JP6669653B2 - Polyvalent carboxylic acid, polyvalent carboxylic acid composition containing the same, epoxy resin composition, thermosetting resin composition, cured product thereof, and optical semiconductor device - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention is particularly suitable for optical semiconductor encapsulation, for use in a part where high transparency and low coloring properties are required, such as an optical semiconductor reflector, particularly when used in an optical semiconductor reflector or an optical semiconductor device including the same. A polyvalent carboxylic acid which can sufficiently raise the glass transition temperature of a cured product and has excellent moldability and a polyvalent carboxylic acid composition containing the same, a thermosetting resin composition, an epoxy resin composition, and curing them. And an optical semiconductor device.

Epoxy resin compositions are used as resins having excellent heat resistance in fields such as construction, civil engineering, automobiles, and aircraft. In recent years, especially in the field of semiconductor-related materials, products such as camera-equipped mobile phones, ultra-thin liquid crystal and plasma TVs, and lightweight notebook personal computers have been flooded with products where the key is light, thin, short, and small. Very high characteristics are also required for package materials represented by resins.
Furthermore, in recent years, the use in optoelectronics-related fields has attracted attention, and with the advancement of information technology, technology that utilizes optical signals instead of signal transmission using conventional electrical wiring in order to smoothly transmit and process vast amounts of information. In the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, the development of resin compositions that give cured products having excellent transparency has been desired.
As an epoxy resin curing agent generally used in the optoelectronics-related field, an acid anhydride-based compound can be used. In particular, acid anhydrides formed of saturated hydrocarbons are often used because cured products have excellent light resistance. As these acid anhydrides, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and tetrahydrophthalic anhydride are generally used, and among them, methyltetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Phthalic anhydride is mainly used because of its easy handling.

However, when the above alicyclic acid anhydride is used as a curing agent for epoxy resin, these compounds have a high vapor pressure and a part of the compound evaporates during curing. When this is done, the acid anhydride itself volatilizes into the atmosphere. As a result, an epoxy resin composition resulting from environmental pollution due to the release of harmful substances to the atmosphere, adverse effects on the human body, contamination of production lines, and the absence of a predetermined amount of carboxylic anhydride (curing agent) in the cured product. This causes problems such as poor curing. Variations in curing conditions due to volatilization of the curing agent cause variations in physical properties of the cured product, and it is difficult to obtain a cured product having the intended performance stably.
Further, the problem of volatilization is remarkable when an LED, particularly an SMD (Surface Mount Device) is sealed with a curable resin composition for encapsulating an optical semiconductor which is formed using a conventional acid anhydride as a curing agent. Since the amount of resin used is small, dents occur, and in severe cases, the wires are exposed. Furthermore, there is 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 or the like. However, the polycarboxylic acid described in Patent Literature 1 is difficult to dissolve in an acid anhydride compound, and is difficult to adapt in a field where it is necessary to use a liquid at room temperature (25 ° C).

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

  An acid anhydride used as a curing agent for a thermosetting resin has a problem that it is not suitable for mold molding because of its volatility and low melting point.

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

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

Similarly, the polycarboxylic acid compound has a high melting point (150 ° C. or higher), has high crystallinity, and is difficult to knead with the resin.
Therefore, no compound that can achieve the above object has been found as a conventionally known material.

Japanese Patent No. 3765946 WO 2005/049597 pamphlet WO 2005/121202 pamphlet

  When the present invention is used for curing in an open system such as an SMD type LED encapsulating material, the volatilization at the time of curing is small and the curability is excellent, and the cured product gives a cured product having excellent transparency and hardness. An object of the present invention is to provide a polycarboxylic acid, a polycarboxylic acid composition containing the same, an epoxy resin composition, and a cured product thereof. Furthermore, the polyvalent carboxylic acid which can sufficiently raise the glass transition temperature of the cured product, is excellent in moldability, and has little coloring to the cured product, a thermosetting resin composition using the same, and such a thermosetting resin Provided is a semiconductor device using the composition as a sealing material or a reflecting material.

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

(In 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. The existing R ¹ and R ⁶ may be the same or different, but among the plurality of R ⁶ , 50 mol% or more is an organic group containing a carboxyl group having 1 to 10 carbon atoms. )
[2] The polyvalent carboxylic acid according to [1], represented by the following formula (1-1).

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

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

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

According to the present invention, an epoxy resin composition containing a polyvalent carboxylic acid having a specific structure having an isocyanuric ring or a polyvalent carboxylic acid composition containing the same has excellent volatilization during curing and excellent curability, and Since the cured product gives a cured product having excellent transparency and hardness, it is required to form a cured product of high transparency and a thin film, and is extremely useful as a material, particularly a resin for encapsulating an optical semiconductor (such as an LED).
In addition, a polyvalent carboxylic acid having a sufficient glass transition temperature of the cured product, having excellent moldability, and being less colored when the cured product is obtained, a thermosetting resin composition using the same, and the thermosetting resin thereof An optical semiconductor device using the composition as a sealing material or a reflecting material can be provided. Furthermore, by suppressing the softening point, handling becomes easy and sufficient kneading becomes possible, so that a cured product having excellent cured properties can be provided. In addition, a thermosetting resin composition having excellent toughness of the cured product and excellent reactivity of the resin can be provided.

3 is a GPC chart of the polyvalent carboxylic acid (A-1) obtained in Example 1. 9 is a GPC chart of the polyvalent carboxylic acid (A-2) obtained in Example 9. 13 is a GPC chart of the polyvalent carboxylic acid (A-3) obtained in Example 10. 19 is a GPC chart of the polyvalent carboxylic acid composition (C-8) obtained in Example 23.

  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 an organic group containing a hydrogen atom or a carboxyl group having 1 to 10 carbon atoms.

Specific examples of R ¹ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, an isobutylene group, an isopentylene group, a neopentylene group, an isohexylene group, and a cyclohexylene group. However, from the viewpoint of 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 a hydrogen atom or an organic group containing a carboxyl group having 1 to 10 carbon atoms. Here, the organic group, H, C, N, an O atom only consists group, R ⁶ may be any from 1 to 10 carbon atoms, an ester bond, an ether bond, a urethane bond, an amide bond, a carbonyl It may contain a group.
The organic group containing a carboxyl group having 1 to 10 carbon atoms contains one or more carboxyl groups.

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

In the formula (1), 50 mol% or more of a plurality of R ⁶ is an organic group containing a carboxyl group having 1 to 10 carbon atoms. When the content is 50 mol% or more, the cured product has excellent mechanical strength. Further, it is more preferably at least 70 mol%.

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

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

Specific examples of the alkyl group having 1 to 6 carbon atoms in R ^2a 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, Examples thereof include a cyclopentyl group, a hexyl group, an isohexyl group, and a cyclohexyl group, and a methyl group is preferable from the viewpoint of heat resistance and transparency of the obtained cured product.

Among R ^2a , a methyl group and a carboxyl group are preferable, and the viewpoint that the viscosity at room temperature (25 ° C.) of the polycarboxylic acid composition (C) containing the polycarboxylic acid (A) is not excessively increased is obtained. A methyl group is preferred from the viewpoint of transparency of the cured product, and a carboxyl group is particularly preferred from the viewpoint of gas barrier properties, 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 noninylene group, a desinylene group, an isopropylene group, an isobutylene group, an isopentylene group, and a neopentylene group. Group, isohexylene group, isoheptylene group, isooctylene group, isononinylene group, isodecinylene group, dimethylpropylene group, diethylpropylene group, diethylbutylene group, diethylpentylene group, diethylpentylene group, diethylhexylene group, and the like. From the viewpoint of transparency, an ethylene group, a propylene group, and a diethylpropylene group are preferable, and the propylene group is particularly preferable because the softening point and the viscosity at room temperature (25 ° C.) of the polycarboxylic acid (A) of the present invention are low. preferable.

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

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

  The polycarboxylic acid (A) represented by the formula (1) includes a trishydroxyalkyl isocyanurate compound represented by the following formula (10), a carboxylic acid anhydride compound represented by the following formula (14) and And / or an addition reaction with a carboxylic 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 Formula (15), R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer of 1 to 9 respectively, and in Formula (15), even when a plurality of R ³ are the same, They can be different. Specific examples of the alkyl group having 1 to 4 carbon atoms in R ³ include a methyl group, an ethyl group, a propyl group, and a butyl group. m represents an integer of 1 to 9, preferably 1 to 5, and particularly preferably 1 or 2, from the viewpoint of heat 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 viewpoints of transparency and gas barrier properties of the cured product.

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

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

The production of the polycarboxylic acid (A) of the present invention can be carried out with or without a solvent. As the solvent, any solvent that does not react with the trishydroxyalkyl isocyanurate compound represented by the above formula (10) or the carboxylic anhydride compound represented by the formula (14) or (15) can be used without any particular limitation. it can. Solvents that can be used include, for example, aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, and acetonitrile; ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone; and aromatic hydrocarbons such as toluene and xylene. Hydrogen and the like are mentioned, and among 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 used is represented by the trishydroxyalkyl isocyanurate compound represented by the above formula (10) and the carboxylic anhydride compound represented by the formula (14) and / or the formula (15). The amount is preferably 0.5 to 300 parts by mass with respect to 100 parts by mass of the total of the carboxylic anhydride compound.

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

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

When a catalyst is used, one kind or a mixture of two or more kinds can be used.
The amount used when a catalyst is used is represented by the trishydroxyalkyl isocyanurate compound represented by the formula (10) and the carboxylic acid anhydride compound represented by the formula (14) and / or the formula (15). The amount is preferably 0.05 to 10 parts by mass based on 100 parts by mass of the total amount of the carboxylic anhydride compound.
The catalyst may be added directly or in a state of being dissolved in a soluble solvent or the like. At this time, use of an alcoholic solvent such as methanol or ethanol or water should be avoided because it will react with unreacted carboxylic anhydride compounds represented by the formulas (14) and (15). Is preferred.
In the present invention, from the viewpoint of improving transparency and heat-resistant transparency, a zinc carboxylate such as zinc octylate is used in the obtained cured product of the polyvalent carboxylic acid (A) or the polyvalent carboxylic acid composition (C). It can be preferably used as a catalyst, and it is preferable to perform the reaction without a catalyst from the viewpoint of reducing the coloring of the obtained polycarboxylic acid (A) or polycarboxylic acid composition (C).
Among them, in order to obtain a cured product excellent in transparency and sulfidation resistance, particularly, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc mistyphosphate) and zinc phosphate ester ( Zinc compounds such as zinc octyl phosphate and zinc stearyl phosphate are preferably used.

  The reaction temperature at the time of producing the polycarboxylic acid (A) of the present invention is usually 20 to 160 ° C, preferably 50 to 150 ° C, particularly preferably 60 to 145 ° C, although it depends on the amount of the catalyst and the solvent used. . The total reaction time is usually 1 to 20 hours, preferably 3 to 18 hours. The reaction may be carried out in two or more stages. For example, after reacting at 20 to 100 ° C for 1 to 8 hours, the reaction may be performed at 100 to 160 ° C for 1 to 12 hours. This is particularly because the carboxylic acid anhydride compounds represented by the formulas (14) and (15) often have high volatility, and when such compounds are used, they are preliminarily reacted at 20 to 100 ° C. By reacting at ~ 160 ° C, volatilization can be suppressed. This not only suppresses the diffusion of harmful substances into the atmosphere, but also makes it possible to more reliably obtain the polycarboxylic acid (A) as designed.

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

  When producing the polycarboxylic acid (A) of the present invention, gel permeation chromatography (GPC) ＰＣmeasurement conditions; column: SHOdex GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2 pieces), flow rate: 0.4 ml / min. Column temperature: 40 ° C., Solvent used: THF (tetrahydrofuran), Detector: RI (differential refraction detector)｝, the retention time of which is earlier than the peak of the compound represented by the formula (1) and the retention time which is later. Peak compounds are mixed. As the peak of the early retention time (hereinafter, referred to as peak f), there is a compound having a retention time that is 1 to 3 minutes earlier than the peak of the compound of formula (1) of the present application, for example, 18 to 20 minutes. The area% of GPC of the compound having the peak f is preferably 1 to 30 area%, and particularly preferably 1 to 10 area% from the viewpoint of an increase in mechanical strength. Further, there may be two or three peaks of the slow retention time (hereinafter, referred to as peak s), and the retention time is 1 to 5 minutes later than the peak of the compound of the formula (1), for example, Compounds of 21 to 25 minutes correspond. The area% of GPC of the compound having the peak s is preferably 1 to 10 area% from the viewpoint of improving the adhesiveness, and more preferably 1 to 5 area%. Further, a multimer of a polyvalent carboxylic acid represented by the following formula (16) may be formed. It is considered that these compounds correspond to the compound of peak f.

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

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

In the formula (18), R ¹ , R ⁴ and R ⁵ represent the same meaning as described above, and indicate that R ⁵ in the formula (16) is bonded to the oxygen atom bonded to the site of ***. Represent.

  It is preferable that the multivalent carboxylic acid represented by the formula (16) is contained in the polyvalent carboxylic acid (A) because the mechanical strength of the cured product is improved. In order not to excessively increase the viscosity of A), the amount is preferably 50 parts by mass or less based on 100 parts by mass of the polycarboxylic acid (A).

  When producing the polyvalent carboxylic acid (A) of the present invention, a divalent carboxylic acid represented by the following formula (19) may be produced. The compound is considered to correspond to the compound of peak s. Here, the GPC area% of the compound represented by the following formula (19) of the polycarboxylic acid (A) obtained by the above-mentioned production method is preferably 1 to 30 area%, more preferably 1 to 20 area%.

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

  It is preferable that the divalent carboxylic acid represented by the formula (15) is contained in the polyvalent carboxylic acid (A) because the adhesion of the cured product to the substrate is improved. Since the mechanical strength is inferior, the amount is preferably 20 parts by mass or less based on 100 parts by mass of the polycarboxylic acid (A).

  When producing the polyvalent carboxylic acid (A) of the present invention, a monovalent carboxylic acid represented by the following formula (19 ') may be produced. The compound is considered to correspond to the compound of peak s. Here, the GPC area% of the compound represented by the following formula (19 ') of the polycarboxylic acid (A) obtained by the above-mentioned production method is preferably 1 to 10 area%, more preferably 1 to 5 area%.

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

  It is preferable that the monovalent carboxylic acid represented by the formula (19 ′) is contained in the polyvalent carboxylic acid (A) because the adhesion of the cured product to the substrate is improved. Is preferably 20 parts by mass or less based on 100 parts by mass of the polyvalent carboxylic acid (A).

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

The acid value (measured by the method described in JIS K-2501) of the produced polycarboxylic acid (A) of the present invention is preferably from 150 to 415 mgKOH / g, more preferably from 185 to 375 mgKOH / g, In particular, those having 200 to 320 mgKOH / g are preferable. An acid value of 150 mgKOH / g or more is preferable because the mechanical properties of the cured product are improved, and an acid value of 415 mgKOH / g or less is preferable because the cured product does not become too hard and has an appropriate elastic modulus.
Further, the functional 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 polycarboxylic acid composition (C) of the present invention contains the polycarboxylic acid (A) of the present invention as an essential component.
Further, among the polycarboxylic acid composition (C) of the present invention, the polycarboxylic acid composition (C ′) essentially includes the polycarboxylic acid (A) of the present invention and the carboxylic anhydride compound (B). Ingredients.

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 can be obtained by uniformly mixing the above components at room temperature or under heating. For example, a spoon, an extruder, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, etc., and sufficiently mixed until uniform, and if necessary, a filtration treatment with a SUS mesh or the like. It is prepared by performing.
During preparation, an epoxy resin (D), a curing accelerator (E), an adhesion aid, an antioxidant, a light stabilizer, and the like, which will be described later, may be mixed together.

  The polycarboxylic acid composition (C) of the present invention can be used as a varnish or ink by mixing a solvent as necessary. The solvent is used for the polycarboxylic acid (A), the carboxylic anhydride compound (B), the epoxy resin (D), the curing accelerator (E), the adhesion assistant, the antioxidant, the light stabilizer and the like of the present invention. Any substance having high solubility and not reacting with them 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 aromatic hydrocarbons such as toluene and xylene. Among them, aromatic hydrocarbons and ketones are preferable.

In the polycarboxylic acid composition (C ′) of the present invention, the carboxylic acid anhydride compound represented by the formula (14) and / or the carboxylic acid compound represented by the formula (15) in the production of the polycarboxylic acid (A) described above. When the carboxylic acid anhydride compound represented and the carboxylic acid anhydride compound (B) in the polyvalent carboxylic acid composition (C ′) are the same, when the polyvalent carboxylic acid (A) is produced, the compound represented by the formula (10) Is reacted in an excess of the carboxylic anhydride compound (B) with the trishydroxyalkyl isocyanurate compound represented by the formula (1), and when the production of the polycarboxylic acid (A) is completed, the polycarboxylic acid (A) ) And carboxylic anhydride (B).
The ratio of the two charged at the time of this reaction is 0.001 to 0.7 equivalent, in terms of the functional group equivalent and 1 equivalent of the acid anhydride group, in terms of the hydroxyl equivalent of the trishydroxyalkyl isocyanurate compound. Preferably, it is charged in the range of 0.01 to 0.5 equivalent.

  By mixing the polycarboxylic acid composition (C ′) thus obtained with the carboxylic anhydride (B), the polycarboxylic acid (A) in the polycarboxylic acid composition (C ′) is mixed. Can be adjusted.

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

  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, and one or more carboxylic acid compounds selected from the following formulas (2) to (7) An acid anhydride compound 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 anhydride compound (B) is such that The amount of the acid anhydride compound (B) is preferably from 1 to 1,000 parts by mass, more preferably from 10 to 800 parts by mass, particularly preferably from 50 to 500 parts by mass.

  The polycarboxylic acid (A) or polycarboxylic acid composition (C) of the present invention functions as a curing agent for an epoxy resin, and may contain another epoxy resin curing agent. For example, an amine-based curing agent, a phenol-based curing agent, and a polycarboxylic acid resin are exemplified, and a polyvalent carboxylic acid resin is preferable.

  The polyvalent carboxylic 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 polycarboxylic acid resin is not only a polycarboxylic 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. The composition also includes a composition, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin.

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

Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- Compounds such as (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane and the like, among which 2-ethyl-2-butyl-1,3-propanediol, Neopentyl glycol, 2,4-diethylpentanediol, 1,4-sic Rohexanedimethanol, tricyclodecanedimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxy Alcohols having a branched or cyclic structure, such as compounds such as methyl-1,3-dioxane, are more preferred. From the viewpoint of imparting high sulfuration resistance, 2,4-diethylpentanediol, tricyclodecanedimethanol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxy) Compounds such as ethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane are particularly preferred. Among them, particularly in a branched structure, it is preferable to have two or more branched chains, and it is particularly preferable that the branched chains extend from different carbon atoms. Here, the alcohol having the branched chain structure or the cyclic structure preferably has 5 to 25 carbon atoms, and particularly preferably 5 to 20 carbon atoms.
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 formula (20), A ₁ represents an alkylene group having 1 to 10 carbon atoms which may be linked via an ether bond, A ₂ represents a methyl group or a phenyl group, and s is the number of repetitions and means an average value. And 1 to 100.)

The above-mentioned (a); the polyhydric alcohol compound containing two or more hydroxyl groups in the molecule may be used alone or in combination of two or more.
The obtained polyvalent carboxylic acid resin is used in a liquid state and imparts high sulfuration resistance. In order to impart high sulfide resistance, the above-mentioned polyhydric alcohol having a siloxane structure and an alcohol having a branched or cyclic structure having 5 to 25 carbon atoms are used. Are preferably used in combination.
When a polyhydric alcohol having a siloxane structure and an alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms are used as a mixture, the amount used is the total amount of the alcohol compound (polyhydric alcohol having a siloxane structure) / (Alcohol having a branched chain structure or cyclic structure having 5 to 25 carbon atoms) is preferably 1 to 20, and from the viewpoint of heat resistance and transparency of the cured product and appropriate viscosity of the polyvalent carboxylic acid resin, 5 to 15 Is preferred, and 6 to 10 are particularly preferred.

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

  When the polycarboxylic acid (A) or the polycarboxylic acid composition (C) of the present invention is used in combination with another epoxy resin curing agent, the polycarboxylic acid (A) or the polycarboxylic acid (A) of the present invention may be contained in all the epoxy resin curing agents. The proportion of the polycarboxylic acid composition (C) is preferably from 30 to 99 parts by mass, particularly preferably from 60 to 97 parts by mass. If the amount is less than 30 parts by mass, the cured product may have poor heat resistance and transparency.

  Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition in the present invention is characterized by containing a polycarboxylic acid (A) or a polycarboxylic acid composition (C) and an epoxy resin (D).

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

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

  Examples of the epoxy resin which is a glycidyl etherified product of the various novolak resins include various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and naphthols. Glycidyl etherified products of various novolak resins such as novolak resin, phenol novolak resin having a xylylene skeleton, phenol novolak resin having a dicyclopentadiene skeleton, phenol novolak resin having a biphenyl skeleton, and phenol novolak resin having a fluorene skeleton.

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

  Examples of copolymers of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds include Marproof (trade name) G-0115S and G-0130S in the products available from the market. G-0250S, G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation) and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate and methacrylic acid. Glycidyl acid, 4-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. 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 another silicon compound is, for example, a hydrolysis condensate of an alkoxysilane compound having an epoxy group and an alkoxysilane having a methyl group or a phenyl group, or having an epoxy group. This refers to a condensate of an alkoxysilane compound with polydimethylsiloxane having a silanol group, polydimethyldiphenylsiloxane having a silanol group, polyphenylsiloxane having a silanol group, or a condensation 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, and 3-glycidoxypropyltrimethoxysilane. And 3-glycidoxypropylmethyldimethoxysilane. Examples of the alkoxysilane compound having a methyl group or a phenyl group include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane. . Examples of polydimethylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group include X-21-5841 and KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-873, which are commercially available. PRX413 (manufactured by Dow Corning Toray Co., Ltd.) XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Japan GK) DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, PDS-0338, PDS-1615 (manufactured by Gelest) and the like.

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

In the formula (21), R ⁷ represents a hydrocarbon group having 1 to 6 carbon atoms, X represents an organic group containing an epoxy group or a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3, respectively. . A plurality of R ⁷ and X present in the formula may be the same or different. However, among a plurality of Xs, two or more are organic groups 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, and from the viewpoint of heat resistance and transparency of the cured product, a methyl group and a phenyl group are preferable. A methyl group is particularly preferred from the viewpoint of ease of production.
The organic group for X represents a compound consisting of C, H, N, and O atoms. Specific examples of the epoxy group-containing organic group include a 2,3-epoxycyclohexylethyl group and a 3-glycidoxypropyl group. From the viewpoint of heat resistance and transparency of the cured product, a 2,3-epoxycyclohexylethyl group is preferred. Here, the number of carbon atoms in the organic group is preferably from 1 to 20, and more preferably from 3 to 15. In addition, it is preferably a group in which 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. Thus, a methyl group and a phenyl group are preferred, and a methyl group is particularly preferred from the viewpoint of ease of production.
n is preferably 2 from the viewpoint of easy production of the compound.

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

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

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

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

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

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

  Epoxy resin (D) is obtained by adding 1 equivalent of carboxylic acid group in polyvalent carboxylic acid (A) and / or carboxylic acid anhydride of carboxylic acid anhydride compound (B) in polyvalent carboxylic acid composition (C ′). It is preferable to use the epoxy group within a range of 0.5 to 3.0 equivalents with respect to the equivalents. When it is 0.5 equivalent or more, the heat resistance and transparency of the cured product are improved, and when it is 3.0 or less, the mechanical properties of the cured product are improved.

It is preferable that the epoxy resin composition of the present invention further contains an epoxy resin curing accelerator (E).
As the epoxy resin curing accelerator (E), any one capable of accelerating the curing reaction between the polyvalent carboxylic acid (A) or the polyvalent carboxylic acid composition (C) of the present invention and the epoxy resin (D) can be used. Examples of the curing accelerator (E) which can be used but can be used include ammonium salt-based curing accelerators, phosphonium salt-based curing accelerators, metal soap-based curing accelerators, imidazole-based curing accelerators, and amine-based curing accelerators. Examples include a curing accelerator, a phosphine-based curing accelerator, a phosphite-based curing accelerator, and a Lewis acid-based curing accelerator.
In the epoxy resin composition of the present invention, the mixing ratio of the epoxy resin curing accelerator (E) is preferably such that 0.001 to 15 parts by weight of curing accelerator is used per 100 parts by weight of the epoxy resin composition.

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

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

  In order to obtain a cured product having excellent transparency and sulfidation resistance, carbon such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate, zinc palmitate, etc. A zinc salt composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as zinc carboxylate having several tens to 30 zinc zinc 12-hydroxystearate can be preferably used. Among them, particularly, from the viewpoint of excellent pot life and sulfidation resistance, zinc stearate, a zinc salt composed of a monocarboxylic acid compound having 10 to 20 carbon atoms such as zinc undecylenate, and a hydroxyl group such as zinc 12-hydroxystearate. Zinc salts comprising a monocarboxylic acid compound having 15 to 20 carbon atoms can be preferably used, more preferably zinc stearate, zinc undecylenate, and zinc 12-hydroxystearate, and particularly preferably zinc stearate, 12- Zinc hydroxystearate can be used.

  Examples of the ammonium salt-based curing accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, and 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 ethyl triphenyl phosphonium bromide, tetraphenyl phosphonium tetraphenyl borate, methyl tributyl phosphonium dimethyl phosphate, methyl tributyl phosphonium diethyl phosphate and the like.

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

  As the epoxy resin curing accelerator (E), either a solid compound or a liquid compound at room temperature (25 ° C.) can be used. When the epoxy resin composition of the present invention is used for an application that needs to be liquid at room temperature (25 ° C.), when a compound that is solid at room temperature (25 ° C.) is used as a curing accelerator, Can also be used by dissolving it. Further, a compound which is solid at room temperature (25 ° C.) can be used by dispersing it in a resin.

The viscosity of the composition can be adjusted and the hardness of the cured product can be complemented by using a coupling agent as needed in the epoxy resin composition of the present invention.
Examples of usable coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate; Titanium-based coupling agents such as neoalkoxytri (p-N- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples include zirconium such as xithris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, 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, as necessary.

  In the epoxy resin composition of the present invention, by using a nano-order inorganic filler as needed, it is possible to supplement the mechanical strength and the like without inhibiting transparency. As a guideline at the nano order level, it is preferable to use a filler having an average particle diameter of 500 nm or less, particularly, an average particle diameter of 200 nm or less from the viewpoint of transparency. 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, fosterite, steatite, spinel, titania, talc and the like. And the like, but are not limited to these. These fillers may be used alone or in combination of two or more. As the content of these inorganic fillers, an amount occupying 0 to 95% by weight in the epoxy resin composition of the present invention is used.

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 antioxidants.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and tetrakis (2,2,6,6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6- Tramethyl-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] me Butylmalonate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester decandioate, a reaction product of 1,1-dimethylethyl hydroperoxide and octane, N , N ', N "", N "'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine- 2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine.N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl- Polycondensate of 1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-tri Gin-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7 -Oxa-3,20-diazaspiro [5.1.11.2] heneikosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / Tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7 Oxa-3,20-diazadispiro [5,1,11,2] heneikosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11, 2] -Heneicosan-20-propanoic acid dodecyl ester / tetradecyl ester, propane dioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4- Hindered amine compounds such as piperidinyl), benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1, , 3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl)- 5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl ) Benzotriazole, the reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazole-2) Benzotriazole compounds such as -yl) -6-dodecyl-4-methylphenol; Benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl ) -5-[(hexyl) oxy] phenol and other triazine compounds, etc., with hindered amine compounds being particularly preferred.

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

  The phosphorus-based compound is not particularly limited. For example, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Phosph , Tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)- , 4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3 '-Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'- Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite , Bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di -N-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl Phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. It is below.

  Commercial products can also be used as the phosphorus compound. The commercially available phosphorus compounds are not particularly limited. For example, ADEKA products such as ADK STAB (trade name) PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, and ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, and the like.

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

  Commercial products can also be used as the phenolic compound. The commercially available phenolic compounds are not particularly limited. For example, IRGANOX (trade name) 1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1520 as IRGANOX manufactured by Ciba Specialty Chemicals Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-330, manufactured by Sumitomo Chemical Co., Ltd. Sumilizer (trade name) GA-80, Sumilizer M P-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

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

  It is preferable to contain at least one or more of the above-mentioned phosphorus compounds, amine compounds, and phenol compounds, and the amount thereof is not particularly limited, but is preferably 0 to the total weight of the epoxy resin composition of the present invention. It is in the range of 0.005 to 5.0% by weight.

  Further, the epoxy resin composition of the present invention may optionally contain a binder resin. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, and silicone resin. However, the present invention is not limited to these. The compounding amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, per 100 parts by weight of the resin component. Parts by weight are used as needed.

  An inorganic filler can be added to the epoxy resin composition of the present invention as needed. 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, fosterite, steatite, spinel, titania, talc and the like. And the like, but are not limited to these. These may be used alone or in combination of two or more. As the content of these inorganic fillers, an amount occupying 0 to 95% by weight in the curable resin composition of the present invention is used. Further, to the curable resin composition of the present invention, various compounding agents such as a silane coupling agent, a releasing agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, a pigment, and various thermosetting resins are added. can do.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at room temperature or under heating. For example, by using an extruder, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, etc., thoroughly mix the mixture until uniform, and optionally perform a filtration treatment with a SUS mesh or the like. Prepared.

  The epoxy resin composition of the present invention comprises the polycarboxylic acid (A) of the present invention or the polycarboxylic acid composition (C) and the epoxy resin (D), and optionally a curing accelerator (E), an antioxidant, It is prepared by sufficiently mixing additives such as a stabilizer and can be used as a sealing material. As a mixing method, mixing is carried out at room temperature or by heating using a medicine spoon, kneader, three-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, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. A prepreg obtained by impregnating a substrate such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and drying by heating is subjected to hot press molding to obtain a cured product of the epoxy resin composition of the present invention. can do. In this case, the solvent is used in an amount that usually accounts for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent. Also, an epoxy resin cured product containing carbon fibers can be obtained by the RTM method as it is in the liquid composition.

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

  Further, there are general uses in which a thermosetting resin such as an epoxy resin is used, and examples thereof include an adhesive, a paint, a coating agent, a molding material (including a sheet, a film, and FRP), and an insulating material (a printed board, In addition to its use as an encapsulant, as a sealant, a cyanate resin composition for a substrate, and as an additive to other resins, such as an acrylate-based resin as a curing agent for a resist, Applications and the like.

  Examples of the adhesive include adhesives for electronic materials, in addition to adhesives for civil engineering, construction, automobiles, general office use, and medical care. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( (ACF), mounting adhesives such as anisotropic conductive paste (ACP), and the like.

  As a sealing agent, potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chips, etc. Sealing (including a reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

  The cured product obtained by the present invention can be used for various applications including optical component materials. The optical material generally indicates a material used for the purpose of transmitting 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 can be mentioned. It is a liquid crystal display device peripheral material such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a liquid crystal film such as a polarizer protective film in the liquid crystal display field. In addition, encapsulants for color PDPs (plasma displays) expected as next-generation flat panel displays, antireflection films, optical correction films, housing materials, front glass protection films, front glass replacement materials, adhesives, and LED displays LED molding material, LED sealing material, front glass protective film, front glass substitute material, adhesive used for the device, substrate material for plasma addressed liquid crystal (PALC) display, light guide plate, prism sheet, deflection plate , Retardation film, viewing angle correcting film, adhesive, polarizer protective film, protective film for front glass in organic EL (electroluminescence) display, alternative material for front glass, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the field of optical recording, VD (video disk), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disk), disk substrate material for optical card, Examples include a pickup lens, a protective film, a sealing material, and an adhesive.

  In the field of optical equipment, it is a lens material for a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor unit. Also, it is a shooting lens and a finder of a video camera. Further, it is a projection lens of a projection television, a protective film, a sealing material, an adhesive or the like. Materials for optical sensing devices such as lenses, sealing materials, adhesives, and films. In the field of optical components, there are fiber materials, lenses, waveguides, sealing materials for elements, adhesives, etc. around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. In the case of optical passive components and optical circuit components, there are a lens, a waveguide, an LED sealing material, a CCD sealing material, an adhesive and the like. Substrate materials, fiber materials, sealing materials for elements, adhesives, etc. around the optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is used for sensors and displays / signs for industrial use, such as lighting and light guides for decorative displays, and optical fibers for communication infrastructure and for connecting digital equipment in homes. The semiconductor integrated circuit peripheral material is a resist material for microlithography for LSI and VLSI materials. In the field of automobiles and transport equipment, lamp reflectors for automobiles, bearing retainers, gear parts, corrosion-resistant coatings, switch parts, headlamps, engine internal parts, electrical components, various interior and exterior parts, drive engines, brake oil tanks, automotive protection Rusted steel plates, interior panels, interior materials, wire harnesses for protection and bundling, fuel hoses, automotive lamps, and glass substitutes. Further, it is a double glazing for railway vehicles. Further, they are toughness imparting agents for structural materials of aircraft, engine peripheral members, wire harnesses for protection and binding, and corrosion-resistant coatings. In the architectural field, they are interior and processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a film for house covering. Next-generation organic materials for optical and electronic functions include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, and elements. Sealant, adhesive and the like.

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

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

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

  Next, a thermosetting resin composition containing the polyvalent carboxylic acid (A) of the present invention and a thermosetting resin will be described. The thermosetting resin composition of the present invention has an ICI cone plate viscosity in a range of 100 to 200 ° C. and in a 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 thermosetting resin composition of the present invention has an ICI cone plate viscosity in the range of 100 to 200 ° C. and 0.01 to 10 Pa · s, and is solid at room temperature, it is a prepolymer when it is liquid. Kneading, which was not possible without pretreatment such as chemical conversion, is possible without pretreatment. Also, since it is solid, it has a feature in that it can be easily formed 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 this range, it becomes solid at room temperature (25 ° C.), molding becomes easy, and defects such as voids can be effectively prevented. In addition, by setting such a low-viscosity thermosetting resin composition, each component, which had a high softening point or melting point because of its conventional crystallinity and was difficult to knead, was sufficiently melted and dispersed in the curing agent. As a result, the crystals are broken and are sufficiently kneaded with the epoxy resin as the main agent, whereby the respective components are effectively arranged and a cured product having excellent physical properties can be obtained. The softening point is preferably from 20 to 150 ° C, more preferably from 40 to 130 ° C, even more preferably from 50 to 100 ° C, and particularly preferably from 70 to 100 ° C. With such a softening point, sufficient kneading can be easily performed.
By adjusting to this range, various components can be easily stirred and mixed by a mixer or the like, and further kneaded or melt-kneaded by a mixing roll, an extruder, a kneader, a roll, an extruder, etc., and then cooled and pulverized. It is possible to do.

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

Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl When hexahydrophthalic anhydride is 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, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, and carboxylic acids such as hydrogenated pyromellitic anhydride or The acid anhydride has a high softening point or melting point due to its crystallinity, and a specific melting point is 150 ° C. to 300 ° C., which may cause a problem in molding. On the other hand, the melting points of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride are lower than room temperature, which may cause problems in molding. Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and Among the methylhexahydrophthalic anhydrides, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hydrogenated pyromellitic acid, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, Hydrophthalic anhydride is preferred, and cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are more preferred.
Examples of the cyclohexanetricarboxylic anhydride include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride. In the present invention, these acid anhydrides can be used in combination, but cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferred.

  In the thermosetting resin composition of the present invention, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic The total amount of one or more compounds selected from acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride is 1% by weight to 90% by weight in the proportion of the thermosetting resin composition. Preferably, there is. If it is lower than 1% by weight, the glass transition temperature will not be sufficiently high, and if it is higher than 90% by weight, the melting point will be high and handling may be difficult. More preferably, it is 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 that can be contained as a component of the curing agent for a thermosetting resin of the present invention includes a molecule represented by the following formula (22). A polyvalent carboxylic acid having an ester structure (preferably two ester structures) therein and having a plurality of carboxyl groups at a terminal.

(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, nitrogen atoms and phosphorus atoms, and R represents an aliphatic group having 2 to 20 carbon atoms. Represents a hydrocarbon group, n and k represent 1 to 6 on average, and the total of n is 2 or more and less than 12.
Among them, it is preferable that the polyvalent carboxylic acid of the formula (22) is a compound obtained by an esterification reaction of a 2- to 6-functional polyhydric alcohol having 6 or more carbon atoms with 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. In the cycloalkane skeleton, substituted or unsubstituted Is particularly preferred from the viewpoint of optical properties of the cured product. The norbornane skeleton is preferably a norbornane or methylnorbornane structure. Here, examples of the substituent applicable to the substituted one include an alkyl group having 1 to 3 carbon atoms, a carboxyl group, and the like.
The linking group P is a residue of a polyhydric alcohol having 2 to 10 carbon atoms (a residue obtained by removing a hydroxyl group from the polyhydric alcohol used in the reaction), and is preferably a branched cross-linking group or a cycloalkyl group. Particularly, P is preferably a divalent crosslinking group defined by the following (a) or (b).

(A) a linear alkyl chain having a branched structure having 6 to 20 carbon atoms, wherein the linear alkyl chain has a linear main chain having 3 to 12 carbon atoms and 2 to 4 side chains; A crosslinking group having at least one of its side chains having 2 to 10 carbon atoms,
Or
(B) a divalent crosslink obtained by removing two hydroxyl groups from at least one crosslinked polycyclic diol selected from tricyclodecanedimethanol and pentacyclopentadecanedimethanol, which may have a methyl group on the cyclo ring. However, when P is (b), when the connecting group R is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent R ⁹ in Formula (2A) described later represents a group other than a hydrogen atom. Is more preferable.
The softening point of the polycarboxylic acid is usually 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher. Although the upper limit is not particularly limited, it is usually 500 ° C or lower, preferably 300 ° C or lower, more preferably 200 ° C or lower.

The above particularly preferred polyvalent carboxylic acid can be obtained by performing an addition reaction of a divalent to hexafunctional polyhydric alcohol having 6 or more carbon atoms and a saturated aliphatic cyclic acid anhydride.
These polycarboxylic acids may be a mixture containing two polycarboxylic acids. As a method of obtaining a polyvalent carboxylic acid mixture containing at least two types of polyvalent carboxylic acids, a method of mixing at least two types of the single polyvalent carboxylic acids obtained by the above method, or a method of mixing the above-mentioned polyvalent carboxylic acids When synthesizing a compound, as the saturated aliphatic cyclic anhydride, a mixture of at least two kinds of saturated aliphatic cyclic anhydrides selected below or a mixture of two kinds of the polyhydric alcohols is used. There is a way to carry out the reaction.

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

As the 2- to 6-functional polyhydric alcohol having 6 or more carbon atoms used in the synthesis of the polycarboxylic acid, specifically, a polyhydric alcohol having a hydroxyl group attached to the terminal of the crosslinking group P in the above formula (21) Carboxylic acids can be mentioned.
In the formula (21), the crosslinking group represented by P is preferably a divalent crosslinking group defined in the above (a) or (b), and these will be specifically described below.
The divalent cross-linking group defined in the above (a) is a divalent chain alkyl chain obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure having 6 to 20 carbon atoms. The structure has an alkyl chain sandwiched between two alcoholic hydroxyl groups as 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, a case where the side chain is branched from a carbon atom to which an alcoholic hydroxyl group is bonded (terminal carbon atom of the main chain). Any crosslinking group having 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 bond with an oxygen atom on both sides of P in the formula (21) is indicated by an asterisk.
The alkylene bridging group defined in the above (a) is not particularly limited as long as it has an alkyl branched chain (side chain) with respect to the main chain alkylene group, but the main chain has 3 or more carbon atoms in the main chain. And those having at least one alkyl side chain are preferable, and those having two or more alkyl side chains are particularly preferable. More preferable examples include a cross-linking group having a linear main chain having 3 to 12 carbon atoms and 2 to 4 side chains, and at least one of the side chains having 2 to 10 carbon atoms. Can be. In this case, a crosslinking group in which at least two of the side chains have 2 to 10 carbon atoms is more preferable. Further, it is preferable that 2 to 4 side chains are branched from different carbon atoms in the main chain.
As a more specific compound, a compound in which a hydroxyl group is bonded at the position of the mark * in the crosslinking group described in the formula (a1) can be mentioned.
Among the polyhydric alcohols used as a raw material, polyhydric alcohols having at least two side chains and at least two of the side chains having 2 to 4 carbon atoms are preferable.
Particularly preferred polyhydric alcohols in such a skeleton include 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, and 2-ethyl-1,3- Hexanediol and the like can be mentioned, and in particular, 2,4-diethyl-1,5-pentanediol can be mentioned.

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

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

In the formula, a plurality of R ^{8 's} each independently represent a hydrogen atom or a methyl group. Among them, a cross-linking group in which all of R ⁸ are hydrogen atoms is preferable.
Specific examples 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. In the present invention, a reaction without a catalyst is particularly preferable.
When a catalyst is used, examples of the usable catalyst include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid and trichloroacetic acid, sodium hydroxide, and hydroxide. Metal hydroxides such as potassium, calcium hydroxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7 -Heterocyclic compounds such as ene, imidazole, triazole, tetrazole, etc., tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethyl Ammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, And quaternary ammonium salts such as trioctylmethylammonium acetate. These catalysts may be used alone or in combination of two or more. Among them, triethylamine, pyridine and dimethylaminopyridine are preferred.

The amount of the catalyst used is not particularly limited, but it is generally preferable to use 0.001 to 5 parts by weight based on 100 parts by weight of the total weight of the raw materials, if necessary.
In this reaction, a reaction without a solvent is preferable, but an organic solvent may be used. The amount of the organic solvent used is 0.005 to 1 part by weight, preferably 0.005 to 0.7 part, based on 1 part of the total amount of the acid anhydride and the polyhydric alcohol as the reaction substrate. And more preferably 0.005 to 0.5 part (that is, 50% by weight or less). If the amount of the organic solvent used exceeds 1 part by weight based on 1 part by weight of the reaction substrate, it is not preferable because the progress of the reaction becomes extremely slow. Specific examples of usable organic solvents include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, and diethyl ether. And ether compounds such as tetrahydrofuran and dioxane, and ester compounds such as ethyl acetate, butyl acetate and methyl formate.

  This reaction proceeds sufficiently even at a temperature of about 20 ° C. The reaction temperature is preferably from 30 to 200 ° C, more preferably from 40 to 200 ° C, particularly preferably from 40 to 150 ° C, from the viewpoint of the reaction time. In particular, when this reaction is carried out in the absence of a solvent, 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 the acid anhydride volatilizes.

The reaction ratio between the acid anhydride and the polyhydric alcohol is theoretically preferably equimolar, but can be changed as necessary.
As a specific charging ratio of the two at the time of the reaction, the functional alcohol equivalent, 1 equivalent of the acid anhydride group, the polyhydric alcohol, the hydroxyl equivalent, 0.001 to 2 equivalents, Preferably, it is charged at a ratio of preferably 0.01 to 1.5 equivalents, more preferably 0.1 to 1.2 equivalents.
In the present invention, the obtained polycarboxylic acid is preferably solid, and in order to obtain a solid resinous polycarboxylic acid, it is ideally preferable to use a polyhydric alcohol having an equimolar equivalent or more. However, fluidity is important because the filler is added, and in order to secure the fluidity, a slight balance may be broken in the range of maintaining the solid (softening point of 50 ° C. or more) from the viscosity balance.
Specifically, the equivalent ratio of the alcoholic hydroxyl group to the acid anhydride equivalent is preferably 0.85 to 1.20 molar equivalents, and particularly preferably 0.90 to 1.10 molar equivalents.

  The reaction time depends on the reaction temperature, the amount of the catalyst, and the like, but from the viewpoint of industrial production, a long reaction is not preferable because a large amount of energy is consumed. A reaction time that is too short means that the reaction is rapid, which is not preferable from the viewpoint of safety. A preferred range is about 1 to 48 hours, preferably 1 to 36 hours, more preferably 1 to 24 hours, and even more preferably about 2 to 10 hours.

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

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

The polycarboxylic acid or the mixture containing the polycarboxylic acid thus obtained usually shows a colorless to pale yellow solid resinous state (crystallized in some cases). The softening point of the polycarboxylic acid is preferably from 50 to 190C, more preferably from 55 to 150C, and particularly preferably from 60 to 120C. By mixing a polycarboxylic acid having such a softening point directly into a thermosetting resin composition without making it into a liquid state, it will have an extremely high reflectance retention, and even when subjected to a heat resistance test, the reflectance will be high. It is possible to provide a reflection member that is difficult to reduce.
Usually, when the cross-linking group is an alkylene group having a side chain defined in (a), it shows a colorless to pale yellow solid resinous state.
In the present invention, since the most suitable method for using such a thermosetting resin composition containing a polycarboxylic acid is transfer molding, the polycarboxylic acid is a solid resin.
When the cross-linking group is the cross-linking group defined in (b), when the aliphatic hydrocarbon group has a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, all of the alicyclic substituents have many hydrogen atoms. Polyvalent carboxylic acids are colored during curing and are not particularly suitable for severe optical applications. When the aliphatic hydrocarbon group has a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, a compound having a methyl group or a carboxyl group as a substituent has less such coloring, and its optical properties are improved.

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

(In the above formula, P represents the same meaning as described above, and R ⁹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group.)
Here, in the above formula (2A), an alkyl group or a carboxyl group in which R ⁹ has 1 to 3 carbon atoms can be suitably used 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.

  Furthermore, in the thermosetting resin composition of the present invention, the polycarboxylic acid represented by the above formula (1) and trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, and pyromellitic Functional groups in a mixture of one or more compounds selected from acids, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride When the equivalent weight is 250 g / eq. And preferably 240 g / eq. It is more preferred that: By being in this range, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride , Hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride, the effect of the amount of one or more compounds selected from the compounds is effectively exerted, and a cured product having excellent heat resistance can be obtained.

  The weight ratio of the polycarboxylic acid represented by the above formula (1): (trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic Acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and one or more compounds selected from methylhexahydrophthalic anhydride) are 99: 1 to 10:90. It is preferably 90:10 to 20:80, and particularly preferably 80:20 to 50:50. When the ratio is in the above range, the thermosetting resin composition is extremely excellent in heat resistance, has a low viscosity and can be sufficiently kneaded, and thus has excellent cured physical properties.

  Further, the polycarboxylic acid (A) represented by the above formula (1), trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, Heat containing a curing agent for a thermosetting resin containing one or more compounds selected from pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride In the curable resin composition, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, Selected from hexahydrophthalic anhydride and methylhexahydrophthalic anhydride One or more compound preferably accounts for 1% to 90% by weight of the thermosetting resin composition. By being the weight%, a kneading property and a moldability are further improved, and a thermosetting resin composition having excellent curing properties is obtained.

  Examples of the curing agent that can be used in combination include an amine compound, an acid anhydride compound having an unsaturated ring structure, an acid anhydride having an organosiloxane skeleton, an amide compound, a phenol compound, and a carboxylic acid compound. . Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and pyromeritic anhydride. Acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2.2 .1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bisphenol A, bisphenol F, bisphenol S, fluorenebisulfate Knol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone , Resorcinol, 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, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4 -Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis Examples include polycondensates with (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, condensates of terpenes and phenols, 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 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 in the present invention, the epoxy resin It is desirable to use

  The epoxy resin can be used without any particular limitation as long as it is usually compounded as a conventional thermosetting resin composition or epoxy resin composition. For example, phenolized novolak type epoxy resin, epoxidized novolak resin of phenols and aldehydes including ortho-cresol novolak type epoxy resin, bisphenol A, bisphenol F, bisphenol S, diglycidyl ether such as alkyl-substituted bisphenol, Glycidylamine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin, alicyclic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, diglycidyl isocyanurate, triglycidyl isocyanate Nurate, silsesquioxane compounds and the like can be mentioned, and these may be used alone or in combination of two or more. Among these epoxy resins, those having high heat resistance are preferable, and specifically, from the viewpoints of melt viscosity, coloring of the obtained cured product, glass transition temperature, etc., glycidyl ether type epoxy resin, alicyclic epoxy Resins and triglycidyl isocyanurate are preferred.

  Epoxy resin, polycarboxylic acid (A) of the present invention, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride The compounding ratio of a curing agent for a thermosetting resin containing one or more compounds selected from hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride is as follows: The active group (acid anhydride group or hydroxyl group) in the thermosetting resin curing agent capable of reacting with the epoxy group is 0.5 to 1.5 equivalent (1 equivalent of carboxylic acid is equivalent to 1 equivalent of epoxy group). , Acid anhydrides are considered to be monofunctional), and particularly preferably 0.5 to 1.2 equivalents. When the amount is less than 0.5 equivalent or more than 1.5 equivalents to 1 equivalent of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained, and coloring may be easily performed. There are also problems.

A curing accelerator can be added to the curable resin composition of the present invention as needed. As the curing accelerator, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′) ) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole ( 1 ′)) Ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazo (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole , 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, various imidazoles, and those imidazoles and phthalic acid, isophthalic acid, terephthalic acid , Salts with polycarboxylic acids such as trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid, amides such as dicyandiamide, and 1,8-diaza-bicyclo [5.4.0] undecene-7. Diaza compounds such as tetraphenylborate, Salts such as enol novolak, salts with the above-mentioned polycarboxylic acids or phosphinic acids, quaternary ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, hexadecyltrimethylammonium hydroxide (preferably C1-C20 alkylammonium salts, phosphines such as triphenylphosphine, tri (tolyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate and the like; phosphonium compounds; phenols such as 2,4,6-trisaminomethylphenol , Amine adducts, metal compounds such as tin octylate, zinc octoate, zinc stearate, copper naphthenate, cobalt naphthenate, and the like, and Microcapsule type curing accelerator or the like of these curing accelerators to the microcapsules and the like. Which one of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. Preferred in the present invention are a phosphonium compound (more preferably a quaternary phosphonium) or zinc stearate. Examples of quaternary phosphonium products available from the market include PX-4ET and PX-4MP (all manufactured by Nippon Chemical Industry 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, as additives other than the above-mentioned additives, commonly used additives for epoxy resins, for example, dyes, optical brighteners, reinforcing materials, fillers, white pigments or other pigments, nucleating agents , A surfactant, a plasticizer, a viscosity modifier, a fluidity modifier, a flame retardant, an antioxidant, an ultraviolet absorber, and a light stabilizer.

Examples of the above-mentioned 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 compounding amount of the inorganic filler is preferably from 1 to 1,000 parts by weight, more preferably from 1 to 800 parts by weight, based on 100 parts by weight of the total amount of the curable resin composition.

The above-mentioned white pigment is not particularly limited, but for example, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, basic zinc carbonate, kaolin, calcium carbonate and the like can be used. The white pigment may be a hollow particle. The white pigment may be appropriately surface-treated with a silicon compound, an aluminum compound, an organic substance, or the like. These may be used alone or in combination of two or more. The average particle size of the white pigment is preferably in the range of 0.01 to 50 μm. If it is less than 0.01 μm, the particles tend to agglomerate and the dispersibility tends to be poor. If it exceeds 50 μm, the cured product tends to have insufficient reflection characteristics. The average particle diameter can be measured, for example, using a laser diffraction / scattering particle size distribution meter. In the present invention, it is preferable to use a powder of titanium oxide, particularly titanium dioxide. This is because whiteness, light reflectivity, and hiding power are high, the dispersibility is excellent in stability, and it is easy to obtain. The crystal form of titanium oxide is not particularly limited, and may be a rutile type, an anatase type, or a mixture of both, but the anatase type has a photocatalytic function and deteriorates the resin. Therefore, in the present invention, the rutile type is preferable. For example, a commercially available product includes CR-95 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.).
The content of the white pigment is in the range of 10% by weight to 95% by weight, more preferably 50% to 95%, based on the entire resin composition. If the total content is less than 10% by weight, the light reflection properties of the cured product tend not to be sufficiently obtained. If the total content exceeds 95% by weight, the moldability of the resin composition becomes poor, and the production of the substrate tends to be difficult. It is in.

It is desirable that the melt viscosity of the curing agent for a thermosetting resin under high temperature conditions during molding be higher than that of a conventional acid anhydride curing agent and the like. It is desirably 0.01 Pa · s to 10 Pa · s. If it is smaller than 0.01 Pa · s, burrs are likely to occur. On the other hand, if it is larger than 10 Pa · s, the productivity is reduced.
In the present embodiment, the ICI viscosity of the thermosetting resin curing agent at 150 ° C. is preferably 0.01 Pa · s to 10 Pa · s, more preferably 0.05 Pa · s to 5 Pa · s. .

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

It is desirable that the glass transition temperature of the cured product is higher than the molding temperature. If the glass transition temperature of the cured product is below the molding temperature, the cured product in the mold is in a low-elastic rubber state, so the rubber-like cured product must be removed from the mold, and when the ejector is pushed in, There is a possibility that a defect may occur due to deformation. Specifically, the glass transition temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
Here, in the present invention, the glass transition temperature of the cured product is preferably 150 ° C. or lower, more preferably 140 ° C. or lower.

  The thermosetting resin composition of the present invention can be obtained by uniformly dispersing and mixing the various components described above. Although there is no particular limitation on the method, a method in which various components are sufficiently uniformly stirred and mixed by a mixer or the like, and then kneaded or melt-kneaded by a mixing roll, an extruder, a kneader, a roll, an extruder, etc., and then cooled and pulverized. Can be mentioned. The conditions for kneading or melt-kneading may be determined according to the types and amounts of the components, and are not particularly limited, but it is more preferable to knead the mixture in a range of 20 to 100 ° C. for 5 to 40 minutes. If the kneading temperature is lower than 20 ° C., the dispersibility of each component is reduced, and it is difficult to sufficiently knead. If the kneading temperature is higher than 100 ° C., the crosslinking reaction of the resin composition proceeds, There is a risk that the object will be cured.

  It is desirable that the thermosetting resin composition of the present invention can be pressurized (tablet) molded at room temperature of 0 to 30 ° C. before heat molding. The pressure molding may be performed, for example, under a condition of 0.01 to 10 MPa for about 1 to 5 seconds. The mold used for pressurizing (tablet) molding is not particularly limited, and includes, for example, a punch (upper mold) and a die (lower mold) made of a ceramic material or a fluorine resin material. It is preferable to use one that is used.

  INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention is useful in applications such as optical semiconductor encapsulating materials and optical semiconductor reflectors that require a high glass transition temperature and high transmittance.

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

  In the optical semiconductor device of the present invention, as a specific example of a typical structure, as described in WO2012 / 124147, a light reflection preventing member having a cylindrical hollow portion is arranged on a substrate, The optical semiconductor element is arranged on the substrate in the internal space of the hollow part. Then, one end of the optical semiconductor element and the substrate are connected by a wire, and a sealing resin is sealed in the hollow portion.

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

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

A polycarboxylic acid (A) in which R ⁶ in the formula (1) is an organic group containing a carboxyl group represented by the formula (8) in which R ^2a is a methyl group, and a liquid polycarboxylic acid; Example implemented as composition (C)-
Each physical property value in Synthesis Examples and Examples was measured by the following methods. Here, parts are parts by mass unless otherwise specified.

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

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

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

Example 1: Production of polycarboxylic acid (A-1) 26.1 g of tris (2-hydroxyethyl) isocyanurate and Rikacid MH-T (manufactured by Shikoku Chemicals Co., Ltd.) were applied to a 500-ml separable flask made of glass while performing a nitrogen purge. 52.1 g of 4-methylhexahydrophthalic acid) and 70 g of toluene were charged, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 115 ° C., and the reaction was allowed to proceed for 7 hours.
The obtained reaction solution was concentrated under reduced pressure at 100 ° C., and toluene was distilled off to obtain 71.5 g of a polycarboxylic 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. The melting point (peak peak value) using DSC was 57.0 ° C, and the thermal weight loss was -3.4%. FIG. 1 shows a GPC chart of the obtained compound.

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

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

Example 4: Production of polyvalent carboxylic acid composition (C-3) In a 50 ml glass bottle, 3 g of the polyvalent carboxylic acid (A-1) obtained in Production Example 1 and RIKACID MH-T (manufactured by Shikoku Chemicals) 7 g of 4-methylhexahydrophthalic acid) was charged, and the mixture was heated in an oven heated to 80 ° C. Two hours later, the mixture was taken out, mixed well with a spoon, and further heated for 2 hours to obtain 10 g of a polyvalent carboxylic acid composition (C-3). The obtained polyvalent carboxylic acid composition (C-3) is a colorless and transparent liquid, and the purity by GPC is 34.3 for a polyvalent carboxylic acid ((A-1) represented by the formula (23)). Area%, 4-methylhexahydrophthalic acid was 2.6 area%, and 4-methylhexahydrophthalic anhydride was 63.1 area%. The functional group equivalent was 187 g / eq, the viscosity was 1,884 mPa · s, and the thermal weight loss was −28.2%.

Comparative Example 1: Dissolution test of polyvalent carboxylic acid having isocyanuric acid skeleton in carboxylic anhydride compound In a 50 ml glass bottle, 3 g of tris (3-carboxypropyl) isocyanurate represented by the following formula (25), licaside 7 g of MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Kasei Kogyo Co., Ltd.) was charged, and the mixture was heated in an oven heated to 80 ° C. After 2 hours, take out and mix well with a medicine spoon, put the rotor in a glass bottle, and heat with stirring on a magnetic stirrer heated to 90 ° C for 5 hours, but tris (3-carboxypropyl) isocyanurate is recyacid It did not dissolve in MH-T. When the stirring was stopped and it was confirmed after 15 hours in a room temperature (25 ° C.) environment, tris (3-carboxypropyl) isocyanurate was precipitated.

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

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

  As is clear from the results in Table 1, the polycarboxylic acid (A-1) and the polycarboxylic acid composition (C-1 to C-3) containing the polycarboxylic acid (A-1) were not heated. Is small, whereas the weight loss of 4-methylhexahydrophthalic anhydride of Comparative Example A is large. In Comparative Example 1, a cloudy liquid was formed, and precipitation was confirmed upon standing. However, since the polyvalent carboxylic acid compositions (C-1 to C-3) were colorless and transparent liquids, they were used in a liquid state. It is suitable for use in applications where is required.

Example 5: Preparation of epoxy resin composition The polyvalent carboxylic acid composition (C-1) obtained in Example 2, 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate as an epoxy resin ( CEL2021P, manufactured by Daicel Co., Ltd.) Zinc octylate as a curing accelerator was placed in a polypropylene container at the ratio shown in Table 2 below, mixed, and defoamed for 5 minutes to obtain the epoxy resin composition of the present invention. Obtained.

Example 6: Preparation of epoxy resin composition Except that polyvalent carboxylic acid composition (C-1) of Example 5 was changed to polyvalent carboxylic acid composition (C-2) obtained in Example 3 In the same manner as in Example 5, an epoxy resin composition of the present invention was obtained.

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

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

Comparative Example 2 Preparation of Epoxy Resin Composition Ricacid MH-T (4-methylhexahydrophthalic anhydride, manufactured by Shin Nihon Rika Co., Ltd.) as an epoxy resin curing agent, and 3 ′, 4′-epoxycyclohexylmethyl 3 as an epoxy resin , 4-epoxycyclohexanecarboxylate (manufactured by Daicel Co., Ltd., CEL2021P) and zinc octylate as a curing accelerator in a ratio shown in Table 2 below in a polypropylene container, mixed, and defoamed for 5 minutes. An epoxy resin composition of a comparative example was obtained.

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

Example 5-8, the compounding ratio and viscosity of the epoxy resin compositions obtained in Comparative Examples 2 and 3, the weight loss during curing, the transmittance of the cured product, the hardness of the cured product, and the results of the presence or absence of gold wire exposure. Are shown in Table 2. The tests in Table 2 were performed as follows.
(1) Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
(2) Weight loss during curing 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 weighed in advance, 30 mm × 20 mm × height. It was gently poured onto a glass substrate on which a dam was formed with a heat-resistant tape so as to have a thickness of 0.8 mm, and the mass after the casting was weighed. The cast was cured at 150 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour, and the weight after curing was weighed to calculate the weight loss rate during curing.

(3) Permeability of cured product The epoxy resin composition obtained in each of Examples 5 to 8 and Comparative Examples 2 and 3 was subjected to vacuum degassing for 5 minutes, and then a heat-resistant tape having a size of 30 mm x 20 mm x 0.8 mm in height. The glass was gently cast on the glass substrate on which the dam was created. The cast was cured at 150 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a 0.8 mm thick test piece for transmittance. 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) Hardness of cured product Durometer hardness was measured by the method described in JIS K6253.
(5) Exposure of gold wire After performing the epoxy resin compositions obtained in Examples 5 to 8 and Comparative Examples 2 and 3 in vacuum for 5 minutes, filling the syringes, and using a precision discharge device, the light emission wavelength of 450 nm was used. A light emitting element having a surface-mounted LED using a gold wire (having an opening of 2.3 × 0.4 mm and a depth of 0.4 mm, and the top of the gold wire having a depth of 0.1 mm from the opening). (Existing in position) was cast such that the opening was flat. After pre-curing at 120 ° C. × 1 hour, curing was performed at 150 ° C. × 3 hours, and the surface-mounted LED was sealed. Visually evaluate whether the gold wire is exposed (the upper end of the gold wire is higher than the uppermost surface of the cured product and is not completely sealed) due to the volatilization of the curing agent after sealing in this way. did. In the table, A: gold wire is not exposed, B: gold wire is exposed.

* Since the cured product was brittle and cracked, it could not be removed from the glass substrate.

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

A polycarboxylic acid (A) in which R ⁶ in the above formula (1) is an organic group containing a carboxyl group represented by the formula (9) wherein R ^2b is an ethylene group and a propylene group, Example implemented as polyvalent carboxylic acid composition (C)-
GPC, acid value, functional group equivalent, viscosity, and thermogravimetric loss in Synthesis Examples and Examples were measured by the same methods as described above. Here, parts are parts by mass unless otherwise specified.

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

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

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

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

Comparative Example 4: Dissolution test of polycarboxylic acid having isocyanuric acid skeleton in carboxylic acid anhydride compound In a 50 ml glass bottle, 3 g of tris (3-carboxypropyl) isocyanurate represented by the above formula (25), licaside 7 g of MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Kasei Kogyo Co., Ltd.) was charged and placed in an oven heated to 80 ° C. and heated. After 2 hours, take out and mix well with a medicine spoon, put the rotor in a glass bottle, and heat with stirring on a magnetic stirrer heated to 90 ° C for 5 hours, but tris (3-carboxypropyl) isocyanurate is recyacid It did not dissolve in MH-T. When the stirring was stopped and it was confirmed after 15 hours in a room temperature (25 ° C.) environment, tris (3-carboxypropyl) isocyanurate was precipitated.

(Evaluation test)
The polyvalent carboxylic acids 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 (Shin Nihon) as Comparative Example B Table 3 summarizes the measurement results of the content of each component, acid value or functional group equivalent, viscosity, and thermogravimetric loss of Rikashid MH-T manufactured by Rikasha Co., Ltd.

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

  As is clear from the results in Table 3, the polycarboxylic acids A-2 and A-3 and the polycarboxylic acid compositions C-3 and C-4 containing the polycarboxylic acids A-2 and A-3, respectively. Shows a small weight loss during heating, whereas 4-methylhexahydrophthalic anhydride of Comparative Example B has a large weight loss. In Comparative Example 4, a cloudy liquid was formed, and precipitation was confirmed on standing. However, the polycarboxylic acid compositions C-3 and C-4 and the polycarboxylic acids A-2 and A-3 were colorless and transparent liquids. For this reason, it is particularly suitable for use in applications requiring use in a liquid state.

Example 13: Preparation of epoxy resin composition The polyvalent carboxylic acid (A-2) obtained in Example 9 and 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (( CEL2021P, manufactured by Daicel Co., Ltd.) Zinc octylate as a curing accelerator was placed in a polypropylene container at a ratio shown in Table 4 below, mixed, and defoamed for 5 minutes to obtain an epoxy resin composition of the present invention. Was.

Example 14 Preparation of Epoxy Resin Composition Example was the same as Example 9 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. In the same manner as in Example 13, an epoxy resin composition of the present invention was obtained.

Example 15: Preparation of epoxy resin composition Example 13 was the same as 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. The same operation was performed to obtain the epoxy resin composition of the present invention.

Example 16 Preparation of Epoxy Resin Composition Example was the same as Example 13 except that the polycarboxylic acid (A-1) in Example 13 was changed to the polycarboxylic acid composition (C-4) obtained in Example 12. In the same manner as in Example 13, an epoxy resin composition of the present invention was obtained.

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

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

  Example 13-16, the mixing ratio of the epoxy resin compositions obtained in Comparative Examples 5 and 6, and their viscosities, weight loss during curing, cured product transmittance, cured product hardness, and the results of the presence or absence of gold wire exposure. Are shown in Table 4. The tests in Table 4 were performed as described above.

* Since the cured product was brittle and cracked, it could not be removed from the glass substrate.

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

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

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

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

Synthesis Example 2 (C-6 for thermosetting resin)

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

A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen by 98.1 parts of tricyclodecane dimethanol and methylhexahydrophthalic anhydride (Rikashid MHT, manufactured by Nippon Rika Co., Ltd.) 166. Then, 2.0 parts of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical) and 266.4 parts of MEK were added, and the mixture was reacted at 60 ° C. for 1 hour. By heating and stirring at 80 ° C. for 5 hours, a MEK solution of the compound represented by the formula (30) was obtained. Thereto, 59.4 parts of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical) was added, and the mixture was heated and stirred at 80 ° C. for 2 hours. Thereafter, the solvent was removed at 150 ° C. for 1 hour to obtain a curing agent (C-6) for a thermosetting resin.
The obtained curing agent was colorless and solid. The functional group equivalent was 195 g / eq. Met. The ICI viscosity was 0.53 Pa · s at 150 ° C. The softening point was 84.7 ° C.

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

Preparation of thermosetting resin composition for light reflection (Examples 17 to 19)
TEPIC-S (triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd.), EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), celloxide 2021P (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), Curing agent C-5 for thermosetting resin, C-6 curing agent for thermosetting resin, RICIDID MH-T (curing agent for epoxy resin manufactured by Nippon Rika), Hishicolin PX-4MP (curing manufactured by Nippon Chemical Industry Co., Ltd.) Using a catalyst), each component was blended according to the blending table shown in Table 5, and the mixture was sufficiently kneaded by a mixer, melt-kneaded under a predetermined condition by a mixing roll, cooled, and pulverized. Nineteen thermosetting resin compositions were prepared. The unit of the amount of each component in Table 5 is parts by weight, and a blank column indicates that the component is not used.

Evaluation of thermosetting resin composition For the resin compositions of Examples 17 to 19, the DMA, TMA, and transmittance of the cured product were measured by the following methods. Table 5 shows the results.

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

(B) Thermomechanical analysis (TMA)
The thermomechanical analysis (TMA) was measured using a test piece prepared as described below and using a TMA / SS6100 device manufactured by SII Nanotechnology Co., Ltd. under the following conditions. The glass transition temperature (Tg) is defined as a point at which the coefficient of linear expansion of the obtained data changes.
(Method of preparing TMA test piece)
The resin composition of each Example and each Comparative Example was transfer-molded under the conditions of a mold temperature of 150 ° C., a molding pressure of 10.4 MPa, and a cure time of 300 seconds, and was post-cured at 150 ° C. for 3 hours to obtain a thickness of 4 A test piece of 0.0 mm was produced.
(TMA measurement conditions)
Heating condition: 2 ° C / min Measurement mode: Compression

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

  From the above results, the thermosetting resin composition using the thermosetting resin curing agent of the present invention has a sufficiently high glass transition temperature, a low coefficient of linear expansion, and gives a cured product with less coloring of the cured product. You can see that.

Preparation of thermosetting resin composition for light reflection (Examples 20, 21)
TEPIC-S (triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd.), glycidyl ether type epoxy resin B-1, Hishicolin PX-4MP (curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), CR-95 (oxidation manufactured by Ishihara Sangyo Co., Ltd.) Using titanium), the respective components were blended according to the blending table shown in Table 6, kneaded sufficiently by a mixer, melt-kneaded under predetermined conditions by a mixing roll, cooled and pulverized. A thermosetting resin composition was prepared. The unit of the amount of each component in Table 6 is parts by weight, and a blank column indicates that the component is not used.

  From the above results, the thermosetting resin composition using the thermosetting resin curing agent of the present invention has a sufficiently high glass transition temperature, a low coefficient of linear expansion, and gives a cured product with less coloring of the cured product. You can see that.

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

Preparation of thermosetting resin composition for light reflection (Example 22)
EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), curing agent C-7 for thermosetting resin, Hishicolin PX-4MP (curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), CR-95 (Ishihara Sangyo Co., Ltd.) Using titanium oxide (manufactured by Co., Ltd.), the respective components were blended according to the blending table shown in Table 7, kneaded well by a mixer, then melt-kneaded under predetermined conditions by a mixing roll, cooled, pulverized, and carried out. A thermosetting resin composition of Example 22 was prepared. In addition, the unit of the compounding amount of each component in Table 7 is part by weight, and a blank column indicates that the component is not used.

  From the above results, the thermosetting resin composition using the thermosetting resin curing agent of the present invention has a sufficiently high glass transition temperature, a low coefficient of linear expansion, and gives a cured product with less coloring of the cured product. You can see that.

Example 23: Production of polyvalent carboxylic acid composition (C-8) The THEIC-G (tris (2-hydroxyethyl isocyanurate) manufactured by Shikoku Chemicals Co., Ltd.) was applied to a glass 300 ml four-necked flask while purging with nitrogen. 8 g, HTMAn-S (hydrogenated trimellitic anhydride manufactured by Mitsubishi Gas Chemical) and 50 g of MEK were charged, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in a water bath. The water bath was heated, the internal temperature was maintained at 65 ° C., and the reaction was allowed to proceed for 6 hours. Thereafter, 49.4 g of RIKACID MH-T (4-methylhexahydrophthalic acid manufactured by Shin Nippon Rika) and 50 g of MEK were added, the water bath was heated, and the reaction was continued for 4 hours while maintaining the internal temperature at 65 ° C.
The peak area of trishydroxyethyl isocyanuric acid was confirmed to be 1% or less by GPC, the obtained reaction solution was concentrated under reduced pressure at 150 ° C., and MEK was distilled off to obtain a polyvalent compound having the following formula (a1) as a main component. 90.4 g of a polycarboxylic acid composition (C-8), which was a mixture of a carboxylic acid and a carboxylic anhydride compound, was obtained. The appearance of the obtained compound is a colorless solid, and the purity by GPC (GPC area%) is 2.4% for the polyvalent carboxylic acid high molecular weight mixture represented by the formula (a2 to a4), and the formula (a1) 82.9% of the polycarboxylic acid represented by the formula (a5), 1.5% of cyclohexane-1,2,4-tricarboxylic acid represented by the formula (a5), and 4-methylhexa represented by the formula (a6). Hydrophthalic acid was 5.4% and 4-methylhexahydrophthalic anhydride 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. FIG. 4 shows a GPC chart of the obtained compound.

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

  In the formulas (a2 to a4), R9 has the same meaning as described above.

Example 24: Preparation of thermosetting resin composition for light reflection Polyvalent carboxylic acid composition (C-8) obtained in Example 23, EHPE-3150 (Alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.) ), Hishicolin PX-4MP (curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), FB-910 (silica manufactured by Denki Kagaku Kogyo Co., Ltd.), CR-75 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) After blending the components according to the blending table shown in Table 8, sufficiently kneading with a mixer, melt-kneading under predetermined conditions with a mixing roll, cooling and pulverizing to prepare a thermosetting resin composition of Example 24. did.

  Table 8 shows the compounding ratio of the thermosetting resin composition obtained in Example 24 and the results of its glass transition temperature, linear expansion coefficient, and reflectance. In addition, the unit of the compounding amount of each component in Table 8 is part by weight, and a blank column indicates that the component is not used.

Example 25: Preparation of thermosetting resin composition for light reflection The polyvalent carboxylic acid (A-3) obtained in Example 10, EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), Using Hishicolin PX-4MP (curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), FB-910 (silica manufactured by Denki Kagaku Kogyo Co., Ltd.), CR-75 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) Each component was blended according to the blending table shown in No. 9, sufficiently kneaded by a mixer, then melt-kneaded under predetermined conditions by a mixing roll, cooled and pulverized to prepare a thermosetting resin composition of Example 25.

  Table 9 shows the mixing ratio of the thermosetting resin composition obtained in Example 25 and the results of its glass transition temperature, linear expansion coefficient, and reflectance. In addition, the unit of the compounding amount of each component in Table 9 is part by weight, and a blank column indicates that the component is not used.

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

  The polycarboxylic acid of the present invention and the polycarboxylic acid composition containing the same have less volatilization during curing and have excellent curability, and the cured product gives a cured product having excellent transparency and hardness. The epoxy resin composition used is useful for electric and electronic materials, particularly for optical semiconductor encapsulation and as an optical semiconductor reflector. Moreover, the polyvalent carboxylic acid of the present invention and the polycarboxylic acid composition containing the same can sufficiently increase the glass transition temperature of the cured product, have excellent moldability, and have less coloring to the cured product. Is useful as a sealing material and a reflecting material for a semiconductor device.

Claims (16)

A reactant obtained by reacting a trishydroxyalkyl isocyanurate compound represented by the following formula (10) with methylhydrophthalic anhydride,
Includes a polyvalent carboxylic acid represented by the following formula (1-1), and multimers of the polycarboxylic acid,
GPC area% of polyvalent carboxylic acid represented by the following formula (1-1) is 92% or less,
Reactants.

(In Formula (10), R ¹ represents an alkylene group having 1 to 6 carbon atoms. In Formula (10), a plurality of R ¹ may be the same or different.)

(In the formula (1-1), R ¹ has the same meaning as described above, and R ^2a represents a methyl group. In the formula (1-1), a plurality of R ¹ may be the same or different. It doesn't matter.)   A polyvalent carboxylic acid composition containing the reactant according to claim 1.   The polycarboxylic acid composition according to claim 2, further comprising a carboxylic anhydride compound. The polycarboxylic acid composition according to claim 3, wherein the carboxylic anhydride compound is at least one selected from compounds represented by the following formulas (2) to (7).

  An epoxy resin composition comprising the reactant according to claim 1 or the polycarboxylic acid composition according to any one of claims 2 to 4 and an epoxy resin.   The epoxy resin composition according to claim 5, further comprising an epoxy resin curing accelerator.   The epoxy resin composition according to claim 6, wherein the epoxy resin curing accelerator is a metal soap.   The epoxy resin composition according to claim 7, wherein the metal soap is a zinc carboxylate compound.   A cured product obtained by curing the epoxy resin composition according to claim 5.   A thermosetting resin composition containing the reactant according to claim 1 and a thermosetting resin, and having an ICI cone plate viscosity in a range of 100 to 200 ° C and in a range of 0.01 Pa · s to 10 Pa · s. .   The thermosetting resin composition according to claim 10, wherein the softening point is in a range of 20C to 150C. Further trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and Including a curing agent for a thermosetting resin containing one or more compounds selected from methylhexahydrophthalic anhydride,
Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl The thermosetting resin composition according to claim 10 or 11, wherein one or more compounds selected from hexahydrophthalic anhydride account for 1% to 90% by weight of the whole.   The thermosetting resin composition according to any one of claims 10 to 12, wherein the cured product has a glass transition temperature (Tg) of 30 ° C or higher.   A cured product obtained by thermally curing the thermosetting resin composition according to claim 10.   An optical semiconductor device sealed with the cured product according to claim 14.   An optical semiconductor device using the cured product according to claim 14 as a reflector.

Images