KR20170048357A - Polycarboxylic acid and polycarboxylic acid composition containing same, epoxy resin composition, thermosetting resin composition, and cured material of same, and optical semiconductor device - Google Patents

Abstract

(식(1) 중, R¹은 탄소수 1~6의 알킬렌기를, R⁶은 수소원자 또는 탄소수 1~10의 카르복실기를 함유하는 유기기를 각각 나타낸다. 식(1) 중, 복수 존재하는 R¹, R⁶은 각각 동일해도 상관없고 달라도 상관없지만, 복수 존재하는 R⁶ 중, 50몰% 이상은 탄소수 1~10의 카르복실기를 함유하는 유기기이다.)The present invention relates to a cured product which is low in volatilization and excellent in curing property at the time of curing, is excellent in transparency and hardness and can sufficiently increase the glass transition temperature of the cured product, An epoxy resin composition, a thermosetting resin composition, a cured product thereof, and a semiconductor device.
The polyvalent carboxylic acid of the present invention is represented by the following formula (1).

(Formula (1) of, R ¹ is an alkylene group having 1 to 6, R ⁶ is a hydrogen atom or represents respectively an organic group containing a carboxyl group having 1 to 10 carbon atoms. In the formula (1), a plurality existence R ¹ to And R ⁶ may be the same or different, but among the plural R ^{6 s} , at least 50 mol% is an organic group containing a carboxyl group having 1 to 10 carbon atoms.)

Description

TECHNICAL FIELD [0001] The present invention relates to a polycarboxylic acid and a polyvalent carboxylic acid composition containing the polycarboxylic acid, an epoxy resin composition, a thermosetting resin composition, a cured product thereof, and a photonic semiconductor device using the polycarboxylic acid composition. MATERIAL OF SAME, AND OPTICAL SEMICONDUCTOR DEVICE}

Particularly, the present invention relates to an optical semiconductor reflective material which is suitable for use in a part where high transparency and low coloring property are required, particularly for optical semiconductor encapsulation and optical semiconductor reflective material, A polyvalent carboxylic acid composition excellent in moldability and a polyvalent carboxylic acid composition containing the same, a thermosetting resin composition, an epoxy resin composition, a cured product obtained by curing the composition, and an optical semiconductor device.

BACKGROUND ART Epoxy resin compositions are resins having excellent heat resistance and are used in fields such as construction, civil engineering, automobiles, and aircraft. In recent years, especially in the field of semiconductor related materials, there are overflow products such as lightweight, thin, short, and small keywords such as mobile phones with a camera, ultra-thin liquid crystal, plasma TV and lightweight notebook computer, Materials have been required to have very high characteristics.

In recent years, attention has been focused on the use in the field related to optoelectronics. In order to smoothly transmit and process vast amounts of information according to high-level informationization, techniques utilizing optical signals instead of conventional signal transmission by electric wiring have been developed In the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, it is desired to develop a resin composition which gives a cured product excellent in transparency.

As the curing agent of the epoxy resin generally used in the field of optoelectronics, an acid anhydride-based compound can be mentioned. Particularly, the acid anhydrides formed from saturated hydrocarbons are often used because the cured products are excellent in light resistance. As these acid anhydrides, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride are typical. Of these, methyltetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride, which are liquid at room temperature, It is mainly used because of easiness.

However, when these alicyclic acid anhydrides are used as curing agents for epoxy resins, these compounds have a high vapor pressure and partly evaporate during curing. Therefore, when these compounds are used as curing agents for epoxy resins and thermally cured in an open system, And volatilize. As a result, the curing of the epoxy resin composition due to the environmental pollution due to the release of harmful substances into the atmosphere, the adverse effect on the human body, the contamination of the production line, and the absence of a predetermined amount of carboxylic anhydride (curing agent) Problems such as failure occur. The deviation of the curing conditions caused by the volatilization of the curing agent becomes a deviation of the physical properties of the cured product, and it becomes difficult to stably obtain a cured product having a desired performance.

In addition, the problem of volatilization is remarkable when an LED, particularly an SMD (Surface Mount Device) is sealed with a curable resin composition for optical semiconductor encapsulation using a conventional acid anhydride as a curing agent, and the amount of resin used is small, , And when the wire is severely exposed, the wire is exposed. Further, there arises a problem that it is difficult to withstand cracking, peeling, and long-term lighting during solder reflow.

On the other hand, a polyvalent carboxylic acid having an isocyanuric ring is known as a curing agent for an epoxy resin in, for example, Patent Document 1. However, it is difficult to dissolve the polyvalent carboxylic acid described in Patent Document 1 in an acid anhydride compound, and thus it has been difficult to apply the polyvalent carboxylic acid in a liquid state at room temperature (25 DEG C).

When the thermosetting resin composition is used as a sealing material for semiconductors or as a reflective material for semiconductors, the light transmittance of the thermosetting resin composition is high because the lightness of the optical semiconductor is lowered when the thermosetting resin composition absorbs the light emitted by the optical semiconductor, And less coloring due to heat. Therefore, a curing agent to be mixed with the thermosetting resin composition is required to have high transmittance and little coloring due to light or heat. From the viewpoints 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 it is important that the softening point and viscosity of the curing agent are also within a certain range from the viewpoint of moldability.

The acid anhydrides used as the curing agent for thermosetting resins are volatile and have a low melting point, which is not suitable for mold formation.

Although tetracarboxylic acid anhydrides are not volatile, they are difficult to handle as a liquid resin composition because they have a high melting point (150 ° C or higher) and are poor in moldability. Therefore, considering the difficulty in use for the purpose of molding a liquid resin, It is not suitable for the use as.

Although an example in which a carboxylic acid is used as a curing agent for an epoxy resin is also known, it has a comparatively high melting point (150 DEG C or more) and has the same problems as those described above. In addition to this, there is a problem that it is very difficult to secure a high transmittance It is not suitable for the intended use.

Likewise, polycarboxylic acid compounds also have a high melting point (150 DEG C or higher), high crystallinity and difficulty in resin kneading, and coloring problems, which can not be used in an intended use.

Therefore, no compound capable of achieving the above object could be found as a conventionally known material.

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

In particular, when the present invention is used for curing in an open system such as an SMD type LED sealing material, the cured product is less volatile at the time of curing and excellent in curing property. The cured product is a polyvalent carboxylic acid which gives a cured product of excellent transparency and hardness, , An epoxy resin composition, and a cured product thereof. In addition, a polyvalent carboxylic acid which can sufficiently increase the glass transition temperature of the cured product, is excellent in moldability and is hardly colored as a cured product, a thermosetting resin composition using the thermosetting resin composition and a semiconductor device using such a thermosetting resin composition as a sealing material or a reflective material to provide.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in view of the above-mentioned circumstances and have found that a polyvalent carboxylic acid having an isocyanuric ring or a polyvalent carboxylic acid composition containing the polyvalent carboxylic acid, an epoxy resin composition containing the polyvalent carboxylic acid or a thermosetting resin composition Has solved the above problems, and has reached the present invention.

That is, the present invention relates to the following [1] to [18].

[1] A polybasic carboxylic acid represented by the following formula (1).

(Formula (1) of, R ¹ is an alkylene group having 1 to 6, R ⁶ is a hydrogen atom or represents respectively an organic group containing a carboxyl group having 1 to 10 carbon atoms. In the formula (1), a plurality existence R ¹ to And R ⁶ may be the same or different, but among the plural R ^{6 s} , at least 50 mol% is an organic group containing a carboxyl group having 1 to 10 carbon atoms.)

[2] A polyvalent carboxylic acid represented by the following formula (1-1) and described in [1].

(In formula (1-1) wherein R ¹ represents the same meanings as defined above, R ^2a represents an alkyl group or a carboxyl group of a hydrogen atom, a group having 1 to 6 carbon atoms, respectively. In the formula (1-1) wherein R ¹ to present a plurality , And R < ^2a > may be the same or different.

[3] The polyvalent carboxylic acid according to [1], which is represented by the following formula (1-2).

(In the formula (1-2), R ¹ has the same meaning as defined above, and R ^2b represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ¹ and R ^2b may be the same or different.

[4] A polybasic carboxylic acid composition containing a polybasic carboxylic acid according to any one of [1] to [3].

[5] The polybasic carboxylic acid composition according to [4] further containing a carboxylic acid anhydride compound.

[6] The polybasic carboxylic acid composition according to [5], wherein the carboxylic acid anhydride compound is at least one selected from the compounds represented by the following formulas (2) to (7).

[7] An epoxy resin composition comprising a polyvalent carboxylic acid according to any one of [1] to [3], or a polyvalent carboxylic acid composition according to any one of [4] to [6], and an epoxy resin.

[8] An epoxy resin composition according to [7], further comprising 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 zinc carboxylate compound.

[11] A cured product obtained by curing the epoxy resin composition according to any one of [7] to [10].

[12] A resin composition comprising the polyvalent carboxylic acid according to any one of [1] to [3] and a thermosetting resin, wherein the ICI cone plate viscosity is in the range of 100 to 200 ° C in the range of 0.01 Pa · s to 10 Pa · s Thermosetting resin composition.

[13] The thermosetting resin composition according to [12], wherein the softening point is in a range of 20 ° C to 150 ° C.

[14] A thermosetting resin composition comprising a thermosetting resin composition comprising trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic anhydride, Further comprising a curing agent for thermosetting resin containing at least one compound selected from the group consisting of phthalic anhydride, phthalic anhydride, and methylhexahydrophthalic anhydride,

But are not limited to, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride , And methylhexahydrophthalic anhydride. The thermosetting resin composition according to [12] or [13], wherein the thermosetting resin composition comprises 1 to 90% by weight of the whole compound.

[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 thermally curing the thermosetting resin composition according to any one of [12] to [15].

[17] A photosemiconductor device sealed with a cured product according to [16].

[18] A photosemiconductor device using the cured product described in [16] as a reflective material.

(Effects of the Invention)

INDUSTRIAL APPLICABILITY According to the present invention, an epoxy resin composition containing a polybasic carboxylic acid having a specific structure and an isocyanuric ring, or a polybasic carboxylic acid composition containing the polybasic carboxylic acid composition has low volatilization during curing and excellent curability, And hardness, it is very useful as a sealing resin for a material which requires high transparency and the formation of a cured product of a thin film, in particular, an optical semiconductor (LED or the like).

Also disclosed is a polyvalent carboxylic acid having a sufficient glass transition temperature, excellent moldability and little discoloration when made into a cured product, a thermosetting resin composition using the same, and an optical semiconductor using the thermosetting resin composition as a sealing material or a reflective material Device can be provided. In addition, by suppressing the softening point, handling is facilitated, and sufficient kneading is enabled, and it is possible to provide a cured product excellent in cured properties. In addition, it is possible to provide a thermosetting resin composition which is also excellent in the toughness of the cured product and the reactivity of the resin.

1 is a GPC chart of the polyvalent carboxylic acid (A-1) obtained in Example 1. Fig.
2 is a GPC chart of the polyvalent carboxylic acid (A-2) obtained in Example 9. Fig.
3 is a GPC chart of the polyvalent carboxylic acid (A-3) obtained in Example 10. Fig.
4 is a GPC chart of the polyvalent carboxylic acid composition (C-8) obtained in Example 23. Fig.

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

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

R ⁶ is an organic group containing a hydrogen atom or a carboxyl group having 1 to 10 carbon atoms. Herein, the organic group is a group consisting of only H, C, N, and O atoms. R ⁶ may have 1 to 10 carbon atoms, and may contain an ester bond, an ether bond, a urethane bond, an amide bond or a carbonyl group.

The organic group containing a carboxyl group having 1 to 10 carbon atoms contains at least one carboxyl group.

In the formula (1), plural R ¹ and R ^{6 present} may be the same or different.

Of the R ^{6 s} present in the formula (1), at least 50 mol% of the R ⁶ present is an organic group containing a carboxyl group having 1 to 10 carbon atoms. And the mechanical strength of the cured product is excellent because it is 50 mol% or more. Further, it is more preferably 70 mol% or more.

As the organic group containing a carboxyl group having 1 to 10 carbon atoms in R ⁶ , organic groups represented by the following formulas (8) and (9) are exemplified.

In formula (8), R ^2a represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, and R ^2b represents a linear or branched alkylene group having 1 to 10 carbon atoms, ) And (*) in (9) are bonded to the oxygen atom in formula (1).

Specific examples of the alkyl group having 1 to 6 carbon atoms in R ^{2 a} include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, , A hexyl group, an isohexyl group, and a cyclohexyl group. From the viewpoint of heat resistance and transparency of the resulting cured product, a methyl group is preferable.

R ^2a is preferably a methyl group or a carboxyl group and that the viscosity of the polyvalent carboxylic acid composition (C) containing the polyvalent carboxylic acid (A) at room temperature (25 ° C) is not excessively elevated and that the transparency of the obtained cured product , The methyl group is preferable, and the carboxyl group is particularly preferable from the viewpoints of gas barrier property, high glass transition temperature (Tg) and hardness of the resulting cured product.

Specific examples of R ^2b include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonynylene group, a decynylene group, an isopropylene group, an isobutylene group, An isopentylene group, an isopentylene group, an isohexylene group, an isononylene group, an isodecylene group, a dimethylpropylene group, a diethylpropylene group, a diethylbutylene group, a diethylpentylene group, a diethylhexylene group Propylene group and diethylpropylene group are preferable from the viewpoint of heat resistance and transparency of the obtained cured product, and the softening point of the polyvalent carboxylic acid (A) of the present invention and the viscosity at room temperature (25 ° C) The propylene group is particularly preferable.

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

(Wherein * has the same meaning as described above.)

The polyvalent carboxylic acid (A) represented by the formula (1) is obtained by reacting an isocyanuric acid trishydroxyalkyl compound represented by the following formula (10) with a carboxylic acid anhydride compound represented by the following formula (14) and / Can be obtained by an addition reaction of a carboxylic acid anhydride compound represented by the formula (15).

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

In the formula (14), R ^2a has the same meaning as described above.

In the formula (15), R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 9, and in the formula (15), plural R ³ groups present may be the same or 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 is an integer of 1 to 9 and is preferably 1 to 5, particularly preferably 1 to 2, from the viewpoint of thermal resistance and transparency of the obtained cured product.

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

Among the compounds represented by the formula (14), the compounds represented by the following formulas (5) to (7) are particularly preferable.

Among the compounds represented by the formula (15), it is preferable that the compounds represented by the following formulas (2) to (4) are selected from the group consisting of heat-resistant transparency of the cured product, viscosity of the polyvalent carboxylic acid (A), viscosity of the polyvalent carboxylic acid composition And the like. Among them, a compound represented by the following formula (4) is preferable.

The polyvalent carboxylic acid (A) of the present invention can be produced in a solvent or in a solvent. The solvent is not particularly limited as long as it is a solvent that does not react with the isocyanuric acid trihydroxyalkyl compound represented by the formula (10) and the carboxylic acid anhydride compound represented by the formula (14) or (15) . Examples of usable solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran and acetonitrile; ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone; , Aromatic hydrocarbons such as toluene and xylene, and the like. Of these, aromatic hydrocarbons and ketones are preferable.

These solvents may be used alone or in combination of two or more. When the solvent is used, the amount of the solvent to be used may be selected from the group consisting of the isocyanuric acid trishydroxyalkyl compound represented by the formula (10), the carboxylic anhydride compound represented by the formula (14) and / or the carboxyl The amount is preferably 0.5 to 300 parts by mass per 100 parts by mass of the total amount of the acid anhydride compound.

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

The polyvalent carboxylic acid (A) of the present invention can be produced without using a catalyst, and can also be produced using a catalyst. When a catalyst is used, the catalyst that can be used is an acidic compound such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, para toluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid, etc., sodium hydroxide, potassium hydroxide, A metal hydroxide such as magnesium hydroxide, an amine compound such as triethylamine, tripropylamine or tributylamine, an amine compound such as pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undeca- , Triazole, and tetrazole, and heterocyclic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium Hydroxides such as hydroxides, trimethylbutylammonium hydroxides, trimethylcetylammonium hydroxides, trioctylmethylammonium hydroxides, tetramethylammonium hydroxides, Quaternary ammonium salts such as tetraethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate and trioctylmethylammonium acetate, orthotitanic acids such as tetraethyl orthotitanate and tetramethyl orthotitanate, , Cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, and potassium octylate.

When a catalyst is used, one or more of them may be used in combination.

When the catalyst is used, the amount of the catalyst to be used may be selected from the group consisting of the isocyanuric acid trishydroxyalkyl compound represented by the formula (10), the carboxylic acid anhydride compound represented by the formula (14) and / or the carboxyl Is preferably 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the acid anhydride compound.

The catalyst may be added directly or dissolved in a soluble solvent or the like. At this time, it is preferable to use an alcoholic solvent or water such as methanol or ethanol because it reacts with the carboxylic acid anhydride compound represented by the unreacted formula (14) or formula (15).

In the present invention, from the viewpoint of improving transparency and heat-resistant transparency in the obtained cured product of the polyvalent carboxylic acid (A) or polyvalent carboxylic acid composition (C), zinc carboxylate such as zinc octylate is preferably used as a catalyst , And it is preferable to carry out the reaction in the absence of a catalyst from the viewpoint of reducing the coloration of the obtained polyvalent carboxylic acid (A) or polyvalent carboxylic acid composition (C).

Among them, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate) and zinc phosphate (zinc stearate) are particularly preferable in order to obtain a cured product excellent in transparency and resistance to sulfidization Zinc octylphosphate, zinc stearyl phosphate, etc.) can be preferably used.

The reaction temperature in the production of the polyvalent carboxylic acid (A) of the present invention is usually from 20 to 160 캜, preferably from 50 to 150 캜, and particularly preferably from 60 to 145 캜, though it depends on the amount of the catalyst and the solvent used. The total amount of the 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, the reaction may be carried out at 20 to 100 ° C for 1 to 8 hours and then at 100 to 160 ° C for 1 to 12 hours. In particular, the carboxylic acid anhydride compound represented by the formula (14) or the formula (15) is often highly volatile. When such a compound is used, the reaction is carried out at 20 to 100 ° C in advance and then at 100 to 160 ° C, 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.

(A) and / or the polycarboxylic acid composition (C), the catalyst may be removed as required, and the catalyst may be left as it is. May be used as a curing accelerator of the epoxy resin composition.

When the washing step is carried out, it is preferable to add a solvent which can be separated from water depending on the kind of the solvent used. Examples of the preferable solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hexane, cyclohexane, toluene, xylene and the like And the like.

When a solvent is used for the reaction or washing, it can be removed by concentration under reduced pressure or the like.

In the production of 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 (two), flow rate: 0.4 ml / min. A peak of the retention time faster than the peak of the compound represented by the formula (1) and a slow retention time in the compound of the formula (1) in the column temperature: 40 캜, the solvent used: THF (tetrahydrofuran) Lt; / RTI > are mixed. As the peak of the fast retention time (hereinafter referred to as peak f), there is a compound whose retention time is 1 to 3 minutes faster than that of the compound of the formula (1), for example, 18 to 20 minutes. The area% of the GPC of the compound having the peak f is preferably 1 to 30% by area from the viewpoint of increasing the mechanical strength, and particularly preferably 1 to 10% by area. It is also possible that there are two to three peaks of the slow retention time (hereinafter referred to as peak s), and the retention time is one to five minutes slower than the peak of the compound of the present invention (1) For 21 to 25 minutes. The area% of the GPC of the compound having the peak s is preferably 1 to 10% by area from the viewpoint of improving the adhesiveness, more preferably 1 to 5% by area. In addition, a multimer of a polyvalent carboxylic acid represented by the following formula (16) may be produced. These compounds are considered to correspond to the compounds of peak f.

In the formula (16), R ¹ has the same meaning as above, R ⁴ has the same meaning as R ^2b or a structure represented by the following formula (17), R ⁵ represents a hydrogen atom or a group represented by the following formula Represents the structure shown.

In the formula (17), R ^2a has the same meaning as described above, and ** indicates that it is bonded to the adjacent carbonyl carbon of R ^{4 in} the formula (16).

Formula (18) of, R ^1, R ^4, R ⁵ indicates that combines with oxygen atom to which R ⁵ in the combination shown in the same meaning as described hereinbefore. *** site of the expression (16).

When the polyvalent carboxylic acid represented by the formula (16) is contained in the polyvalent carboxylic acid (A), the mechanical strength of the cured product is improved. However, the polyvalent carboxylic acid (A) It is preferably 50 parts by mass or less based on 100 parts by mass of the polycarboxylic acid (A).

Further, when preparing the polyvalent carboxylic acid (A) of the present invention, a bivalent carboxylic acid represented by the following formula (19) may be produced. It is also believed that the compound corresponds to a compound of peak s. Here, the GPC area% of the compound represented by the following formula (19) of the polyvalent carboxylic acid (A) obtained by the above production method is preferably 1 to 30% by area, more preferably 1 to 20% by area.

In the formula (19), R ¹ and R ⁴ have the same meanings as above.

When the divalent carboxylic acid represented by the above formula (15) is contained in the polyvalent carboxylic acid (A), the adhesion of the cured product to the substrate is improved. However, since the mechanical strength of the cured product is lowered by inclusion of the polyvalent carboxylic acid, It is preferably 20 parts by mass or less based on 100 parts by mass of the acid (A).

Further, in producing the polyvalent carboxylic acid (A) of the present invention, a monovalent carboxylic acid represented by the following formula (19 ') may be produced. It is also believed that the compound corresponds to a compound of peak s. Here, the GPC area% of the compound represented by the following formula (19 ') of the polyvalent carboxylic acid (A) obtained by the above production method is preferably 1 to 10% by area, more preferably 1 to 5% by area.

In the formula (19 '), R ¹ and R ⁴ have the same meanings as described above.

When the monovalent carboxylic acid represented by the above formula (19 ') is contained in the polycarboxylic acid (A), the adhesion of the cured product to the substrate is improved. However, since the mechanical strength of the cured product tends to be lowered It is preferably 20 parts by mass or less based on 100 parts by mass of the polyvalent carboxylic acid (A).

In addition, as the compound corresponding to the peak s, when an alcohol is used as a solvent, a reaction product or a solvent of the alcohol with the carboxylic acid anhydride compound represented by the formula (14) and / or the compound represented by the formula (15) A reaction product of a water content in the air with a carboxylic acid anhydride compound represented by the formula (14) and / or a compound represented by the formula (15), and unreacted acid anhydride. Here, a reaction product of the alcohol and the compound represented by the formula (9) or the solvent and the moisture in the air and the carboxylic acid anhydride compound represented by the formula (14) and / or the compound represented by the formula (15) Is preferably not more than 5% by area, more preferably not more than 3% by area in view of the mechanical strength of the cured product.

The acid value (measured by the method described in JIS K-2501) of the polyvalent carboxylic acid (A) of the present invention produced is preferably 150 to 415 mgKOH / g, more preferably 185 to 375 mgKOH / g , Particularly preferably from 200 to 320 mg KOH / g. If the acid value is 150 mgKOH / g or more, the mechanical properties of the cured product are improved, and if it is 415 mgKOH / g or less, the cured product is not excessively hardened and the modulus of elasticity is suitable.

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.

Also, in the polyvalent carboxylic acid composition (C) of the present invention, the polyvalent carboxylic acid composition (C ') contains the polyvalent carboxylic acid (A) and the carboxylic anhydride compound (B) of the present invention as essential components.

The polycarboxylic acid composition (C ') can be obtained by mixing the polycarboxylic acid (A) and the carboxylic anhydride compound (B).

The polyvalent carboxylic acid composition (C ') of the present invention is obtained by uniformly mixing the above components at room temperature or under heating. For example, the mixture is thoroughly mixed using a spoon, an extruder, a kneader, a three-roll mixer, a universal mixer, a planetary mixer, a homomixer, a homodisper, and a bead mill until homogeneous, Followed by filtration.

(D), a curing accelerator (E), an adhesion promoter, an antioxidant, a light stabilizer, and the like may be mixed together at the time of preparation.

The polyvalent carboxylic acid composition (C) of the present invention may be used as varnishes or inks by mixing solvents as required. The solvent has a high solubility with respect to the polyvalent carboxylic acid (A), the carboxylic acid anhydride compound (B), the epoxy resin (D), the curing accelerator (E), the adhesion aid, the antioxidant and the light stabilizer, Can be used. Specific examples thereof include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, and ketones such as toluene and xylene. Aromatic hydrocarbons, etc. Among them, aromatic hydrocarbons and ketones are preferable.

In the polyvalent carboxylic acid composition (C ') of the present invention, the carboxylic acid anhydride compound represented by the formula (14) and / or the carboxylic acid anhydride compound represented by the formula (15) in the preparation of the polyvalent carboxylic acid (A) When the carboxylic acid anhydride compound and the carboxylic acid anhydride compound (B) in the polyvalent carboxylic acid composition (C ') are the same, the isocyanurate represented by the formula (10) in the production of the polycarboxylic acid (A) The reaction is carried out in excess of the carboxylic acid anhydride compound (B) relative to the acid trishydroxyalkyl compound, and the polyvalent carboxylic acid (A) and the carboxylic anhydride ( B). ≪ / RTI >

The proportion of the both in the reaction is preferably in the range of 0.001 to 0.7 equivalents, more preferably 0.01 to 0.5 equivalents in terms of the hydroxyl group equivalent of the isocyanuric acid trishydroxyalkyl compound to 1 equivalent of the acid anhydride group in the functional group equivalent thereof .

The concentration of the polyvalent carboxylic acid (A) in the polyvalent carboxylic acid composition (C ') can be adjusted by mixing the carboxylic acid anhydride (B) with the thus obtained polyvalent carboxylic acid composition (C').

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

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 may be a carboxylic acid anhydride compound selected from one or more of the following formulas (2) to Is preferable 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 acid anhydride compound (B) is 100 parts by mass based on 100 parts by mass of the polyvalent carboxylic acid (A) The amount of the 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 a curing agent for the epoxy resin, and may contain other curing agents for epoxy resins. For example, an amine-based curing agent, a phenol-based curing agent, and a polycarboxylic acid resin can be mentioned, and a polycarboxylic 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 means 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 polycarboxylic acid composition, , They are collectively referred to as a polycarboxylic acid resin.

As the polycarboxylic acid resin, a carboxylic acid having 2 to 6 functional groups is particularly preferable, and (a); (B) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule; A compound obtained by the reaction of a compound containing at least one acid anhydride group in the molecule is more preferable. Here, in the reactants (a) and (b), other alcohol compounds may be further 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, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, , Tricyclodecane dimethanol, norbornene diol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) 1,3-dioxane, and the like, triols such as glycerin, trimethylol ethane, trimethylol propane, trimethylol butane and 2-hydroxymethyl-1,4-butanediol, pentaerythritol, dimethylol propane And hexaols such as dipentaerythritol, etc., terminal alcohol polyesters, terminal alcohol polycarbonates, terminal alcohols Polyether, there may be mentioned polyhydric alcohols and having a siloxane structure.

Particularly preferred alcohols are alcohols having 5 or more carbon atoms, and particularly preferred are alcohols having 5 or more carbon atoms such as 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, Butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol, 2,2'-bis (4-hydroxycyclohexyl) Dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane and the like, among which 2-ethyl- 1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, norbornenediol, 2,2'-bis (4- (Cyclohexyl) propane, and 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane. Alcohols are more preferable. (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-pyrrolidone) Hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane and the like are particularly preferable. Among them, in particular, in the branched chain structure, it is preferable that two or more branched groups are present, and in particular, the branched chain is preferably extended from other carbon atoms. Here, the alcohols having the branched chain structure or the cyclic structure preferably have 5 to 25 carbon atoms, particularly preferably 5 to 20 carbon atoms.

The polyhydric alcohol having a siloxane structure is not particularly limited, and for example, a silicone oil represented by the following formula can be used.

(In the formula (20), A ₁ represents an alkyl group having 1 to 10 carbon atoms which may be bonded through an ether bond, A ₂ represents a methyl group or a phenyl group, s represents an average value in terms of the number of repeating units, to be.)

(A) above; The polyhydric alcohol compound containing two or more hydroxyl groups in the molecule may be used alone or in combination of two or more.

It is preferable to use a polyhydric alcohol having a siloxane structure and a branched chain structure having 5 to 25 carbon atoms or alcohols having a cyclic structure in order to impart a high resistance to sulfidation using the obtained polyvalent carboxylic acid resin as a liquid phase Do.

When a polyhydric alcohol having a siloxane structure and a branched chain structure having 5 to 25 carbon atoms or alcohols having a cyclic structure are mixed and used, the amount of the polyhydric alcohol having a siloxane structure (polyvalent alcohol having a siloxane structure) / (number of carbon atoms: 5 to 25 Is preferably from 1 to 20, and is preferably from 5 to 15, particularly preferably from 6 to 10 from the viewpoints of the heat-resistant transparency of the cured product and the suitable viscosity of the polycarboxylic acid resin.

(b); Examples of the compound containing at least one acid anhydride group in the molecule include methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2.2 Heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid- , 4-anhydride, anhydrous glutaric acid, 2,4-diethyl anhydroglutaric acid, succinic anhydride and the like are preferable, and among them, methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid- But are not limited to, 3,4-anhydride, 2,4-diethyl anhydroglutaric acid, 1,2,3,4-butanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride . Here, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable for increasing the hardness, and methylhexahydrophthalic anhydride is preferable for increasing the roughness retention, and the polycarboxylic acid resin 2,4-diethylglutaric acid and glutaric acid are preferable in order to suppress the excessive increase of the viscosity.

The conditions for the addition reaction can be the same as in the preparation 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 together with other epoxy resin curing agents, the polyvalent carboxylic acid (A) or polyvalent carboxylic acid The proportion of the composition (C) is preferably from 30 to 99 parts by mass, particularly preferably from 60 to 97 parts by mass. If it is less than 30 parts by mass, the heat-resistant transparency of the cured product may deteriorate.

Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition according to the present invention is characterized by containing 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 which is a glycidyl ether compound of a phenol compound, an epoxy resin which is a glycidyl ether compound of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin , A glycidyl ester-based epoxy resin, a glycidylamine-based epoxy resin, an epoxy resin obtained by glycidylating halogenated phenols, a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, A condensation product of a silicon compound and other silicon compounds, and a silicone-modified epoxy resin.

Examples of the epoxy resin which is a glycidyl ether compound of the phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- Bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetra Bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1- (4-hydroxyphenyl) -2- [4- (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl- 6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, fluoroglucinol, phenols having a diisopropylidene skeleton, 1,1-di-4-hydroxyphenylfluorene Phenol having a fluorene skeleton such as phenolated polybutadiene, And an epoxy resin which is a glycidyl ether compound of the compound.

Examples of the epoxy resin which is the glycidyl etherified product of the various novolac resins include phenols such as phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenols such as bisphenol A, bisphenol F and bisphenol S, Phenolic novolak resins containing a dicyclopentadiene skeleton, phenol novolak resins containing a biphenyl skeleton, and phenol novolac resins containing a fluorene skeleton, and the like, And glycidyl ether compounds of various novolac resins.

Examples of the alicyclic epoxy resin include alicyclic skeletons such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate, Containing 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 above-mentioned heterocyclic epoxy resin include heterocyclic epoxy resins having heterocyclic rings such as isocyanuric ring and hydantoin ring.

Examples of the glycidyl ester-based epoxy resin include epoxy resins composed of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.

Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.

Examples of the epoxy resin obtained by glycidylating the halogenated phenols include halogenated phenols such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolak, chlorinated bisphenol S and chlorinated bisphenol A And epoxy resins obtained by glycidylation.

G-0115S, G-0130S, G-0250S, G-0250S, and G-0250S may be used as the copolymer of the polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, 4-ethylhexyl acrylate, -Vinyl-1-cyclohexene-1,2-epoxide, and the like. Examples of other polymerizable unsaturated compounds include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and vinylcyclohexane. have. These epoxy resins may be used alone or in combination of two or more.

The condensate of the silicon compound having an epoxy group and the other silicon compound means a condensation product of an alkoxysilane compound having an epoxy group and a hydrolyzed condensate of an alkoxysilane having a methyl group or a phenyl group and a condensation product of an alkoxysilane compound having an epoxy group and a silanol , A condensate of polyphenyldimethylsiloxane having silanol groups, or a condensed compound 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, 3- Propyltrimethoxysilane, 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, Ethoxy silane, and the like. Examples of polydimethyldiphenylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group include X-21-5841 and KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16 DMS-S12, DMS-S14, DMS-S14, and DMS-S73 were used. The results are shown in Table 1 below. S15, DMS-S21, DMS-S27, DMS-S31, PDS-0338 and PDS-1615 (manufactured by Gelest).

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

In the formula (21), R ⁷ represents a hydrocarbon group of 1 to 6 carbon atoms, X represents an organic group containing an epoxy group or a hydrocarbon group of 1 to 6 carbon atoms, and n represents an integer of 1 to 3, respectively. R ⁷ and X which are plural in the formula may be the same or different. Provided that at least two of X groups present are an organic group containing an epoxy group.

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, but a methyl group and a phenyl group are preferable from the viewpoint of heat resistance and transparency of a cured product, Do.

The organic group in X represents a compound composed of C, H, N and O atoms. Specific examples of the organic group containing an epoxy group include a 2,3-epoxycyclohexylethyl group and a 3-glycidoxypropyl group. From the viewpoint of heat resistance transparency, a 2,3-epoxycyclohexylethyl group is preferable. Here, the number of carbon atoms in the organic group is preferably 1 to 20, more preferably 3 to 15. It is also preferable that a 2,3-epoxycyclohexylethyl group and a 3-glycidoxypropyl group are added via an alkylene group having 1 to 5 carbon atoms.

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 resistance and transparency of the cured product, , And a methyl group is particularly preferable from the viewpoint of ease of production.

n is preferably 2 from the ease of preparation of the compound.

The cyclic silicone-modified epoxy resin represented by the formula (21) can be obtained by a hydrosilylation reaction between a cyclic hydrogen siloxane 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, pentaphenylpentacyclooxysiloxane, and the like. Tetramethyltetrasiloxane is preferred for its ease of use.

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 resistance and transparency of the cured product, , 2-epoxycyclohexane are preferable.

As the catalyst for the hydrosilylation reaction, for example, known metal complexes such as rhodium, palladium and platinum can be used. Specific examples thereof include tris (triphenylphosphine) rhodium chloride, hexachloroplatinic acid, hexahydrate, and the like, and hexachloroplatinic acid hexahydrate is preferable from the viewpoint of transparency of the cured product.

From the viewpoint of workability, it is preferable to use the catalyst used in the hydrolysis reaction as a solution in a solvent. The solvent which can be used is any solvent which can dissolve the catalyst, but tetrahydrofuran and toluene are preferable 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.

The cyclic silicone-modified epoxy resin represented by the formula (21) specifically includes the 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), alicyclic epoxy resins, condensation products of silicon compounds having an epoxy group with other silicon compounds, and silicon-modified epoxy resins are preferably used in view of transparency, heat resistance transparency and light fastness. Among them, a cyclic silicone-modified epoxy resin having an epoxy cyclohexane structure in the skeleton is preferable.

The epoxy resin (D) is used in an amount of 1 equivalent of the carboxylic acid group in the polyvalent carboxylic acid (A) and / or 1 equivalent of the carboxylic acid anhydride of the carboxylic acid anhydride compound (B) in the polyvalent carboxylic acid composition (C ' It is preferable that the epoxy group is used in a range of 0.5 to 3.0 equivalents. When the equivalent weight is 0.5 or more, the heat resistance of the cured product is improved, so that the heat resistance is preferably improved, and if it is 3.0 or less, the mechanical properties of the cured product are improved.

The epoxy resin composition of the present invention preferably further contains an epoxy resin curing accelerator (E).

As the epoxy resin curing accelerator (E), it is possible to use both the polyvalent carboxylic acid (A) or the polyvalent carboxylic acid composition (C) of the present invention and those having an ability to accelerate the curing reaction of the epoxy resin (D) Examples of the hardening accelerator (E) that can be used include ammonium salt-based hardening accelerator, phosphonium salt hardening accelerator, metal soap hardening accelerator, imidazole hardening accelerator, amine hardening accelerator, phosphine hardening accelerator, phosphite hardening accelerator, A curing accelerator and the like.

The mixing ratio of the epoxy resin curing accelerator (E) in the epoxy resin composition of the present invention is preferably 0.001 to 15 parts by weight, based on 100 parts by weight of the epoxy resin composition, of a curing accelerator.

Specific examples of epoxy resin curing accelerators (E) that can be used in the epoxy resin composition of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole Benzimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1- 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl- Triazine, 2,4-diamino-6 (2'-undecylimidazole (1 ')) ethyl-s-triazine, 2,4- (2 '-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2,4-diamino- -Methylimidazole is a 2: 3 adduct of isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl- - hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2- 3,5-dicyanoethoxymethylimidazole, and imidazoles of imidazoles thereof with at least one of phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, Diacid compounds such as 1,8-diaza-bicyclo [5.4.0] undecene-7, and their tetraphenylborates, phenol novolacs, Boric acid and the like, salts with polycarboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide and trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) phosphine , Tetraphenylphosphonium bromide, and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, amines such as aminodextrin and tin octylate Compounds and the like, and microcapsule type curing accelerators in which these curing accelerators are microcapsules. Which of these curing accelerators are used is appropriately selected depending on properties required for the obtained transparent resin composition such as transparency, curing rate, and working conditions.

Among these, the metal soap hardening accelerator is excellent from the viewpoint of transparency of the hardened product, and among the metal soap hardening accelerators, the zinc carboxylate compound is particularly preferable from the viewpoint of transparency of the cured product.

Examples of the metal soap hardening accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, potassium octylate, calcium stearate, zinc stearate, magnesium stearate, Aluminum stearate, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxyphosphate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate Hydroxystearic acid, sodium 12-hydroxystearate, calcium montanate, zinc montanate, magnesium montanate, aluminum montanate, lithium montanate, sodium montanate, sodium montanate, Calcium laurate, zinc laurate, lithium barium laurate, lithium laurate, calcium laurate, calcium laurate, calcium laurate, calcium laurate, Zinc decylate, zinc ricinoleate, barium ricinoleate, zinc myristate, and zinc palmitate. These catalysts may be used alone or in combination of two or more.

In order to obtain a cured product excellent in transparency and resistance to sulfidation, it is particularly preferable to use a curing agent such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate and zinc palmitate A zinc salt of a carboxylic acid having 10 to 30 carbon atoms and a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as 12-hydroxystearic acid can be preferably used. Among them, particularly preferred are zinc salts such as zinc stearate, zinc salts of monocarboxylic acid compounds having 10 to 20 carbon atoms such as undecylenic acid, and zinc salts such as 12-hydroxystearic acid zinc having a hydroxyl group A zinc salt of a monocarboxylic acid compound having 15 to 20 carbon atoms can be preferably used, and zinc stearate, zinc undecylenic acid and zinc 12-hydroxystearate are more preferably used, Zinc stearate, and zinc 12-hydroxystearate can be used.

Examples of the ammonium salt-based curing accelerator include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl ethyl ammonium 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-based curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, and methyltributylphosphonium diethylphosphate.

Other general-purpose applications include the ammonium salt-based curing accelerator, the phosphonium salt-based curing accelerator, the metal soap-based curing accelerator, the imidazole-based curing accelerator, the amine-based curing accelerator, the heterocyclic compound-based curing accelerator, Accelerators, Lewis acid-based curing accelerators and the like.

The above-mentioned epoxy resin curing accelerator (E) can be used as a solid compound at room temperature (25 캜), and can also be used as a liquid compound. When a solid compound is used as a curing accelerator at room temperature (25 占 폚) in the case where the epoxy resin composition of the present invention is used in a liquid state at room temperature (25 占 폚), it may be dissolved in a resin beforehand. It is also possible to use a solid compound dispersed in a resin at room temperature (25 캜).

In the epoxy resin composition of the present invention, the viscosity of the composition can be adjusted and the hardness of the cured product can be compensated by using a coupling agent as required.

Examples of the coupling agent that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Methacryloxypropyltrimethoxysilane, ethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, A silane-based coupling agent such as 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like; (Dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neo alkoxy tri (meth) acrylate, (pN- (p-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytris neodecane oil zirconate, neoalkoxytris (dodecane oil) benzenesulfonyl zirconate, neo Zirconium such as alkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Or an aluminum-based coupling agent.

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

The coupling agent is contained in the epoxy resin composition of the present invention in an amount of usually 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, if necessary.

The epoxy resin composition of the present invention can supplement mechanical strength and the like without impairing transparency by using an inorganic filler having a nano-order level as required. It is preferable from the viewpoint of transparency to use a filler having an average particle diameter of 500 nm or less, particularly an average particle diameter of 200 nm or less as a reference as a nano-order level. Examples of the inorganic filler include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania, talc, Beads, and the like. However, the present invention is not limited to these. These fillers may be used singly or in combination of two or more kinds. The content of these inorganic fillers is in the range of 0 to 95% by weight in the epoxy resin composition of the present invention.

For the purpose of preventing coloration, 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-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 , 6-pentamethyl-4-piperidino and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecaneoxy-2,2,6,6-tetramethylpiperidin- - 2,2,6,6-tetramethyl-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis Pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- Ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis , 6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] methyl] butyl malonate, decane diacid bis N, N '', N '' '- N'-diphenylmethane diisocyanate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, Tetrakis- (4,6-bis- (N - methyl- 2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin- -Diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl- A polycondensation product of 6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, a poly [6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [ - tetramethyl-4-piperidyl) Mino], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, 2,2,4,4-tetramethyl-20- (β- Oxycarbonyl) ethyl-7-oxa-3,20-diazabicyclo [5.1.11.2] heneic acid-21-one, beta -alanine, N, - (2,2,6,6- Acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine -2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispyro [5,1,11,2] heneic acid-21- 4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -henate acid-20-propanoate dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl- N, N'-bis (2,2,6,6-tetramethyl-4-piperazin-1-yl) 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) - (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide- , 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5- chlorobenzotriazole, 2- The reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol, 2- (2H-benzotriazol- Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like; Based compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] phenol and the like, The hindered amine compound All.

As the amine compound as the light stabilizer, a commercially available product represented by the following formula can be used.

Examples of commercially available amine compounds include, but are not limited to, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152 and CHIMASSORB 944 as commercial products of Chiba Specialty Chemicals, LA- -57, LA-62, LA-63P, LA-77Y, LA-81, LA-82 and LA-87.

The phosphorus compound is not particularly limited and examples thereof include 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, distearylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, dicyclohexyl penta (Di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (di-tert- butylphenyl) (2,6-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di- Butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert- butyl-4-methylphenyl) phosphite , 2,2'-methylene Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert- butylphenyl) Phenyl) -4,3'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphosphonite, tetrakis Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylene diphosphonite, tributylphosphate, trimethylphosphate, tricresylphosphate, triphenylphosphate, Trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl mono isocecenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like.

Commercially available products of the phosphorus compound may be used. Examples of commercially available phosphorus compounds include, but are not limited to, adekastab (trade name) PEP-4C, adecastab PEP-8, adecastab PEP-24G, adecastab PEP-36, Tabak HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A and the like.

The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3,5- Phenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythritol-tetrakis [ (3-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol-bis [3- (3- Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butyl Phenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'- Butylphenol acrylate, methylene bis (4-ethyl-6-tert-butylphenol), 2-tert- butyl-6- (3- (4-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4'-thiobis (3-methyl- tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) Butylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis Phenol), bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanooic acid] -glycol ester, 2,4-di- Di-tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert- pentylphenyl) ethyl] , 3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] - And the like call ester.

Commercially available products of the phenolic compound may be used. Examples of commercially available phenol compounds include, but are not limited to, IRGANOX (trade name) 1010, IRGANOX1035, IRGANOX1076, IRGANOX11535, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098 and IRGANOX1520L as the Ciba Specialty Chemicals, 50, adecastab AO-60, adecastab AO-70, adecastab AO-80, adecastab AO-40, adecastab AO-50, adecastab AO-60, adecastab AO- Sumilizer (trade name) GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F) and Sumilizer GP as Adekustab AO-330 and Sumitomo Chemical Co., have.

In addition, commercially available additives can be used as the coloring preventing agent for the resin. For example, THINUVIN328, THINUVIN234, THINUVIN326, THINUVIN120, THINUVIN477, THINUVIN479, CHIMASSORB2020FDL, CHIMASSORB119FL and the like can be mentioned as Ciba Specialty Chemicals.

The phosphorus compound, the amine compound, and the phenol compound are preferably contained in an amount of 0.005 to 5.0% by weight based on the total weight of the epoxy resin composition of the present invention, although the amount thereof is not particularly limited.

The epoxy resin composition of the present invention may optionally contain a binder resin. As the binder resin, a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy -NBR resin, a polyamide resin, a polyimide resin, But the present invention is not limited thereto. The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the resin component.

An inorganic filler may be added to the epoxy resin composition of the present invention if necessary. Examples of the inorganic filler include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania, talc, Beads, 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 in the curable resin composition of the present invention is 0 to 95% by weight. To the curable resin composition of the present invention, various compounding agents such as a silane coupling agent, stearic acid, palmitic acid, zinc stearate, a release agent such as calcium stearate, a pigment, and various thermosetting resins may be further added.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above components at room temperature or under heating. For example, the mixture is sufficiently mixed by using an extruder, a kneader, a three-stage roll, an all-purpose mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, etc. until homogeneous, .

The epoxy resin composition of the present invention can be obtained by sufficiently adding additives such as the polyvalent carboxylic acid (A) or the polyvalent carboxylic acid composition (C) and the epoxy resin (D) of the present invention and optionally a curing accelerator (E) And they can be used as a sealing material. As the mixing method, mixing is carried out at room temperature or by using a spoon, kneader, three-stage roll, 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, dimethyl formamide, dimethylacetamide and N- methylpyrrolidone to prepare an epoxy resin composition varnish , A prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper or the like with heating and drying is hot-pressed to obtain a cured product of the epoxy resin composition of the present invention . The amount of the solvent used in the mixture of the epoxy resin composition of the present invention and the solvent is usually 10 to 70% by weight, preferably 15 to 70% by weight. Further, an epoxy resin cured product containing carbon fibers may be obtained by an RTM method in the state of being a liquid composition.

The epoxy resin composition of the present invention can also be used as a modifier for film-like compositions. Concretely, it can be used in the case of improving the flexibility in the B-stage. When such a film-like resin composition is obtained, the epoxy resin composition of the present invention is applied as a varnish on the release film, the solvent is removed under heating, and B staging is carried out to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Further, general applications in which a thermosetting resin such as an epoxy resin is used include adhesives, paints, coating agents, molding materials (including sheets, films, FRP and the like), insulating materials (printed boards, And the like), as a sealing material, a cyanate resin composition for a sealing material and a substrate, and an acrylic ester resin as a curing agent for a resist, as an additive to other resins, and the like.

As the adhesive, adhesives for electronic materials, in addition to adhesives for civil engineering, construction use, automobile use, general office use, and medical use, can be mentioned. Among these, examples of the adhesive for electronic materials include an interlayer adhesive of a multilayer substrate such as a build-up substrate, a die bonding agent, an adhesive for semiconductor such as underfill, an underfill for BGA reinforcement, an anisotropic conductive film (ACF), an anisotropic conductive paste And an adhesive for mounting of the adhesive layer.

Examples of the sealing agent include potting, dipping, transfer mold sealing such as capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, potting sealing such as COB, COF, TAB for IC and LSI, underfill for QFP, BGA, CSP, and the like (including reinforcing underfill), and the like.

The cured product obtained in the present invention can be used for various applications including optical component materials. The optical material refers to a general material used for passing light such as visible light, infrared light, ultraviolet light, X-ray, and laser through the material. More specifically, in addition to LED sealing materials such as a lamp type and an SMD type, the following materials may be mentioned. A liquid crystal film such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle compensation film, an adhesive, and a polarizer protective film in the field of liquid crystal displays. In addition, LEDs used in LED PDPs, anti-reflection films, optical compensation films, housing materials, front glass protection films, front glass substitute materials, adhesives, and LED display devices, which are expected to be the next generation of flat panel displays A light guide plate, a prism sheet, a deflecting plate, a retardation plate, a viewing angle compensating film, an adhesive, and a substrate for a plasma addressed liquid crystal display (PALC) A protective film for a front glass in an organic EL (electroluminescence) display, a material for a front glass, an adhesive, various film substrates in a field emission display (FED), a front glass Protective film, front glass replacement material, and adhesive. In the field of optical recording, a disk substrate material for a VD (video disk), a CD / CD-ROM, a CD-R / RW, a DVD-R / DVD-RAM, a MO / MD, a PD A lens, a protective film, a sealing material, and an adhesive.

In the field of optical instruments, it is a lens material for a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor part. It is also a photographing lens and a finder of a video camera. Further, projection lenses, protective films, sealing materials, and adhesives of projection televisions and the like are used. Materials for lenses of optical sensing devices, sealing materials, adhesives, and films. In the field of optical components, fiber materials, lenses, waveguides, sealing materials for devices, adhesives, etc. around optical switches in optical communication systems. An optical fiber material around the optical connector, a ferrule, a sealing material, an adhesive, and the like. Optical passive components, optical circuit components include lenses, waveguides, LED encapsulants, CCD encapsulants, and adhesives. Substrate materials around the optoelectronic integrated circuit (OEIC), fiber materials, sealing materials for devices, and adhesives. In the optical fiber field, it is an optical fiber for connection to digital devices such as illumination / light guide for decorative display, industrial use sensors, display / mark, communication infrastructure, and home digital devices. In the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and super LSI materials. In the field of automobiles and transportation vehicles, lamp reflector, bearing retainer, gear part, corrosion coat, switch part, head lamp, engine parts, electric parts, various internal and external parts, driving engine, brake oil tank, Panels, interiors, wire harnesses for protection and bonding, fuel hoses, automotive lamps, and glass substitutes. Further, it is a multilayer glass for a railway car. In addition, the toughness-imparting agent of the structural material of the aircraft, the members around the engine, the wire harness for protection and binding, and the corrosion-resistant coat. In the construction sector, it is used for interior and working materials, electric covers, sheets, glass interlayers, glass substitutes, and solar cell materials. For agricultural use, it is a house film. As a next-generation optoelectronic functional organic material, organic EL device peripheral materials, organic photoreflective devices, optical amplifiers as optical-to-optical conversion devices, optical computing devices, substrate materials around organic solar cells, fiber materials, , And adhesives.

Examples of other uses of the optical material include general use in which the curable resin composition A is used. Examples of the optical material include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, , Wire coating and the like), additives to resins other than the sealing agent, and the like. As the adhesive, adhesives for electronic materials, in addition to adhesives for civil engineering, construction use, automobile use, general office use, and medical use, can be mentioned. Among these, adhesives for electronic materials include adhesives for semiconductors such as die-bonding agents and underfills, underfill for BGA reinforcement, anisotropic conductive films (ACF), and anisotropic conductive pastes (ACP) Adhesive for mounting, and the like.

BACKGROUND ART An optical semiconductor device such as a high-brightness white LED generally has a semiconductor chip such as GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN, etc. stacked on a substrate of sapphire, spinel, SiC, Is adhered to a lead frame, a heat sink or a package using an adhesive (die bond material). There is a type in which a wire such as a gold wire is connected to make a current flow. The optical semiconductor element is sealed with a sealing material such as an epoxy resin in order to protect the semiconductor chip from heat or moisture and also to serve as a lens function. The epoxy resin composition of the present invention can be used as this sealing material.

As a molding method of the sealing material, there are a molding method in which a sealing material is injected into a mold in which a substrate on which an optical semiconductor element is fixed is injected, followed by heat curing and molding, a sealing material is preliminarily injected onto the mold, A compression molding method in which a device is immersed and heat-cured and then released from a mold is used.

As the injection method, a dispenser or the like can be mentioned.

Heating can be carried out using a hot air circulation type, an infrared ray or a high frequency wave. The heating conditions are preferably, for example, 80 to 230 DEG C for about 1 minute to 24 hours. Curing can be performed at 120 to 180 ° C for 30 minutes to 10 hours after pre-curing at 80 to 120 ° C for 30 minutes to 5 hours for the purpose of reducing internal stress generated at the time of heat curing .

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

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. Since the viscosity of the ICI cone plate of the present invention is 0.01 to 10 Pa · s in the range of 100 to 200 ° C. and it is solid at room temperature, it is possible to perform kneading which is impossible without pretreatment such as prepolymerization in the case of liquid phase without pretreatment It becomes. In addition, since it is solid, it is also easy to form 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 above-mentioned range, it becomes solid at room temperature (25 DEG C) to facilitate molding, and it is possible to effectively prevent problems such as voids. Further, by setting such a low-viscosity thermosetting resin composition, each component having a high softening point or melting point due to its high crystallinity and being difficult to be kneaded is sufficiently melted and dispersed in the curing agent, so crystals are broken, 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, even more preferably 50 to 100 ° C, and particularly preferably 70 to 100 ° C. With such softening point, sufficient kneading can be easily performed.

By adjusting to the above-mentioned range, various components can be easily stirred and mixed by a mixer or the like, and it can be kneaded or melt-kneaded by a mixing roll, an extruder, a kneader, a roll or an extruder, and cooled and pulverized.

The thermosetting resin composition of the present invention is a resin composition comprising a polyvalent carboxylic acid (A) represented by the above formula (1), a thermosetting resin and, if necessary, other components. In the thermosetting resin composition of the present invention, a curing agent for a thermosetting resin may be contained as other components. Preferred examples of the component of the curing agent for a thermosetting resin include trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, And one or more compounds selected from pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, polybasic carboxylic acid (A), and other polycarboxylic acids.

But are not limited to, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride , And methylhexahydrophthalic anhydride are present, 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, it is also possible to use an acid anhydride such as trimellitic acid, anhydride trimellitic acid, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride and hydrogenated pyromellitic anhydride Since the carboxylic acid or the acid anhydride has crystallinity, it has a high softening point or melting point, and a specific melting point is 150 ° C to 300 ° C, which is a problem in molding. On the other hand, since the melting point of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride is not more than room temperature, there is a problem in molding. Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydroanhydride Phthalic acid, and methylhexahydrophthalic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, hydrogenated pyromellitic acid, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and Methyl hexahydrophthalic anhydride is preferable, and cyclohexanetricarboxylic acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are more preferable.

As the cyclohexanetricarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2- . In the present invention, these acid anhydrides may be used in combination, but cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferable.

In the thermosetting resin composition of the present invention, it is preferable to use at least one of trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid It is preferable that the total amount of one or two or more compounds selected from the group consisting of acetic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in the thermosetting resin composition is 1 wt% to 90 wt%. If it is lower than 1% by weight, the glass transition temperature does not become sufficiently high. If it is higher than 90% by weight, the melting point becomes high and handling may become difficult. More preferably 10 to 60% by weight, and still more preferably 20 to 50% by weight.

The polyvalent carboxylic acid other than the polyvalent carboxylic acid (A) of the present invention which can be contained as a component of the curing agent for thermosettable resins of the present invention is preferably a polyvalent carboxylic acid having an ester structure (preferably, Two ester structures), and polyvalent carboxylic acids having a plurality of carboxyl groups at the terminals.

(In the formula (22), P represents a residue of a polyhydric alcohol having 2 to 20 carbon atoms which may contain 0 to 6 oxygen atoms, a nitrogen atom or a phosphorus atom, and R represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms. Represents an average of 1 to 6. Also, the total number of n is 2 or more and less than 12.)

Among them, the polyvalent carboxylic acid of the formula (22) is preferably a compound obtained by esterification reaction of a polyhydric alcohol having 2 to 6 functional groups and having 6 or more carbon atoms and a 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 having 4 to 10 carbon atoms or a norbornane skeleton, and the cycloalkane skeleton is preferably a substituted or unsubstituted A methylcyclohexane structure having a cyclohexane structure, particularly a methyl group, is preferable in terms of optical properties in the cured product. The novolac skeleton is preferably a norbornane or methyl norbornane structure. Here, examples of substituents which may be substituted include alkyl groups having 1 to 3 carbon atoms, carboxyl groups, and the like.

The linking group P is preferably a residue of a polyhydric alcohol having 2 to 10 carbon atoms (a residue excluding a hydroxyl group from the polyhydric alcohol used in the reaction), but a branched chain crosslinking group or a cycloalkyl group is preferable, Is preferably a divalent crosslinking group defined by the following formula

(a) a chain alkyl chain having a branched structure having 6 to 20 carbon atoms, the chain alkyl chain having a main chain of a straight chain having 3 to 12 carbon atoms and 2 to 4 side chains, and at least one of the side chains having 2 to 10 carbon atoms In addition,

or

(b) a divalent crosslinking group in which two hydroxyl groups have been removed from at least one crosslinked polycyclic diol selected from tricyclodecane dimethanol and pentacyclopentadecane dimethanol, which may have a methyl group on the cyclo ring,

When P is (b), when the linking group R is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, it is more preferable that the substituent R ⁹ in the formula (2A) described below represents a group other than a hydrogen atom .

The polycarboxylic acid usually has a softening point of 50 DEG C or higher, but is preferably 60 DEG C or higher, more preferably 80 DEG C or higher. The upper limit is not particularly limited, but is usually 500 ° C or lower, preferably 300 ° C or lower, and more preferably 200 ° C or lower.

The particularly preferable polyvalent carboxylic acid can be obtained by addition reaction of a polyhydric alcohol having 2 to 6 functional groups having a carbon number of 6 or more and a saturated aliphatic cyclic acid anhydride.

These polyvalent carboxylic acids may be a mixture containing two polyvalent carboxylic acids. As a method for obtaining a polyvalent carboxylic acid mixture containing at least two polyvalent carboxylic acids, a method of mixing at least two polyvalent carboxylic acids obtained by the above method, or a method of mixing the polyvalent carboxylic acids As the saturated aliphatic cyclic acid anhydride, there may be used a mixture of at least two kinds of saturated aliphatic cyclic acid anhydrides selected from the following, or an addition reaction is carried out by using two kinds of the above-mentioned polyhydric alcohols.

As the saturated aliphatic cyclic acid anhydride used in the synthesis of the polycarboxylic acid, an acid anhydride group having a cyclohexane structure and having a methyl group substitution or a carboxyl group substitution on the cyclohexane ring, or an unsubstituted cyclohexane ring bonded to the cyclohexane ring A compound having at least one (preferably one) in the molecule.

Specific examples thereof include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, trimellitic anhydride, cyclohexanetricarboxylic acid anhydride, At least one acid anhydride selected from the group consisting of acetic acid anhydride, acetic acid anhydride, acetic acid anhydride,

Specific examples of the polyhydric alcohols having 6 to 6 carbon atoms and having 6 or more carbon atoms used for synthesizing the above polyvalent carboxylic acid include a polyvalent carboxylic acid having a hydroxyl group at the terminal of the crosslinking group P in the formula (21).

In the formula (21), the crosslinking group represented by P is preferably a divalent crosslinking group defined by the above (a) or (b), and these will be specifically described below.

The divalent crosslinking group defined by the above (a) is a bivalent straight chain alkyl chain excluding a hydroxyl group from a bivalent alcohol (diol) having a branched structure having 6 to 20 carbon atoms, and an alkyl chain interposed between two alcoholic hydroxyl groups of the diol is a main chain , And an alkyl chain branched from the alkyl chain (referred to as a side chain). The side chain may be branched from any carbon atom constituting the main chain and includes, for example, branched from the carbon atom (terminal carbon atom of the main chain) to which the alcoholic hydroxyl group is bonded. Any crosslinking group having the above structure may be used, and specific examples of such a crosslinking group are shown in the following formula (a1).

In the above formula, the oxygen atom on both sides of P in the formula (21) is bonded to the * symbol.

The alkylene bridging group defined by the above (a) is not particularly limited as long as it has an alkyl branch chain (side chain) with respect to the main chain alkylene group, but is preferably a main chain having 3 or more carbon atoms in the main chain and at least one alkyl side chain , And it is particularly preferable to have two or more alkyl side chains. More preferred examples thereof include a crosslinking group having a main chain of a straight chain having 3 to 12 carbon atoms and 2 to 4 side chains and at least one of the side chains having 2 to 10 carbon atoms. In this case, a crosslinking group in which at least two of the side chains have 2 to 10 carbon atoms is more preferable. It is preferable that two to four side chains are branched from other carbon atoms in the main chain.

As a more specific compound, a compound in which a hydroxyl group is bonded at the position marked with * in the crosslinking group described in the formula (a1) may be mentioned.

Of polyhydric alcohols used as raw materials, polyhydric alcohols having at least two side chains and at least two of the side chains having a side chain of 2 to 4 carbon atoms are preferable.

Particularly preferred polyhydric alcohols among such skeletons include 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl- And 2,4-diethyl-1,5-pentanediol, among others.

The crosslinking group defined by the above-mentioned (b) includes a bivalent group represented by the following formula (b1).

The crosslinked polycyclic diol residue in the case of the crosslinking group defined in the above (b) is a diol residue having a tricyclodecane structure and a pentacyclopentadecane structure as main skeletons and is represented by the following formula (b2).

In the formulas, plural R ^{8 s} present each independently represent a hydrogen atom or a methyl group. Of these, crosslinking groups in which all of R < ⁸ > are hydrogen atoms are preferable.

Specific examples thereof include tricyclodecane dimethanol, methyltricyclodecane 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 is particularly preferable in the absence of a catalyst.

When the catalyst is used, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, para toluenesulfonic acid, nitric acid, trifluoroacetic acid and trichloroacetic acid, Metal hydroxides such as potassium hydroxide, calcium hydroxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undeca- , Heterocyclic compounds such as imidazole, triazole, and tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide , Trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide It can be a seed, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, tri-octyl-methyl ammonium acetate, and the like. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferable.

The amount of the catalyst to be used is not particularly limited, but is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the total weight of the raw materials.

In this reaction, a reaction in a solvent is preferred, but an organic solvent may be used. The amount of the organic solvent to be used is 0.005 to 1 part by weight, preferably 0.005 to 0.7 part by weight, more preferably 0.005 to 0.5 part by weight, based on 1 part by weight of the total amount of the acid anhydride and the polyhydric alcohol as a reaction substrate % Or less). If the amount of the organic solvent used is more than 1 part by weight based on 1 part by weight of the reaction substrate, the progress of the reaction becomes extremely slow, which is not preferable. Specific examples of the organic solvent 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 ananone, Ethers such as tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate can be used.

The reaction proceeds sufficiently at a temperature of about 20 ° C. From the problem of the reaction time, the reaction temperature is preferably 30 to 200 占 폚, more preferably 40 to 200 占 폚, particularly preferably 40 to 150 占 폚. Particularly, when the present reaction is carried out in a solventless manner, the reaction at 100 ° C or lower is preferable and the reaction at 30 to 100 ° C or 40 to 100 ° C is particularly preferable because of the volatilization of the acid anhydride.

The reaction ratio between the acid anhydride and the polyhydric alcohol is theoretically preferable to be equivalent, but it can be changed if necessary.

Specifically, the amount of the polyhydric alcohol is preferably 0.001 to 2 equivalents, more preferably 0.01 to 1.5 equivalents, more preferably 0.1 to 1.5 equivalents, based on the equivalent of the acid anhydride group, To 1.2 equivalents of the total amount of water.

In the present invention, the polyvalent carboxylic acid to be obtained is preferably solid, and in order to obtain a solid dendritic carboxylic acid, polyhydric alcohol having an equimolar equivalent or more is preferably used. However, fluidity becomes important because a filler is added, In order to secure this fluidity, some balance may be broken in a range where the solidity is maintained in the viscosity balance (softening point is 50 ° C or more).

Concretely, the equivalent ratio of the alcoholic hydroxyl group to the acid anhydride equivalent is preferably 0.85 to 1.20, more preferably 0.90 to 1.10.

The reaction time is also dependent on the reaction temperature, the amount of catalyst, etc. However, a long reaction time from the viewpoint of industrial production is not preferable because it consumes a large amount of energy. In addition, an excessively short reaction time means that the reaction is rapid, which 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 2 to 10 hours.

When the catalyst is used after completion of the reaction, the catalyst is removed by neutralization, washing with water, adsorption, etc., and the solvent is distilled off to obtain the intended polyvalent carboxylic acid. On the other hand, when the reaction is carried out in the absence of a catalyst, the objective polyvalent carboxylic acid can be obtained by distilling off the solvent as necessary. Further, when a solvent is used, the desired polyvalent carboxylic acid can be obtained by removing the solvent. Further, in the case of a solventless or no catalyst, a desired polyvalent carboxylic acid can be obtained by withdrawing it directly.

As a most preferred production method, the acid anhydride and the polyhydric alcohol are allowed to react at 40 to 150 ° C under a non-catalytic condition to remove the solvent and withdraw the solvent.

The mixture containing the polycarboxylic acid or the polycarboxylic acid thus obtained usually exhibits a colorless to light yellow solid resin phase (which crystallizes in some cases). The polycarboxylic acid preferably has a softening point of 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 forming it into a liquid, it is possible to provide a reflecting member having a very high reflectance retention rate and a reflectance which is hardly lowered even when the heat resistance test is performed.

Usually, when the crosslinking group is an alkylene group having a side chain defined by (a), it represents a colorless to light yellow solid resinous phase.

In the present invention, the polycarboxylic acid is a solid dendritic resin because the transfer method is the optimum method of using the thermosetting resin composition containing the polyvalent carboxylic acid.

In the case of a crosslinking group defined as a crosslinking group (b), a polycarboxylic acid in which all alicyclic substituents are hydrogen atoms is colored when the aliphatic hydrocarbon group is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton Which is not particularly desirable for stringent optical applications. When the aliphatic hydrocarbon group is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, such a compound having a substituent group of methyl group or carboxyl group is less colored and its optical characteristics are improved.

Also in the compound of the crosslinking group defined in the above (a), when the aliphatic hydrocarbon group is a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, the substituent is a compound of a methyl group or a carboxyl group.

That is, when such a polyvalent carboxylic acid mixture contains a polycarboxylic acid having a cycloalkane skeleton having 4 to 10 carbon atoms or a novolak skeleton, the substituent is preferably a methyl group or a carboxyl group, Of a polyvalent carboxylic acid is preferred. In the case of a polyvalent carboxylic acid mixture comprising at least two 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 above-mentioned alkyl group, preferably a methyl group or a carboxyl group A polybasic carboxylic acid) in an amount of 50 mol% or more based on the total amount of the polycarboxylic acid. More preferably, a polyvalent carboxylic acid mixture containing 70 mol% or more, and 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. And the remainder is a polyvalent carboxylic acid of the formula (2A) wherein 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 preferable polycarboxylic acid other than the polyvalent carboxylic acid of the present invention.

(Wherein P has 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 formula (2A), R ⁹ may preferably be an alkyl group having 1 to 3 carbon atoms or a carboxyl group for the reasons described above.

The terminal carboxylic acid oligoester is preferably a polyvalent carboxylic acid having a number average molecular weight Mn of 300 or more.

In the thermosetting resin composition of the present invention, the polyvalent carboxylic acid represented by the above formula (1) is reacted with trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid The equivalent of the functional group in the mixture of one or more compounds selected from acetic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride is 250 g / eq. Or less, more preferably 240 g / eq. Or less. These ranges include trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride , Hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride, the effect of the compounding amount of one or more compounds selected from the group consisting of hexahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride can be effectively exhibited, and a cured product having excellent heat resistance can be obtained.

As the weight ratio, the polyvalent carboxylic acid represented by the above formula (1): (trimellitic acid, anhydrous trimellitic acid, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic acid anhydride, pyromellitic acid, At least one member selected from the group consisting of maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, More preferably from 90:10 to 20:80, and particularly preferably from 80:20 to 50:50. Since the ratio is in the above range, the thermosetting resin composition is excellent in heat resistance and low in viscosity and can be sufficiently kneaded.

The polyvalent carboxylic acid (A) represented by the above-mentioned formula (1), and the polyvalent carboxylic acid (A) represented by the above formula (1) and the polyvalent carboxylic acid A thermosetting resin composition comprising a thermosetting resin-containing curing agent comprising at least one compound selected from pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride It is preferable to use at least one of trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic anhydride, Phthalic anhydride, and methylhexahydrophthalic anhydride is used as the thermosetting water It accounts for 1% by weight of the composition to 90% by weight is preferred. By the above weight%, the thermosetting resin composition is further improved in kneading property and moldability and also in curing properties.

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 polyamides synthesized by dimer of diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid and ethylene diamine A resin selected from the group consisting of resin, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic acid Bis [2, 3] dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bisphenol A, bisphenol F, bisphenol S, Fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4 '-Diol, hydroquinone, resorcin, naphthalene diol, 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, Hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) - biphenylacetaldehyde, (Methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis ) And benzene, and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, imidazoles, trifluoroborane-amine complexes, guanidine derivatives, condensates of terpenes and phenols, and the like. . 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, and it is preferable to use an epoxy resin in the present invention.

As the epoxy resin, any conventional thermosetting resin composition or epoxy resin composition may be used as long as it is normally blended. Examples thereof include phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, epoxidized novolac resins of phenols and aldehydes, diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S and alkyl substituted bisphenols Glycidylamine type epoxy resins obtained by the reaction of epichlorohydrin with polyamines such as cidyl ether, diaminodiphenylmethane and isocyanuric acid, alicyclic epoxy resins obtained by oxidation of olefin bonds with peracid such as peracetic acid, Polyglycidyl isocyanurate, diglycidyl isocyanurate, triglycidyl isocyanurate, and silsesquioxane compounds. These may be used alone or in combination of two or more. From the viewpoints of the melt viscosity, the coloration of the resulting cured product, and the glass transition temperature, among these epoxy resins, those having high heat resistance are preferred, and glycidyl ether type epoxy resins, alicyclic epoxy resins, And the like.

An epoxy resin, and a polyvalent carboxylic acid (A) of the present invention, and at least one member selected from the group consisting of trimellitic acid, anhydrous trimellitic acid, cyclohexanetricarboxylic acid and cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, The blending ratio of the thermosetting resin curing agent comprising one or two or more compounds selected from pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride is preferably in the range of 1 equivalent of the epoxy group in the epoxy resin (Acid anhydride group or hydroxyl group) in the curing agent for thermosetting resin capable of reacting with the epoxy group is preferably 0.5 to 1.5 equivalents (the carboxylic acid is considered as one functional group and the acid anhydride as one functional group), particularly preferably 0.5 To 1.2 equivalents. When the amount is less than 0.5 equivalents or exceeds 1.5 equivalents with respect to one equivalent of the epoxy group, curing is incomplete in all cases, and there is a possibility that good curing properties may not be obtained.

A curing accelerator may be added to the curable resin composition of the present invention if necessary. Examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl- Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole Sol (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4-methylimidazole (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, a 2: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenyl Imidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl- - phenyl-3,5-dicyanoethoxymethylimidazole, and imidadoles and derivatives thereof. Salts of polycarboxylic acids such as acetic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid, amides such as dicyandiamide, Cyclo [5.4.0] undecene-7, and salts thereof such as tetraphenylborate and phenol novolac, salts with polycarboxylic acids or phosphines, tetrabutylammonium bromide, cetyltrimethyl Quaternary ammonium salts such as ammonium bromide, trioctylmethylammonium bromide and hexadecyltrimethylammonium hydroxide (preferably C1 to C20 alkylammonium salts, triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, Phosphonium compounds such as tetraphenylphosphonium tetraphenylborate and the like, phenols such as 2,4,6-trisaminomethylphenol, aminodecane, tin octylate, zinc octanoate, And cobalt naphthenate, and microcapsule-type curing accelerators containing these curing accelerators in the form of microcapsules. Examples of the curing accelerator to be used are transparency, transparency, Curing speed, working conditions and the like of the obtained transparent resin composition. Preferable examples of the present invention include a phosphonium compound (more preferably, quaternary phosphonium) or zinc stearate. Examples of products of quaternary phosphonium available from the market include PX-4ET and PX-4MP (both manufactured by Nippon Kayaku Co., Ltd.).

The curing accelerator is used in an amount of usually 0.001 to 15 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the epoxy resin.

If necessary, additives such as a dye, a fluorescent whitening agent, a reinforcing agent, a filler, a white pigment or other pigment, a nucleating agent, a surfactant, a plasticizer, a viscosity adjusting agent, A flow control agent, a flame retardant, an antioxidant, an ultraviolet absorber, and a light stabilizer 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, more preferably 1 to 800 parts by weight based on 100 parts by weight of the total amount of the curable resin composition.

Examples of the white pigment include, but are not limited to, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, basic zinc carbonate, kaolin and calcium carbonate. The white pigment may be hollow particles. Further, the white pigment may be suitably subjected to surface treatment with a silicon compound, an aluminum compound, an organic material, or the like. These may be used alone or in combination of two or more. The average particle diameter of the white pigment is preferably in the range of 0.01 to 50 탆. If it is less than 0.01 mu m, the particles tends to agglomerate easily and the dispersibility tends to deteriorate. If it exceeds 50 mu m, the cured product tends not to be sufficiently obtained. 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 titanium oxide, especially titanium dioxide powder. This is because it has high whiteness, light reflectivity and hiding power, excellent dispersibility stability, and is easy to obtain. The crystal form of the titanium oxide is not particularly limited and may be a rutile type, an anatase type or a mixture of both. The anatase type may have a photocatalytic function and may deteriorate the resin. Therefore, in the present invention, . For example, commercially available products from the market include CR-95 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.).

The content of the white pigment is in the range of 10 wt% to 95 wt%, more preferably 50 wt% to 95 wt% with respect to the whole resin composition. When the total content is less than 10% by weight, the light reflection property of the cured product tends to be insufficient. When the total content exceeds 95% by weight, the moldability of the resin composition is deteriorated and the production of the substrate tends to be difficult.

It is preferable that the curing agent for a thermosetting resin under a high temperature condition at the time of molding is higher in melt viscosity than that of a conventional acid anhydride curing agent or the like. Specifically, the curing agent for a thermosetting resin is preferably at a temperature in the range of 100 ° C to 200 ° C in the range of 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, if it is larger than 10 Pa · s, productivity decreases.

In the present embodiment, the ICI viscosity of the thermosetting resin curing agent at 150 캜 is preferably 0.01 Pa · s to 10 Pa · s, more preferably 0.05 Pa · s to 5 Pa · s.

The softening point is preferably in the range of 20 占 폚 to 150 占 폚. More specifically, the temperature 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 preferably higher than the molding temperature. If the glass transition temperature of the cured product is lower than the molding temperature, the cured product in the mold is in a rubbery state of low elasticity, so that the rubbery cured product is taken out of the mold and deformed when the ejector is pushed thereinto. Specifically, the glass transition temperature is preferably 30 占 폚 or higher, more preferably 40 占 폚 or higher, and still more preferably 50 占 폚 or higher.

Here, in the present invention, the glass transition temperature of the cured product is preferably 150 占 폚 or lower, more preferably 140 占 폚 or lower.

The thermosetting resin composition of the present invention is obtained by uniformly dispersing and mixing the above-mentioned various components. Although the method is not particularly limited, a method of sufficiently mixing and mixing various components uniformly with a mixer or the like and then kneading or melt-kneading the mixture with a mixing roll, an extruder, a kneader, a roll or an extruder, . The conditions of kneading or melt-kneading may be determined depending on the type and amount of the components, and are not particularly limited, and it is more preferable to knead the mixture at 20 to 100 占 폚 for 5 to 40 minutes. If the kneading temperature is lower than 20 캜, the dispersibility of each component is lowered and it is difficult to sufficiently knead the resin composition. If the temperature is higher than 100 캜, the crosslinking reaction of the resin composition proceeds and the resin composition may be cured.

The thermosetting resin composition of the present invention is preferably capable of press forming (tablet) at room temperature of 0 to 30 占 폚 before thermoforming. The pressure molding may be carried out under the conditions of, for example, 0.01 to 10 MPa and 1 to 5 seconds. The mold used for pressurizing (tablet) molding is not particularly limited. For example, it is possible to use a mold made of a ceramic material or a fluorine resin material, .

The thermosetting resin composition of the present invention is useful in applications such as optical semiconductor sealing materials and reflective materials for optical semiconductors which require high glass transition temperature and high transmittance.

In the case of using as a light-use film, the production method is not particularly limited, but it is preferable to produce the thermosetting resin composition of the present invention by transfer molding, for example. The thermosetting resin composition of the present invention is poured into a mold and is cured for 60 to 800 seconds under the conditions of, for example, a mold temperature of 150 to 190 DEG C and a molding pressure of 2 to 20 MPa, Lt; 0 > C for 1 to 3 hours.

As an example of a typical structure of the optical semiconductor device of the present invention, a light reflection preventing member having a cylindrical hollow portion is disposed on a substrate as described in International Publication No. 2012/124147, and a cylindrical hollow portion An optical semiconductor element is arranged on a substrate in an internal space. Then, one end of the optical semiconductor element and the substrate are connected by a wire, and the hollow portion is sealed with a sealing resin.

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

Example

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 examples and examples.

- The polyvalent carboxylic acid (A) in which R ⁶ in the formula (1) is an organic group containing a carboxyl group represented by the formula (8) wherein R ^2a is a methyl group is used as a liquid polyvalent carboxylic acid composition (C) Examples -

Each physical property value in Synthesis Examples and Examples was measured by the following method. Unless otherwise specified, parts denote parts by weight.

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-

Flow rate: 0.4 ml / min.

Column temperature: 40 ° C

Solvents used: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

Acid value: Measured by the following method.

About 0.15 g of the sample was weighed, dissolved in 20 ml of methyl ethyl ketone and 20 ml of ethanol, titrated with 0.1 N sodium hydroxide solution using a titration apparatus AT-610 manufactured by Kyoto Denshi Co., and the acid value was measured.

○ Functional equivalent: Measured by the following method.

About 0.15 g of the polycarboxylic acid composition was weighed, dissolved in 40 ml of methanol (reagent grade), and stirred at 20 to 28 ° C for 10 minutes to obtain a measurement sample. The measurement sample was titrated using a 0.1 N sodium hydroxide solution using a titration apparatus AT-610 manufactured by Kyoto Denshi Co., and the value obtained as the acid value was calculated as the functional group equivalent.

○ Melting point using DSC:

The melting point 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 占 폚 using an E-type viscometer (TV-20) manufactured by Toray Industries, Ltd.

Reduction in thermal weight: The weight reduction rate was measured after heating to 120 deg. C at 30 deg. C / min at 30 deg. C using Shimadzu Seisakusho TG / DTA6200 and holding at 120 deg. C for 60 min. During the measurement, air was caused to flow at 200 ml / min.

Example 1; Preparation of polyvalent carboxylic acid (A-1)

26.1 g of isocyanuric acid tris (2-hydroxyethyl), 52.1 g of ricaside MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Chemicals) and 70 g of toluene were placed in a glass 500 ml separable flask, The flask was immersed in an oil bath with a demultiplex cooler, a stirrer, and a thermometer. The oil bath was heated to maintain the internal temperature at 115 占 폚, and the reaction was continued for 7 hours.

The resulting reaction solution was concentrated under reduced pressure at 100 占 폚, 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 GPC purity (GPC area%) of the obtained compound was 92%, the acid value was 203.4 mgKOH / g, and the appearance was a white solid. In addition, the melting point (peak peak value) using DSC was 57.0 占 폚, and the decrease in thermogravimetry was -3.4%. A GPC chart of the obtained compound is shown in Fig.

Example 2: Preparation of polyvalent carboxylic acid composition (C-1)

26.1 g of isocyanuric acid tris (2-hydroxyethyl) and 123.4 g of ricardized MH-T (4-methylhexahydrophthalic anhydride of Shikoku Chemicals) were charged into a glass 500 ml separable flask while purging with nitrogen, , A Dimroth condenser, a stirrer, and a thermometer, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 78 占 폚, and the reaction was continued for 4 hours. 1% or less of the peak of isocyanuric acid tris (2-hydroxyethyl) was confirmed by GPC to obtain 147 g of a polycarboxylic acid composition (C-1) which is a mixture of a polycarboxylic acid and a carboxylic acid anhydride compound . The obtained mixture was a colorless transparent liquid, and the purity by GPC was 59.5% by area of the polyvalent carboxylic acid (A-1) represented by the formula (23), 4-methylhexahydrophthalic acid 1.3% by area, and 4-methylhexahydrophthalic anhydride was 39.3% by area. The functional group equivalent was 206 g / eq, the viscosity was 32154 mPa · s, and the thermogravimetric reduction was -20.8%.

Example 3: Preparation of polyvalent carboxylic acid composition (C-2)

20 g of the polyvalent carboxylic acid composition (C-1) obtained in Example 2 and 6.67 g of Ricaside MH-T (4-methylhexahydrophthalic acid, manufactured by Shikoku Seiko Co., Ltd.) were put into a container made of polypropylene and mixed with about a spoon 26.6 g of the polycarboxylic acid composition (C-2) was obtained. The obtained mixture was a colorless transparent liquid phase, and the purity by GPC was 46.2% by area of a polyvalent carboxylic acid ((A-1) represented by the above formula (23)), 4-methylhexahydrophthalic acid ) Was 3.9% by area, and 4-methylhexahydrophthalic anhydride was 49.9% by area. The functional group equivalent was 187 g / eq, the viscosity was 24678 mPa · s, and the thermogravimetric reduction was -31.7%.

Example 4; Preparation of polycarboxylic acid composition (C-3)

3 g of the polyvalent carboxylic acid (A-1) obtained in Example 1 and 7 g of ricaside MH-T (4-methylhexahydrophthalic acid, manufactured by Shikoku Seiko Co., Ltd.) were introduced into a glass 50 ml bottle, And warmed. The mixture was withdrawn after 2 hours, mixed well with a spoon, and then warmed for another 2 hours to obtain 10 g of the polycarboxylic acid composition (C-3). The obtained polyvalent carboxylic acid composition (C-3) was a colorless transparent liquid, and its purity by GPC was 34.3% by area in the polyvalent carboxylic acid (A-1 represented by the formula (23) Hexahydrophthalic acid was 2.6% by area and 4-methylhexahydrophthalic anhydride was 63.1% by area. The functional group equivalent was 187 g / eq, the viscosity was 1884 mPa · s, and the thermogravimetric reduction was -28.2%.

Comparative Example 1; Dissolution test of polycarboxylic acid having isocyanuric acid skeleton to carboxylic acid anhydride compound

3 g of isocyanuric acid tris (3-carboxypropyl) represented by the following formula (25) and 7 g of ricaside MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Seiko Co., Ltd.) were added to a glass 50 ml bottle, In a heated oven. After 2 hours, the mixture was withdrawn and mixed well with a spoon. The mixture was heated in a magnetic stirrer heated to 90 DEG C with stirring for 5 hours, but isocyanuric acid tris (3-carboxypropyl) -T did not dissolve. Stirring was stopped, and after 15 hours at room temperature (25 캜), it was confirmed that isocyanuric acid tris (3-carboxypropyl) had precipitated.

(Evaluation test)

4-methylhexahydrophthalic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., Riccad MH-T) as the polyvalent carboxylic acid obtained in Example 1, the polyvalent carboxylic acid composition obtained in Examples 2 to 4 and Comparative Example 1, , The acid value, the functional group equivalent, the viscosity and the thermogravimetric reduction of the respective components are summarized in Table 1.

* Indicates that the data is area% of the GPC chart.

As is apparent from the results in Table 1, the polyvalent carboxylic acid compositions (C-1 to C-3) containing the polyvalent carboxylic acid (A-1) and the polyvalent carboxylic acid (A- The amount of 4-methylhexahydrophthalic anhydride of Comparative Example A was reduced by a large amount. In Comparative Example 1, precipitation was confirmed by standing as a clouding liquid. However, since the polyvalent carboxylic acid compositions (C-1 to C-3) are colorless and transparent liquids, Lt; / RTI >

Example 5; Preparation of epoxy resin composition

(3), 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Co., Ltd., CEL2021P) as the epoxy resin, and the polyvalent carboxylic acid composition (C- As a promoter, zinc octylate was placed in a polypropylene container in the proportions shown in Table 2 below, mixed and defoamed for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 6; Preparation of epoxy resin composition

An epoxy resin composition of the present invention was obtained in the same manner as in Example 5 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 .

Example 7; Preparation of epoxy resin composition

The epoxy resin composition of the present invention was obtained in the same manner as in Example 5 except that zinc octylate in Example 5 was changed to a curing accelerator U-CAT5003 (manufactured by San Jae Pro) of a quaternary phosphonium bromide salt.

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 zinc octylate was added to the curing accelerator U-CAT5003 of quaternary phosphonium bromide salt (Manufactured by SAN-PRO), the procedure of Example 5 was repeated to obtain an epoxy resin composition of the present invention.

Comparative Example 2; Preparation of epoxy resin composition

(4-methylhexahydrophthalic anhydride, manufactured by Shin-Nippon Rikagaku Co., Ltd.) as an epoxy resin curing agent, 3 parts by weight of 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ), CEL2021P) and zinc octylate as a curing accelerator were placed in a container made of polypropylene in the proportions shown in Table 2 below, followed by mixing and defoaming for 5 minutes to obtain an epoxy resin composition of a comparative example.

Comparative Example 3; Preparation of epoxy resin composition

An epoxy resin composition of a comparative example was obtained in the same manner as in Comparative Example 2 except that zinc octylate of Comparative Example 3 was changed to a curing accelerator U-CAT5003 (manufactured by San Aro Co.) of a quaternary phosphonium bromide salt.

Table 2 shows the mixing ratios of the epoxy resin compositions obtained in Examples 5 to 8 and Comparative Examples 2 and 3, the viscosity thereof, the weight loss at the time of curing, the cured product permeability, the hardness of the cured product, The tests in Table 2 were carried out as follows.

(1) Viscosity

The measurement was carried out at 25 캜 using an E-type viscometer (TV-20) manufactured by Toki Sangyo Corporation.

(2) Weight reduction during curing

After the epoxy resin composition obtained in Examples 5 to 8 and Comparative Examples 2 and 3 was subjected to vacuum degassing for 5 minutes, a glass substrate on which a dam was formed with a heat-resistant tape so as to have a mass of 30 mm x 20 mm x height of 0.8 mm And the mass after the mold was weighed. The preform was pre-cured at 120 ° C for 1 hour and then cured at 150 ° C for 3 hours. The weight after curing was weighed to calculate the weight reduction rate at the time of curing.

(3) Cured product permeability

The epoxy resin compositions obtained in Examples 5 to 8 and Comparative Examples 2 and 3 were subjected to vacuum degassing for 5 minutes and then gently cast on a glass substrate on which a dam was formed with heat resistant tape so as to have a size of 30 mm x 20 mm x height 0.8 mm. The preform was pre-cured at 120 ° C for 1 hour and then cured at 150 ° C for 3 hours 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: 2.0 nm

Scan speed: 120 nm / min

(4) Cured hardness

The durometer hardness was measured by the method described in JIS K6253.

(5) Exposure of gold wire

The epoxy resin compositions obtained in Examples 5 to 8 and Comparative Examples 2 and 3 were subjected to vacuum degassing for 5 minutes, then filled in a syringe, and a light emitting element having an emission wavelength of 450 nm was formed using a precision ejection apparatus, The mold was molded so that the openings were flat on the surface mount type LED (openings of 2.3 mm x 0.4 mm, depth of 0.4 mm, and uppermost portions of the gold wires were located at positions 0.1 mm from the openings). Preliminarily cured at 120 ° C for 1 hour, and then cured at 150 ° C for 3 hours to seal the surface mount type LED. The presence or absence of the exposure of the gold wire due to the volatilization of the curing agent after the sealing (the upper end of the gold wire was located above the uppermost surface of the cured product and the wire was not completely sealed) was visually evaluated. In the table, A; Gold wire is not exposed, B; It indicates that the gold wire is exposed.

* Since the cured product was shattered, it could not be drawn out from the glass substrate.

As is clear from the results in Table 2, the compositions of Examples 5 to 8 are suitable for use as an LED sealing material, and exhibit excellent workability due to a reduction in thermal weight at the time of curing. In addition, although the cured products had a high cured product permeability and hardness and no gold wire of the surface mount type LED sealed with them was exposed, Comparative Examples 2 and 3, which were cured with only 4-methylhexahydrophthalic anhydride, The weight loss of the hour was remarkable, and the gold wire was exposed. From the above, the epoxy resin composition using the polyvalent carboxylic acid composition of the present invention is particularly preferable as the curable resin composition for optical semiconductor encapsulation.

Wherein the formula (1) R ⁶ a, R ^2b is an ethylene group and a propylene group formula (9) indicated an organic group polyvalent carboxylic acid (A) a polyvalent carboxylic acid composition in a liquid comprising a carboxyl group that is in of the (C ) Example -

GPC, acid value, functional group equivalent, viscosity, and thermal weight loss in the examples of synthesis and examples were measured by the same method as described above. Unless otherwise specified, parts denote parts by weight.

Example 9; Preparation of polyvalent carboxylic acid (A-2)

26.1 g of isocyanuric acid tris (2-hydroxyethyl), 31.0 g of anhydrous succinic acid, and 100 g of methyl isobutyl ketone were charged into a glass 500 ml separable flask while purging with nitrogen, and a dimer cooler, a stirrer, a thermometer And settled the flask in the oil bath. The oil bath was heated, and the internal temperature was maintained at 80 DEG C, and the reaction was continued for 62 hours.

The obtained reaction solution was concentrated under reduced pressure at 100 占 폚 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 was 90.0% for the compound represented by the formula (26), 2.1% for the multimer of the compound represented by the formula (26), 4.6% for the compound represented by the formula (27) , And succinic acid was 2.6%. The acid value of A-2 was 218.1 mg KOH / g and the appearance was a pale yellow transparent liquid. In addition, the thermogravimetric reduction was -0.6%. A GPC chart of the obtained A-2 is shown in Fig.

Example 10; Preparation of polyvalent carboxylic acid (A-3)

26.1 g of isocyanuric acid tris (2-hydroxyethyl), 35.5 g of anhydrous glutaric acid, and 100 g of toluene were charged into a glass 500 ml separable flask while purging with nitrogen, and a dimer cooler, stirrer, thermometer And soaked the flask in an oil bath. The oil bath was heated, and the internal temperature was maintained at 90 占 폚, and the reaction was continued for 32.5 hours.

The obtained reaction solution was concentrated under reduced pressure at 100 占 폚, 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), 4.3% for the anhydroglutaric acid and 1.3% for the glutaric acid. The acid value of A-3 was 285.6 mgKOH / g and the appearance was a pale yellow transparent liquid. In addition, the thermogravimetric reduction was -0.7%. A GPC chart of the obtained A-3 is shown in Fig.

Example 11; Preparation of polycarboxylic acid composition (C-3)

5 g of the polyvalent carboxylic acid (A-2) obtained in Example 9 and 5 g of ricardized MH-T (4-methylhexahydrophthalic anhydride in the product of Shikoku) were added to a glass bottle of 50 ml, Lt; / RTI > The mixture was withdrawn after 2 hours, mixed well with a spoon, and then heated for another 2 hours to obtain 10 g of a polycarboxylic acid composition (C-3). The obtained polyvalent carboxylic acid composition (C-3) was a colorless transparent liquid. The GPC area% of the obtained polyvalent carboxylic acid composition (C-3) was 48.8% Was 1.3%, the compound represented by the formula (27) was 0.3%, the anhydrous succinic acid was 1.4%, and the 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 thermogravimetric reduction was -19.9%.

Example 12; Production of polyvalent carboxylic acid composition (C-4)

5 g of the polyvalent carboxylic acid (A-3) obtained in Example 10 and 5 g of ricaside MH-T (4-methylhexahydrophthalic anhydride, manufactured by Shikoku Chemicals Co., Ltd.) were fed into a glass 50 ml bottle, Lt; / RTI > The mixture was withdrawn after 2 hours, mixed well with a spoon, and then heated for another 2 hours to obtain 10 g of a polycarboxylic acid composition (C-4). The obtained polyvalent carboxylic acid composition (C-4) was a colorless transparent liquid. The GPC area% of the obtained polyvalent carboxylic acid composition (C-4) was 40.6% Was 11.5%, the anhydroglutaric acid was 3.7%, the glutaric acid was 0.7%, and the 4-methylhexahydrophthalic anhydride was 43.5%. The functional group equivalent of C-4 was 308 mgKOH / g, the viscosity was 5356 mPa · s, and the thermogravimetric reduction was -24.7%.

Comparative Example 4; Dissolution Test of Polyvalent Carboxylic Acid Having Isocyanuric Acid Structure with Carboxylic Anhydride Compound

3 g of isocyanuric acid tris (3-carboxypropyl) represented by the above formula (25) and 7 g of ricaside MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Seiko Co., Ltd.) were added to a glass bottle of 50 ml, In a heated oven. After 2 hours, the mixture was withdrawn and mixed well with a spoon. The mixture was warmed with stirring on a magnetic stirrer heated to 90 DEG C for 5 hours with a rotator placed in a glass bottle, but isocyanuric acid tris (3-carboxypropyl) -T did not dissolve. Stirring was stopped, and after 15 hours at room temperature (25 캜), it was confirmed that isocyanuric acid tris (3-carboxypropyl) had precipitated.

(Evaluation test)

The polyvalent carboxylic acid compositions obtained in Examples 9 and 10, the polyvalent carboxylic acid compositions obtained in Examples 11 and 12 and Comparative Example 4, and 4-methylhexahydrophthalic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., Rikasid MH- T, the acid value, the functional group equivalent, the viscosity and the thermogravimetric reduction of the respective components are summarized in Table 3.

* Viscosity at 25 ° C could not be measured because A-2 and A-3 are liquids of a high viscosity.

The content of components in Examples 9 to 12 represents data on the area% of GPC.

As is clear from the results in Table 3, the polyvalent carboxylic acid compositions C-3 and C-4 each containing the polyvalent carboxylic acids A-2 and A-3 and the polyvalent carboxylic acids A- The weight loss of the 4-methylhexahydrophthalic anhydride of Comparative Example B was large, while the weight loss of the sample was small. The polyvalent carboxylic acid compositions C-3 and C-4 and the polyvalent carboxylic acids A-2 and A-3 were colorless and transparent liquids, It is suitable for use in applications where it is required to be used as a catalyst.

Example 13; Preparation of epoxy resin composition

(A-2) obtained in Example 9, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Daicel, CEL2021P) as the epoxy resin, As a promoter, zinc octylate was placed in a polypropylene vessel in the proportions shown in Table 4 below, mixed and defoamed for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 14; Preparation of epoxy resin composition

An epoxy resin composition of the present invention was obtained in the same manner as in Example 13 except that the polyvalent carboxylic acid (A-2) of Example 9 was changed to the polyvalent carboxylic acid composition (C-3) obtained in Example 11.

Example 15; Preparation of epoxy resin composition

An epoxy resin composition of the present invention was obtained in the same manner as in 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.

Example 16; Preparation of epoxy resin composition

An epoxy resin composition of the present invention was obtained in the same manner as in Example 13 except that the polyvalent carboxylic acid (A-1) of Example 13 was changed to the polyvalent carboxylic acid composition (C-4) obtained in Example 12.

Comparative Example 5; Preparation of epoxy resin composition

(4-methylhexahydrophthalic anhydride, manufactured by Shin-Nippon Rikagaku Co., Ltd.) as an epoxy resin curing agent, 3 parts by weight of 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ), CEL2021P), and zinc octylate as a curing accelerator were charged into a container made of polypropylene in the proportions shown in Table 4, followed by mixing and defoaming for 5 minutes to obtain an epoxy resin composition of a comparative example.

Comparative Example 6; Preparation of epoxy resin composition

The epoxy resin composition of Comparative Example 5 was obtained in the same manner as in Comparative Example 5, except that zinc octylate of Comparative Example 5 was changed to a curing accelerator U-CAT5003 (manufactured by San A Co.) of quaternary phosphonium bromide salt.

Table 4 shows the compounding ratios of the epoxy resin compositions obtained in Examples 13 to 16 and Comparative Examples 5 and 6, the viscosity thereof, the weight loss upon curing, the cured product permeability, the hardness of the cured product, The tests in Table 4 were carried out in the same manner as described above.

* Since the cured product was shattered, it could not be drawn out from the glass substrate.

As is clear from the results in Table 4, the compositions of Examples 13 to 16 are suitable for use as an LED sealing material, and have excellent workability because of a reduced weight loss upon curing. In addition, although the cured products thereof had a high cured product permeability and hardness, and no gold wire of the surface mount type LED sealed with them was exposed, Comparative Examples 5 and 6, which were cured with only 4-methylhexahydrophthalic anhydride, The weight loss of the hour was remarkable, and the gold wire was exposed. From the above, the epoxy resin composition using the polyvalent carboxylic acid composition of the present invention is particularly preferable as the curable resin composition for optical semiconductor encapsulation.

- Examples in which R ⁶ in the formula (1) is a solid thermosetting resin composition which is a polyvalent carboxylic acid (A) which 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.

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 was a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the eluent was tetrahydrofuran and the flow rate was 1 ml / min. The column temperature was 40 캜, and the detection was carried out by RI (Reflective index). The calibration curve was standard polystyrene standardized by Shodex. The functional group equivalent was calculated from the ratio calculated from GPC, and the value was determined by making one equivalent of each of carboxylic acid and acid anhydride.

2) ICI viscosity

And the melt viscosity in the cone plate method at 150 占 폚 was measured.

3) Softening point

It was measured by the method according to JIS K-7234.

Synthesis Example 1 (Curing agent for thermosetting resin C-5)

A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 104.5 parts of isocyanuric acid tris (2-hydroxyethyl), 10 parts of methylhexahydrophthalic anhydride (manufactured by Shinnippon Pharmaceutical Co., Ltd., MHT) and 306.0 parts of MEK were added, and the mixture was heated and stirred at 70 占 폚 for 7 hours to obtain a MEK solution of the compound represented by the formula (29). And 61.3 parts of methylhexahydrophthalic anhydride (Rikaside MHT, manufactured by Shin-Nippon Rikagaku) was added thereto, and the mixture was heated and stirred at 70 ° C for 1 hour. Thereafter, the solvent was removed under the conditions of 120 占 폚 for 1 hour to obtain a curing agent for thermosetting resin (C-5).

The curing agent obtained was colorless and solid. The functional group equivalent was 232 g / eq. The ICI viscosity was 0.36 Pa · s at 150 ° C. The softening point was 82.9 ° C.

Synthesis Example 2 (Curing agent for thermosetting resin C-6)

(In the formula (30), R ¹⁰ represents a methyl group or a carboxyl group, respectively. In formula (30), plural R ^{10 s} present may be the same or different.)

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 98.1 parts of tricyclodecane dimethanol, 166.3 parts of methyl hexahydrophthalic anhydride (Rikacid MHT, manufactured by Shin-Nippon Rika KK), 10.0 parts of cyclohexane -1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Company, H-TMAn) and 266.4 parts of MEK were added and reacted at 60 ° C for 1 hour, followed by heating and stirring at 80 ° C for 5 hours To obtain a MEK solution of the compound represented by the formula (30). 59.4 parts of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Company) was added and the mixture was heated and stirred at 80 ° C for 2 hours. Thereafter, the solvent was removed under the condition of 150 占 폚 for 1 hour to obtain a curing agent for thermosetting resin (C-6).

The curing agent obtained was colorless and solid. The functional group equivalent was 195 g / eq. 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 a phenol compound (TPA1) (TrisP-PA Honshu Kagaku Co., Ltd., , 370 parts of epichlorohydrin, 37 parts of methyl glycidyl ether and 37 parts of methanol were added, and the water bath was heated to 75 占 폚. When the internal temperature exceeded 65 캜, 42 parts of sodium hydroxide on the flakes was dividedly added over 90 minutes, and then the reaction was further performed at 70 캜 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 400 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. 8 parts of an aqueous solution of 30% by weight of sodium hydroxide was added under stirring to conduct a reaction for 1 hour, followed by washing with water until the washing water became neutral. The resulting solution was treated with a rotary evaporator at 180 캜 under reduced pressure to give methyl isobutyl ketone Was distilled off to obtain 182 parts of an epoxy resin (B-1). The obtained epoxy resin had an epoxy equivalent of 222 g / eq., A softening point of 59.6 ° C, an ICI melt viscosity of 0.10 Pa · s (150 ° C) and a color of 0.2 or less (Gardner 40% MEK solution). Mn was 582, Mw was 695, and Mw / Mn was 1.19 (in terms of polystyrene). Total chlorine was 960 ppm.

Preparation of thermosetting light-sensitive resin composition (Examples 17 to 19)

(Trade name: TEPIC-S (triglycidylisocyanurate manufactured by Nissan Kagaku K.K.), EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), Celloxide 2021P (Curing agent for epoxy resin made by Shin-Nippon Rikagaku), Hishikolin PX-4MP (manufactured by Nippon Kagaku Kogyo Co., Ltd.), a thermosetting resin curing agent C-5, a thermosetting resin curing agent C- Each component was compounded in accordance with the formulation table shown in Table 5, and sufficiently kneaded by a mixer, and then melt-kneaded under a predetermined condition by a mixing roll, followed by cooling and pulverization. The thermosetting resin composition of Example 19 was prepared. The unit of the blending amount of each component in Table 5 is parts by weight, and the blank indicates that the above components are not used.

Evaluation of thermosetting resin composition

With respect to the resin compositions of Examples 17 to 19, DMA, TMA and transmittance of the cured product were measured by the following methods. The results are shown in Table 5.

(a) DMA

With respect to the dynamic mechanical analysis (DMA), a test specimen prepared as described below was subjected to a method described in JIS K7244 and JIS K7244-4, using a DMS6100 viscoelasticity measuring device manufactured by SII Eye Nanotechnology Co., Ltd. Lt; / RTI > The glass transition temperature Tg represents the temperature at which the maximum value of the loss coefficient (tan? = E "/ E ') expressed on the storage elastic modulus (E') and the loss elastic modulus (E").

(DMA specimen preparation method)

The resin compositions of each of the examples and comparative examples were transferred and molded under the conditions of a mold temperature of 150 캜, a molding pressure of 10.4 MPa and a cure time of 300 seconds and then post-cured at 150 캜 for 3 hours to obtain a resin composition having a length of 50.0 mm, Mm test pieces were produced.

(DMA measurement condition)

Initial tension: 0.1 N

Frequency: 10㎐

Measurement mode: Tensile vibration

Measuring temperature: 30 ° C to 280 ° C

Heating rate: 2 캜 / min

(b) Thermomechanical analysis (TMA)

The thermomechanical analysis (TMA) was carried out using the test piece prepared as described below and measuring under the following conditions using a TMA / SS6100 device manufactured by SIA i NANO TECHNOLOGY CO., LTD. The glass transition temperature (Tg) is defined as a point of change in the linear expansion coefficient of the obtained data.

(TMA specimen preparation method)

The resin compositions of each of the examples and comparative examples were transfer-molded under the conditions of a mold temperature of 150 캜, a molding pressure of 10.4 MPa, and a cure time of 300 seconds, and then post-cured at 150 캜 for 3 hours to prepare test pieces having a thickness of 4.0 mm.

(TMA measurement condition)

Temperature rise condition: 2 ° C / minute

Measurement mode: Compression

(d) Transmittance

The resin compositions of each of the examples and comparative examples were transfer-molded under the conditions of a molding die temperature of 150 캜, a molding pressure of 10.4 MPa, and a cure time of 300 seconds, and post-curing was performed at 150 캜 for 3 hours to produce a test piece having a thickness of 1.0 mm. Then, the transmittance at a wavelength of 460 nm was measured with an integral spherical spectrophotometer UV-3600 (manufactured by Shimadzu Seisakusho Co., Ltd.), and the coloration of each test piece was evaluated.

From the above results, it can be seen that the thermosetting resin composition using the thermosetting resin curing agent of the present invention gives a cured product having a sufficiently high glass transition temperature, low linear expansion rate, and little coloration of the cured product.

Preparation of thermosetting light-use resin composition (Examples 20 and 21)

(Glycidyl ether type epoxy resin B-1, Hikikolin PX-4MP (a curing catalyst manufactured by Nippon Kayaku Co., Ltd.)), TEPIC-S (triglycidyl isocyanurate manufactured by Nissan Kagaku K.K.) , And CR-95 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) were used, and the respective components were blended according to the formulation table shown in Table 6, sufficiently kneaded by a mixer, and melt-kneaded under a predetermined condition by a mixing roll, And pulverized to prepare thermosetting resin compositions of Examples 20 and 21. The unit of the blending amount of each component in Table 6 is parts by weight, and the blank indicates that the above components are not used.

From the above results, it can be seen that the thermosetting resin composition using the thermosetting resin curing agent of the present invention gives a cured product having a sufficiently high glass transition temperature, low linear expansion rate, and little coloration of the cured product.

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 130.6 parts of isocyanuric acid tris (2-hydroxyethyl), 10 parts of methylhexahydrophthalic anhydride (manufactured by Shinnippon Pharmaceutical Co., Ltd., MHT), 59.9 parts of anhydrous glutaric acid, and 350.0 parts of MIBK were added, and the mixture was heated and stirred at 85 ° C for 9 hours to obtain a desired compound MIBK solution. Thereafter, the solvent was removed under the conditions of 150 ° C for 1 hour to obtain a curing agent for thermosetting resin (C-7).

The curing agent obtained was colorless and solid. The functional group equivalent was 242 g / eq. The ICI viscosity was 0.51 Pa · s at 150 ° C. The softening point was 77.6 ° C.

Preparation of thermosetting light-sensitive resin composition (Example 22)

EHPE-3150 (a cycloaliphatic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), a curing agent for thermosetting resin C-7, Hishikolin PX-4MP (a curing catalyst manufactured by Nippon Kagaku Kogyo K.K.), CR- Titanium oxide produced by Sankyo Co., Ltd.) was used and each component was compounded in accordance with the formulation table shown in Table 7, sufficiently kneaded by a mixer, and then melt-kneaded under a predetermined condition by a mixing roll, followed by cooling and pulverization, 22 < / RTI > The unit of the blending amount of each component in Table 7 is parts by weight, and the blank indicates that the above components are not used.

From the above results, it can be seen that the thermosetting resin composition using the thermosetting resin curing agent of the present invention gives a cured product having a sufficiently high glass transition temperature, low linear expansion rate, and little coloration of the cured product.

Example 23; Preparation of polyvalent carboxylic acid composition (C-8)

A glass 300 mL four-necked flask was charged with 25.8 g of THEIC-G (isocyanuric acid tris (2-hydroxyethyl), manufactured by Shikoku Chemicals Co., Ltd.), HTMAn-S (hydrogenated trimellitic anhydride ), And 50 g of MEK were put into the flask, and the flask was immersed in a water bath by installing a demultiplex cooler, a stirrer, and a thermometer. The water bath was heated to maintain the internal temperature at 65 占 폚, and the reaction was continued for 6 hours. Thereafter, 49.4 g of Ricassid MH-T (4-methylhexahydrophthalic acid manufactured by Shin-Etsu Chemical Co., Ltd.) and 50 g of MEK were added, and the water bath was heated to maintain the internal temperature at 65 캜 and reacted for 4 hours.

The reaction solution obtained by confirming that the peak area of trihydroxyethyl isocyanuric acid was 1% or less by GPC was concentrated under reduced pressure at 150 ° C and the MEK was distilled off to obtain a polyvalent carboxylic acid and a carboxyl 90.4 g of a polycarboxylic acid composition (C-8) which is a mixture of acid anhydride compounds was obtained. The appearance of the obtained compound was a colorless solid, and the purity (GPC area%) by GPC was 2.4% for the mixture of the polyvalent carboxylic acid high molecular weight compound represented by the formula (a2 to a4), the polyvalent carboxyl represented by the formula , An acid was 82.9%, a cyclohexane-1,2,4-tricarboxylic acid represented by the formula (a5) was 1.5%, a 4-methylhexahydrophthalic acid represented by the formula (a6) was 5.4%, 4-methylhexahydrophthalic acid The anhydride content was 7.8%. The functional group equivalent was 188.8 g / eq, the ICI viscosity at 150 ° C was 1.49 Pa · s, and the softening point was 95.3 ° C. A GPC chart of the obtained compound is shown in Fig.

In the formula (a1), R ⁹ is a methyl group or a carboxyl group.

In the formulas (a2 to a4), R ⁹ has the same meaning as described above.

Example 24; Preparation of thermosetting light-sensitive resin composition

The polyvalent carboxylic acid composition (C-8), EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), Hikikolin PX-4MP (manufactured by Nippon Kayaku Kogyo Co., Ltd.) ), FB-910 (silica produced by Denki Kagaku Kogyo Co., Ltd.) and CR-75 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) were used to blend each component in accordance with the formulation table shown in Table 8, After kneading, the mixture was melt-kneaded under a predetermined condition by a mixing roll, followed by cooling and pulverization to prepare a thermosetting resin composition of Example 24.

Table 8 shows the compounding ratio of the thermosetting resin composition obtained in Example 24, the glass transition temperature, the coefficient of linear expansion and the reflectance. The unit of the blending amount of each component in Table 8 is parts by weight, and the blank indicates that the above components are not used.

Example 25; Preparation of thermosetting light-sensitive resin composition

(A-3), EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), Hikikolin PX-4MP (a curing catalyst manufactured by Nippon Kayaku Kogyo Co., Ltd.) , Each component was blended according to the formulation table shown in Table 9 using FB-910 (silica manufactured by Denki Kagaku Kogyo Co., Ltd.) and CR-75 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) Then, the mixture was melt-kneaded under a predetermined condition by a mixing roll, followed by cooling and pulverization to prepare a thermosetting resin composition of Example 25.

Table 9 shows the compounding ratio of the thermosetting resin composition obtained in Example 25, the glass transition temperature, the coefficient of linear expansion and the reflectance. The unit of the blending amount of each component in Table 9 is parts by weight, and the blank indicates that the above components are not used.

Although the present invention has been described in detail with reference to specific embodiments thereof, 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 present invention.

This application is also a continuation-in-part of Japanese Patent Application No. 2014-150862 filed on July 24, 2014, Japanese Patent Application No. 2014-212176 filed on October 17, 2014, December 16, 2014 (Japanese Patent Application No. 2014-254374), filed on the same date, and the entirety thereof is cited by reference. In addition, all references cited herein are incorporated by reference in their entirety.

≪ Industrial Availability >

INDUSTRIAL APPLICABILITY The polyvalent carboxylic acid of the present invention and the polyvalent carboxylic acid composition containing the polyvalent carboxylic acid of the present invention exhibit less volatilization and excellent curability at the time of curing and the cured product imparts a cured product having excellent transparency and hardness, It is useful for material applications, especially for optical semiconductor encapsulation, as a light semiconductor reflector. Further, 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, so that the molded product is excellent in moldability and less colored in a cured product. Therefore, Sealing materials for devices, and reflective materials.

Claims (18)

A polyvalent carboxylic acid represented by the following formula (1).

(Formula (1) of, R ¹ is an alkylene group having 1 to 6, R ⁶ is a hydrogen atom or represents respectively an organic group containing a carboxyl group having 1 to 10 carbon atoms. In the formula (1), a plurality existence R ¹ to And R ⁶ may be the same or different, but among the plural R ^{6 s} , at least 50 mol% is an organic group containing a carboxyl group having 1 to 10 carbon atoms.) The method according to claim 1,
A polyvalent carboxylic acid represented by the following formula (1-1).

(In formula (1-1) wherein R ¹ represents the same meanings as defined above, R ^2a represents an alkyl group or a carboxyl group of a hydrogen atom, a group having 1 to 6 carbon atoms, respectively. In the formula (1-1) wherein R ¹ to present a plurality , And R < ^2a > may be the same or different. The method according to claim 1,
A polyvalent carboxylic acid represented by the following formula (1-2).

(In the formula (1-2), R ¹ has the same meaning as defined above, and R ^2b represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ¹ and R ^2b may be the same or different. A polybasic carboxylic acid composition containing the polybasic carboxylic acid according to any one of claims 1 to 3. 5. The method of claim 4,
A polycarboxylic acid composition further comprising a carboxylic acid anhydride compound. 6. The method of claim 5,
Wherein the carboxylic acid anhydride compound is at least one selected from the compounds represented by the following formulas (2) to (7).

A polyvalent carboxylic acid composition according to any one of claims 1 to 3, or a polyvalent carboxylic acid composition according to any one of claims 4 to 6, and an epoxy resin composition containing an epoxy resin. 8. The method of claim 7,
And an epoxy resin curing accelerator. 9. The method of claim 8,
Wherein the epoxy resin curing accelerator is a metal soap. 10. The method of claim 9,
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 7 to 10. A thermosetting resin composition comprising a polyvalent carboxylic acid according to any one of claims 1 to 3 and a thermosetting resin and having an ICI cone plate viscosity in a range of 100 to 200 占 폚 in a range of 0.01 Pa · s to 10 Pa · s . 13. The method of claim 12,
And the softening point is in the range of 20 占 폚 to 150 占 폚. The method according to claim 12 or 13,
But are not limited to, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride , And methylhexahydrophthalic anhydride, and a curing agent for a thermosetting resin containing one or more compounds selected from methylhexahydrophthalic anhydride,
But are not limited to, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride , And methylhexahydrophthalic anhydride is 1% by weight to 90% by weight of the total amount of the compound. 15. The method according to any one of claims 12 to 14,
Wherein the cured product has a glass transition temperature (Tg) of 30 占 폚 or higher. A cured product obtained by thermally curing the thermosetting resin composition according to any one of claims 12 to 15. A photosemiconductor device sealed with the cured product according to claim 16. A photosemiconductor device using the cured product according to claim 16 as a reflective material.

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