A carboxylic acid compound (J) obtained by subjecting a silicone oil (a) represented by the formula (b) to a compound (b) having one or more carboxylic anhydride groups in the molecule;
Polyvalent carboxylic acid obtained by addition reaction of saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher alcoholic hydroxyl group and compound (d) having one or more carboxylic anhydride groups in the molecule And a compound (K).
The polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) used in the production of the polyvalent carboxylic acid composition of the present invention are prepared in accordance with the following, and each raw material is allowed to react sequentially even if they are individually adjusted and mixed. May be.

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 and no ether bond, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene; ₃ H ₆ —O—C ₂ H ₄ —, —C ₂ H ₄ —O—C ₂ H ₄ —, —C ₃ H ₆ —O—C ₃ H ₆ — etc. 10 alkylene groups are mentioned. Of these, a propylene group or —C ₃ H ₆ —O—C ₂ H ₄ — is preferable because of easy availability in the market.
In the case where the chain of R ₁ exceeds 10 carbon atoms, for example, a commercially available product includes a polyethylene oxide adduct, but this is not preferable in terms of heat resistance and light resistance.
The preferred molecular weight range of the silicone oil (a) is 500 to 5000, more preferably 600 to 4000, and particularly preferably 600 to 2500 in terms of weight average molecular weight. The most preferable range is 600 to 1500. When the molecular weight is less than 500, the intermolecular force of the obtained product is increased and the viscosity is likely to increase. When the molecular weight is greater than 5000, the compatibility with other components is poor and the system often becomes cloudy. That is not preferable.
Such a carbinol-modified silicone compound can be synthesized, for example, using a technique described in Japanese Patent Application Laid-Open No. 2007-508424. The commercially available compounds include Dow Corning 5562 (manufactured by Dow Corning Toray), X22-160-AS, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical), XF42-B0970 (manufactured by Momentive ), Silaplane FM-4411, FM-4421, FM-4425 (manufactured by Chisso) and the like.

Examples of the saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher alcoholic hydroxyl group include conventionally known alcohols, and from the viewpoint of a balance between heat resistance, light resistance and toughness, particularly preferred is a functional group. It is preferably a polyhydric alcohol having 2 to 6 groups, and the total number of carbon atoms in one molecule is 5 to 20. More preferred are chain alkylene diols having a branched structure, diols having a cyclic structure, triols, tetraols, hexaols and the like.
Specific examples of the chain alkylene diol having a branched structure include neopentyl glycol, 2-ethyl-2-butylpropylene-1,3-diol, 2,4-diethylpentane-1,5-diol and the like.
Examples of the diol having a cyclic structure include tricyclodecane diol, pentacyclopentadecane diol, 1,4-cyclohexane diol, norbornane diol, dioxane glycol, spiro glycol and the like.
Examples of the triol include glycerin and trimethylolpropane, examples of the tetraol include pentaerythritol and ditrimethylolpropane, and examples of the hexaol include dipentaerythritol.
From the viewpoint of excellent optical properties, heat-resistant coloring properties, and light-resistant coloring properties, it is preferable to use 2,4-diethylpentane-1,5-diol, tricyclodecanediol, or pentaerythritol.
In this invention, it is not limited to these specific examples, Furthermore, you may use 1 type or in mixture of 2 or more types.

Compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule (compounds (b) and (d) may be the same or different) may be used as molecules Those having one or two carboxylic anhydride groups therein are preferred. Specifically, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Examples include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, cyclobutanetetracarboxylic acid dihydrate, butanetetracarboxylic dianhydride, and the like.
Among these, from the viewpoint of optical properties, a compound having a saturated hydrocarbon structure is particularly preferable. Further, from the viewpoint of a balance between heat resistance and toughness, those having a cyclic saturated hydrocarbon structure as a mother skeleton are particularly preferable. Specifically, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2 , 4-tricarboxylic acid-1,2-anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclobutanetetracarboxylic acid dihydrate, butanetetracarboxylic acid dianhydride, etc. Although not limited to these, you may use 1 type or in mixture of 2 or more types.
In the present invention, from the viewpoint of ease of handling, those having one carboxylic anhydride group are particularly preferred, and among them, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4- Tricarboxylic acid-1,2-anhydride and bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride are preferred. In particular, methylhexahydrophthalic anhydride or cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is particularly preferable from the viewpoint of optical properties.

Such as addition reaction between silicone oil (a) and compound (b) having a carboxylic acid anhydride group, or addition reaction between polyhydric alcohol (c) and compound (d) having a carboxylic acid anhydride group, The reaction for adding an alcohol and an acid anhydride is generally an addition reaction using an acid or a base as a catalyst. However, in the present invention, from the viewpoint of simplicity of post-treatment and removal of adverse effects due to residual catalyst on the product. In particular, a catalyst-free reaction is preferred. Further, since removal is a problem, it is preferable to use one or more selected from among accelerators and additives used in the curable resin composition described below, since subsequent purification is not necessary.
When using a catalyst, for example, hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, calcium hydroxide, water Metal hydroxides such as magnesium oxide, amine compounds such as triethylamine, tripropylamine, tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole, triazole, Heterocyclic compounds such as tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide Trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium Examples include quaternary ammonium salts such as acetate. 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 usually 0.001 to 5 parts by weight with respect to 100 parts by weight of the total weight of the raw materials.

In this reaction, a reaction without a solvent is preferable, but an organic solvent may be used. The organic solvent is used in a weight ratio of 0.005 to 1, preferably 0.005 to 0.7, more preferably 0.005 to 0.5 (that is, outside) with respect to a total amount of reaction substrate of 1. 50% by weight or less). When the weight ratio exceeds 1, the progress of the reaction is extremely slow, which is not preferable. 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.

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 a reaction at 40 to 100 ° C., particularly 40 to 80 ° C. is preferred because of the volatilization of acid anhydride.
When a compound having high crystallinity at room temperature, such as cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, is used, the reaction is performed at 100 to 150 ° C. in order to sufficiently dissolve the crystal. It is preferable.
Moreover, when using the acid anhydride which is easy to volatilize, and the acid anhydride with high crystallinity, it is also possible to prevent volatilization of an acid anhydride by raising temperature in steps.

The reaction ratio of the compounds (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. Is preferable, but can be changed as necessary. That is, as will be described later, in the curing agent composition of the present invention, when the acid anhydride used in combination with the acid anhydride used here is the same as necessary, 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 of the acid anhydride and the polyvalent carboxylic acid composition of the present invention can be used.
As a specific reaction ratio, the functional group equivalent is compared. When (b) (or (d)) is 1, the molar ratio (a) (or (c)) is 0.001 to 1. 0, more preferably 0.01 to 1.0, still more preferably 0.1 to 1.0. As mentioned above, when producing the mixture of the polyvalent carboxylic acid composition of the present invention and other acid anhydrides, the ratio is preferably in the range of 0.01 to 0.7, preferably 0.01 to 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 great deal of energy. An excessively short reaction time means that the reaction is abrupt and is not preferable from the viewpoint of safety. A preferred range is 1 to 48 hours, preferably 1 to 36 hours, and more preferably 1 to 24 hours.

When the catalyst is used after completion of the reaction, the desired polycarboxylic acid (J) or (K) is obtained by removing the catalyst by neutralization, washing with water, adsorption, etc., and distilling off the solvent. .
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) or the polyvalent carboxylic acid (K) can be obtained by taking it out as it is. .

The most preferred production method is a method of reacting at 40 to 150 ° C. under the conditions of no catalyst and no solvent, and taking it 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 the polyvalent carboxylic acid (K) thus obtained. The ratio by weight is (J) / (K) = 99.7 / 0.3 to 50/50, more preferably 99.7 / 0.3 to 40/40. If the amount of the polyvalent carboxylic acid (J) is too large, there will be a problem in the corrosion gas permeability and reflow resistance of the cured product. If the amount of the polyvalent carboxylic acid (K) is too large, it will be solidified and difficult to handle. Become.
Here, the ratio of (J) / (K) is particularly preferably 99/1 to 80/20, and more preferably 99/1 to 85/15. By mixing one or more (K) by weight ratio, the performance of corrosion-resistant gas permeability is particularly improved, and by mixing (J) by 80 or more by weight ratio, the light resistance is excellent, and This is because peeling and cracking are unlikely to occur, and it is possible to realize performance that hardly causes deterioration of illuminance when used as an LED sealing material. In particular, by mixing (J) in a weight ratio of 85 or more, the above characteristics can be balanced.

In the present invention, the polyvalent carboxylic acid (J) and the polyvalent carboxylic acid (K) can also be produced simultaneously. Specific methods include (i)
Compounds (b) and (d) having one or more carboxylic acid anhydride groups in the molecule are charged into a mixture of silicone oil (a) and polyhydric alcohol (c) and reacted simultaneously.
(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 acid anhydride groups in the molecule Step (B): Saturated aliphatic having bifunctional or higher alcoholic hydroxyl group The step of reacting the polyhydric alcohol (c) with the compound (d) having one or more carboxylic acid anhydride groups in the molecule. That is, the method of (ii) is the step (A) (or step (B)). After performing, the compounds to be used in step (B) (or step (A)) are sequentially added, and reaction and mixing are performed in the 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 polyhydric alcohol (c)) and one or more in the molecule The compound (b) (= (d)) having a carboxylic acid anhydride group is charged and reacted, and then the polyhydric alcohol (c) (or silicone oil (a)) is charged and reacted.

The polycarboxylic acid composition of the present invention thus obtained is usually a colorless liquid to semi-solid substance.
The polyvalent carboxylic acid composition of the present invention has excellent transparency, a curing agent for a curable resin such as an epoxy resin, a paint, an adhesive, a molded product, a semiconductor, a resin for an optical semiconductor encapsulant, and an optical semiconductor die bond material Useful as raw materials and modifiers for resins, polyamide resins, polyimide resins, plasticizers and lubricating oil raw materials, intermediates for pharmaceuticals and agricultural chemicals, raw materials for paint resins, and resin for toners, especially useful as a curing agent for epoxy resins It is.
When the polyvalent carboxylic acid composition of the present invention is used as a curing agent for an epoxy resin, the polyvalent carboxylic acid composition of the present invention exhibits excellent curability and the transparency of the cured product is excellent. It is extremely useful as a curing agent for epoxy resins used for sealing of other white semiconductor LEDs and other optical semiconductors.

When the polyvalent carboxylic acid composition of the present invention is used as a curing agent for a curable resin such as an epoxy resin, particularly as a liquid composition, the polyvalent carboxylic acid composition of the present invention and another acid anhydride are mixed. It is preferably used in the form of a curing agent composition.
As the acid anhydride that can be used, a compound (e) having one or more carboxylic acid anhydride groups in the molecule is preferable, and an acid anhydride having no aromatic ring in its structure is particularly preferable. Specific examples of the compound (e) having one or more carboxylic anhydride groups in the molecule include 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, etc. Is mentioned.
When used as a curing agent composition in a mixture with an acid anhydride, the proportion of the polyvalent carboxylic acid composition of the present invention is the total weight of the other acid anhydride and the polyvalent carboxylic acid composition of the present invention. On the other hand, it is 0.1 to 50% by weight, preferably 0.1 to 30% by weight. By using together in such a range, there is an effect in terms of fluidity of the composition and heat resistant mechanical strength of the cured product.
Hereinafter, the curable resin composition of the present invention including the polyvalent carboxylic acid 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-hydroxyacetofu 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.

When using especially the curable resin composition of this invention for an optical use, an alicyclic epoxy resin and / or an epoxy-group containing silicone resin are preferable, and the epoxy resin of 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 more 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 Tyschenco reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and transesterification of cyclohexene carboxylic acid ester Examples thereof include an oxidized product of a compound that can be produced by a reaction (a 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. Diols, diols such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc. 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 mixture and then 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, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited thereto (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 composition (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, and 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 total curing agent to the epoxy resin is 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups of the epoxy resin (note that acid anhydride groups are considered to be monofunctional). The amount is particularly 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 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 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.

In the present invention, it is preferable to contain 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, cetyl group and the like.
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.

The particularly preferred zinc carboxylate in the present invention preferably has an alkyl group having a chain-branched structure or an alkyl group having a functional group such as an olefin in the compound, and among them, those having 3 to 30 carbon atoms are preferred. In particular, those having 5 to 20 carbon atoms are preferred. These are preferable in terms of compatibility, and when the number of carbon atoms is too large (when the number of carbon atoms exceeds 30), or when they do not have a structure such as a branched structure or a functional group, the compatibility with the resin is poor, which is not preferable.
Specific examples include zinc 2-ethylhexylate, zinc isostearate and zinc undecylenate.

As a preferable phosphoric acid ester body to be obtained in the present invention, a zinc salt and / or a zinc complex of phosphoric acid, phosphoric acid ester (monoalkyl ester body, dialkyl ester body, trialkyl ester body, or a mixture thereof) is preferable. You may contain an ester 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 trimethylsilylation treatment.
Such zinc salt and / or zinc complex of zinc phosphate ester can be obtained, for example, by reacting a phosphate ester with, for example, zinc carbonate, zinc hydroxide, etc. (Patent Document EP 699708).

As for 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. . Particularly preferred is 1.4 to 1.9. That is, in a particularly preferred 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, some molecules are ion-bonded (or arranged). Those having a structure related by coordinate bond) are preferred. Such a zinc salt and / or zinc complex can also be obtained, for example, by the technique described in Japanese Patent Publication No. 2003-51495.

As such compounds, commercially available products such as zinc carboxylate are Zn-St, Zn-St 602, Zn-St NZ, ZS-3, ZS-6, ZS-8, ZS-8, ZS-7, ZS. -10, ZS-5, ZS-14, ZS-16 (manufactured by Nitto Kasei Kogyo), XK-614 (manufactured by King Industry), 18% octope Zn, 12% octope Zn, 8% octope Zn (manufactured by Hope Pharmaceutical) Examples of the phosphate ester and / or zinc phosphate include LBT-2000B (manufactured by SC Organic Chemical) and XC-9206 (manufactured by King Industry).

Which of these curing accelerators is used is appropriately selected depending on the characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. The curing accelerator is usually used in an amount of 0.001 to 15 parts by weight, more preferably 0.01 to 5 parts by weight, and particularly preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the epoxy resin. In this reaction, curing is possible without using a curing accelerator, but from the viewpoint of coloring during curing, addition of a curing accelerator is preferred. In particular, the use of zinc salts and / or zinc complexes is preferred in order to prevent coloring and to obtain corrosion-resistant gas permeability characteristics.

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 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. Phosphate 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 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, 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 amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component in the curable resin composition of the present invention. It is.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. 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-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-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-t-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-hydroxybenzyl phosphonate-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) calcium 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 antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyll-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-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpenta Erythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite , Tris 2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2 , 4-Di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2 ′ -Methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2 -Tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene Diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, Tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, 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-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′-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, Examples include 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.
For example, 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, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, and ADK STAB C 135A, ADK STAB 3010, and ADK STAB TPP.
In the present invention, the amount of the phosphorus compound used is 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight with respect to the epoxy resin.

These antioxidants can be used alone, but two or more kinds 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-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-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] bu Lumalonate, 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]], Polymer of dimethyl acid 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 / tetra Decyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7- Oki -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, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4- And hindered amine compounds such as piperidinyl).
The following commercially available products can be used as the amine compound that is the light stabilizer.
For example, as manufactured by Ciba Specialty Chemicals, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, manufactured by ADEKA, 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 an amount of 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight with respect to the epoxy resin.
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 appears, which is not preferable.

Furthermore, a binder resin can be blended with the curable resin composition of the present invention as required. 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 within 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 used in an amount of 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 addition amount thereof is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.

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, AerosilR202, AerosilR202, AerosilR202 Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

The curable resin composition of the present invention can be obtained by uniformly mixing each component. 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 at 80 to 150 ° C., and post-curing is performed at 100 to 200 ° C. As the curing stage, the temperature is preferably increased in 2 to 8 stages, more preferably 2 to 4 stages.

In addition, 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. In this case, the solvent is used in an amount usually accounting for 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 containing a carbon fiber can also be obtained with a RTM (Resin * Transfer * Molding) system with a liquid composition.

The curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve flexibility in the B-stage. As a method for obtaining such a film-type resin composition, first, the curable resin composition of the present invention is used as the curable resin composition varnish as described above, and this is applied onto a release film and heated under a solvent. A method of forming a B-stage after removing the film is mentioned, whereby a film-type sealing composition can be obtained as 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 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 using the curable resin composition of the present invention as a sealing material or die bond material for an optical semiconductor such as a high-intensity white LED, a curing agent (curing agent composition) containing the polyvalent carboxylic acid of the present invention, In addition to the epoxy resin, a curable resin composition is prepared by sufficiently mixing additives such as a curing accelerator, a coupling material, an antioxidant, and a light stabilizer. 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 may be used at room temperature or with heating. The obtained curable resin composition can be used for a sealing material, or both a die-bonding material and a sealing material.

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 periphery of such a semiconductor chip is sealed with a sealing material such as an epoxy resin. The sealing material is used to protect the semiconductor chip from heat and moisture and to play a role of a lens function. 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 on the substrate by dispenser, potting or screen printing, and then the curable resin is used. There is a method in which a semiconductor chip is placed on the composition 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.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. 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 then molded, and the sealing material on the mold A compression molding method is used in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from the mold.
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.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. 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 application of the curable resin composition of the present invention is not limited to the above application, and can be applied to general applications in which a thermosetting resin such as an epoxy resin is used. Specifically, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, substrates Examples of the cyanate resin composition for resist and additives for other resins such as an acrylic ester resin as a curing agent for resist.

Examples of adhesives include civil engineering, architectural, automotive, general office, and medical adhesives, as well as 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 materials, potting, dipping and 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 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 field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate materials 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 parts. 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 material, ferrule, sealing material, adhesive, 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, and automotive defenses 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. The next generation of 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. In the examples, gel permeation chromatography (hereinafter referred to as “GPC”) was measured under the following conditions.
Column: Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802)
Linked eluent: tetrahydrofuran, flow rate 1 ml / min.
Column temperature: 40 ° C, detection is RI (Reflective index)
Calibration curve: Standard polystyrene manufactured by Shodex

Synthesis example 1
Both ends carbinol-modified silicone X22-160AS (in Shin-Etsu Chemical Co., Ltd., formula (1), R ₁ = −C ₃ H) while purging nitrogen with a stirrer, a reflux condenser, and a stirrer. _6- O—C ₂ H ₄ —, R ₂ ═CH ₃ , weight average molecular weight is about 1000) 500 parts, HTAn (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, Mitsubishi Gas Chemical Co., Ltd. )) 99 parts, MH-700 (a mixture of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, manufactured by Shin Nippon Chemical Co., Ltd.), 84 parts, and 50 parts of toluene were charged in a reaction vessel and reacted at 90 ° C. for 2 hours. When the temperature was raised to 130 ° C. and GPC was measured 3 hours later, the acid anhydride peak disappeared. Thereafter, the reaction was further continued for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 681 parts of a colorless to pale yellow liquid carboxylic acid compound (J-1).

Synthesis example 2
A flask equipped with a stirrer, reflux condenser, and stirrer was charged with 98 parts of tricyclodecanediol, HTMan (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, Mitsubishi Gas Chemical ( 99 parts), MH-700 (mixture of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, manufactured by Nippon Nippon Chemical Co., Ltd.), 84 parts, and 10 parts of toluene were charged in a reaction vessel at 100 ° C. for 1 hour. The reaction was carried out at 2 ° C. for 2 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 280 parts of a colorless solid resin carboxylic acid compound (K-1).

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 68.3 parts of the carboxylic acid compound (J-1) while purging with nitrogen, and the mixture was stirred at 100 ° C., and the carboxylic acid compound (K -1) 28.1 parts were added, and the mixture was stirred as it was for 1 hour to be compatible with each other to obtain a polyvalent carboxylic acid composition (MA-1) of the present invention as a colorless transparent liquid.

Example 2 and Comparative Example 1
The polyvalent carboxylic acid composition (MA-1) of the present invention obtained in Example 1 and, as a comparative example, MH-700 (a mixture of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) (Hereinafter referred to as H1) as a curing agent, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate as epoxy resin (UVR-6105 manufactured by Dow Chemical) (hereinafter referred to as epoxy resin (EP1)), curing Hexadecyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25% methanol solution, hereinafter referred to as C1) is used as an accelerator, blended at the blending ratio (parts by weight) shown in Table 1 below, and desorbed for 20 minutes. Foaming was performed to obtain a curable resin composition of the present invention.

Using the obtained curable resin composition, an LED sealing test was performed in the following manner. The results are shown in Table 1. The curing conditions are 150 ° C. × 3 hours after 120 ° C. × 1 hour pre-curing.

(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. Type outer diameter 5 mm square surface-mount type LED package inner diameter 4.4 mm, outer wall height 1.25 mm) was cast into LED. Thereafter, a test LED was obtained by curing under predetermined curing conditions.
Evaluation item Volatility: The presence or absence of dents on the surface of the cured product after sealing was visually evaluated. In the table, ◯: no dent is observed, Δ: some dent is observed, x: many dents are observed (there is an exposed wire).

 

Comparison of Example 2 and Comparative Example 1 shows that the curable resin composition of the present invention has a small amount of volatilization and does not cause problems such as wire exposure even when the LED is sealed. Furthermore, it can be seen that there is a tendency to reduce cracks during reflow. From the above results, it can be seen that the polyvalent carboxylic acid of the present invention and the curing agent composition containing the polyvalent carboxylic acid can give a curable resin composition effective for volatility.

Synthesis example 4
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (59.1 parts), polydimethyldiphenylsiloxane having a silanol group having a molecular weight of 1700 (measured by GPC) 130.6 parts, 0.5 wt% KOH methanol solution 10.0 The portion was charged into a reaction vessel and heated to 75 ° C. After raising the temperature, the mixture was reacted at 75 ° C. under reflux for 8 hours. After the reaction, 135 parts of methanol was added, 25.9 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with a 5 wt% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 170 parts of methyl isobutyl ketone (MIBK) was added for washing, and washing with water was repeated three times. Subsequently, 162 parts of epoxy resins (EP2) were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic layer. The epoxy equivalent of the obtained compound was 707 g / eq, the weight average molecular weight was 2680, and the appearance was colorless and transparent.

Example 3
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 500 parts of both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) while purging with nitrogen, MH (methylhexahydrophthalic anhydride, 168 parts (manufactured by Nippon Nippon Chemical Co., Ltd.) and reacted at 70 ° C. for 2 hours, 80 parts of Kyowadiol PD9 (2,4-diethylpentane-1,5-diol, manufactured by Kyowa Hakko Chemical), HTAn (1,2,4- 198 parts of cyclohexanetricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Inc.) are added, and the reaction is carried out at 70 ° C. for 1 hour and at 130 ° C. for 5 hours, thereby producing the polyvalent carboxylic acid composition of the present invention. (MA-2) was obtained. The polyvalent carboxylic acid composition obtained was a colorless and transparent liquid (semi-solid but fluid at room temperature). (Although it cannot be calculated accurately, polycarboxylic acid (J) derived from carbinol-modified silicone at both ends is about 70% by weight, polycarboxylic acid derived from 2,4-diethylpentane-1,5-diol (K) About 30% by weight)

Example 4
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while carrying both ends of the carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) 500 parts, MH (methylcyclohexanedicarboxylic anhydride, 168 parts by Nippon Nippon Chemical Co., Ltd., 80 parts by Kyowadiol PD9 (2,4-diethylpentane-1,5-diol manufactured by Kyowa Hakko Chemical), HTAn (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride) 198 parts by Mitsubishi Gas Chemical Co., Ltd.), reacted at 70 ° C. for 2 hours and 130 ° C. for 5 hours, cooled to 50 ° C., and then MH (methylhexahydrophthalic anhydride, Shin Nippon Rika) Product) 33.6 parts was added and completely mixed to obtain the polyvalent carboxylic acid composition (MA-3) of the present invention. The obtained polyvalent carboxylic acid composition was a colorless and transparent liquid. (Although it cannot be calculated accurately, polycarboxylic acid (J) derived from carbinol-modified silicone at both ends is about 70% by weight, polycarboxylic acid derived from 2,4-diethylpentane-1,5-diol (K) About 27% by weight and about 3% by weight of acid anhydride)

Examples 5 and 6, Comparative Examples 2 and 3
The polyvalent carboxylic acid composition of the present invention (MA-2, MA-3) obtained in Examples 3 and 4, as a comparative example, the carboxylic acid (J-1) prepared in Synthesis Example 1, an acid anhydride ( H1) is used as a curing agent, the epoxy resin (EP2) obtained in Synthesis Example 4 is used as an epoxy resin, and hexadecyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25% methanol solution, (Hereinafter referred to as “C1”), and blended at a blending ratio (parts by weight) shown in Table 2 below, followed by defoaming for 20 minutes to obtain a curable resin composition for the present invention or for comparison.
Using the obtained curable resin composition, various tests were performed in the following manner. The results are shown in Table 2.

(1) dent test;
The curable resin compositions obtained in Examples 5 and 6 and Comparative Examples 2 and 3 were vacuum degassed for 20 minutes, then filled into a syringe and mounted with a light emitting element having an emission wavelength of 465 nm using a precision discharge device. The surface mounted LED was cast so that the opening was flat. After pre-curing at 120 ° C. for 3 hours, curing was performed at 150 ° C. for 1 hour to seal the surface-mounted LED. The presence or absence of dents on the resin surface accompanying the volatilization of the curing agent after sealing in this way was visually evaluated. In the table, ○: No dent is observed, △: Some dent is observed, ×: Many dents are observed (exposure of wire)
(2) Reflow test;
The curable resin compositions obtained in Examples 5 and 6 and Comparative Examples 2 and 3 were vacuum degassed for 20 minutes, then filled into a syringe and mounted with a light emitting element having an emission wavelength of 465 nm using a precision discharge device. The surface mounted LED was cast so that the opening was flat. After pre-curing at 120 ° C. for 3 hours, curing was performed at 150 ° C. for 1 hour to seal the surface-mounted LED. After the obtained test LED absorbs moisture at 30 ° C. and 70% × 72 hours, generation of cracks in the test LED under the following reflow conditions using a high-temperature observation device (SMT Scope SK-5000 manufactured by Sanyo Seiko Co., Ltd.) Was visually observed. The test is performed with n = 3, and the evaluation is made with (OK number) / (test number).
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., then 1.3 ° C. It cools to room temperature at / second.
(3) Gas permeation resistance test (corrosion gas permeability test);
The curable resin compositions obtained in Examples 5 and 6 and Comparative Examples 2 and 3 were vacuum degassed for 20 minutes, filled in a syringe, and mounted with a chip having a central emission wave of 465 nm using a precision discharge device. A 5 mm-diameter surface-mount LED package (inner diameter: 4.4 mm, outer wall height: 1.25 mm) was cast. 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.
<Measurement conditions>
Corrosion gas: 20% by weight aqueous solution of ammonium sulfide (turns 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 the longer the discoloration time, the better the corrosion resistance gas permeability.

As is apparent from the results shown in Table 2, it can be seen that the epoxy resin composition of the present invention has a dent and is excellent not only in reflow resistance but also in a cured product excellent in corrosion resistance and gas permeability.

Examples 7 to 13, Synthesis Examples 6 and 7
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while both ends carbinol-modified silicone compound (one selected from SI-1 and SI-2), saturated aliphatic polyhydric alcohol (AL -1 and AL-2) and an acid anhydride (at least one selected from H1, H2, and H3) in the amounts shown in Table 3 below, at 70 ° C for 5 hours, at 90 ° C By reacting for 3 hours, polyvalent carboxylic acid compositions (MA-4 to MA10) and carboxylic acid resins (J-2, J-3) were obtained as colorless and transparent liquids.
In addition, SI-1: Chisso FM-4411, SI-2: Shin-Etsu Chemical X22-160AS, AL-1: Kyowa Hakko Chemical Kyowajiru PD-9, AL-2: OXEA TCDAlchol-DM, H1 : Rikacid MH-700, manufactured by Shin Nippon Rika, H2: Rikacid MH, manufactured by Shin Nippon Rika, H3: H-TMAn, manufactured by Mitsubishi Gas Chemical.

  

Synthesis example 8
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 100 parts of acid anhydride (H2) and saturated aliphatic polyhydric alcohol (AL-1) while purging with nitrogen, and at 70 ° C. for 3 hours. Stirring at 30 ° C. for 30 minutes gave 120 parts of a mixture of a colorless and transparent carboxylic acid compound and an acid anhydride. The ratio of the obtained carboxylic acid to acid anhydride was approximately 52:48 as a result of measurement by gel permeation chromatography.

Examples 14 and 15
With respect to 1 part (Example 14) and 2 parts (Example 15) of the mixture of the colorless and transparent carboxylic acid compound and acid anhydride obtained in Synthesis Example 8, the polyvalent carboxylic acid compound obtained in Synthesis Example 6 ( J-2) 100 parts were added and dissolved uniformly. As a result, colorless polyvalent carboxylic acid compositions MA-11 and MA-12 were obtained.

Synthesis Example 9
β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 39.4 parts, weight average molecular weight 1900 (GPC measured value) silanol-terminated methylphenyl silicone oil 137 parts (silanol equivalent 950, weight average molecular weight measured using GPC) 10 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 10 hours. As a manufacturing process (ii), after adding 140 parts of methanol, 17.3 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and reacted at 75 ° C. 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 at 80 ° C. Subsequently, 200 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic layer at 100 ° C. under reduced pressure, 152 parts of an epoxycyclohexyl group-containing organopolysiloxane (EP-3) was obtained. The epoxy equivalent of the obtained compound (EP-3) was 1040 g / eq. The weight average molecular weight was 2290, and the appearance was a colorless and transparent liquid resin.

Synthesis Example 10
375 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) (silanol equivalent 950, half of the weight average molecular weight measured using GPC) 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours. After adding 655 parts of methanol, 144 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. 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 at 80 ° C. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. The solvent was removed from the obtained organic layer at 100 ° C. under reduced pressure to obtain 647 parts of an epoxycyclohexyl group-containing organopolysiloxane (EP-4). The epoxy equivalent of the obtained compound (EP-4) was 541 g / eq. The weight average molecular weight was 2,100, and the appearance was a colorless and transparent liquid resin.

Examples 16 to 19 and Comparative Example 4
The polyvalent carboxylic acid composition of the present invention (MA-4, MA-5, MA-6, MA-10), as a comparative example, a polyvalent carboxylic acid resin (J-3) is used as a curing agent, and an epoxy resin Using the epoxy resin (EP-4) obtained in Synthesis Example 10, zinc octylate (18% Octopus Zn, hereinafter referred to as C2) manufactured by Hope Pharmaceutical, and light stabilizer (LA-81 or less, manufactured by ADEKA) were added as a curing accelerator. And an antioxidant (made by ADEKA, ADEKA 260, called additive AD-2)), and blended at the blending ratio (parts by weight) shown in Table 4 below, and removed for 20 minutes. Foaming was performed to obtain a curable resin composition of the present invention and a comparative curable resin composition.
Using the obtained curable resin composition, a test was conducted in the following manner, and the results are shown in Table 4. The curing conditions are 150 ° C. × 5 hours after preliminary curing at 120 ° C. × 2 hours, unless otherwise specified.
(1) Tensile test Conforms to JIS K 6911 Sample Thickness 0.9 ± 0.05 mm Cross-sectional area 4.5 ± 0.2 mm ²
Speed 5mm / min, Chuck distance 15mm
(2) Thermal durability transmittance test The obtained curable resin composition was gently cast on a glass substrate on which a dam was formed with a heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. The cast was cured at 120 ° C. for 1 hour after pre-curing at 120 ° C. for 3 hours to obtain a test piece for transmittance having a thickness of 1 mm.
Using these test pieces, the transmittance (measurement wavelength: 400 nm) before and after being left for 72 hours in a 150 ° C. oven was measured with a spectrophotometer, and the rate of change was calculated.
Evaluation: When the transmittance decrease is less than 5%, ○, when 5% or more and less than 10%, Δ when 10% or more, and x.

  

Examples 20-22, Comparative Example 5
The polyvalent carboxylic acid composition of the present invention (MA-7, MA-8, MA-9), as a comparative example, the polyvalent carboxylic acid resin (J-3) was used as a curing agent, and the epoxy resin was synthesized in Synthesis Example 9, 10 using the epoxy resins (EP-3, EP-4) obtained in No. 10, using the curing accelerator (C2) and additives (AD-1, AD-2), and the mixing ratios (weights) shown in Table 5 below. Part) and defoaming for 20 minutes to obtain a curable resin composition of the present invention and a comparative curable resin composition.
Using the obtained curable resin composition, a test was conducted in the following manner, and the results are shown in Table 5. The curing conditions are 150 ° C. × 5 hours after preliminary curing at 120 ° C. × 2 hours.
(1) Peel test Conforms to JIS K 6911 Support: Use of copper foil rough surface, Sample width: 10 mm, Peeling speed: 3 mm / min
(2) Tensile test Conforms to JIS K 6911 Sample Thickness 0.9 ± 0.05 mm Cross-sectional area 4.5 ± 0.2 mm ²
Speed 5mm / min, Chuck distance 15mm

 

From the above results, it can be seen that the curable resin composition of the present invention is excellent in adhesion, toughness, and heat durability.

Examples 23 and 24, Comparative Example 6
The polyhydric carboxylic acid composition (MA-11, MA-12) of the present invention and, as a comparative example, the polycarboxylic acid resin (J-2) as a curing agent and the epoxy obtained in Synthesis Example 10 as an epoxy resin Using resin (EP-4), using curing accelerator (C2) and additives (AD-1, AD-2), blending ratios (parts by weight) shown in Table 6 below, and defoaming for 20 minutes The curable resin composition of the present invention and a comparative curable resin composition were obtained.
Using the obtained curable resin composition, a test was conducted in the following manner, and the results are shown in Table 6. The curing conditions are 150 ° C. × 5 hours after preliminary curing at 120 ° C. × 2 hours.
(1) Tensile test Conforms to JIS K 6911 Sample Thickness 0.9 ± 0.05 mm Cross-sectional area 4.5 ± 0.2 mm ²
Speed 5mm / min, Chuck distance 15mm
(2) LED lighting test After carrying out vacuum defoaming for 20 minutes with the curable resin compositions obtained in Examples and Comparative Examples, a syringe is filled and a light emitting element having an emission wavelength of 465 nm is mounted using a precision discharge device. Was cast into a surface-mounted LED (Φ5 mm). Then, LED for lighting test is obtained by making it harden | cure on predetermined hardening conditions. The lighting test was performed at 210 mA, which is 7 times the specified current, for the acceleration test. Detailed conditions are shown below. As a measurement item, the illuminance before and after lighting for 20 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
Detailed lighting conditions Light emission wavelength: 465nm
Drive method: constant current method, 210 mA (light emitting element specified current is 30 mA)
Driving environment: 25 ° C, 65% RH
(3) Gas permeation resistance test (corrosion gas permeability test);
The package of the LED prepared with the obtained curable resin composition was left in a corrosive gas under the following conditions, and the change in the color of the silver-plated lead frame inside the seal was observed.
<Measurement conditions>
Corrosive 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 blackened (referred to as blackening) was observed every hour, and it was judged that the longer the color changing time, the better the corrosion resistance gas resistance.

 

Example 25
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 365 parts of both ends carbinol-modified silicone compound (SI-2), pentaerythritol (hereinafter referred to as saturated aliphatic polyhydric alcohol AL-3) while purging with nitrogen. 9 parts) and 168 parts of acid anhydride (H2) were charged and reacted at 90 ° C. for 2 hours and at 110 ° C. for 3 hours to obtain 542 parts of a polyvalent carboxylic acid composition (MA-13) as a colorless transparent liquid. Obtained. (Weight of polycarboxylic acid derived from SI-2 (J) / weight of polycarboxylic acid derived from AL-3 (K) = 90/10)

Example 26, Comparative Example 7
The polyvalent carboxylic acid composition (MA-13) of the present invention, as a comparative example, the polycarboxylic acid resin (J-3) was used as a curing agent, and the epoxy resin obtained in Synthesis Examples 9 and 10 as an epoxy resin ( EP-3, EP-4), using curing accelerator (C2) and additives (AD-1, AD-2), and blending ratios (parts by weight) shown in Table 7 below, for 20 minutes Defoaming was performed to obtain a curable resin composition of the present invention and a comparative curable resin composition.
Using the obtained curable resin composition, a test was conducted in the following manner, and the results are shown in Table 7. The curing conditions are 150 ° C. × 5 hours after preliminary curing at 120 ° C. × 2 hours.
(1) Peel test Conforms to JIS K 6911 Support: Use of copper foil rough surface, Sample width: 10 mm, Peeling speed: 3 mm / min
(2) Tensile test Conforms to JIS K 6911 Sample Thickness 0.9 ± 0.05 mm Cross-sectional area 4.5 ± 0.2 mm ²
Speed 5mm / min, Chuck distance 15mm
(3) LED lighting test After carrying out vacuum defoaming for 20 minutes with the curable resin compositions obtained in Examples and Comparative Examples, a syringe is filled and a light emitting element having an emission wavelength of 465 nm is mounted using a precision discharge device. Was cast into a surface-mounted LED (Φ5 mm). Then, LED for lighting test is obtained by making it harden | cure on predetermined hardening conditions. The lighting test was performed at 210 mA, which is 7 times the specified current, for the acceleration test. 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.
Detailed lighting conditions Light emission wavelength: 465nm
Drive method: constant current method, 210 mA (light emitting element specified current is 30 mA)
Driving environment: 25 ° C, 65% RH
(4) Gas permeation resistance test (corrosion gas permeability test);
The package of the LED prepared with the obtained curable resin composition was left in a corrosive gas under the following conditions, and the change in the color of the silver-plated lead frame inside the seal was observed.
<Measurement conditions>
Corrosive 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 during which the lead frame inside the LED package was blackened (referred to as blackening) was observed every hour, and it was judged that the longer the color changing time, the better the corrosion resistance.

 

As is clear from the above results, the epoxy resin composition of the present invention is not only excellent in heat resistance and light resistance, but also in a cured product excellent in adhesion, toughness, and corrosion resistance gas permeability. I know you give it.

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.
This application is based on a Japanese patent application filed on October 6, 2009 (Japanese Patent Application No. 2009-232113), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (12)

1. Following formula (1)
   

   

   
   
   (In Formula (1), R ₁ represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, R ₂ represents a methyl group or a phenyl group, n represents a repeating unit, and Formula (1) The weight average molecular weight of the compound represented by) is 500 to 5000. The addition reaction of the silicone oil (a) represented by) and the compound (b) having one or more carboxylic anhydride groups in the molecule. A carboxylic acid compound (J) obtained by
   Polyvalent carboxylic acid obtained by addition reaction of saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher alcoholic hydroxyl group and compound (d) having one or more carboxylic anhydride groups in the molecule Compound (K),
   Containing a polyvalent carboxylic acid composition.
2. The polyvalent carboxylic acid composition according to claim 1, wherein the compounds (b) and (d) are acid anhydrides having a cyclic saturated hydrocarbon as a mother skeleton.
3. The compounds (b) and (d) are methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and bicyclo [2,2,1] heptane- 3. The polyvalent carboxylic acid composition according to claim 1, wherein the polycarboxylic acid composition is at least one acid anhydride selected from the group consisting of 2,3-dicarboxylic acid anhydrides.
4. The polyvalent carboxylic acid composition according to claim 3, wherein the compounds (b) and (d) essentially comprise methylhexahydrophthalic anhydride.
5. 5. The polyhydric alcohol according to claim 1, wherein the compound (c) is a polyhydric alcohol having 2 to 6 functional groups, and the total number of carbon atoms in one molecule is 5 to 20. Carboxylic acid composition.
6. A method for producing a polyvalent carboxylic acid composition according to any one of claims 1 to 5,
   Compounds (b) and (d) having one or more carboxylic anhydride groups in the molecule are added to a mixture containing silicone oil (a) and a saturated aliphatic polyhydric alcohol (c) having a bifunctional or higher functional alcoholic hydroxyl group. And the addition reaction between the silicone oil (a) and the compound (b) and the addition reaction between the compound (c) and the compound (d) are performed simultaneously. Production method.
7. A method for producing a polyvalent carboxylic acid composition according to any one of claims 1 to 5,
   A method for producing a polyvalent carboxylic acid composition, wherein the following step (A) and step (B) are sequentially reacted in one pot.
   Step (A): Addition reaction of silicone oil (a) and compound (b) having one or more carboxylic anhydride groups in the molecule Step (B): Saturated fat having a bifunctional or higher functional alcoholic hydroxyl group A step of addition reaction of an aromatic polyhydric alcohol (c) and a compound (d) having one or more carboxylic anhydride groups in the molecule
8. 8. The polyvalent carboxylic acid according to claim 6, wherein the addition reaction is carried out at 40 to 150 ° C. in an organic solvent in an amount of 50% by weight or less based on the total amount of the reaction substrate in the raw material to be used without solvent. A method for producing an acid composition.
9. A curable resin composition comprising the polyvalent carboxylic acid composition according to any one of claims 1 to 5 and an epoxy resin.
10. 10. The curable resin composition according to claim 9, wherein the epoxy resin is an alicyclic epoxy resin and / or an epoxy group-containing silicone resin.
11. 10. The curable resin composition according to claim 9, wherein the epoxy resin is an epoxy group-containing silicone resin.
12. A cured product obtained by curing the curable resin composition according to any one of claims 9 to 11.