JP6595329B2 - Polyvalent carboxylic acid and polyvalent carboxylic acid composition, epoxy resin composition, thermosetting resin composition, cured product thereof, and optical semiconductor device containing the same - Google Patents

Description

  The present invention is particularly suitable for use in a portion where high transparency and low colorability are required, such as for optical semiconductor sealing and for optical semiconductor reflectors, particularly when used for an optical semiconductor reflector or an optical semiconductor device having the same. The glass transition temperature of the cured product can be sufficiently increased, and the polyvalent carboxylic acid having excellent moldability and the polyvalent carboxylic acid composition, the thermosetting resin composition, the epoxy resin composition containing the same are cured. It relates to a cured product and an optical semiconductor device.

Epoxy resin compositions are used in fields such as architecture, civil engineering, automobiles, and aircraft as resins having excellent heat resistance. In recent years, especially in the field of semiconductor-related materials, products such as mobile phones with cameras, ultra-thin liquid crystals and plasma TVs, lightweight notebook computers, etc., have become a key word for light, thin, short and small. The packaging material represented by resin is also required to have extremely high characteristics.
In recent years, the use in the field of optoelectronics has attracted attention, and with the advancement of information technology, in order to smoothly transmit and process a huge amount of information, the technology that uses optical signals instead of conventional signal transmission using electrical wiring. In the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resin compositions that give cured products with excellent transparency is desired.
Generally, epoxy resin curing agents used in the field of optoelectronics include acid anhydride compounds. In particular, acid anhydrides formed with saturated hydrocarbons are often used because the cured product has excellent light resistance. As these acid anhydrides, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride are generally used. Phthalic anhydride is mainly used because of its easy handling.

However, when these alicyclic acid anhydrides are used as curing agents for epoxy resins, these compounds have high vapor pressures and partly evaporate during curing, so they can be used as curing agents for epoxy resins and thermoset in an open system. In this case, the acid anhydride itself volatilizes in the atmosphere. As a result, the epoxy resin composition is caused by environmental pollution due to the release of harmful substances to the atmosphere, adverse effects on human bodies, production line pollution, and the absence of a predetermined amount of carboxylic acid anhydride (curing agent) in the cured product. Problems such as poor curing occur. Variation in curing conditions due to volatilization of the curing agent results in variations in the physical properties of the cured product, making it difficult to stably obtain a cured product having the intended performance.
In addition, the problem of volatilization is significant when LEDs, particularly SMD (Surface Mount Device) are sealed with a curable resin composition for encapsulating optical semiconductors that uses conventional acid anhydrides as curing agents. Since the amount of resin used is small, dents are generated, and in severe cases, the wires are exposed. Furthermore, there is a problem that it is difficult to endure cracking, peeling, and long-term lighting during solder reflow.
On the other hand, polyvalent carboxylic acid having an isocyanuric ring is known as a curing agent for epoxy resin in Patent Document 1, for example. However, it is difficult to dissolve the polyvalent carboxylic acid described in Patent Document 1 in an acid anhydride compound, and it is difficult to apply it in a field where it is necessary to use it in liquid form at room temperature (25 ° C.).

  When the thermosetting resin composition is used as a semiconductor encapsulant or as a semiconductor reflector, the illuminance of the optical semiconductor decreases when the thermosetting resin composition absorbs light emitted from the optical semiconductor. Therefore, it is desirable that the thermosetting resin composition has a high transmittance and is less colored by light or heat. Therefore, the curing agent blended in the thermosetting resin composition is also required to have high transmittance and little coloring due to light or heat. In addition, from the viewpoint of heat resistance, moldability, and reliability, it is important that the glass transition temperature of the cured product is a certain temperature or more, and from the viewpoint of moldability, the softening point and viscosity of the curing agent are within a certain range. It is important to be.

  Since the acid anhydride used as a curing agent for thermosetting resins is volatile and has a low melting point, it has been a problem that it is not suitable for mold molding.

  Tetracarboxylic acid anhydride is not volatile, but has a high melting point (150 ° C. or higher), so it is difficult to handle as a liquid resin composition and has poor moldability. Considering the difficulty of use, it is not suitable for the intended use.

  An example of using carboxylic acid as a curing agent for epoxy resin is also known, but it has a relatively high melting point (150 ° C. or higher) and has the same problem as above. Since it is extremely difficult to ensure, it is not suitable for the intended use.

Similarly, a polycarboxylic acid compound also has a high melting point (150 ° C. or higher), high crystallinity, difficulty in resin kneading, and coloration, and cannot be used in the intended application.
Therefore, as a conventionally known material, no compound that can achieve the above object has been found.

Japanese Patent No. 3765946 International Publication No. 2005/049597 Pamphlet International Publication No. 2005/121202 Pamphlet

  The present invention, particularly when used for curing in an open system such as an SMD type LED encapsulant, has low volatilization during curing and excellent curability, and the cured product provides a cured product with excellent transparency and hardness. An object of the present invention is to provide a polyvalent carboxylic acid, a polyvalent carboxylic acid composition containing the same, an epoxy resin composition, and a cured product thereof. Furthermore, a polyvalent carboxylic acid that can sufficiently increase the glass transition temperature of the cured product, has excellent moldability and is less colored to the cured product, a thermosetting resin composition using the same, and such a thermosetting resin Provided is a semiconductor device using the composition as a sealing material or a reflective material.

As a result of intensive investigations in view of the actual situation as described above, the present inventors have found that a polyvalent carboxylic acid having an isocyanuric ring or a polyvalent carboxylic acid composition containing the same, an epoxy resin composition containing any of them, or The present inventors have found that a thermosetting resin composition solves the above problems and have completed the present invention.
That is, the present invention relates to the following [1] to [18].
[1] A polyvalent carboxylic acid represented by the following formula (1).

(In formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ⁶ represents an organic group containing a hydrogen atom or a carboxyl group having 1 to 10 carbon atoms. R ¹ and R ^{6 present} may be the same or different from each other, but in a plurality of R ⁶ , 50 mol% or more is an organic group containing a carboxyl group having 1 to 10 carbon atoms. )
[2] The polyvalent carboxylic acid represented by the following formula (1-1) and described in [1].

(In Formula (1-1), R ¹ represents the same meaning as described above, and R ^2a represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group. In Formula (1-1), a plurality of R ^1a are present. R ¹ and R ^2a may be the same or different.)
[3] The polyvalent carboxylic acid according to [1] represented by the following formula (1-2).

(In Formula (1-2), R ¹ represents the same meaning as described above, and R ^2b represents an alkylene group having a linear or branched structure having 1 to 10 carbon atoms. In Formula (1-2), plural R ¹ and R ^{2b present} may be the same or different.)
[4] A polyvalent carboxylic acid composition containing the polyvalent carboxylic acid according to any one of [1] to [3].
[5] The polyvalent carboxylic acid composition according to [4], further containing a carboxylic acid anhydride compound.
[6] The polyvalent carboxylic acid composition according to [5], wherein the carboxylic anhydride compound is one or more selected from compounds represented by the following formulas (2) to (7).

[7] A polycarboxylic acid according to any one of [1] to [3] or a polycarboxylic acid composition according to any one of [4] to [6] and an epoxy resin. An epoxy resin composition.
[8] The epoxy resin composition according to [7], further containing an epoxy resin curing accelerator.
[9] The epoxy resin composition according to [8], wherein the epoxy resin curing accelerator is a metal soap.
[10] The epoxy resin composition according to [9], wherein the metal soap is a carboxylate zinc compound.
[11] A cured product obtained by curing the epoxy resin composition according to any one of [7] to [10].
[12] The polyvalent carboxylic acid according to any one of [1] to [3] and a thermosetting resin, and 0.01 Pa · s in a range of ICI cone plate viscosity of 100 to 200 ° C. Thermosetting resin composition in the range of 10 Pa · s.
[13] The thermosetting resin composition according to [12], wherein the softening point is in the range of 20 ° C to 150 ° C.
[14] Furthermore, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride A curing agent for a thermosetting resin containing an acid and one or more compounds selected from methylhexahydrophthalic anhydride,
Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl The thermosetting resin composition according to [12] or [13], wherein one or more compounds selected from hexahydrophthalic anhydride account for 1% to 90% by weight of the total.
[15] The thermosetting resin composition according to any one of [12] to [14], wherein the cured product has a glass transition temperature (Tg) of 30 ° C or higher.
[16] A cured product obtained by thermosetting the thermosetting resin composition according to any one of [12] to [15].
[17] An optical semiconductor device sealed with the cured product according to [16].
[18] An optical semiconductor device using the cured product according to [16] as a reflector.

According to the present invention, the epoxy resin composition containing a polyvalent carboxylic acid having a specific structure having an isocyanuric ring or a polyvalent carboxylic acid composition containing the same has low volatilization at the time of curing and is excellent in curability. Since the cured product gives a cured product having excellent transparency and hardness, it is required to form a cured product having high transparency and a thin film, and is extremely useful as a sealing resin for materials, particularly optical semiconductors (LEDs, etc.).
Also, a polyvalent carboxylic acid having a sufficient glass transition temperature of the cured product, excellent moldability, and less coloring when converted into a cured product, a thermosetting resin composition using the same, and the thermosetting resin thereof An optical semiconductor device using the composition as a sealing material or a reflecting material can be provided. Furthermore, by suppressing the softening point, handling becomes easy and sufficient kneading is possible, and a cured product having excellent cured properties can be provided. Moreover, the thermosetting resin composition excellent also in the toughness of hardened | cured material and the reactivity of resin can be provided.

2 is a GPC chart of the polyvalent carboxylic acid (A-1) obtained in Example 1. 2 is a GPC chart of the polyvalent carboxylic acid (A-2) obtained in Example 1. 3 is a GPC chart of the polyvalent carboxylic acid (A-3) obtained in Example 2.

  The polyvalent carboxylic acid (A) of the present invention is a polyvalent carboxylic acid having an isocyanuric ring represented by the following formula (1).

In formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ⁶ represents an organic group containing a hydrogen atom or a carboxyl group having 1 to 10 carbon atoms.

Specific examples of R ¹ include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, isobutylene group, isopentylene group, neopentylene group, isohexylene group, cyclohexylene group, and the like. However, from the viewpoint of heat-resistant transparency of the resulting cured product, a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.

R ⁶ is a hydrogen atom or an organic group containing a C 1-10 carboxyl group. Here, the organic group is a group composed of only H, C, N, and O atoms, and R ⁶ may have 1 to 10 carbon atoms, such as an ester bond, an ether bond, a urethane bond, an amide bond, and a carbonyl. It may contain a group.
The organic group containing a C1-C10 carboxyl group contains one or more carboxyl groups.

In the formula (1), a plurality of R ¹ and R ⁶ may be the same or different.

In the formula (1), a plurality of R ⁶ , 50 mol% or more is an organic group containing a C 1-10 carboxyl group. By being 50 mol% or more, the mechanical strength of the cured product is excellent. Moreover, 70 mol% or more is more preferable.

Examples of the organic group containing a carboxyl group having 1 to 10 carbon atoms in R ⁶ include organic groups represented by the following formulas (8) and (9).

In formula (8), R ^2a represents a hydrogen atom or an alkyl group or carboxyl group having 1 to 6 carbon atoms, and in formula (9), R ^2b represents an alkylene group having a straight chain or branched structure having 1 to 10 carbon atoms. In the formulas (8) and (9), the symbol * indicates that they are bonded to the oxygen atom in the formula (1).

Specific examples of the alkyl group having 1 to 6 carbon atoms in R ^2a include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, A cyclopentyl group, a hexyl group, an isohexyl group, a cyclohexyl group and the like can be mentioned, and a methyl group is preferable from the viewpoint of heat-resistant transparency of the obtained cured product.

Among R ^2a , a methyl group and a carboxyl group are preferable, and the viscosity of the polyvalent carboxylic acid composition (C) containing the polyvalent carboxylic acid (A) is not excessively increased at room temperature (25 ° C.). From the viewpoint of transparency of the cured product, a methyl group is preferable, and from the viewpoint of gas barrier properties, high glass transition temperature (Tg), and hardness of the obtained cured product, a carboxyl group is particularly preferable.

Specific examples of R ^2b include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonynylene group, decynylene group, isopropylene group, isobutylene group, isopentylene group, neopentylene group. Group, isohexylene group, isoheptylene group, isooctylene group, isononinylene group, isodecynylene group, dimethylpropylene group, diethylpropylene group, diethylbutylene group, diethylpentylene group, diethylhexylene group, etc., but the heat resistance of the resulting cured product From the viewpoint of transparency, an ethylene group, a propylene group, and a diethylpropylene group are preferable, and the propylene group is particularly preferable because the polyvalent carboxylic acid (A) of the present invention has a low softening point and a low viscosity at room temperature (25 ° C.). preferable.

Specific examples of the organic group containing a carboxyl group having 1 to 10 carbon atoms in R ⁶ are represented by the following formulas (8-1) to (8-3) and (9-1) to (9-3). Organic group.

  (In the formula, * represents the same meaning as described above.)

  The polyvalent carboxylic acid (A) represented by the formula (1) includes an isocyanuric acid trishydroxyalkyl compound represented by the following formula (10), a carboxylic acid anhydride compound represented by the following formula (14), and It can be obtained by addition reaction with a carboxylic acid anhydride compound represented by the formula (15).

In formula (10), R ¹ represents the same meaning as described above.

In formula (14), R ^2a represents the same meaning as described above.
In Formula (15), R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in Formula (15), a plurality of R ³ may be the same. It can be different. Specific examples of the alkyl group having 1 to 4 carbon atoms in R ³ include a methyl group, an ethyl group, a propyl group, and a butyl group. m represents an integer of 1 to 9, and 1 to 5 is preferable and 1 to 2 is particularly preferable from the viewpoint of heat-resistant transparency of the obtained cured product.

  Among the compounds represented by the formula (10), compounds represented by the following formulas (11) to (13) are preferable from the viewpoint of transparency of the cured product and gas barrier properties.

  Of the compounds represented by the formula (14), compounds represented by the following (5) to (7) are particularly preferred.

  Among the compounds represented by the formula (15), the compounds represented by the following formulas (2) to (4) are the heat-resistant transparency of the cured product, the viscosity of the polyvalent carboxylic acid (A), and the polyvalent carboxylic acid composition. It is mentioned as a preferable compound from a viewpoint of the viscosity of a thing (C). Among these, a compound represented by the following formula (4) is preferable.

The production of the polyvalent carboxylic acid (A) of the present invention can be carried out in a solvent or without a solvent. The solvent is not particularly limited as long as it is a solvent that does not react with the trishydroxyalkyl compound of isocyanuric acid represented by the above formula (10) or the carboxylic acid anhydride compound represented by formula (14) or formula (15). it can. Solvents that can be used include, for example, aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, and aromatic carbonization such as toluene and xylene. Hydrogen etc. are mentioned, Among these, aromatic hydrocarbons and ketones are preferable.
These solvents may be used alone or in combination of two or more. The amount used in the case of using a solvent is represented by the above-mentioned isocyanuric acid trishydroxyalkyl compound represented by the formula (10) and the carboxylic acid anhydride compound represented by the formula (14) and / or the formula (15). 0.5-300 mass parts is preferable with respect to a total of 100 mass parts of a carboxylic anhydride compound.

  Since the polycarboxylic acid (A) of the present invention is often solid at room temperature (25 ° C.), it is preferable to synthesize it in a solvent from the viewpoint of workability.

  The polyvalent carboxylic acid (A) of the present invention can be produced without a catalyst or with a catalyst. When a catalyst is used, usable catalysts are hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, water Metal hydroxides such as calcium oxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, Heterocyclic compounds such as imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium Roxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctyl Quaternary ammonium salts such as methylammonium acetate, orthotitanic acid such as tetraethyl orthotitanate, tetramethyl orthotitanate, tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, Examples include metal soaps such as potassium octylate.

When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.
The amount used in the case of using a catalyst is represented by the above-mentioned trishydroxyalkyl compound isocyanurate represented by the formula (10), the carboxylic acid anhydride compound represented by the formula (14) and / or the formula (15). 0.05-10 mass parts is preferable with respect to a total of 100 mass parts of a carboxylic anhydride compound.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. At this time, use of an alcoholic solvent such as methanol or ethanol or water should be avoided because it reacts with an unreacted carboxylic acid anhydride compound represented by formula (14) or formula (15). Is preferred.
In the present invention, in the cured product of the obtained polyvalent carboxylic acid (A) or polyvalent carboxylic acid composition (C), zinc carboxylate such as zinc octylate is used from the viewpoint of improving transparency and heat-resistant transparency. It can be preferably used as a catalyst, and it is preferable to carry out the reaction without a catalyst from the viewpoint of reducing the coloring of the resulting polyvalent carboxylic acid (A) or polyvalent carboxylic acid composition (C).
Among them, in order to obtain a cured product having excellent transparency and sulfidation resistance, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylate) and zinc phosphate ester ( Zinc compounds such as zinc octyl phosphate and zinc stearyl phosphate are preferably used.

  The reaction temperature during the production of the polyvalent carboxylic acid (A) of the present invention is usually 20 to 160 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 145 ° C., although it depends on the amount of catalyst and the solvent used. . The total reaction time is usually 1 to 20 hours, preferably 3 to 18 hours. The reaction may be carried out in two or more stages, for example, after reacting at 20 to 100 ° C. for 1 to 8 hours, it may be allowed to react at 100 to 160 ° C. for 1 to 12 hours. In particular, many of the carboxylic acid anhydride compounds represented by the formula (14) and the formula (15) are highly volatile, and when such compounds are used, after reacting in advance at 20 to 100 ° C., 100 By reacting at ˜160 ° C., volatilization can be suppressed. As a result, not only the diffusion of harmful substances into the atmosphere can be suppressed, but also the polyvalent carboxylic acid (A) as designed can be obtained more reliably.

When the production is carried out using a catalyst, the catalyst can be removed by quenching and / or washing with water if necessary, but it is left as it is, and the polyvalent carboxylic acid (A) and / or the polyvalent carboxylic acid is left as it is. It can also be used as a curing accelerator for an epoxy resin composition containing the composition (C).
When performing a water washing process, it is preferable to add the solvent which can be isolate | separated from water depending on the kind of solvent currently used. Examples of preferable solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. it can.
When a solvent is used for the reaction or washing with water, it can be removed by vacuum concentration or the like.

  In producing the polyvalent carboxylic acid (A) of the present invention, gel permeation chromatography (GPC) {measurement conditions; column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2), flow rate: 0.4 ml / min. Column temperature: 40 ° C., solvent used: THF (tetrahydrofuran), detector: RI (differential refraction detector)}, the peak of the retention time earlier than the peak of the compound represented by the formula (1) of this application and the slow retention time Peak compounds are mixed. Examples of the peak of the fast retention time (hereinafter referred to as peak f) include a compound whose retention time is 1 to 3 minutes earlier than the peak of the compound of formula (1), for example, 18 to 20 minutes. The area percentage of GPC of the compound of peak f is preferably 1 to 30 area% from the viewpoint of increasing mechanical strength, and particularly preferably 1 to 10 area%. Further, there may be 2 to 3 peaks of the slow retention time (hereinafter referred to as peak s), and the retention time is 1 to 5 minutes later than the peak of the compound of the formula (1). This corresponds to a compound of 21 to 25 minutes. The area percentage of GPC of the compound of peak s is preferably 1 to 10 area% from the viewpoint of improving adhesiveness, and more preferably 1 to 5 area%. In addition, a multimer of polyvalent carboxylic acid represented by the following formula (16) may be generated. These compounds are considered to correspond to the compound of peak f.

In formula (16), R ¹ represents the same meaning as described above, R ⁴ represents the same meaning as R ^2b or a structure represented by the following formula (17), and R ⁵ represents a hydrogen atom or the following formula (18). The structure represented by is represented.

In formula (17), R ^2a represents the same meaning as described above, and ** represents a bond to the carbonyl carbon adjacent to R ⁴ in formula (16).

In the formula ^(18), R ^1, R 4, ^{R 5} are as defined above, that it is bound with the oxygen atom to which ^{R 5} in the formula (16) are attached at the site of *** To express.

  When the polyvalent carboxylic acid represented by the formula (16) is contained in the polyvalent carboxylic acid (A), it is preferable because the mechanical strength of the cured product is improved. In order not to excessively increase the viscosity of A), it is preferably 50 parts by mass or less with respect to 100 parts by mass of the polyvalent carboxylic acid (A).

  Moreover, when manufacturing polyvalent carboxylic acid (A) of this invention, the bivalent carboxylic acid represented by following formula (19) may produce | generate. In addition, it is thought that the said compound corresponds to the compound of the peak s. Here, the GPC area% of the compound represented by the following formula (19) of the polyvalent carboxylic acid (A) obtained by the production method is preferably 1 to 30 area%, and more preferably 1 to 20 area%.

In formula (19), R ¹ and R ⁴ represent the same meaning as described above.

  When the divalent carboxylic acid represented by the formula (15) is contained in the polyvalent carboxylic acid (A), it is preferable because the adhesion of the cured product to the base material is improved. Since mechanical strength is inferior, it is preferably 20 parts by mass or less with respect to 100 parts by mass of the polyvalent carboxylic acid (A).

  Further, when the polyvalent carboxylic acid (A) of the present invention is produced, a monovalent carboxylic acid represented by the following formula (19 ′) may be generated. In addition, it is thought that the said compound corresponds to the compound of the peak s. Here, the GPC area% of the compound represented by the following formula (19 ′) of the polyvalent carboxylic acid (A) obtained by the production method is preferably 1 to 10 area%, and more preferably 1 to 5 area%.

In formula (19 ′), R ¹ and R ⁴ represent the same meaning as described above.

  When the monovalent carboxylic acid represented by the formula (19 ′) is contained in the polyvalent carboxylic acid (A), it is preferable because the adhesion of the cured product to the base material is improved. Since the mechanical strength tends to be inferior, it is preferably 20 parts by mass or less with respect to 100 parts by mass of the polyvalent carboxylic acid (A).

  In addition, as a compound corresponding to the peak s, when alcohol is used as a solvent, the alcohol and the carboxylic acid anhydride compound represented by the above formula (14) and / or the above formula (15) are represented. Reaction product of compound, moisture in solvent or air, carboxylic acid anhydride compound represented by formula (14) and / or reactant of compound represented by formula (15), unreacted acid anhydride Is mentioned. Here, the alcohol, the compound represented by the above formula (9), the water in the solvent or the air, the carboxylic acid anhydride compound represented by the above formula (14) and / or the above formula (15) are represented. The area percentage of GPC of the reaction product of the compound is preferably 5 area% or less, more preferably 3 area% or less from the viewpoint of the mechanical strength of the cured product.

The acid value (measured by the method described in JIS K-2501) of the produced polycarboxylic acid (A) of the present invention is preferably 150 to 415 mgKOH / g, more preferably 185 to 375 mgKOH / g, Particularly preferred is 200 to 320 mg KOH / g. If the acid value is 150 mgKOH / g or more, it is preferable because the mechanical properties of the cured product are improved, and if it is 415 mgKOH / g or less, the cured product is not excessively hard and the elastic modulus is appropriate.
The functional group equivalent of the polyvalent carboxylic acid (A) of the present invention is preferably 135 to 312 g / eq, more preferably 150 to 300 g / eq, and particularly preferably 180 to 280 g / eq.

Next, the polyvalent carboxylic acid composition (C) of the present invention will be described.
The polyvalent carboxylic acid composition (C) of the present invention contains the polyvalent carboxylic acid (A) of the present invention as an essential component.
Of the polyvalent carboxylic acid composition (C) of the present invention, the polyvalent carboxylic acid composition (C ′) requires the polyvalent carboxylic acid (A) of the present invention and the carboxylic anhydride compound (B). Ingredients.

The polyvalent carboxylic acid composition (C ′) can be obtained by mixing the polyvalent carboxylic acid (A) and the carboxylic acid anhydride compound (B).
The polyvalent carboxylic acid composition (C ′) of the present invention can be obtained by uniformly mixing the above components at ordinary temperature or under heating. For example, mix thoroughly until uniform using a cartridge case, extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. It is prepared by doing.
When preparing, you may mix together the epoxy resin (D) mentioned later, a hardening accelerator (E), an adhesion assistant, antioxidant, a light stabilizer, etc.

  The polyvalent carboxylic acid composition (C) of the present invention can be used as a varnish or ink by mixing a solvent as required. The solvent is used for the polyvalent carboxylic acid (A), carboxylic anhydride compound (B), epoxy resin (D), curing accelerator (E), adhesion aid, antioxidant, light stabilizer, etc. of the present invention. Any one having high solubility and not reacting with these can be used. Specific examples thereof include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene. Among these, aromatic hydrocarbons and ketones are preferable.

In the polycarboxylic acid composition (C ′) of the present invention, the carboxylic acid anhydride compound represented by the formula (14) and / or the formula (15) in the production of the polyvalent carboxylic acid (A) described above. When the carboxylic acid anhydride compound represented and the carboxylic acid anhydride compound (B) in the polyvalent carboxylic acid composition (C ′) are the same, the formula (10) Is reacted with an excess of the trishydroxyalkyl compound of isocyanurate represented by the formula (B), and when the production of the polyvalent carboxylic acid (A) is completed, the polyvalent carboxylic acid (A ) And a carboxylic acid anhydride (B).
As the charging ratio of both in the reaction, 0.001 to 0.7 equivalent of the hydroxyl equivalent of the trishydroxyalkyl compound of isocyanurate with respect to 1 equivalent of the acid anhydride group in terms of the functional group equivalent, It is preferable to charge in the range of 0.01 to 0.5 equivalent.

  The polyvalent carboxylic acid (A) in the polyvalent carboxylic acid composition (C ′) is obtained by mixing the carboxylic acid anhydride (B) with the polyvalent carboxylic acid composition (C ′) thus obtained. Can be adjusted.

  When the excess carboxylic acid anhydride compound (B) is charged and reacted during the production of the polyvalent carboxylic acid (A), the excess carboxylic acid anhydride compound (B) is hydrolyzed by water during the washing step. Therefore, it is better to avoid the water washing process described above.

  The carboxylic acid anhydride compound (B) used in the present invention is not particularly limited as long as it is a compound having a carboxylic acid anhydride group in the molecule, but one or more selected from the following formulas (2) to (7) An acid anhydride compound is preferred from the viewpoint of transparency of the cured product.

  In the polyvalent carboxylic acid composition (C ′) of the present invention, the proportion of the polyvalent carboxylic acid (A) and the carboxylic anhydride compound (B) is carboxylic with respect to 100 parts by mass of the polyvalent carboxylic acid (A). The acid anhydride compound (B) is preferably 1 to 1000 parts by mass, more preferably 10 to 800 parts by mass, and particularly preferably 50 to 500 parts by mass.

  The polyvalent carboxylic acid (A) or polyvalent carboxylic acid composition (C) of the present invention functions as an epoxy resin curing agent, and can also contain other epoxy resin curing agents. For example, an amine type curing agent, a phenol type curing agent, and a polyvalent carboxylic acid resin are exemplified, and a polyvalent carboxylic acid resin is preferable.

  The polycarboxylic acid resin is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton. In the present invention, the polyvalent carboxylic acid resin is not only a polyvalent carboxylic acid compound having a single structure, but also a mixture of a plurality of compounds having different substituent positions or different substituents, that is, a polyvalent carboxylic acid. A composition is also included, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin.

As the polyvalent carboxylic acid resin, a bi- to hexafunctional carboxylic acid is particularly preferable. (A): a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule; and (b); one or more in the molecule. More preferred are compounds obtained by reaction with a compound containing an acid anhydride group. Here, in the reactants (a) and (b), another alcohol compound may be reacted, and two or more compounds corresponding to the component (a) or (b) may be used. .
(A): The polyhydric alcohol compound containing two or more hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two or more alcoholic hydroxyl groups in the molecule, but ethylene glycol, propylene glycol, 1, 3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2 -Butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) ) Geo such as-5-ethyl-5-hydroxymethyl-1,3-dioxane Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, dipentaerythritol, etc. And the like, a terminal alcohol polyester, a terminal alcohol polycarbonate, a terminal alcohol polyether, and a polyhydric alcohol having a siloxane structure.

Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- And compounds such as (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, among which 2-ethyl-2-butyl-1,3-propanediol, Neopentyl glycol, 2,4-diethylpentanediol, 1,4-cycl Rhohexanedimethanol, tricyclodecane dimethanol, norbornenediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxy Alcohols having a branched chain structure or a cyclic structure such as a compound such as methyl-1,3-dioxane are more preferred. From the viewpoint of imparting high sulfidation resistance, 2,4-diethylpentanediol, tricyclodecane dimethanol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxy) Compounds such as ethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane are particularly preferred. Among them, in particular, in a branched chain structure, it is preferable to have two or more branched chains, and it is particularly preferable that the branched chains extend from different carbon atoms. Here, the alcohol having the branched chain structure or the cyclic structure preferably has 5 to 25 carbon atoms, and particularly preferably 5 to 20 carbon atoms.
Although the polyhydric alcohol which has a siloxane structure is not specifically limited, For example, the silicone oil represented by a following formula can be used.

(In the formula (20), A ₁ represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, A ₂ represents a methyl group or a phenyl group, and s is a repeating number and means an average value 1 to 100.)

As described above, (a): the polyhydric alcohol compound containing two or more hydroxyl groups in the molecule may be used alone or in combination of two or more.
In order to use the obtained polycarboxylic acid resin in a liquid state and impart high resistance to sulfuration, the polyhydric alcohol having the siloxane structure described above and the alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms are used. It is preferable to use a mixture.
When using a mixture of a polyhydric alcohol having a siloxane structure and an alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms, the amount used is in the total alcohol compound (polyhydric alcohol having a siloxane structure). / (Alcohols having a branched chain structure or cyclic structure having 5 to 25 carbon atoms) is preferably 1 to 20, from the viewpoint of heat-resistant transparency of the cured product and appropriate viscosity of the polyvalent carboxylic acid resin. Is preferable, and 6 to 10 is particularly preferable.

(B); compounds containing one or more acid anhydride groups in the molecule include, in particular, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane Tetracarboxylic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3 , 4-tricarboxylic acid-3,4-anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, succinic anhydride and the like are preferred, and among them, methylhexahydrophthalic anhydride, cyclohexane-1,3,4- Tricarboxylic acid-3,4-anhydride, 2,4-diethyl glutaric anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, Hexane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic dianhydride is preferred. Here, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable for increasing the hardness, and methylhexahydrophthalic anhydride is preferable for increasing the illuminance retention. In order to suppress an excessive increase in viscosity of the polyvalent carboxylic acid resin, 2,4-diethylglutaric acid and glutaric acid are preferable.
The addition reaction can be performed under the same conditions as in the production of the polyvalent carboxylic acid (A) of the present invention described above.

  When the polyvalent carboxylic acid (A) or the polyvalent carboxylic acid composition (C) of the present invention is used in combination with another epoxy resin curing agent, the polyvalent carboxylic acid (A) of the present invention or the total epoxy resin curing agent is used. The proportion of the polyvalent carboxylic acid composition (C) is preferably 30 to 99 parts by mass, particularly preferably 60 to 97 parts by mass. If it is less than 30 parts by mass, the heat-resistant transparency of the cured product may be inferior.

  Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition in the present invention contains a polyvalent carboxylic acid (A) or a polyvalent carboxylic acid composition (C) and an epoxy resin (D).

  Examples of the epoxy resin (D) include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, Glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds having an epoxy group with other polymerizable unsaturated compounds, epoxy Examples thereof include condensates of silicon compounds having a group with other silicon compounds, silicone-modified epoxy resins, and the like.

  Examples of the epoxy resin that is a glycidyl etherified product of a phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3 -Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, Dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) Ethyl) phenyl] propane, 2,2′-methyl -Bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglicinol, Examples thereof include phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  Examples of epoxy resins that are glycidyl etherified products of various novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. And glycidyl etherified products of various novolac resins such as a novolak resin, a phenol novolac resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolac resin containing a fluorene skeleton.

Examples of the alicyclic epoxy resin include alicyclic rings having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. And a formula epoxy resin.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester-based epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
Examples of epoxy resins obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like. An epoxy resin obtained by glycidylating any of the halogenated phenols.

  As a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound other than that, there are Marproof (trade name) G-0115S, G-0130S, G-0250S, G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation) and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, methacrylic acid, and the like. Examples thereof include glycidyl acid and 4-vinyl-1-cyclohexene-1,2-epoxide. Examples of other polymerizable unsaturated compounds include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane and the like. These epoxy resins may be used alone or in combination of two or more.

  Examples of the condensate of the silicon compound having an epoxy group and another silicon compound include a hydrolysis condensate of an alkoxysilane compound having an epoxy group and an alkoxysilane having a methyl group or a phenyl group, or an epoxy group. It is a condensate of an alkoxysilane compound and a polydimethylsiloxane having a silanol group, a polydimethyldiphenylsiloxane having a silanol group, a polyphenylsiloxane having a silanol group, or a condensate obtained by using them in combination. Examples of the alkoxysilane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldimethoxysilane and the like. Examples of the alkoxysilane compound having a methyl group or a phenyl group include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane. . As polydimethylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group, for example, X-21-5841, KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-873 are available from the market. PRX413 (manufactured by Dow Corning Toray) XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Japan GK) DMS-S12, DMS-S14, DMS-S15, DMS-S21, Examples thereof include DMS-S27, DMS-S31, PDS-0338, and PDS-1615 (manufactured by Gelest).

  The silicone-modified epoxy resin is a compound having a silicone chain (Si-O chain) as a main skeleton and two or more epoxy groups in one molecule. The silicone chain may be linear, branched, cyclic, cage type, or ladder type. A cyclic silicone-modified epoxy resin represented by the following formula (21) is a particularly preferable example from the viewpoint of transparency and mechanical strength of the obtained cured product, but is not limited thereto.

In formula (21), R ⁷ represents a hydrocarbon group having 1 to 6 carbon atoms, X represents an organic group containing 1 epoxy group or a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3, respectively. . A plurality of R ⁷ and X present in the formula may be the same or different. However, in the plurality of X, two or more are epoxy group-containing organic groups.

Specific examples of R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group. From the viewpoint of heat-resistant transparency of the cured product, a methyl group and a phenyl group are preferable. From the viewpoint of ease of production, a methyl group is particularly preferred.
The organic group in X represents a compound composed of C, H, N, and O atoms. Specific examples of the epoxy group-containing organic group include 2,3-epoxycyclohexylethyl group and 3-glycidoxypropyl group. 2,3-epoxycyclohexylethyl group is preferable from the viewpoint of heat-resistant transparency of the cured product. Here, it is preferable that carbon number in an organic group is 1-20, and it is more preferable that it is 3-15. Further, a group to which a 2,3-epoxycyclohexylethyl group or 3-glycidoxypropyl group is added via an alkylene group having 1 to 5 carbon atoms is preferable.
Specific examples of the hydrocarbon group having 1 to 6 carbon atoms in X include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group. From the viewpoint of heat-resistant transparency of the cured product Therefore, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable from the viewpoint of ease of production.
n is preferably 2 in view of the ease of production of the compound.

The cyclic silicone-modified epoxy resin represented by the formula (21) can be obtained by a hydrosilylation reaction between a cyclic hydrogensiloxane compound and an olefin compound having an epoxy group in the molecule.
Specific examples of the cyclic hydrogensiloxane compound include trimethyltricyclosiloxane, triphenyltricyclosiloxane, tetramethyltetracyclosiloxane, tetraphenyltetracyclosiloxane, pentamethylpentacyclosiloxane, pentaphenylpentacyclosiloxane, and the like. Tetramethyltetrasiloxane is preferred because of ease of production.
Examples of the olefin compound having an epoxy group in the molecule include 4-vinyl-1,2-epoxycyclohexane and 3-glycidoxy-1,2-propene. From the viewpoint of heat-resistant transparency of the cured product, 4-vinyl- 1,2-epoxycyclohexane is preferred.

  In the hydrosilylation reaction, a known metal complex such as rhodium, palladium, or platinum can be used as the catalyst. Specific examples include tristriphenylphosphine rhodium chloride and hexachloroplatinic acid hexahydrate, and hexachloroplatinic acid hexahydrate is preferred from the viewpoint of transparency of the cured product.

The catalyst used for the hydrosilylation reaction is preferably dissolved in a solvent and used as a solution from the viewpoint of workability. The solvent that can be used can be any solvent that dissolves the catalyst, but tetrahydrofuran and toluene are preferred from the viewpoints of solubility and workability.
When used as a solution, the catalyst is adjusted to 0.05 to 50% by weight and added to the reaction solution.

  Specific examples of the cyclic silicone-modified epoxy resin represented by the formula (21) include compounds represented by the following formulas (21-1) to (21-6).

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

  Among the above-mentioned epoxy resins (D), from the viewpoint of transparency, heat-resistant transparency and light-resistant transparency, alicyclic epoxy resins, condensates of silicon compounds having an epoxy group with other silicon compounds, silicone-modified epoxies The combined use of resins is preferred. Among these, a cyclic silicone-modified epoxy resin having an epoxycyclohexane structure in the skeleton is preferable.

  The epoxy resin (D) contains 1 equivalent of a carboxylic acid group in the polyvalent carboxylic acid (A) and / or a carboxylic acid anhydride 1 of the carboxylic acid anhydride compound (B) in the polyvalent carboxylic acid composition (C ′). It is preferable to use the epoxy group within a range of 0.5 to 3.0 equivalents relative to equivalents. If it is 0.5 equivalent or more, the heat resistant transparency of the cured product is improved, and if it is 3.0 or less, the mechanical property of the cured product is improved.

The epoxy resin composition of the present invention preferably further contains an epoxy resin curing accelerator (E).
Any epoxy resin curing accelerator (E) capable of accelerating the curing reaction between the polyvalent carboxylic acid (A) or polyvalent carboxylic acid composition (C) of the present invention and the epoxy resin (D) is used. Examples of curing accelerators (E) that can be used but can be used include ammonium salt curing accelerators, phosphonium salt curing accelerators, metal soap curing accelerators, imidazole curing accelerators, amines Examples thereof include a curing accelerator, a phosphine-based curing accelerator, a phosphite-based curing accelerator, and a Lewis acid-based curing accelerator.
In the epoxy resin composition of the present invention, the epoxy resin curing accelerator (E) is preferably used in an amount of 0.001 to 15 parts by weight of a curing accelerator with respect to 100 parts by weight of the epoxy resin composition.

  Specific examples of the epoxy resin curing accelerator (E) that can be used in the epoxy resin composition of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl. -4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine 2,4-diamino-6 (2'-ethyl, 4-methylimidazo Ru (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-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5 -Various imidazoles of dicyanoethoxymethylimidazole, and salts of these imidazoles with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid Amides such as dicyandiamide, 1,8-diaza-bishi (B) Diaza compounds such as [5.4.0] undecene-7 and salts thereof such as tetraphenylborate and phenol novolak, salts with the above polycarboxylic acids or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide Ammonium salts such as trioctylmethylammonium bromide, phosphines and phosphonium compounds such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, 2,4,6-trisaminomethylphenol Phenol compounds such as amines, metal compounds such as amine adducts, tin octylate, etc., and microcapsule type curing accelerators in which these curing accelerators are microcapsules, etc. Is mentioned. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions.

Among these, from the viewpoint of transparency of the cured product, the metal soap curing accelerator is excellent, and among the metal soap curing accelerators, a zinc carboxylate compound is particularly preferable from the viewpoint of transparency of the cured product.
Examples of the metal soap type curing accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, potassium octylate, calcium stearate, zinc stearate, magnesium stearate, stearin Aluminum oxide, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxyphosphate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, 12-hydroxystearic acid Barium, lithium 12-hydroxystearate, sodium 12-hydroxystearate, calcium montanate, zinc montanate, mon Magnesium phosphate, aluminum montanate, lithium montanate, sodium montanate, calcium behenate, zinc behenate, magnesium behenate, lithium behenate, sodium behenate, silver behenate, calcium laurate, zinc laurate, barium laurate , Lithium laurate, zinc undecylate, zinc ricinoleate, barium ricinoleate, zinc myristate, zinc palmitate and the like. These catalysts may be used alone or in combination of two or more.

  Carbons such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate, and zinc palmitate are used to obtain cured products with excellent transparency and sulfidation resistance. A zinc salt composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as zinc carbonate having several tens to thirty or zinc 12-hydroxystearate can be preferably used. Among these, from the viewpoint of excellent pot life and sulfidation resistance, a zinc salt composed of a monocarboxylic acid compound having 10 to 20 carbon atoms such as zinc stearate and zinc undecylenate, and a hydroxyl group such as 12-hydroxyzinc stearate. A zinc salt composed of a monocarboxylic acid compound having 15 to 20 carbon atoms is preferably used, more preferably zinc stearate, zinc undecylenate, zinc 12-hydroxystearate, particularly preferably zinc stearate, 12- Zinc hydroxystearate can be used.

  Examples of the ammonium salt curing accelerator include 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 acetate and the like. Examples of the phosphonium salt curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium diethylphosphate, and the like.

  In addition to the above-mentioned ammonium salt-based curing accelerators, phosphonium salt-based curing accelerators, metal soap-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, and heterocyclic compound-based curing accelerators. A phosphine-based curing accelerator, a phosphite-based curing accelerator, a Lewis acid-based curing accelerator, or the like can be used.

  The epoxy resin curing accelerator (E) described above can be used as a solid compound or a liquid compound at room temperature (25 ° C.). When the epoxy resin composition of the present invention is used for an application that needs to be liquid at room temperature (25 ° C.), when using a solid compound as a curing accelerator at room temperature (25 ° C.), a resin is previously used. It can also be used by dissolving in Further, it is also possible to use a solid compound dispersed in a resin at room temperature (25 ° C.).

In the epoxy resin composition of the present invention, it is possible to supplement the viscosity adjustment of the composition and the hardness of the cured product by using a coupling agent as necessary.
Examples of coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples thereof include zirconium such as xylitol (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum coupling agent.
These coupling agents may be used alone or in combination of two or more.
A coupling agent is 0.05-20 weight part normally in the epoxy resin composition of this invention, Preferably 0.1-10 weight part is contained as needed.

  The epoxy resin composition of the present invention can be supplemented with mechanical strength and the like without impairing transparency by using a nano-order level inorganic filler as necessary. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the epoxy resin composition of the present invention.

For the purpose of preventing coloring, the epoxy resin composition of the present invention may contain an amine compound as a light stabilizer, or a phosphorus compound and a phenol compound as an antioxidant.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (2,2,6) decanedioate , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6,- Tramethyl-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] me L) butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 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) -triazine- 2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine · 1,3,5-triazine · N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl- Polycondensate of 1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-tri Gin-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7 -Oxa-3,20-diazadispiro [5 · 1 · 11 · 2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / Tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7 Oxa-3,20-diazadispiro [5,1,11,2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11, 2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4- Hindered amine compounds such as piperidinyl), benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1, , 3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl)- 5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) ) Benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazole-2) -Yl) -6-dodecyl-4-methylphenol and other benzotriazole compounds, Benzoate series such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl ) -5-[(hexyl) oxy] phenol and other triazine compounds, and the like, particularly preferably hindered amine compounds.

The following commercially available products can be used as the amine compound that is the light stabilizer.
It is not particularly limited as a commercially available amine compound, for example, as manufactured by Ciba Specialty Chemicals, as TINUVIN (trade name) 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB (trade name) 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.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)- , 4′-biphenylenediphosphonite, 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'- Biphenylene diphosphonite, 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, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. It is below.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as an ADEKA product, ADK STAB (brand name) PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A and the like.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). Propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol- Bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, penta Lithricyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethyleneglycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butyl) Ruphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di) -Tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl- 6-tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4′-thiobis (3-methyl- 6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) ), Bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di -Tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis -(4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  A commercial item can also be used for the said phenolic compound. The commercially available phenolic compound is not particularly limited. For example, IRGANOX (trade name) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 1598, IRGANOX 1598, IRGANOX 1520, manufactured by Ciba Specialty Chemicals, , ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, manufactured by Sumitomo Chemical As Sumilizer (trade name) GA-80, Sumilizer M P-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

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

  It is preferable to contain at least one of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0 with respect to the total weight of the epoxy resin composition of the present invention. 0.005 to 5.0% by weight.

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

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

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at room temperature or under heating. For example, mix thoroughly until uniform using an extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. Prepared.

  The epoxy resin composition of the present invention comprises the polyvalent carboxylic acid (A) or the polyvalent carboxylic acid composition (C) of the present invention and an epoxy resin (D) and optionally a curing accelerator (E), an antioxidant, light It is prepared by thoroughly mixing additives such as a stabilizer and can be used as a sealing material. As a mixing method, it is mixed at room temperature or warm using a shell, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill or the like.

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

  Moreover, the epoxy resin composition of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. When obtaining such a film-type resin composition, the epoxy resin composition of the present invention is applied as a varnish on a release film, the solvent is removed under heating, and a B-stage adhesive is formed. Get as. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

  Furthermore, general applications in which a thermosetting resin such as an epoxy resin is used are mentioned, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed boards, In addition to the use as a sealing material, as a sealing material, a cyanate resin composition for a substrate, an acrylic ester resin as a resist curing agent, and the like as an additive to other resins Applications are listed.

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

  Sealing agents include capacitors, transistors, diodes, light emitting diodes, potting, dipping, transfer mold sealing for IC, LSI, potting sealing for IC, LSI COB, COF, TAB, flip chip, etc. Underfill, and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

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

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

  Other uses of the optical material include general uses in which the curable resin composition A is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins and the like can be mentioned. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  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 optical semiconductor element is sealed with a sealing material such as epoxy resin in order to protect the semiconductor chip from heat and moisture and to play a role of a lens function. The epoxy resin composition of this invention can be used for this sealing material.

As a molding method of the sealing material, an injection method in which the sealing material is injected into a mold with a substrate on which the optical semiconductor element is fixed is inserted and then heat-cured and then molded, and a sealing material is injected on the mold in advance. In addition, a compression molding method is used in which an optical semiconductor element fixed on a substrate is immersed therein and heat-cured and then released from a mold.
Examples of the injection method include a dispenser.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. The heating conditions are preferably about 80 to 230 ° C. and 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 at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

  Next, a thermosetting resin composition containing the polyvalent carboxylic acid (A) of the present invention and a thermosetting resin will be described. The thermosetting resin composition of the present invention has an ICI cone plate viscosity in the range of 0.01 Pa · s to 10 Pa · s in the range of 100 to 200 ° C.

  By using the polyvalent carboxylic acid (A) of the present invention, excellent durability can be realized and a thermosetting resin composition suitable for kneading can be obtained. The thermosetting resin composition of the present invention has an ICI corn plate viscosity in the range of 100 to 200 ° C., 0.01 to 10 Pa · s, and is solid at room temperature. Kneading, which was impossible without pretreatment such as conversion, becomes possible without pretreatment. Moreover, since it is solid, it has the characteristics also in the point which is easy to shape | mold as a tablet.

In the thermosetting resin composition of the present invention, the ICI cone plate viscosity is 0.01 to 10 Pa · s in the range of 100 to 200 ° C.
By adjusting to the said range, it becomes solid at normal temperature (25 degreeC), becomes easy to shape | mold, and can prevent troubles, such as a void, effectively. In addition, by setting such a low-viscosity thermosetting resin composition, each component that has been conventionally difficult to knead because of its high crystallinity has a high softening point or melting point, and is sufficiently melted and dispersed in the curing agent. Therefore, the crystals are broken and sufficiently kneaded with the epoxy resin as the main agent, and each component is effectively arranged, and a cured product having excellent physical properties can be obtained. The softening point is preferably 20 to 150 ° C, more preferably 40 to 130 ° C, still more preferably 50 to 100 ° C, and particularly preferably 70 to 100 ° C. By being at such a softening point, sufficient kneading can be easily performed.
By adjusting to this range, various components can be easily stirred and mixed with a mixer, etc., and further kneaded or melt-kneaded with a mixing roll, extruder, kneader, roll, extruder, etc., cooled, pulverized It becomes possible to do.

  The thermosetting resin composition of the present invention is a resin composition containing a polyvalent carboxylic acid (A) represented by the above formula (1), a thermosetting resin, and other components as necessary. In the thermosetting resin composition of this invention, the hardening | curing agent for thermosetting resins can be contained as another component. Suitable thermosetting resin curing agent components include trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, Examples thereof include one or more compounds selected from hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and polyvalent carboxylic acids other than polyvalent carboxylic acid (A).

Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl In the presence of hexahydrophthalic anhydride, a cured product having a high crosslinking density can be obtained, so that a cured product having a high glass transition temperature can be obtained. However, carboxylic acids such as trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, and hydrogenated pyromellitic acid anhydride or An acid anhydride has crystallinity and thus has a high softening point or melting point, and a specific melting point is 150 ° C. to 300 ° C., which may cause a problem in molding. On the other hand, since hexahydrophthalic anhydride and methylhexahydrophthalic anhydride have a melting point of not more than room temperature, there may be a problem in molding. Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride, and Among methylhexahydrophthalic anhydrides, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, hydrogenated pyromellitic acid, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahexan anhydride are difficult to color. Hydrophthalic anhydride is preferred, with cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride being more preferred.
Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride. In the present invention, these acid anhydrides may be used in combination, but cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferred.

  In the thermosetting resin composition of the present invention, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic The total of one or more compounds selected from acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride is 1% by weight to 90% by weight in the ratio of the thermosetting resin composition. Preferably there is. If it is lower than 1% by weight, the glass transition temperature is not sufficiently high, and if it is higher than 90% by weight, the melting point becomes high, which may make handling difficult. More preferably, it is 10-60 weight%, More preferably, it is 20-50 weight%.

  Moreover, as polyvalent carboxylic acid other than polyvalent carboxylic acid (A) of this invention which can be contained as a component of the hardening | curing agent for thermosetting resins of this invention, the molecule | numerator represented by following formula (22) is shown. Examples thereof include polyvalent carboxylic acids having an ester structure (preferably two ester structures) and having a plurality of carboxyl groups at the terminals.

(In the formula (22), P is a residue of a polyhydric alcohol having 2 to 20 carbon atoms which may contain 0 to 6 oxygen atoms, nitrogen atoms and phosphorus atoms, and R is an aliphatic having 2 to 20 carbon atoms. Represents a hydrocarbon group, and n and k are 1 to 6 on average, and the total of n is 2 or more and less than 12.
Especially, it is preferable that the polyhydric carboxylic acid of the said Formula (22) is a compound obtained by esterification reaction of C6-C6 or more bifunctional polyhydric alcohol and saturated aliphatic cyclic acid anhydride.

More specifically, in the polyvalent carboxylic acid represented by the formula (22), the linking group R is preferably a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, and the cycloalkane skeleton is substituted or unsubstituted. The cyclohexane structure, particularly the methylcyclohexane structure having a methyl group is preferred from the optical properties of the cured product. The norbornane skeleton is preferably a norbornane or methylnorbornane structure. Here, examples of the substituent that can be applied to the substituted one include an alkyl group having 1 to 3 carbon atoms and a carboxyl group.
The linking group P is a residue of a polyhydric alcohol having 2 to 10 carbon atoms (residue obtained by removing a hydroxyl group from the polyhydric alcohol used in the reaction), and is preferably a branched cross-linking group or a cycloalkyl group. In particular, P is preferably a divalent crosslinking group defined by the following (a) or (b).

(A) a chain alkyl chain having a branched structure having 6 to 20 carbon atoms, the chain alkyl chain having a linear main chain having 3 to 12 carbon atoms and 2 to 4 side chains; And at least one of the side chains has 2 to 10 carbon atoms,
Or
(B) a divalent bridge obtained by removing two hydroxyl groups from at least one bridged polycyclic diol selected from tricyclodecane dimethanol and pentacyclopentadecane dimethanol, which may have a methyl group on the cyclo ring. Group However, when P is (b) and the linking group R is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent R ⁹ represents a group other than a hydrogen atom in the formula (2A) described later. It is more preferable.
In addition, although the softening point of the said polyhydric carboxylic acid is 50 degreeC or more normally, 60 degreeC or more is preferable and 80 degreeC or more is more preferable. Although there is no restriction | limiting in particular in an upper limit, Usually, it is 500 degrees C or less, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 200 degrees C or less.

The particularly preferable polyvalent carboxylic acid can be obtained by addition reaction of a bifunctional or polyfunctional alcohol having 6 or more carbon atoms with a saturated aliphatic cyclic acid anhydride.
These polyvalent carboxylic acids may be a mixture containing two types of polyvalent carboxylic acids. As a method of obtaining a polyvalent carboxylic acid mixture containing at least two polycarboxylic acids, a method of mixing at least two single polycarboxylic acids obtained by the above method, or the above polyvalent carboxylic acid Is added as the above saturated aliphatic cyclic acid anhydride using at least two mixtures selected from the following saturated aliphatic cyclic acid anhydrides or using two kinds of the above polyhydric alcohols There is a method of performing a reaction.

The saturated aliphatic cyclic acid anhydride used for the synthesis of the polyvalent carboxylic acid has a cyclohexane structure, has a methyl group substitution or a carboxyl group substitution on the cyclohexane ring, or is unsubstituted and bonded to the cyclohexane ring And compounds having one or more (preferably one) acid anhydride groups in the molecule.
Specifically, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride And at least one acid anhydride selected from the group consisting of hydrogenated pyromellitic acid anhydride.

Specifically, the bifunctional or polyfunctional alcohol having 6 or more carbon atoms used for the synthesis of the above polyvalent carboxylic acid is specifically a polyvalent alcohol in which a hydroxyl group is attached to the terminal of the crosslinking group P in the formula (21). Carboxylic acid can be mentioned.
In the formula (21), the crosslinkable group represented by P is preferably a divalent crosslinkable group defined by the above (a) or (b), which will be specifically described below.
The divalent crosslinking group defined in (a) above is a divalent chain alkyl chain obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure having 6 to 20 carbon atoms. This is a structure having an alkyl chain sandwiched between two alcoholic hydroxyl groups as a main chain and an alkyl chain (referred to as a side chain) branched from the alkyl chain. The side chain may be branched from any carbon atom constituting the main chain, and includes, for example, a case where the side chain is branched from a carbon atom to which an alcoholic hydroxyl group is bonded (terminal carbon atom of the main chain). Any crosslinking group having such a structure may be used, and a specific example of such a crosslinking group is shown in the following formula (a1).

In the above formula, it is bonded to oxygen atoms on both sides of P in the formula (21) with * mark.
The alkylene bridging group defined in (a) is not particularly limited as long as it has a structure having an alkyl branched chain (side chain) with respect to the main chain alkylene group, but the main chain has 3 or more carbon atoms in the main chain. In particular, those having at least one alkyl side chain are preferred, and those having two or more alkyl side chains are particularly preferred. More preferable examples include a straight-chain main chain having 3 to 12 carbon atoms and a cross-linking group having 2 to 4 side chains and at least one of the side chains having 2 to 10 carbon atoms. Can do. In this case, a crosslinking group in which at least two of the side chains have 2 to 10 carbon atoms is more preferable. Moreover, it is preferable that the 2-4 side chain is branched from the carbon atom from which a principal chain differs.
More specific examples of the compound include a compound in which a hydroxyl group is bonded to the position of * in the crosslinking group described in the formula (a1).
Among the polyhydric alcohols used as raw materials, polyhydric alcohols having at least two side chains and at least two of which are side chains having 2 to 4 carbon atoms are preferred.
Among such skeletons, particularly preferred polyhydric alcohols include 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-1,3- Examples include hexanediol, and particularly 2,4-diethyl-1,5-pentanediol.

  Examples of the crosslinking group defined by (b) include a divalent group represented by the following formula (b1).

  In the case of the crosslinking group defined in (b) above, the crosslinked polycyclic diol residue is a diol residue having a tricyclodecane structure or a pentacyclopentadecane structure as the main skeleton, and is represented by the following formula (b2). Is done.

In the formula, a plurality of R ⁸ each independently represents a hydrogen atom or a methyl group. Among these, a bridging group in which all R ⁸ are hydrogen atoms is preferable.
Specific examples include tricyclodecane dimethanol, methyl tricyclodecane dimethanol, and pentacyclopentadecane dimethanol.

The reaction between the acid anhydride and the polyhydric alcohol is generally an addition reaction using an acid or a base as a catalyst, but in the present invention, a reaction without a catalyst is particularly preferable.
When using a catalyst, examples of the catalyst that can be used include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, hydroxide Metal hydroxides such as potassium, calcium hydroxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7 -Heterocyclic compounds such as ene, imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethyl Ammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, A quaternary ammonium salt such as trioctylmethylammonium acetate can be used. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

Although there is no restriction | limiting in particular in the usage-amount of a catalyst, It is preferable to use 0.001-5 weight part normally as needed with respect to 100 weight part of total weight of a raw material.
In this reaction, a reaction without a solvent is preferable, but an organic solvent may be used. The amount of the organic solvent used is 0.005 to 1 part by weight, preferably 0.005 to 0.7 part, based on 1 part of the total amount of the acid anhydride and the polyhydric alcohol as reaction substrates. More preferably, it is 0.005-0.5 part (namely, 50 weight% or less). When the amount of the organic solvent used exceeds 1 part by weight with respect to 1 part by weight of the reaction substrate, it is not preferable because the progress of the reaction becomes extremely slow. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, diethyl ether , Ethers such as tetrahydrofuran and dioxane, and ester compounds such as ethyl acetate, butyl acetate and methyl formate can be used.

  This reaction proceeds sufficiently even at a temperature of about 20 ° C. From the problem of reaction time, the reaction temperature is preferably from 30 to 200 ° C, more preferably from 40 to 200 ° C, particularly preferably from 40 to 150 ° C. In particular, when this reaction is carried out in the absence of a solvent, the reaction at 100 ° C. or lower is preferred, and the reaction at 30 to 100 ° C. or 40 to 100 ° C. is particularly preferred because of the volatilization of the acid anhydride.

The reaction ratio between the acid anhydride and the polyhydric alcohol is theoretically preferably equimolar, but can be changed as necessary.
Specifically, the charge ratio of the two at the time of the reaction is 0.001 to 2 equivalents in terms of the functional group equivalent, and 1 equivalent of the acid anhydride group, the polyhydric alcohol in terms of the hydroxyl equivalent. It is preferable to charge at a ratio of preferably 0.01 to 1.5 equivalents, more preferably 0.1 to 1.2 equivalents.
In the present invention, the polyvalent carboxylic acid obtained is preferably solid, and in order to obtain a solid resinous polyvalent carboxylic acid, ideally, an equimolar equivalent or more of polyhydric alcohol is preferably used. However, fluidity becomes important because the filler is added, and in order to secure this fluidity, some balance may be lost in the range where the solid is maintained (softening point 50 ° C. or higher) from the viscosity balance.
Specifically, the equivalent ratio of the alcoholic hydroxyl group to the acid anhydride equivalent is preferably 0.85 to 1.20 molar equivalent, particularly preferably 0.90 to 1.1.0 molar equivalent.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a large amount of energy. An excessively short reaction time means that the reaction is abrupt and is not preferable from the viewpoint of safety. The preferred range is 1 to 48 hours, preferably 1 to 36 hours, more preferably 1 to 24 hours, and still more preferably about 2 to 10 hours.

  When a catalyst is used after completion of the reaction, the catalyst is removed by neutralization, water washing, adsorption, etc., and the solvent is distilled off to obtain the desired polyvalent carboxylic acid. On the other hand, when the reaction is carried out without a catalyst, the target polyvalent carboxylic acid can be obtained by distilling off the solvent as necessary. Moreover, when a solvent is used, the target polyvalent carboxylic acid is obtained by removing the solvent. Further, in the case of no solvent and no catalyst, the desired polycarboxylic acid can be obtained by taking it out as it is.

  The most preferable production method is a method in which the acid anhydride and the polyhydric alcohol are reacted at 40 to 150 ° C. under non-catalytic conditions to remove the solvent and then taken out.

The polyvalent carboxylic acid thus obtained or the mixture containing the polyvalent carboxylic acid usually shows a colorless to pale yellow solid resinous form (which may crystallize in some cases). The softening point of the polyvalent carboxylic acid is preferably 50 to 190 ° C, more preferably 55 to 150 ° C, and particularly preferably 60 to 120 ° C. By mixing the polyvalent carboxylic acid having such a softening point directly into the thermosetting resin composition without making it into a liquid, it has an extremely high reflectance retention, and even when subjected to a heat resistance test It is possible to provide a reflecting member that is less likely to decrease.
Usually, when the crosslinking group is an alkylene group having a side chain defined by (a), it shows a colorless to pale yellow solid resinous form.
In the present invention, since the optimum method of using such a thermosetting resin composition containing a polyvalent carboxylic acid is transfer molding, the polyvalent carboxylic acid is in the form of a solid resin.
In the case where the bridging group is a bridging group defined by (b), when the aliphatic hydrocarbon group is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, all of the alicyclic substituents contain many hydrogen atoms. Divalent carboxylic acids are colored during curing and are not suitable for particularly severe optical applications. When the aliphatic hydrocarbon group is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, such a coloring is less in a compound having a methyl group or a carboxyl group, and the optical characteristics are improved.

Also in the compound of the crosslinking group defined in (a) above, when the aliphatic hydrocarbon group is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent is a compound having a methyl group or a carboxyl group. This is preferable because optical characteristics are improved.
That is, when such a polyvalent carboxylic acid mixture includes a polyvalent carboxylic acid having a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent is preferably a formula having a methyl group or a carboxyl group, or both. The mixture containing polyvalent carboxylic acid (22) is preferred. In the case of a polyvalent carboxylic acid mixture containing two or more of the polyvalent carboxylic acids, at least the polyvalent carboxylic acid of the formula (22) in which the substituent is not a hydrogen atom (the substituent is the alkyl group, preferably a methyl group, or A mixture containing 50 mol% or more of the polyvalent carboxylic acid having a carboxyl group) with respect to the total amount of the polyvalent carboxylic acid is preferable. More preferably, a polyvalent carboxylic acid mixture containing 70 mol% or more, most preferably 90 mol% or more of the polyvalent carboxylic acid of the formula (22) in which the substituent is not a hydrogen atom is preferable. The balance is a polyvalent carboxylic acid of the following formula (2A) in which R ³ is a hydrogen atom.
In the thermosetting resin composition of the present invention, a polyvalent carboxylic acid represented by the following formula (2A) is used as a suitable polyvalent carboxylic acid other than the polyvalent carboxylic acid of the present invention.

(In the above formula, P represents the same meaning as described above, and R ⁹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group.)
Here, in the above formula (2A), reasons as described above, R ⁹ is preferably used an alkyl group or a carboxyl group having 1 to 3 carbon atoms.
The terminal carboxylic acid oligoester is preferably a polyvalent carboxylic acid having a number average molecular weight Mn of 300 or more.

  Furthermore, in the thermosetting resin composition of the present invention, the polyvalent carboxylic acid represented by the above formula (1) and trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic Functional group in one or a mixture of two or more compounds selected from acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride The equivalent weight is 250 g / eq. Or less, preferably 240 g / eq. The following is more preferable. By being in this range, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride The effect of the compound amount of one or more compounds selected from hexahydrophthalic anhydride and methylhexahydrophthalic anhydride is effectively exhibited, and a cured product having excellent heat resistance can be obtained.

  The weight ratio of the polyvalent carboxylic acid represented by the above formula (1): (trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic 99, 1 to 10:90 of one or more compounds selected from acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride) It is preferably 90:10 to 20:80, more preferably 80:20 to 50:50. By being in the said ratio, while being extremely excellent in heat resistance, it becomes possible to fully knead | knead low viscosity, Therefore It becomes a thermosetting resin composition excellent also in cured | curing physical property.

  In addition, the polyvalent carboxylic acid (A) represented by the above formula (1), trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, Heat containing a curing agent for thermosetting resin containing one or more compounds selected from pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride In the curable resin composition, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, Selected from hexahydrophthalic anhydride and methylhexahydrophthalic anhydride One or more compound preferably accounts for 1% to 90% by weight of the thermosetting resin composition. By being the said weight%, kneadability and moldability improve more and it becomes a thermosetting resin composition which is excellent also in hardened | cured material property.

  Examples of the curing agent that can be used in combination include an amine compound, an acid anhydride compound having an unsaturated ring structure, an acid anhydride having an organosiloxane skeleton, an amide compound, a phenol compound, and a carboxylic acid compound. . Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and phthalic anhydride, pyromellitic anhydride. Acid, 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, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol Diol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone , Resorcinol, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene , Dihydroxynaphthalene, etc.) 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'-bis (chloromethyl) benzene, 1,4'-bis Examples include polycondensates with (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, and condensates of terpenes and phenols. However, it is not limited to these. These may be used alone or in combination of two or more.

  The thermosetting resin composition in the present invention is a composition containing a thermosetting resin such as an epoxy resin, a phenol resin, a urea resin, a melamine resin, and an unsaturated polyester resin. In the present invention, the epoxy resin It is desirable to use

  As an epoxy resin, if it is normally mix | blended as a conventional thermosetting resin composition or an epoxy resin composition, it can be used without a restriction | limiting in particular. For example, epoxidized phenol and aldehyde novolac resins such as phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted bisphenol, Glycidylamine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin, alicyclic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, diglycidyl isocyanurate, triglycidyl isocyanate Examples thereof include nurate and silsesquioxane compounds, and these may be used alone or in combination of two or more. Among these epoxy resins, those having high heat resistance are preferable. Specifically, from the viewpoints of melt viscosity, coloring of the cured product and glass transition temperature, glycidyl ether type epoxy resin, alicyclic epoxy A resin, triglycidyl isocyanurate is preferred.

  Epoxy resin, polyvalent carboxylic acid (A) of the present invention, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride , A hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and one or more compounds selected from methylhexahydrophthalic anhydride are included in the epoxy resin. The active group (acid anhydride group or hydroxyl group) in the curing agent for thermosetting resin capable of reacting with the epoxy group is 0.5 to 1.5 equivalents (one functional group of carboxylic acid) The acid anhydride is considered to be monofunctional), 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, in any case, curing may be incomplete and good cured properties may not be obtained, and coloration is likely to occur. There is also a problem.

If necessary, a curing accelerator can be added to the curable resin composition of the present invention. Examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 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′-methylimidazole (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-dihydroxymethylimidazole , 2-phenyl-4-hydroxymethyl-5-methylimidazole, various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid , Salts with polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo [5.4.0] undecene-7 Diaza compounds such as tetraphenylborate, Salts such as enol novolak, salts with the above polyvalent carboxylic acids or phosphinic acids, quaternary ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, hexadecyltrimethylammonium hydroxide (preferably C1-C20 alkylammonium salts, phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol Metal compounds such as amine adducts, tin octylate, zinc octoate, zinc stearate, copper naphthenate, cobalt naphthenate, and the like, and Microcapsule type curing accelerator or the like of these curing accelerators to the microcapsules and the like. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. In the present invention, preferred are phosphonium compounds (more preferably quaternary phosphonium) and zinc stearate. Examples of quaternary phosphonium products available from the market include PX-4ET and PX-4MP (both manufactured by Nippon Chemical Industry Co., Ltd.).
A hardening accelerator is 0.001-15 weight part normally with respect to 100 weight part of epoxy resins, Preferably it is used in 0.01-5 weight part.

  If necessary, as additives other than those mentioned above, generally used additives for epoxy resins, such as dyes, fluorescent whitening agents, reinforcing materials, fillers, white pigments or other pigments, nucleating agents , Surfactants, plasticizers, viscosity modifiers, fluidity modifiers, flame retardants, antioxidants, ultraviolet absorbers, and light stabilizers may be added.

Examples of the filler include, but are not limited to, crystalline silica, fused silica, antimony oxide, titanium oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, and alumina. These may be used alone or in combination of two or more.
The blending amount of the inorganic filler is preferably 1 to 1000 parts by weight, and more preferably 1 to 800 parts by weight with respect to 100 parts by weight of the total amount of the curable resin composition.

Although it does not specifically limit as a white pigment mentioned above, For example, an alumina, magnesium oxide, antimony oxide, titanium oxide, a zirconium oxide, a zinc oxide, basic zinc carbonate, a kaolin, a calcium carbonate etc. can be used. The white pigment may be a hollow particle. Moreover, you may surface-treat with a silicon compound, an aluminum compound, organic substance etc. suitably with respect to a white pigment. These may be used alone or in combination of two or more. Moreover, it is preferable that the average particle diameter of the said white pigment exists in the range of 0.01-50 micrometers. If it is less than 0.01 μm, the particles tend to aggregate and the dispersibility tends to be poor, and if it exceeds 50 μm, the reflective properties of the cured product tend to be insufficient. The average particle diameter can be measured using, for example, a laser diffraction / scattering particle size distribution meter. In the present invention, it is preferable to use a powder of titanium oxide, particularly titanium dioxide. This is because whiteness, light reflectivity, and hiding power are high, dispersibility stability is excellent, and availability is easy. The crystal form of titanium oxide is not particularly limited, and may be a rutile type, anatase type, or a mixture of both, but the anatase type has a photocatalytic function and deteriorates the resin. In the present invention, the rutile type is preferable. For example, CR-95 (Ishihara Sangyo Co., Ltd. titanium oxide) etc. are mentioned as a product available from a market.
Moreover, content of a white pigment is 10 to 95 weight% with respect to the whole resin composition, More preferably, it is the range of 50 to 95%. If the total content is less than 10% by weight, the light reflection characteristics of the cured product tend not to be obtained sufficiently, and if it exceeds 95% by weight, the moldability of the resin composition tends to be poor and it becomes difficult to produce a substrate. It is in.

It is desirable that the melt viscosity of the thermosetting resin curing agent under high temperature conditions during molding is higher than that of a conventional acid anhydride curing agent or the like. Specifically, it is 0 at a molding temperature range of 100 ° C. to 200 ° C. It is desirable to set it to 0.01 Pa · s to 10 Pa · s. If it is less than 0.01 Pa · s, burrs are likely to occur. On the other hand, when it is larger than 10 Pa · s, the productivity is lowered.
In the present embodiment, the ICI viscosity of the thermosetting resin curing agent at 150 ° C. is preferably 0.01 Pa · s to 10 Pa · s, and more preferably 0.05 Pa · s to 5 Pa · s. .

  The softening point is desirably in the range of 20 ° C to 150 ° C. More specifically, it is preferably in the range of 30 ° C to 130 ° C, and more preferably in the range of 40 ° C to 120 ° C.

The glass transition temperature of the cured product is desirably higher than the molding temperature. When the glass transition temperature of the cured product is lower than the molding temperature, the cured product in the mold is in a low elastic rubber state, so the rubber-like cured product will be taken out of the mold, and when the ejector is pushed in There is a risk of malfunction due to deformation. Specifically, the glass transition temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
Here, in this invention, 150 degreeC or less is preferable and, as for the glass transition temperature of hardened | cured material, 140 degreeC or less is more preferable.

  The thermosetting resin composition of the present invention can be obtained by uniformly dispersing and mixing the various components described above. Although the method is not particularly limited, a method in which various components are sufficiently uniformly stirred and mixed by a mixer or the like and then kneaded or melt-kneaded by a mixing roll, an extruder, a kneader, a roll, an extruder, or the like, cooled, and pulverized. Can be mentioned. The conditions for kneading or melt-kneading may be determined according to the type and blending amount of the components, and are not particularly limited. When the kneading temperature is less than 20 ° C., the dispersibility of each component is lowered and it is difficult to sufficiently knead. When the kneading temperature is higher than 100 ° C., the crosslinking reaction of the resin composition proceeds and the resin composition There is a risk that things will harden.

  It is desirable that the thermosetting resin composition of the present invention is capable of being pressure (tablet) molded at room temperature of 0 to 30 ° C. before heat molding. For example, a method of performing pressure molding under conditions of about 0.01 to 10 MPa and about 1 to 5 seconds can be mentioned. In addition, the mold used at the time of pressing (tablet) molding is not particularly limited, and for example, it is composed of a vertical mold (upper mold) and a mortar mold (lower mold) made of a ceramic material, a fluorine resin material, or the like. It is preferable to use what is used.

  The thermosetting resin composition of the present invention is useful in applications such as optical semiconductor sealing materials and optical semiconductor reflectors that require high glass transition temperatures and high transmittance.

  When used for light reflection, the production method is not particularly limited. For example, it is preferable to produce the thermosetting resin composition of the present invention by transfer molding. The thermosetting resin composition of the present invention is poured into a mold and, for example, is cured from 60 to 800 seconds under conditions of a mold temperature of 150 to 190 ° C. and a molding pressure of 2 to 20 MPa. Heat cure at a curing temperature of 150 ° C. to 180 ° C. for 1-3 hours.

  In the optical semiconductor device of the present invention, a specific example of a typical structure is illustrated. As described in International Publication No. 2012/124147, a light reflection preventing member having a cylindrical hollow portion is disposed on a substrate, and a cylinder is formed. An optical semiconductor element is disposed on the substrate in the internal space of the hollow shape. And the one end part and board | substrate of an optical semiconductor element are connected with the wire, and it has the structure by which sealing resin was enclosed with the said hollow part.

  In the present specification, ratios, percentages, parts, weights and the like are based on mass unless otherwise specified. In the present specification, the expression “X to Y” indicates a range from X to Y, and the range includes X and Y.

  Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples.

-Liquid polyvalent carboxylic acid (A), wherein R ⁶ in the formula (1) is an organic group containing a carboxyl group represented by formula (8) wherein R ^2a is a methyl group Example implemented as composition (C)-
Each physical property value in Synthesis Examples and Examples was measured by the following method. Here, a part represents a mass part unless otherwise specified.

○ GPC: GPC was measured under the following conditions.
Various conditions of GPC Manufacturer: Waters column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2)
Flow rate: 0.4 ml / min.
Column temperature: 40 ° C
Solvent used: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

○ Acid value: measured by the following method.
About 0.15 g of a sample is weighed and dissolved in 20 ml of methyl ethyl ketone and 20 ml of ethanol, and then titrated with a 0.1N sodium hydroxide solution using a titration device AT-610 manufactured by Kyoto Electronics Industry, and the acid value is measured. did.
○ Functional group equivalent: Measured by the following method.
About 0.15 g of the polyvalent carboxylic acid composition was weighed and dissolved in 40 ml of methanol (special grade reagent), and then stirred at 20 to 28 ° C. for 10 minutes to obtain a measurement sample. The measurement sample was titrated with a 0.1N sodium hydroxide solution using a titrator AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., and the value obtained as the acid value was calculated as the functional group equivalent.

○ Melting point using DSC:
It was measured by the method described in JIS K7121, and the peak of the melting peak was defined as the melting point.
Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
○ Decrease in thermal weight: Using TG / DTA6200 manufactured by Shimadzu Corporation, the temperature was increased from 30 ° C. at 20 ° C./min, heated to 120 ° C., and the weight decrease rate after holding at 120 ° C. for 60 minutes was measured. During measurement, 200 ml / min. Air was blown on.

Example 1: Production of polyvalent carboxylic acid (A-1) 26.1 g of tris (2-hydroxyethyl) isocyanurate with a nitrogen purge in a 500 ml separable flask made of glass 4-methylhexahydrophthalic acid) (52.1 g) and toluene (70 g) were charged, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 115 ° C., and the reaction was allowed to proceed for 7 hours.
The obtained reaction liquid was concentrated under reduced pressure at 100 ° C., and toluene was distilled off to obtain 71.5 g of a polyvalent carboxylic acid (A-1) having the following formula (23) as a main component. The obtained compound had a GPC purity (GPC area%) of 92%, an acid value of 203.4 mgKOH / g, and a white solid in appearance. The melting point (peak peak value) using DSC was 57.0 ° C., and the thermal weight loss was −3.4%. A GPC chart of the obtained compound is shown in FIG.

Example 2: Production of polyvalent carboxylic acid composition (C-1) 26.1 g of tris (2-hydroxyethyl) isocyanurate and Rikacid MH-T (Shikoku Chemicals) while purging nitrogen in a glass 500 ml separable flask Industrial-use 4-methylhexahydrophthalic anhydride (123.4 g) was charged, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 78 ° C., and the reaction was allowed to proceed for 4 hours. A peak of 1 area% or less of tris (2-hydroxyethyl) isocyanurate was confirmed by GPC, and 147 g of a polyvalent carboxylic acid composition (C-1) which is a mixture of a polyvalent carboxylic acid and a carboxylic acid anhydride compound was obtained. It was. The obtained mixture is a colorless and transparent liquid, and the purity by GPC is 59.5 area% of the polyvalent carboxylic acid (A-1) represented by the above formula (23), and is represented by the following formula (24). 4-methylhexahydrophthalic acid was 1.3 area%, and 4-methylhexahydrophthalic anhydride was 39.3 area%. The functional group equivalent was 206 g / eq, the viscosity was 32154 mPa · s, and the thermal weight loss was −20.8%.

Example 3 Production of Polyvalent Carboxylic Acid Composition (C-2) In a polypropylene container, 20 g of the polycarboxylic acid composition (C-1) obtained in Example 2 and Ricacid MH-T (Shikoku Chemical Industries) (Production 4-methylhexahydrophthalic acid) 6.67 g was charged and mixed with a case to obtain 26.6 g of a polyvalent carboxylic acid composition (C-2). The obtained mixture was a colorless and transparent liquid, and the purity by GPC was 46.2 area% of polycarboxylic acid ((A-1) represented by the above formula (23)), 4-methylhexahydrophthalic acid. (Formula (24)) was 3.9 area%, and 4-methylhexahydrophthalic anhydride was 49.9 area%. The functional group equivalent was 187 g / eq, the viscosity was 24678 mPa · s, and the thermal weight loss was −31.7%.

Example 4 Production of Polyvalent Carboxylic Acid Composition (C-3) In a glass 50 ml bottle, 3 g of the polyvalent carboxylic acid (A-1) obtained in Example 1 and Ricacid MH-T (manufactured by Shikoku Chemicals) 4-methylhexahydrophthalic acid) 7 g was charged and heated in an oven heated to 80 ° C. After 2 hours, the mixture was taken out and mixed well with a bowl, and further heated for 2 hours to obtain 10 g of a polycarboxylic acid composition (C-3). The obtained polyvalent carboxylic acid composition (C-3) is a colorless and transparent liquid, and the purity by GPC is 34.3 when the polyvalent carboxylic acid ((A-1) represented by the above formula (23)) is 34.3. Area%, 4-methylhexahydrophthalic acid was 2.6 area%, and 4-methylhexahydrophthalic anhydride was 63.1 area%. The functional group equivalent was 187 g / eq, the viscosity was 1884 mPa · s, and the thermal weight loss was −28.2%.

Comparative Example 1: Dissolution test of polycarboxylic acid having isocyanuric acid skeleton in carboxylic anhydride compound 3 g of isocyanuric acid tris (3-carboxypropyl) represented by the following formula (25) in a glass 50 ml bottle, Ricacid 7 g of MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Kasei Kogyo) was charged and heated in an oven heated to 80 ° C. After 2 hours, the mixture was taken out and mixed well with a bottle. After adding a rotator to a glass bottle and heating on a magnetic stirrer heated to 90 ° C. for 5 hours with stirring, tris (3-carboxypropyl) isocyanurate was found to be ricacid. It did not dissolve in MH-T. When stirring was stopped and it confirmed after 15 hours in room temperature (25 degreeC) environment, isocyanuric-acid tris (3-carboxypropyl) had precipitated.

(Evaluation test)
The polyvalent carboxylic acid obtained in Example 1, Examples 2 to 4, the polyvalent carboxylic acid composition obtained in Comparative Example 1, and 4-methylhexahydrophthalic anhydride (Shin Nippon Rika Co., Ltd.) as Comparative Example A Table 1 summarizes the measurement results of content of each component, acid value or functional group equivalent, viscosity, and thermogravimetric decrease of Rikacid MH-T).

* Represents area% data on the GPC chart.

  As is clear from the results in Table 1, the polyvalent carboxylic acid composition (C-1 to C-3) containing the polyvalent carboxylic acid (A-1) and the polyvalent carboxylic acid (A-1) is heated. In contrast, the 4-methylhexahydrophthalic anhydride of Comparative Example A has a large weight loss. Moreover, although the comparative example 1 became a cloudy liquid and precipitation was confirmed when it was left to stand, since a polyhydric carboxylic acid composition (C-1 to C-3) is a colorless and transparent liquid, it should be used especially in liquid form. Suitable for use in applications where

Example 5: Preparation of epoxy resin composition Polyvalent carboxylic acid composition (C-1) obtained in Example 2, 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (epoxy resin) (Daicel Co., Ltd., CEL2021P), zinc octylate as a curing accelerator is put in a polypropylene container at the quantitative ratio shown in Table 2 below, mixed and degassed for 5 minutes to obtain the epoxy resin composition of the present invention. Obtained.

Example 6: Preparation of epoxy resin composition Except that the polyvalent carboxylic acid composition (C-1) of Example 5 was changed to the polyvalent carboxylic acid composition (C-2) obtained in Example 3. It carried out similarly to Example 5 and obtained the epoxy resin composition of this invention.

Example 7: Preparation of epoxy resin composition The same procedure as in Example 5 was carried out except that the zinc octylate of Example 5 was changed to a quaternary phosphonium bromide salt curing accelerator U-CAT5003 (manufactured by San Apro). An epoxy resin composition of the present invention was obtained.

Example 8: Preparation of epoxy resin composition The polyvalent carboxylic acid composition (C-1) of Example 5 was changed to the polyvalent carboxylic acid composition (C-2) obtained in Example 3, and octyl was used. The epoxy resin composition of the present invention was obtained in the same manner as in Example 5 except that the zinc acid was changed to a quaternary phosphonium bromide salt curing accelerator U-CAT5003 (manufactured by San Apro).

Comparative Example 2 Preparation of Epoxy Resin Composition Ricacid MH-T (manufactured by Nippon Kayaku Co., Ltd., 4-methylhexahydrophthalic anhydride) as an epoxy resin curing agent, 3 ′, 4′-epoxycyclohexylmethyl 3 as an epoxy resin , 4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, CEL2021P), and zinc octylate as a curing accelerator are placed in a polypropylene container at a quantitative ratio shown in Table 2 below, mixed, and degassed for 5 minutes. The epoxy resin composition of the comparative example was obtained.

Comparative Example 3 Preparation of Epoxy Resin Composition The same procedure as in Comparative Example 2 was performed except that the zinc octylate of Comparative Example 2 was changed to a quaternary phosphonium bromide salt curing accelerator U-CAT5003 (manufactured by San Apro). The epoxy resin composition of the comparative example was obtained.

Example 5-8, the compounding ratio and the viscosity of the epoxy resin composition obtained in Comparative Examples 2 and 3, the weight reduction at the time of curing, the cured product transmittance, the hardness of the cured product, the result of the presence or absence of gold wire exposure Is shown in Table 2. The test in Table 2 was performed as follows.
(1) Viscosity Using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd., the viscosity was measured at 25 ° C.
(2) Weight reduction during curing After the epoxy resin compositions obtained in Examples 5 to 8 and Comparative Examples 2 and 3 were vacuum degassed for 5 minutes, the mass was weighed in advance, 30 mm × 20 mm × high The glass was gently cast on a glass substrate on which a dam was created with a heat-resistant tape so that the thickness was 0.8 mm, and the mass after casting was weighed. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour, the mass after curing was weighed, and the weight reduction rate upon curing was calculated.

(3) Cured product transmittance Heat-resistant tape so that the epoxy resin compositions obtained in Examples 5 to 8 and Comparative Examples 2 and 3 were subjected to vacuum defoaming for 5 minutes and then 30 mm × 20 mm × height 0.8 mm The mold was gently cast on the glass substrate on which the dam was created. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained test piece was taken out from the glass substrate, and the light transmittance at 400 nm was measured under the following conditions.
<Spectrophotometer measurement conditions>
Manufacturer: Hitachi High-Technologies Corporation Model: U-3300
Slit width: 2.0nm
Scan rate: 120 nm / min (4) Hardness of cured product The durometer hardness was measured by the method described in JIS K6253.
(5) Gold wire exposure The epoxy resin compositions obtained in Examples 5 to 8 and Comparative Examples 2 and 3 were vacuum degassed for 5 minutes, filled into a syringe, and a light emission wavelength of 450 nm using a precision discharge device. A light-emitting element having a surface-mounted LED using a gold wire (2.3 × 0.4 mm opening, 0.4 mm deep, the top of the gold wire being 0.1 mm from the opening The mold was cast so that the opening was a flat surface. After pre-curing at 120 ° C. for 1 hour, it was cured at 150 ° C. for 3 hours to seal the surface-mounted LED. Visual evaluation of the presence or absence of gold wire exposure (the upper end of the gold wire is above the uppermost surface of the cured product and not completely sealed) due to the volatilization of the curing agent after sealing in this way did. In the table, A: gold wire is not exposed, B: gold wire is exposed.

* The cured product was brittle and could not be removed from the glass substrate.

  As is apparent from the results in Table 2, the compositions of Examples 5 to 8 have an appropriate viscosity for use as an LED encapsulant, and are excellent in workability with little decrease in thermal weight during curing. Furthermore, those cured products have high cured product transmittance and hardness, and there was no exposure of gold wires of the surface-mounted LED sealed with them, whereas only 4-methylhexahydrophthalic anhydride was used. In Comparative Examples 2 and 3 cured with 1, the weight loss during curing was remarkable, and the exposure of the gold wire was confirmed. From the above, the epoxy resin composition using the polyvalent carboxylic acid composition of the present invention is particularly suitable as a curable resin composition for optical semiconductor encapsulation.

-R ⁶ in the formula (1) is a polyvalent carboxylic acid (A) that is an organic group containing a carboxyl group represented by the formula (9) in which R ^2b is an ethylene group and a propylene group. Example carried out as a divalent carboxylic acid composition (C)
In the synthesis examples and examples, GPC, acid value, functional group equivalent, viscosity, and thermogravimetric decrease were measured by the same method as described above. Here, a part represents a mass part unless otherwise specified.

Example 9: Production of polyvalent carboxylic acid (A-2) 26.1 g of tris (2-hydroxyethyl) isocyanurate, 31.0 g of succinic anhydride, methyl isobutyl, while purging nitrogen in a glass 500 ml separable flask 100 g of ketone was charged, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 80 ° C., and the reaction was allowed to proceed for 62 hours.
The obtained reaction solution was concentrated under reduced pressure at 100 ° C., and methyl isobutyl ketone was distilled off to obtain 67.8 g of a polyvalent carboxylic acid (A-2) having the following formula (26) as a main component. The GPC area% of the obtained compound is 90.0% for the compound represented by the formula (26), 2.1% for the multimer of the compound represented by the formula (26), and represented by the formula (27). The compound was 4.6%, succinic anhydride was 0.8%, and succinic acid was 2.6%. The acid value of A-2 was 218.1 mgKOH / g, and the appearance was a pale yellow transparent liquid. The thermogravimetric decrease was -0.6%. The obtained GPC chart of A-2 is shown in FIG.

Example 10: Production of polyvalent carboxylic acid (A-3) 26.1 g of isocyanuric acid tris (2-hydroxyethyl), 35.5 g of glutaric anhydride, 100 g of toluene while performing a nitrogen purge on a glass 500 ml separable flask. Were installed, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 90 ° C., and the reaction was allowed to proceed for 32.5 hours.
The obtained reaction solution was concentrated under reduced pressure at 100 ° C., and toluene was distilled off to obtain 56.7 g of a polyvalent carboxylic acid (A-3) having the following formula (28) as a main component. The GPC area% of the obtained compound was 73.5% for the compound represented by the formula (28), 20.9% for the multimer of the compound represented by the formula (28), and 4.3% for glutaric anhydride. %, Glutaric acid was 1.3%. The acid value of A-3 was 285.6 mgKOH / g, and the appearance was a pale yellow transparent liquid. The thermogravimetric decrease was -0.7%. The GPC chart of the obtained A-3 is shown in FIG.

Example 11: Production of polyvalent carboxylic acid composition (C-10) In a glass 50 ml bottle, 5 g of polyvalent carboxylic acid (A-2) obtained in Example 9 and Ricacid MH-T (manufactured by Shikoku Chemicals) 4-methylhexahydrophthalic anhydride) 5 g was charged and heated in an oven heated to 80 ° C. After 2 hours, the mixture was taken out and mixed well with a bottle, and further heated for 2 hours to obtain 10 g of a polyvalent carboxylic acid composition (C-10). The obtained polyvalent carboxylic acid composition (C-10) is a colorless and transparent liquid, and the GPC area% of the obtained polyvalent carboxylic acid composition (C-10) is represented by the formula (26). 48.8% of the compound, 1.3% of the multimer of the compound represented by the formula (26), 0.3% of the compound represented by the formula (27), 1.4% of succinic anhydride, 4% -Methylhexahydrophthalic anhydride was 48.2%. The functional group equivalent of C-3 was 278 mgKOH / g, the viscosity was 6216 mPa · s, and the thermal weight loss was −19.9%.

Example 12: Production of polyvalent carboxylic acid composition (C-4) In a glass 50 ml bottle, 5 g of polyvalent carboxylic acid (A-3) obtained in Example 10 and Ricacid MH-T (manufactured by Shikoku Kasei Kogyo) 4-methylhexahydrophthalic anhydride) 5 g was charged and heated in an oven heated to 80 ° C. After 2 hours, the mixture was taken out and mixed well with a bowl, and further heated for 2 hours to obtain 10 g of a polycarboxylic acid composition (C-4). The obtained polyvalent carboxylic acid composition (C-4) is a colorless and transparent liquid, and the GPC area% of the obtained polyvalent carboxylic acid composition (C-4) is represented by the formula (28). 40.6% of the compound, 11.5% of the multimer of the compound represented by the formula (28), 3.7% of glutaric anhydride, 0.7% of glutaric acid, 4-methylhexahydrophthalic anhydride It was 43.5%. The functional group equivalent of C-4 was 308 mgKOH / g, the viscosity was 5356 mPa · s, and the thermal weight loss was −24.7%.

Comparative Example 4: Dissolution test of polyvalent carboxylic acid having isocyanuric acid skeleton in carboxylic acid anhydride compound 3 g of isocyanuric acid tris (3-carboxypropyl) represented by the above formula (25) in a glass 50 ml bottle, Ricacid 7 g of MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Kasei Kogyo) was charged and heated in an oven heated to 80 ° C. After 2 hours, the mixture was taken out and mixed well with a bottle. After adding a rotator to a glass bottle and heating on a magnetic stirrer heated to 90 ° C. for 5 hours with stirring, tris (3-carboxypropyl) isocyanurate was found to be ricacid. It did not dissolve in MH-T. When stirring was stopped and it confirmed after 15 hours in room temperature (25 degreeC) environment, isocyanuric-acid tris (3-carboxypropyl) had precipitated.

(Evaluation test)
The polyvalent carboxylic acid obtained in Examples 9 and 10, the polyvalent carboxylic acid composition obtained in Examples 11 and 12 and Comparative Example 4, and 4-methylhexahydrophthalic anhydride (New Japan) as Comparative Example B Table 3 summarizes the measurement results of content of each component, acid value or functional group equivalent, viscosity, and thermogravimetric reduction of Rikashido MH-T.

* Since A-2 and A-3 are highly viscous liquids, the viscosity at 25 ° C. could not be measured.
The component contents of Examples 9 to 12 represent data on area% of GPC.

  As is clear from the results in Table 3, the polyvalent carboxylic acid compositions C-10 and C-4 containing the polyvalent carboxylic acids A-2 and A-3 and the polyvalent carboxylic acids A-2 and A-3, respectively. Has a small weight loss upon heating, whereas 4-methylhexahydrophthalic anhydride of Comparative Example B has a large weight loss. Further, Comparative Example 4 became a cloudy liquid, and precipitation was confirmed by allowing it to stand. However, the polyvalent carboxylic acid compositions C-10 and C-4 and the polyvalent carboxylic acids A-2 and A-3 were colorless and transparent liquids. Therefore, it is particularly suitable for use in applications that are required to be used in liquid form.

Example 13: Preparation of epoxy resin composition Polyvalent carboxylic acid (A-2) obtained in Example 9, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (( Co., Ltd., CEL2021P), and zinc octylate as a curing accelerator in a quantity ratio shown in Table 4 below in a polypropylene container, mixed and degassed for 5 minutes to obtain the epoxy resin composition of the present invention. It was.

Example 14: Preparation of epoxy resin composition Example except that polyvalent carboxylic acid (A-2) of Example 9 was changed to polyvalent carboxylic acid composition (C-10) obtained in Example 11 In the same manner as in No. 13, an epoxy resin composition of the present invention was obtained.

Example 15: Preparation of epoxy resin composition Example 13 except that the polyvalent carboxylic acid (A-2) of Example 13 was changed to the polyvalent carboxylic acid (A-3) obtained in Example 2. It carried out similarly and the epoxy resin composition of this invention was obtained.

Example 16: Preparation of epoxy resin composition Example except that polyvalent carboxylic acid (A-1) of Example 13 was changed to polyvalent carboxylic acid composition (C-4) obtained in Example 12 In the same manner as in No. 13, an epoxy resin composition of the present invention was obtained.

Comparative Example 5: Preparation of Epoxy Resin Composition Ricacid MH-T (manufactured by Nippon Kayaku Co., Ltd., 4-methylhexahydrophthalic anhydride) as an epoxy resin curing agent, 3 ′, 4′-epoxycyclohexylmethyl 3 as an epoxy resin , 4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, CEL2021P), zinc octylate as a curing accelerator, put in a polypropylene container in the quantitative ratio shown in Table 4 below, mixed, defoamed for 5 minutes, The epoxy resin composition of the comparative example was obtained.

Comparative Example 6: Preparation of epoxy resin composition The same procedure as in Comparative Example 5 was conducted except that the zinc octylate of Comparative Example 5 was changed to a quaternary phosphonium bromide salt curing accelerator U-CAT5003 (manufactured by San Apro). The epoxy resin composition of the comparative example was obtained.

  Results of blending ratio and viscosity of epoxy resin compositions obtained in Examples 13 to 16 and Comparative Examples 5 and 6, weight reduction upon curing, cured product transmittance, hardness of cured product, presence or absence of gold wire exposure Is shown in Table 4. The tests in Table 4 were performed as described above.

* The cured product was brittle and could not be removed from the glass substrate.

  As is apparent from the results in Table 4, the compositions of Examples 13 to 16 have an appropriate viscosity for use as an LED encapsulant, and are excellent in workability with little decrease in thermal weight during curing. Furthermore, those cured products have high cured product transmittance and hardness, and there was no exposure of gold wires of the surface-mounted LED sealed with them, whereas only 4-methylhexahydrophthalic anhydride was used. In Comparative Examples 5 and 6, which were cured in step 1, the weight loss during curing was significant, and exposure of the gold wire was confirmed. From the above, the epoxy resin composition using the polyvalent carboxylic acid composition of the present invention is particularly suitable as a curable resin composition for optical semiconductor encapsulation.

-R ⁶ in the formula (1) is an organic group containing a carboxyl group represented by the formula (8) in which R ^2a is a methyl group or a carboxyl group. Example implemented as a curable resin composition-
In the synthesis examples, gel permeation chromatography (hereinafter referred to as “GPC”), ICI viscosity, and softening point were measured as follows.
1) GPC
The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., the detection was performed by RI (Reflective index), and the standard curve made by Shodex was used for the calibration curve. Further, the functional group equivalent was calculated from the ratio calculated from GPC, and the value was determined with 1 equivalent each of carboxylic acid and acid anhydride.
2) ICI viscosity The melt viscosity in the cone plate method at 150 ° C was measured.
3) Softening point It measured by the method according to JIS K-7234.

Synthesis example 1 (curing agent C-5 for thermosetting resin)

To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, isocyanuric acid tris (2-hydroxyethyl) 104.5 parts, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., 201.8 parts of Ricacid MHT) and 306.0 parts of MEK were added, and the mixture was heated and stirred at 70 ° C. for 7 hours to obtain a MEK solution of the compound represented by the formula (29). Thereto, 61.3 parts of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MHT) was added, followed by heating and stirring at 70 ° C. for 1 hour. Thereafter, the solvent was removed at 120 ° C. for 1 hour to obtain a curing agent for thermosetting resin (C-5).
The obtained curing agent was colorless and solid. The functional group equivalent was 232 g / eq. Met. The ICI viscosity was 0.36 Pa · s at 150 ° C. The softening point was 82.9 ° C.

Synthesis example 2 (curing agent C-6 for thermosetting resin)

(In the formula (30), R ¹⁰ represents a methyl group or a carboxyl group. In the formula (30), a plurality of R ¹⁰ may be the same or different.)

To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, 98.1 parts of isocyanuric acid tris (2-hydroxyethyl), methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., (Licacid MHT) 166.3 parts, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd. H-TMAn) 2.0 parts, MEK 266.4 parts were added, and 1 at 60 ° C. After the reaction for 5 hours, a MEK solution of the compound represented by the formula (30) was obtained by heating and stirring at 80 ° C. for 5 hours. There, 59.4 parts of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 80 ° C. for 2 hours. Thereafter, the solvent was removed at 150 ° C. for 1 hour to obtain a thermosetting resin curing agent (C-6).
The obtained curing agent was colorless and solid. The functional group equivalent was 195 g / eq. Met. The ICI viscosity was 0.53 Pa · s at 150 ° C. The softening point was 84.7 ° C.

Synthesis Example 3 (Glycidyl ether type epoxy resin B-1)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated and purged with nitrogen, and then subjected to a nitrogen purge (twice the volume of the kiln capacity / hr), and a phenol compound (TPA1) (TrisP-PA Honshu Chemical Industry) 142 parts, epichlorohydrin 370 parts, methyl glycidyl ether 37 parts and methanol 37 parts were added, and the temperature of the water bath was raised to 75 ° C. When the internal temperature exceeded 65 ° C., 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 400 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 8 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was obtained at 180 ° C. using a rotary evaporator. By distilling off methyl isobutyl ketone and the like under reduced pressure, 182 parts of epoxy resin (B-1) was obtained. The epoxy equivalent of the obtained epoxy resin is 222 g / eq. The softening point was 59.6 ° C., the ICI melt viscosity was 0.10 Pa · s (150 ° C.), and the hue was 0.2 or less (Gardner 40% MEK solution). Mn was 582, Mw was 695, and Mw / Mn was 1.19 (polystyrene conversion). Total chlorine was 960 ppm.

Preparation of resin composition for thermosetting light reflection (Example 17 to Example 19)
TEPIC-S (Nissan Chemical Co., Ltd. triglycidyl isocyanurate), EHPE-3150 (Daicel Chemical Industries, Ltd. alicyclic epoxy resin), Celoxide 2021P (Daicel Chemical Industries, Ltd. alicyclic epoxy resin), Curing agent C-5 for thermosetting resin, curing agent C-6 for thermosetting resin, Ricacid MH-T (curing agent for epoxy resin manufactured by Shin Nippon Chemical Co., Ltd.), Hishikorin PX-4MP (curing manufactured by Nippon Chemical Industry Co., Ltd.) Catalyst 5), each component was blended according to the blending table shown in Table 5 and sufficiently kneaded with a mixer, then melt-kneaded under a predetermined condition with a mixing roll, cooled and pulverized, Example 17 to Example Nineteen thermosetting resin compositions were prepared. In addition, the unit of the compounding quantity of each component in Table 5 is parts by weight, and the blank represents that the component is not used.

Evaluation of Thermosetting Resin Composition With respect to the resin compositions of Examples 17 to 19, the DMA, TMA, and transmittance of the cured products were measured by the methods described below. The results are shown in Table 5.

(A) DMA
For the measurement of viscoelasticity (DMA: Dynamic Mechanical Analysis), DMS6100 viscoelasticity manufactured by SII NanoTechnology Co., Ltd. according to the method described in JIS K7244 and JIS K7244-4 using a test piece prepared as follows. It measured on condition of the following using a measuring apparatus. The glass transition temperature (Tg) indicates the temperature at which the maximum point of the loss coefficient (tan δ = E ″ / E ′) represented by the quotient of the storage elastic modulus (E ′) and the loss elastic modulus (E ″) is shown. .
(DMA test piece preparation method)
The resin composition of each example and each comparative example was subjected to transfer molding under the conditions of a mold temperature of 150 ° C., a molding pressure of 10.4 MPa, and a curing time of 300 seconds, and then post-cured at 150 ° C. for 3 hours to obtain a length. A test piece having a width of 50.0 mm, a width of 5.0 mm, and a thickness of 0.5 mm was produced.
(DMA measurement conditions)
Initial tension: 0.1N
Frequency: 10Hz
Measurement mode: Tensile vibration Measurement temperature: 30 ° C. to 280 ° C.
Temperature increase rate: 2 ° C / min

(B) Thermomechanical analysis (TMA)
Thermomechanical analysis (TMA) was measured under the following conditions using a TMA / SS6100 apparatus manufactured by SII NanoTechnology Co., Ltd. using a test piece prepared as described below. The glass transition temperature (Tg) is defined as the changing point of the linear expansion coefficient of the obtained data.
(TMA test piece preparation method)
The resin composition of each example and each comparative example was transfer-molded under conditions of a mold temperature of 150 ° C., a molding pressure of 10.4 MPa, and a curing time of 300 seconds, and then post-cured at 150 ° C. for 3 hours to obtain a thickness of 4 A test piece of 0.0 mm was produced.
(TMA measurement conditions)
Temperature rise condition: 2 ° C / min Measurement mode: Compression

(D) Transmittance The resin compositions of Examples and Comparative Examples were transfer molded under conditions of a mold temperature of 150 ° C., a molding pressure of 10.4 MPa, and a curing time of 300 seconds, and then post-cured at 150 ° C. for 3 hours. As a result, a test piece having a thickness of 1.0 mm was produced. Subsequently, the transmittance at a wavelength of 460 nm was measured with an integrating sphere spectrophotometer UV-3600 type (manufactured by Shimadzu Corporation), and the coloring of each test piece was evaluated.

  From the above results, the thermosetting resin composition using the curing agent for thermosetting resins of the present invention gives a cured product having a sufficiently high glass transition temperature, a low coefficient of linear expansion, and little coloration of the cured product. I understand that.

Preparation of thermosetting light reflecting resin composition (Examples 20 and 21)
TEPIC-S (triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd.), glycidyl ether type epoxy resin B-1, Hishicolin PX-4MP (curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), CR-95 (oxidized by Ishihara Sangyo Co., Ltd.) Each component was blended according to the blending table shown in Table 6 using titanium), sufficiently kneaded with a mixer, then melt-kneaded under a predetermined condition with a mixing roll, cooled and pulverized. A thermosetting resin composition was prepared. In addition, the unit of the blending amount of each component in Table 6 is part by weight, and the blank indicates that the component is not used.

  From the above results, the thermosetting resin composition using the curing agent for thermosetting resin of the present invention gives a cured product having a sufficiently high glass transition temperature, a low coefficient of linear expansion, and little coloration of the cured product. I understand that.

In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 130.6 parts of tris (2-hydroxyethyl) isocyanurate with nitrogen purge, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., 164.0 parts of Ricacid MHT), 59.9 parts of glutaric anhydride, and 350.0 parts of MIBK were added and stirred for 9 hours at 85 ° C. to obtain a MIBK solution of the target compound. Thereafter, the solvent was removed at 150 ° C. for 1 hour to obtain a curing agent for thermosetting resin (C-7).
The obtained curing agent was colorless and solid. The functional group equivalent was 242 g / eq. Met. The ICI viscosity was 0.51 Pa · s at 150 ° C. The softening point was 77.6 ° C.

Preparation of thermosetting light reflecting resin composition (Example 22)
EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), C-7 for thermosetting resin, Hishicolin PX-4MP (curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), CR-95 (Ishihara Sangyo) Each component was blended according to the blending table shown in Table 7 using Titanium Oxide Co., Ltd., kneaded sufficiently with a mixer, then melt-kneaded under a predetermined condition with a mixing roll, cooled and pulverized. The thermosetting resin composition of Example 22 was prepared. In addition, the unit of the compounding quantity of each component in Table 7 is parts by weight, and the blank represents that the component is not used.

  From the above results, the thermosetting resin composition using the curing agent for thermosetting resins of the present invention gives a cured product having a sufficiently high glass transition temperature, a low coefficient of linear expansion, and little coloration of the cured product. I understand that.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is a Japanese patent application (Japanese Patent Application No. 2014-150862) filed on July 24, 2014, a Japanese patent application (Japanese Patent Application No. 2014-212176) filed on October 17, 2014, This is based on a Japanese patent application filed on December 16, 2014 (Japanese Patent Application No. 2014-254374), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

  The polyvalent carboxylic acid of the present invention and the polyvalent carboxylic acid composition containing the same are less volatile at the time of curing and excellent in curability, and the cured product gives a cured product with excellent transparency and hardness. The used epoxy resin composition is useful for electrical and electronic material applications, particularly for optical semiconductor sealing and as an optical semiconductor reflector. In addition, the polyvalent carboxylic acid of the present invention and the polyvalent carboxylic acid composition containing the same can sufficiently increase the glass transition temperature of the cured product, are excellent in moldability, and less colored to the cured product. The thermosetting resin composition using is useful as a sealing material and a reflective material for semiconductor devices.

Claims (14)

A polycarboxylic acid that is represented by the following formula (1-1),

(In the formula (1-1), ^{R 1} represents an alkylene group having 1 to 6 carbon ^{atoms, R 2a} is in a methyl group. Formula (1-1), there are R ¹ presence of a plurality of respectively identical May be different.)
A carboxylic acid anhydride compound represented by the following formula (6),

The carboxylic acid anhydride is included at a ratio of 10 to 800 parts by mass with respect to 100 parts by mass of the polyvalent carboxylic acid.
Polyvalent carboxylic acid composition.   A polyvalent carboxylic acid represented by the following formula (1-1);

(In formula (1-1), R ¹ Represents an alkylene group having 1 to 6 carbon atoms, and R ^2a Represents a carboxyl group. In formula (1-1), there are a plurality of R ¹ May be the same or different. )
  A carboxylic acid anhydride compound represented by the following formula (7):

  The carboxylic acid anhydride is included at a ratio of 10 to 800 parts by mass with respect to 100 parts by mass of the polyvalent carboxylic acid.
  Polyvalent carboxylic acid composition. An epoxy resin composition comprising the polyvalent carboxylic acid composition according to claim 1 or 2 and an epoxy resin. Furthermore, the epoxy resin composition of Claim 3 containing an epoxy resin hardening accelerator. The epoxy resin composition according to claim 4 , wherein the epoxy resin curing accelerator is a metal soap. The epoxy resin composition according to claim 5 , wherein the metal soap is a zinc carboxylate compound. A cured product obtained by curing the epoxy resin composition according to any one of claims 3-6. The polyvalent carboxylic acid composition according to claim 1 or 2 and a thermosetting resin, wherein the ICI cone plate viscosity is in the range of 0.01 Pa · s to 10 Pa · s in the range of 100 to 200 ° C. A thermosetting resin composition. The thermosetting resin composition according to claim 8 , wherein the softening point is in the range of 20 ° C to 150 ° C. Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl Including a curing agent for a thermosetting resin containing one or more compounds selected from hexahydrophthalic anhydride,
Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl The thermosetting resin composition according to claim 8 or 9 , wherein one or more compounds selected from hexahydrophthalic anhydride occupy 1% to 90% by weight of the total. The glass transition temperature of the cured product (Tg) of at 30 ° C. or higher, the thermosetting resin composition according to any one of claims 8-10. A cured product obtained by thermally curing the thermosetting resin composition according to any one of claims 8-11. An optical semiconductor device sealed with the cured product according to claim 12 . An optical semiconductor device using the cured product according to claim 12 as a reflective material.

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