JP2017039894A - Polyvalent carboxylic acid and polyvalent carboxylic acid composition containing the same, epoxy resin composition, thermosetting resin composition and cured article and optical semiconductor device thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvalent carboxylic acid compound capable of efficiently enhancing glass transition temperature of a cured article, excellent in moldability, less in coloring on the cured article, a thermosetting resin composition using the compound and a semiconductor device using the thermosetting resin composition as an encapsulation material or a refractive material.SOLUTION: There is provided a curing agent for a thermosetting resin containing a polyvalent carboxylic acid compound represented by the formula (1a), where Pto Pare each independently an organic group containing a hydroxyl group or a C1 to 15 carboxyl group, at least one or more of the plurality of Pto Phas a group binding a hydrocarbon group having a terminal carboxyl group by an ester structure or a group binding a cyclohexyl group having a carboxyl group at ortho position by an ester structure.SELECTED DRAWING: None

Description

  The present invention can sufficiently increase the glass transition temperature of a cured product, is excellent in moldability and has little coloring to the cured product, a thermosetting resin composition using the same, and The present invention relates to an optical semiconductor device using such a thermosetting resin composition as a sealing material or a reflecting material.

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

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

  Since tetracarboxylic acid anhydride has a high melting point (150 ° C. or higher), it is difficult to handle as a liquid resin composition, and its formability is inferior, so it is difficult to use it for molding liquid resins. Then, it is not suitable for the intended use of the present invention.

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

Similarly, polycarboxylic acid compounds also have problems of high melting point (150 ° C. or higher), high crystallinity, difficult resin kneading, and coloring, and cannot be used for the purpose of the present invention.
Therefore, a compound that can solve the above problems has not been found as a conventionally known material.

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

  Polyvalent carboxylic acid capable of sufficiently increasing glass transition temperature of cured product, excellent moldability, and less colored to cured product, thermosetting resin composition using the same, and such thermosetting resin composition Provided is a semiconductor device using as a sealing material or reflecting material.

  In the present invention, the curable resin composition contains a polyvalent carboxylic acid having an isocyanuric ring represented by the formula (1a) of the present application, thereby having a sufficient glass transition temperature when formed into a cured product, and moldability. It has been found that there is little coloring when it is made into a cured product.

式（１ａ）中、Ｐ_１〜Ｐ_４は、ヒドロキシル基又は炭素数１〜１５のカルボキシル基を含有する有機基をそれぞれ表す。式（１ａ）中、複数存在するＰ_１〜Ｐ_４は同一であっても異なっていても構わないが、複数存在するＰ_１〜Ｐ_４中、少なくとも１つ以上は下記式（１ｂ）または（１ｃ）である。

式（１ａ）〜（１ｃ）中、＊印はその場所で結合していることを意味する。
式（１ｂ）中、Ｒ_２は水素原子、炭素数１〜３のアルキル基またはカルボキシル基を表す。
式（１ｃ）中、Ｒ_３は水素原子または炭素数１〜４のアルキル基を、ｍは整数で１〜９をそれぞれ表し、式（１ｃ）中、複数存在するＲ_３は同一であっても異なっていても構わない。
（２）（１）に記載の熱硬化性樹脂用硬化剤のＰ_１〜Ｐ_４のうち、少なくとも一つが下記式で表されることを特徴とする熱硬化性樹脂用硬化剤。

式（１ｃ）中、Ｒ_３は水素原子または炭素数１〜４のアルキル基を、ｍは整数で１〜９をそれぞれ表し、式（１ｃ）中、複数存在するＲ_３は同一であっても異なっていても構わない。
（３）（１）に記載の熱硬化性樹脂用硬化剤、並びに、トリメリット酸、無水トリメリット酸、シクロヘキサントリカルボン酸、シクロヘキサントリカルボン酸無水物、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水グルタル酸、ピロメリット酸、水添ピロメリット酸、ピロメリット酸無水物、水添ピロメリット酸無水物、グルタル酸、およびジエチルグルタル酸から選ばれる１種または２種以上の化合物を含有していてもよいことを特徴とする熱硬化性樹脂用硬化剤であり、請求項１に記載の熱硬化性樹脂用硬化剤：（トリメリット酸、無水トリメリット酸、シクロヘキサントリカルボン酸、シクロヘキサントリカルボン酸無水物、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水グルタル酸、ピロメリット酸、水添ピロメリット酸、ピロメリット酸無水物、水添ピロメリット酸無水物、グルタル酸、およびジエチルグルタル酸から選ばれる１種または２種以上の化合物）が重量比で９９：１〜１０：９０であることを特徴とする熱硬化性樹脂用硬化剤。
（４）ＩＣＩコーンプレート粘度が１００〜２００℃の範囲で０．０１Ｐａ・ｓ〜１０Ｐａ・ｓの範囲にあることを特徴とする、（３）に記載の熱硬化性樹脂用硬化剤。
（５）軟化点が２０℃〜１５０℃の範囲にあることを特徴とする、（３）又は（４）のいずれか一項に記載の熱硬化性樹脂用硬化剤。
（６）（１）〜（５）のいずれか一項に記載の熱硬化性樹脂用硬化剤を含有する熱硬化性樹脂組成物の硬化物のガラス転移温度（Ｔｇ）が３０℃以上である熱硬化性樹脂組成物。
（７）（６）に記載の熱硬化性樹脂組成物を熱硬化してなる硬化物。
（８）（７）に記載の硬化物によって封止された光半導体装置。
（９）（７）に記載の硬化物を反射材として使用した光半導体装置。 That is, the present invention relates to the following (1) to (9).
(1) A curing agent for a thermosetting resin containing a polyvalent carboxylic acid represented by the following formula (1a).

Formula (1a) _in, P 1 to P ₄ each represent an organic group containing a carboxyl group of a hydroxyl group or 1 to 15 carbon atoms. In the formula (1a), a plurality of P _{1 to} P ₄ may be the same or different, but in the plurality of P _{1 to} P ₄ , at least one of the following formulas (1b) or ( 1c).

In the formulas (1a) to (1c), an asterisk (*) means binding at that position.
In formula (1b), R ₂ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group.
In formula (1c), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in formula (1c), a plurality of R ₃ may be the same It can be different.
(2) A thermosetting resin curing agent, wherein at least one of P _{1 to} P ₄ of the thermosetting resin curing agent according to (1) is represented by the following formula.

In formula (1c), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in formula (1c), a plurality of R ₃ may be the same It can be different.
(3) The curing agent for thermosetting resin described in (1), trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexa One or more selected from hydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethyl glutaric acid A curing agent for a thermosetting resin, characterized by comprising a compound, and the curing agent for a thermosetting resin according to claim 1: (trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid , Cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride One or two selected from methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethyl glutaric acid The above compound) is 99: 1 to 10:90 by weight ratio, and a curing agent for thermosetting resin.
(4) The curing agent for thermosetting resin according to (3), wherein the ICI cone plate viscosity is in the range of 0.01 Pa · s to 10 Pa · s in the range of 100 to 200 ° C.
(5) The curing agent for thermosetting resins according to any one of (3) and (4), wherein the softening point is in the range of 20 ° C to 150 ° C.
(6) The glass transition temperature (Tg) of the cured product of the thermosetting resin composition containing the curing agent for thermosetting resin according to any one of (1) to (5) is 30 ° C. or higher. Thermosetting resin composition.
(7) Hardened | cured material formed by thermosetting the thermosetting resin composition as described in (6).
(8) An optical semiconductor device sealed with the cured product according to (7).
(9) An optical semiconductor device using the cured product according to (7) as a reflector.

  According to the present invention, a polyvalent carboxylic acid having a sufficient glass transition temperature of a cured product, excellent moldability, and less colored when made into a cured product, a thermosetting resin composition using the same, and its thermosetting An optical semiconductor device using the conductive resin composition as a sealing material or a reflecting material can be provided. Further, by suppressing the softening point, handling becomes easy, and sufficient kneading is possible, and a cured product having excellent cured properties can be provided. Moreover, the thermosetting resin composition excellent also in the toughness of hardened | cured material and the reactivity of resin can be provided.

式（１ａ）中、Ｐ_１〜Ｐ_４は、ヒドロキシル基又は炭素数１〜１０のカルボキシル基を含有する有機基をそれぞれ表す。式（１ａ）中、複数存在するＰ_１〜Ｐ_４は同一であっても異なっていても構わないが、複数存在するＰ_１〜Ｐ_４中、少なくとも１つは下記式（１ｂ）および／または（１ｃ）である。少なくとも２つであると硬化物の機械強度が優れるため好ましい。

式（１ｂ）〜（１ｃ）中、＊印はその場所で（１ａ）のＰ_１〜Ｐ_４に隣接する炭素原子と結合していることを意味する。
式（１ｂ）中、Ｒ_２は水素原子、炭素数１〜３のアルキル基またはカルボキシル基を表す。
式（１ｃ）中、Ｒ_３は水素原子または炭素数１〜４のアルキル基を、ｍは整数で１〜９をそれぞれ表し、式（１ｃ）中、複数存在するＲ_３は同一であっても異なっていても構わない。Ｒ_３の中の炭素数１〜４のアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基が挙げられる。ｍは、得られる硬化物の耐熱性の観点から、１〜５が好ましく、１〜２が特に好ましい。
即ち、上記式（1ａ）で表される化合物において、複数存在するＰ_１〜Ｐ_４中、全水酸基を１００モル％とした場合、２５モル％以上は下記式（１ｂ）および／または（１ｃ）である。また、少なくとも５０モル％が下記式（１ｂ）および／または（１ｃ）を含有する有機基であると硬化物の機械強度が優れるため好ましい。
また、上記式（１ａ）の含有割合は下記式（５）と下記式（６）〜（７）の反応により得られた多価カルボン酸樹脂中、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）による測定で６０面積％以上であることが好ましく、７０面積％以上であることがより好ましい。 The present invention is described in detail below.
The curing agent for a thermosetting resin and the thermosetting resin composition of the present invention contain a polyvalent carboxylic acid (A) represented by the following formula (1a).

Formula (1a) _in, P 1 to P ₄ each represent an organic group containing a hydroxyl group or a carboxyl group having 1 to 10 carbon atoms. In the formula (1a), a plurality of P _{1 to} P ₄ may be the same or different, but at least one of the plurality of P _{1 to} P ₄ is represented by the following formula (1b) and / or (1c). Since it is excellent in the mechanical strength of hardened | cured material, it is preferable that it is at least two.

In the formulas (1b) to (1c), * means that it is bonded to a carbon atom adjacent to P _{1 to} P ₄ in (1a) at that position.
In formula (1b), R ₂ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group.
In formula (1c), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in formula (1c), a plurality of R ₃ may be the same It can be different. Specific examples of the alkyl group having 1 to 4 carbon atoms in R ₃ include a methyl group, an ethyl group, a propyl group, and a butyl group. From the viewpoint of the heat resistance of the resulting cured product, m is preferably 1 to 5, and particularly preferably 1 to 2.
That is, in the compound represented by the above formula (1a), in the plurality of P _{1 to} P ₄ , when the total hydroxyl group is 100 mol%, 25 mol% or more is represented by the following formula (1b) and / or (1c) It is. Moreover, it is preferable that at least 50 mol% is an organic group containing the following formula (1b) and / or (1c) because the mechanical strength of the cured product is excellent.
Moreover, the content rate of the said formula (1a) is the measurement by gel permeation chromatography (GPC) in the polyhydric carboxylic acid resin obtained by reaction of following formula (5) and following formula (6)-(7). It is preferably 60 area% or more, and more preferably 70 area% or more.

式（１ｄ）中、Ｐ_５〜Ｐ_８はヒドロキシル基、上記式（１ｂ）ないし（１ｃ）等の炭素数１〜１０のカルボキシル基を含有する有機基、下記式（１ｅ）または下記式（１ｆ）をそれぞれ表す。複数存在するＰ_５〜Ｐ_８は同一であっても異なっていても構わないが、複数存在するＰ_５〜Ｐ_８中、少なくとも１つ以上は下記式（１ｅ）および／または（１ｆ）を示す。

式（１ｅ）〜（１ｆ）中、＊印はその場所で（１ｄ）のＰ_５〜Ｐ_８に隣接する炭素原子と結合していることを意味する。
式（１ｅ）中、Ｒ_２は水素原子、炭素数１〜３のアルキル基またはカルボキシル基を表す。
式（１ｆ）中、Ｒ_３は水素原子または炭素数１〜４のアルキル基を、ｍは整数で１〜９をそれぞれ表し、式（１ｆ）中、複数存在するＲ_３は同一であっても異なっていても構わない。Ｒ_３の中の炭素数１〜４のアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基が挙げられる。ｍは、得られる硬化物の耐熱性の観点から、１〜５が好ましく、１〜２が特に好ましい。
２量体としては、多価カルボン酸中、上記式（１ｅ）または上記式（１ｆ）が１つ存在し、＊印の場所で（１ｄ）のＰ_５〜Ｐ_８に隣接する炭素原子と結合しており、残りのＰ_５〜Ｐ_８がヒドロキシル基、上記式（１ｂ）ないし（１ｃ）等の炭素数１〜１０のカルボキシル基を含有する有機基である構造が挙げられる。
さらに、３量体は上記式（１ｄ）および／または式（１ｅ）が２つ存在し、＊印の場所で（１ｄ）のＰ_５〜Ｐ_８に隣接する炭素原子と結合しており、残りのＰ_５〜Ｐ_８がヒドロキシル基、上記式（１ｂ）ないし（１ｃ）等の炭素数１〜１０のカルボキシル基を含有する有機基である構造が挙げられる。
上記２量体の含有割合は下記式（５）と下記式（６）〜（７）の反応により得られた多価カルボン酸樹脂中、ＧＰＣによる測定で１〜３０面積％であることが好ましく、１０〜２０面積％であることがより好ましい。
また、上記３量体の含有割合は下記式（５）と下記式（６）〜（７）の反応により得られた多価カルボン酸樹脂中、ＧＰＣによる測定で１〜１０面積％であることが好ましく、３〜８面積％であることがより好ましい。 The hardening | curing agent for thermosetting resins of this invention can contain the polyvalent carboxylic acid of the multimer of said Formula (1d) with the polyvalent carboxylic acid represented by said Formula (1a). When the multimer is contained, the obtained cured product can have toughness, which is preferable.

In formula (1d), P _{5 to} P ₈ are hydroxyl groups, organic groups containing a carboxyl group having 1 to 10 carbon atoms such as the above formulas (1b) to (1c), the following formula (1e) or the following formula (1f ) Respectively. Plural P _{5 to} P ₈ may be the same or different, but at least one of the plural P _{5 to} P ₈ represents the following formula (1e) and / or (1f). .

In formulas (1e) to (1f), an asterisk (*) means that it is bonded to a carbon atom adjacent to P _{5 to} P ₈ in (1d) at that position.
In formula (1e), R ₂ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group.
In formula (1f), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in formula (1f), a plurality of R ₃ may be the same It can be different. Specific examples of the alkyl group having 1 to 4 carbon atoms in R ₃ include a methyl group, an ethyl group, a propyl group, and a butyl group. From the viewpoint of the heat resistance of the resulting cured product, m is preferably 1 to 5, and particularly preferably 1 to 2.
As the dimer, one of the above formula (1e) or the above formula (1f) is present in the polyvalent carboxylic acid, and is bonded to the carbon atom adjacent to P _{5 to} P ₈ of (1d) at the location of *. And the remaining P _{5 to} P ₈ are hydroxyl groups and organic groups containing a carboxyl group having 1 to 10 carbon atoms such as the above formulas (1b) to (1c).
Further, the trimer has two of the above formula (1d) and / or formula (1e), and is bonded to the carbon atom adjacent to P _{5 to} P ₈ of (1d) at the location of *, and the rest In which P _{5 to} P ₈ are a hydroxyl group and an organic group containing a carboxyl group having 1 to 10 carbon atoms such as the above formulas (1b) to (1c).
The content ratio of the dimer is preferably 1 to 30% by area as measured by GPC in the polyvalent carboxylic acid resin obtained by the reaction of the following formula (5) and the following formulas (6) to (7). 10 to 20 area% is more preferable.
Moreover, the content rate of the said trimer is 1-10 area% by the measurement by GPC in the polyhydric carboxylic acid resin obtained by reaction of following formula (5) and following formula (6)-(7). Is preferable, and it is more preferable that it is 3-8 area%.

In the formula (1a), a plurality of P _{1 to} P ₄ may be the same or different from each other.

The polyvalent carboxylic acid (A) represented by the formula (1a) is selected from ditrimethylolpropane represented by the following formula (5) and compounds represented by the following formulas (6) to (7). It can be obtained by addition reaction with one or more carboxylic acid anhydride compounds.

Wherein (6), _{R 2} represents a hydrogen atom, an alkyl group or a carboxyl group having 1 to 3 carbon atoms.
In Formula (7), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in Formula (1c), a plurality of R ₃ may be the same. It can be different. Specific examples of the alkyl group having 1 to 4 carbon atoms in R ₃ include a methyl group, an ethyl group, a propyl group, and a butyl group. From the viewpoint of the heat resistance of the resulting cured product, m is preferably 1 to 5, and particularly preferably 1 to 2.

Of the compounds represented by the formula (6), compounds represented by the following (8) to (10) are particularly preferred.

Of the compounds represented by the formula (7), compounds represented by the following formulas (11) to (13) are particularly preferable.

The production of the polyvalent carboxylic acid (A) of the present invention can be carried out in a solvent or without a solvent. As the solvent, any solvent that does not react with the ditrimethylolpropane represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6) and / or (7) can be used without particular limitation. Examples of solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, toluene and xylene. An aromatic hydrocarbon etc. are mentioned, Among these, an aromatic hydrocarbon and ketones are preferable.
These solvents may be used alone or in combination of two or more. The amount used in the case of using the solvent is based on 100 parts by mass in total of the ditrimethylolpropane represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6) and / or (7). 0.5 to 300 parts by mass is preferable.

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

The polyvalent carboxylic acid (A) of the present invention can be produced without a catalyst or with a catalyst. When a catalyst is used, usable catalysts are hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, water Metal hydroxides such as calcium oxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, Heterocyclic compounds such as imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium Roxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctyl Quaternary ammonium salts such as methylammonium acetate, orthotitanic acid such as tetraethyl orthotitanate, tetramethyl orthotitanate, tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, Examples include metal soaps such as potassium octylate.
When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.
The amount used in the case of using the catalyst is based on 100 parts by mass in total of the ditrimethylolpropane represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6) and / or (7). 0.05 to 10 parts by mass is preferable.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. In this case, use of alcoholic solvents such as methanol and ethanol and water is avoided because it reacts with the unreacted carboxylic acid anhydride compound represented by the formula (6) and / or (7). It is preferable.
In the present invention, in the cured product of the resulting thermosetting resin composition (C), zinc carboxylate such as zinc octylate can be preferably used as a catalyst from the viewpoint of improving transparency and heat-resistant transparency. From the viewpoint of reducing the coloration of the obtained polyvalent carboxylic acid (A) or thermosetting resin composition (C), the reaction is preferably carried out without a catalyst.
Among them, in order to obtain a cured product excellent in transparency and sulfidation resistance, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylate) and zinc phosphate ester ( Zinc compounds such as zinc octyl phosphate and zinc stearyl phosphate are preferably used.

  The reaction temperature during the production of the polyvalent carboxylic acid (A) of the present invention is usually 20 to 160 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 145 ° C., although it depends on the amount of catalyst and the solvent used. . The total reaction time is usually 1 to 20 hours, preferably 3 to 18 hours. The reaction may be carried out in two or more stages. For example, the reaction may be carried out at 20 to 100 ° C. for 1 to 8 hours and then at 100 to 160 ° C. for 1 to 12 hours. In particular, the carboxylic acid anhydride compound represented by the formula (6) is often highly volatile, and when such a compound is used, it is reacted at 20 to 100 ° C. and then reacted at 100 to 160 ° C. By doing so, volatilization can be suppressed. Thereby, not only can the diffusion of harmful substances into the atmosphere be suppressed, but also the polyvalent carboxylic acid (A) as designed can be obtained.

When the production is carried out using a catalyst, the catalyst can be removed by quenching and / or washing with water as necessary, but the polycarboxylic acid (A) and / or thermosetting resin 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 a water washing process, it is preferable to add the solvent which can be isolate | separated from water depending on the kind of solvent currently used. 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, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.
When a solvent is used for the reaction or washing with water, it can be removed by vacuum concentration or the like.

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

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

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

Next, the thermosetting resin composition of the present invention will be described. The thermosetting resin composition of the present invention is a resin composition containing a polyvalent carboxylic acid (A) represented by the above formula (1) and other components. In the polyvalent carboxylic acid composition of the present invention, a thermosetting resin curing agent can be contained. Suitable curing agents for thermosetting resins include trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride Examples thereof include one or more compounds selected from acids, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, glutaric acid, and diethyl glutaric acid.

Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, In the presence of pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, glutaric acid, and diethyl glutaric acid, a cured product having a high crosslinking density can be obtained, so that a cured product having a high glass transition temperature can be obtained. However, carboxylic acids such as trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, and hydrogenated pyromellitic acid anhydride or An acid anhydride has crystallinity and thus has a high softening point or melting point, and a specific melting point is 150 ° C. to 300 ° C., which may cause a problem in molding. On the other hand, since hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and diethylglutaric acid have a melting point of room temperature or less, they are problematic in molding. Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, Of the pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, glutaric acid, and diethylglutaric acid, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, hydrogenated pyromellitic acid, water Pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric acid, and diethylglutaric acid are preferred, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Glutarate and diethyl glutaric acid, are more preferable.
Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride. In the present invention, these acid anhydrides can be used in combination, but cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferred.

  Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, The total proportion of one or more compounds selected from pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethylglutaric acid accounts for 1% by weight to the thermosetting resin composition. It is characterized by 90% by weight. If it is lower than 1% by weight, the glass transition temperature is not sufficiently high, and if it is higher than 90% by weight, the melting point is too high or too low and handling becomes difficult. More preferably, it is 1-50 weight%, More preferably, it is 1-30 weight%.

（式中、複数存在するＰは０〜６の酸素原子、窒素原子、リン原子を含んでもよい、炭素数２〜２０の多価アルコールの残基を、Ｒは炭素数２〜２０の脂肪族炭化水素基を示す。複数存在するｎ、ｋは独立して存在し、平均で１〜６を示す。またｎの総計は２以上１２以下である。）
の構造を有し、分子内にエステル構造（好ましくは２つのエステル構造）を有する化合物である。また末端に複数のカルボキシル基を有する化合物である。
中でも、前記式（１４）の末端カルボン酸のオリゴエステルが炭素数６以上の２〜６官能の多価アルコールと飽和脂肪族環状酸無水物とのエステル化反応により得られた化合物であることが好ましい。
より具体的には、前記式（１４）に記載の末端カルボン酸のオリゴエステルにおいて、連結基Ｒは炭素数４〜１０のシクロアルカン骨格、もしくはノルボルナン骨格が好ましく、シクロアルカン骨格においては置換、もしくは無置換のシクロヘキサン構造、特にメチル基を具備するメチルシクロヘキサン構造がその硬化物における光学特性から好ましい。またノルボルナン骨格としてはノルボルナン、メチルノルボルナン構造が好ましい。ここで、置換されたものにおいて適用できる置換基としては、炭素数１〜３のアルキル基、カルボキシル基等が挙げられる。
連結基Ｐは炭素数２〜１０の多価アルコールの残基（反応に用いた多価アルコールから水酸基を除いた残基）であるが、分岐鎖状の架橋基、もしくはシクロアルキル基が好ましく、特にＰは下記（ａ）又は（ｂ）で定義される２価の架橋基であることが好ましい。
（ａ）炭素数６〜２０の分岐構造を有する鎖状アルキル鎖であり、該鎖状アルキル鎖が炭素数３〜１２の直鎖の主鎖と、２〜４個の側鎖を有し、かつその側鎖の少なくとも１つが炭素数２〜１０である架橋基、
又は、
（ｂ）シクロ環上にメチル基を有してもよい、トリシクロデカンジメタノール又はペンタシクロペンタデカンジメタノール、から選ばれる少なくとも１種の架橋多環ジオールから、２つの水酸基を取り除いた２価の架橋基
但し、Ｐが（ｂ）の場合、好ましいものは連結基Ｒが炭素数４〜１０のシクロアルカン骨格又はノルボルナン骨格のときは、後述する式（２Ａ）において置換基Ｒ^３が水素原子以外の基を表すことがより好ましい。
尚、上記オリゴエステルの軟化点は通常５０℃以上であるが、６０℃以上が好ましく、８０℃以上がより好ましい。上限値に特に制限はないが通常５００℃以下であり、３００℃以下であることが好ましく、２００℃以下であることがより好ましい。 Moreover, the oligoester of the terminal carboxylic acid which can be contained as a component of the hardening | curing agent for thermosetting resins of this invention is represented by following formula (14).
As a specific structural formula, the following formula (14)

(In the formula, a plurality of P are residues of a polyhydric alcohol having 2 to 20 carbon atoms which may contain 0 to 6 oxygen atoms, nitrogen atoms and phosphorus atoms, and R is an aliphatic having 2 to 20 carbon atoms. A hydrocarbon group, a plurality of n and k are present independently and represent an average of 1 to 6. The total of n is 2 or more and 12 or less.)
And a compound having an ester structure (preferably two ester structures) in the molecule. Moreover, it is a compound which has a some carboxyl group at the terminal.
Among them, the oligoester of the terminal carboxylic acid of the formula (14) is a compound obtained by an esterification reaction of a bifunctional or polyfunctional alcohol having 6 or more carbon atoms and a saturated aliphatic cyclic acid anhydride. preferable.
More specifically, in the oligoester of a terminal carboxylic acid described in the formula (14), the linking group R is preferably a cycloalkane skeleton having 4 to 10 carbon atoms or a norbornane skeleton, and the cycloalkane skeleton is substituted, or An unsubstituted cyclohexane structure, particularly a methylcyclohexane structure having a methyl group is preferred from the optical properties of the cured product. The norbornane skeleton is preferably a norbornane or methylnorbornane structure. Here, examples of the substituent that can be applied to the substituted one include an alkyl group having 1 to 3 carbon atoms and a carboxyl group.
The linking group P is a residue of a polyhydric alcohol having 2 to 10 carbon atoms (residue obtained by removing a hydroxyl group from the polyhydric alcohol used in the reaction), preferably a branched cross-linking group or a cycloalkyl group. In particular, P is preferably a divalent crosslinking group defined by the following (a) or (b).
(A) a chain alkyl chain having a branched structure having 6 to 20 carbon atoms, the chain alkyl chain having a linear main chain having 3 to 12 carbon atoms and 2 to 4 side chains; And at least one of the side chains has 2 to 10 carbon atoms,
Or
(B) a divalent diamine obtained by removing two hydroxyl groups from at least one crosslinked polycyclic diol selected from tricyclodecane dimethanol or pentacyclopentadecane dimethanol, which may have a methyl group on the cyclo ring. Crosslinking group However, when P is (b), when a coupling group R is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent R ³ is other than a hydrogen atom in the formula (2A) described later. It is more preferable to represent this group.
In addition, although the softening point of the said oligoester is 50 degreeC or more normally, 60 degreeC or more is preferable and 80 degreeC or more is more preferable. Although there is no restriction | limiting in particular in an upper limit, Usually, it is 500 degrees C or less, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 200 degrees C or less.

The particularly preferable oligoester of the terminal carboxylic acid in the present invention can be obtained by addition reaction of a bifunctional or polyfunctional alcohol having 6 or more carbon atoms with a saturated aliphatic cyclic acid anhydride.
The oligoester of a terminal carboxylic acid in the present invention may be a composition containing two types of oligoesters of a terminal carboxylic acid. As a method for obtaining an oligoester composition of a terminal carboxylic acid containing at least two oligoesters of a terminal carboxylic acid, a method of mixing at least two kinds of oligoesters of a single terminal carboxylic acid obtained by the above method, or When synthesizing the oligoester of the above terminal carboxylic acid, the saturated aliphatic cyclic acid anhydride is selected from the following saturated aliphatic cyclic acid anhydrides, or a mixture of at least two kinds is used. There is a method of performing an addition reaction using two kinds of alcohols.

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

前記式中、＊印で式（１４）におけるＰの両側の酸素原子と結合する。
上記（ａ）で定義されるアルキレン架橋基は、主鎖アルキレン基に対し、アルキル分岐鎖（側鎖）を有する構造であれば特に制限はないが、主鎖の炭素数が３以上の主鎖であり、少なくとも１個のアルキル側鎖を有するものが好ましく、またアルキル側鎖を２つ以上有するものが特に好ましい。より好ましいものとしては、炭素数３〜１２の直鎖の主鎖と、２〜４個の側鎖を有し、かつその側鎖の少なくとも１つが炭素数２〜１０である架橋基を挙げることができる。この場合、側鎖の少なくとも２つが炭素数２〜１０である架橋基は更に好ましい。また、２〜４個の側鎖は主鎖の異なる炭素原子から分岐していることが好ましい。
より具体的な化合物としては前記式（ａ１）に記載した架橋基において、＊印の位置にヒドロキシル基が結合した化合物を挙げることができる。
原料として使用する多価アルコールの中では、少なくとも２個の側鎖を有し、該側鎖の中で少なくとも２個が炭素数２〜４の側鎖である多価アルコールが好ましい。
このような骨格の中で特に好ましい多価アルコールとしては２，４−ジエチル−１，５−ペンタンジオール、２−エチル−２−ブチル−１，３−プロパンジオール、２−エチル−１，３−ヘキサンジオールなどが挙げられ、特に２，４−ジエチル−１，５−ペンタンジオールが挙げられる。 Specifically, as the C6-C6 bifunctional polyhydric alcohol used in the synthesis of the terminal carboxylic acid oligoester in the present invention, a hydroxyl group is attached to the end of the crosslinking group P in the formula (14). And oligoesters of terminal carboxylic acids.
In the formula (14), the bridging group represented by P is preferably a divalent bridging group defined by the above (a) or (b), which will be specifically described below.
The divalent crosslinking group defined in (a) above is a divalent chain alkyl chain obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure having 6 to 20 carbon atoms. This is a structure having an alkyl chain sandwiched between two alcoholic hydroxyl groups as a main chain and an alkyl chain (referred to as a side chain) branched from the alkyl chain. The side chain may be branched from any carbon atom constituting the main chain, and includes, for example, a case where the side chain is branched from a carbon atom to which an alcoholic hydroxyl group is bonded (terminal carbon atom of the main chain). Any crosslinking group having such a structure may be used, and a specific example of such a crosslinking group is shown in the following formula (a1).

In the above formula, it is bonded to oxygen atoms on both sides of P in the formula (14) by * mark.
The alkylene bridging group defined in (a) is not particularly limited as long as it has a structure having an alkyl branched chain (side chain) with respect to the main chain alkylene group, but the main chain has 3 or more main chain carbon atoms. In particular, those having at least one alkyl side chain are preferred, and those having two or more alkyl side chains are particularly preferred. More preferable examples include a straight-chain main chain having 3 to 12 carbon atoms and a cross-linking group having 2 to 4 side chains and at least one of the side chains having 2 to 10 carbon atoms. Can do. In this case, a crosslinking group in which at least two of the side chains have 2 to 10 carbon atoms is more preferable. Moreover, it is preferable that the 2-4 side chain is branched from the carbon atom from which a principal chain differs.
More specific examples of the compound include a compound in which a hydroxyl group is bonded to the position of * in the crosslinking group described in the formula (a1).
Among the polyhydric alcohols used as raw materials, polyhydric alcohols having at least two side chains and at least two of which are side chains having 2 to 4 carbon atoms are preferred.
Among these skeletons, particularly preferred polyhydric alcohols are 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-1,3- Examples include hexanediol, and particularly 2,4-diethyl-1,5-pentanediol.

前記（ｂ）で定義される架橋基の場合の、架橋多環ジオール残基としては、トリシクロデカン構造、ペンタシクロペンタデカン構造を主骨格とするジオール残基であり、下記式（ｂ２）で表される。 Examples of the crosslinking group defined by (b) include a divalent group represented by the following formula (b1).

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

式中、複数存在するＲ^２はそれぞれ独立して、水素原子、もしくはメチル基を表す。これらの中で、Ｒ^２が全て水素原子である架橋基が好ましい。
具体的にはトリシクロデカンジメタノール、メチルトリシクロデカンジメタノール、ペンタシクロペンタデカンジメタノールなどが挙げられる。

In the formula, a plurality of R ² each independently represents a hydrogen atom or a methyl group. Of these, a bridging group in which all R ² are hydrogen atoms is preferred.
Specific examples include tricyclodecane dimethanol, methyl tricyclodecane dimethanol, and pentacyclopentadecane dimethanol.

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

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

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

The reaction ratio between the acid anhydride and the polyhydric alcohol is theoretically preferably equimolar, but can be changed as necessary.
As a specific charging ratio of both when reacting, 0.001 to 2 equivalents in terms of the functional group equivalent, and 1 equivalent of the acid anhydride group, the polyhydric alcohol in terms of the hydroxyl equivalent, It is preferable to charge at a ratio of preferably 0.01 to 1.5 equivalents, more preferably 0.1 to 1.2 equivalents.
In the present invention, it is preferable that the obtained terminal carboxylic acid oligoester is solid, and in order to obtain a solid resinous terminal carboxylic acid oligoester, ideally an equimolar equivalent or more of polyhydric alcohol is used. However, fluidity is important because the filler is added, and in order to secure this fluidity, even if some balance is lost in the range where the solids are maintained (softening point of 50 ° C. or higher) in order to secure this fluidity. I do not care.
Specifically, the equivalent ratio of the alcoholic hydroxyl group to the acid anhydride equivalent is preferably 0.85 to 1.20 molar equivalent, particularly preferably 0.90 to 1.1.0 molar equivalent.

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

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

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

（上記式中、Ｐは上記と同じ意味を表し、Ｒ^３は水素原子、炭素数１〜３のアルキル基またはカルボキシル基を表す。）
ここで、上記式（２Ａ）においては、上記に記載の通りの理由により、Ｒ^３が炭素数１〜３のアルキル基またはカルボキシル基を好適に使用できる。
末端カルボン酸オリゴエステルは、数平均分子量Ｍｎが３００以上である末端カルボン酸のオリゴエステルであることが好ましい。 The thus obtained terminal carboxylic acid oligoester or the composition containing the terminal carboxylic acid oligoester usually shows a colorless to pale yellow solid resinous form (which may crystallize in some cases). The softening point of the oligoester of the terminal carboxylic acid is preferably 50 to 190 ° C, more preferably 55 to 150 ° C, and particularly preferably 60 to 120 ° C. By mixing the oligoester of a terminal carboxylic acid having such a softening point directly into a thermosetting resin composition without making it liquid, it has an extremely high reflectance retention rate, and even when subjected to a heat test. It is possible to provide a reflecting member whose reflectance is not easily lowered.
Usually, when the crosslinking group is an alkylene group having a side chain defined by (a), it shows a colorless to pale yellow solid resinous form.
In this invention, since the optimal method using the thermosetting resin composition containing the oligoester of terminal carboxylic acid is a shaping | molding by transfer, the oligoester of terminal carboxylic acid is a solid resin form.
When the bridging group is a bridging group defined by (b), when the aliphatic hydrocarbon group is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, all of the alicyclic substituents are at the end of the hydrogen atom. Carboxylic acid oligoesters show coloration upon curing and are not suitable for particularly demanding optical applications. When the aliphatic hydrocarbon group is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, such a coloring is less in a compound having a methyl group or a carboxyl group, and the optical characteristics are improved.
Also in the compound of the bridging group defined in (a), when the aliphatic hydrocarbon group is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent is a methyl group or a carboxyl group. This is preferable because optical characteristics are improved.
That is, when the terminal carboxylic acid oligoester composition of the present invention is 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 (14) having both. A composition comprising an oligoester of a terminal carboxylic acid is preferred. In the case of an oligoester composition of a terminal carboxylic acid containing two or more kinds of oligoesters of the terminal carboxylic acid, at least the terminal carboxylic acid oligoester of the formula (1) in which the substituent is not a hydrogen atom (the substituent is the alkyl group) , Preferably an oligoester of a terminal carboxylic acid having a methyl group or a carboxyl group) is preferably 50 mol% or more based on the total amount of oligoesters of the terminal carboxylic acid. More preferably, a terminal carboxylic acid oligoester composition containing 70 mol% or more, most preferably 90 mol% or more of the terminal carboxylic acid oligoester of the formula (14), in which the substituent is not a hydrogen atom. The remainder is an oligoester of a terminal carboxylic acid of the following formula (2A) in which R ³ is a hydrogen atom.
As the terminal carboxylic acid oligoester suitable for the present invention, a terminal carboxylic acid oligoester represented by the following formula (2A) is used.

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

Further, in the thermosetting resin composition of the present invention, the polyvalent carboxylic acid represented by the above formula (1a) and trimellitic acid, trimellitic acid anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, hexahydrophthalic anhydride Acid, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethyl glutaric acid The functional group equivalent in the mixture of the 1 type, or 2 or more types of compound chosen is 250 g / eq. Or less, preferably 240 g / eq. More preferably, it is 230 g / eq. It is particularly preferred that Within this range, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, pyro Effectively exhibits the effect of the compound amount of one or more compounds selected from merit acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, glutaric acid, and diethyl glutaric acid. Thus, a cured product having excellent heat resistance can be obtained.
The weight ratio of the polycarboxylic acid represented by the above formula (1a): (trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride 1 or 2 selected from methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethylglutaric acid It is preferable that the compound of a seed | species or more is 99: 1-10: 90, and 90: 10-20: 80 is more preferable. By being in the said ratio, while being extremely excellent in heat resistance, it becomes possible to fully knead | knead low viscosity, Therefore It becomes a thermosetting resin composition excellent also in cured | curing physical property.
In addition, the polyvalent carboxylic acid (A) represented by the above formula (1a), trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl One or more selected from hexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethyl glutaric acid And a curing agent for thermosetting resins containing trimellitic acid, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride , Glutaric anhydride, pyromellitic , Hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, glutaric acid, and a mixture of one or more compounds selected from diethyl glutaric acid are added to the thermosetting resin composition. The occupying ratio is preferably 1% by weight to 90% by weight. By being the said weight%, kneadability and moldability improve and it becomes a thermosetting resin composition which is excellent also in hardened | cured material property.

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

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

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

  The compounding ratio of the epoxy resin and the curing agent for thermosetting resin of the present invention is such that the active group (acid) in the curing agent for thermosetting resin capable of reacting with the epoxy group is equivalent to 1 equivalent of the epoxy group in the epoxy resin. (Anhydride group or hydroxyl group) is preferably 0.5 to 1.5 equivalents (the carboxylic acid is considered to be monofunctional and the acid anhydride is assumed to be monofunctional), particularly preferably 0.5 to 1.2 equivalents. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, in any case, curing may be incomplete and good cured properties may not be obtained, and coloration is likely to occur. There is also a problem.

If necessary, a curing accelerator can be added to the curable resin composition of the present invention. Examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole ( 1 ′)) Ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazole) (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole , 2-phenyl-4-hydroxymethyl-5-methylimidazole, various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid , Salts with oligoesters of terminal carboxylic acids such as trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7 and their tetrafes Salts such as ruborate and phenol novolac, oligoesters of the terminal carboxylic acids, salts with phosphinic acids, quaternary compounds such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, hexadecyltrimethylammonium hydroxide Ammonium salts (preferably C1-C20 alkyl ammonium salts, phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, 2,4,6-trisaminomethyl Phenols and other phenols, amine adducts, tin octylate, zinc octoate, zinc stearate, copper naphthenate, naphthenic acid Examples thereof include metal compounds such as cobalt, and microcapsule type curing accelerators in which these curing accelerators are microcapsules. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. In the present invention, preferred are phosphonium compounds (more preferably quaternary phosphonium) and zinc stearate.
A hardening accelerator is 0.001-15 weight part normally with respect to 100 weight part of epoxy resins, Preferably it is used in 0.01-5 weight part.

  If necessary, as additives other than the above-mentioned additives, generally used additives for epoxy resins, such as pigments, dyes, fluorescent brighteners, reinforcing materials, fillers, nucleating agents, surfactants, A plasticizer, a viscosity modifier, a fluidity modifier, a flame retardant, an antioxidant, an ultraviolet absorber, and a light stabilizer may be added.

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

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

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

  The thermosetting resin composition of the present invention can be obtained by uniformly dispersing and mixing the various components described above. Although the method is not particularly limited, a method in which various components are sufficiently uniformly stirred and mixed by a mixer or the like and then kneaded or melt-kneaded by a mixing roll, an extruder, a kneader, a roll, an extruder, or the like, cooled and pulverized. Can be mentioned. The conditions for kneading or melt-kneading may be determined according to the type and blending amount of the components and are not particularly limited, but it is more preferable to knead in the range of 20 to 100 ° C. for 5 to 40 minutes. When the kneading temperature is less than 20 ° C., the dispersibility of each component is lowered and it is difficult to sufficiently knead. When the kneading temperature is higher than 100 ° C., the crosslinking reaction of the resin composition proceeds and the resin composition There is a risk that things will harden.

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

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

When used for light reflection, the production method is not particularly limited. For example, it is preferable to produce the thermosetting resin composition of the present invention by transfer molding. The thermosetting resin composition of the present invention is poured into a mold and, for example, is cured from 60 to 800 seconds under conditions of a mold temperature of 150 to 190 ° C. and a molding pressure of 2 to 20 MPa. It is cured at a curing temperature of 150 ° C. to 180 ° C. for 1 to 5 hours.
(Semiconductor device)
In the semiconductor device of the present invention, a specific example of a typical structure is illustrated. As described in International Publication No. 2012-124147, a light reflection preventing member having a cylindrical hollow portion is arranged on a substrate to form a cylindrical shape. An optical semiconductor element is disposed on the substrate in the internal space of the hollow portion. And the one end part and board | substrate of an optical semiconductor element are connected with the wire, and it has the structure by which sealing resin was enclosed with the said hollow part.

EXAMPLES Hereinafter, although an Example explains in full detail this invention, this invention is not limited to the following description. In the synthesis examples, gel permeation chromatography (hereinafter referred to as “GPC”), ICI viscosity, and softening point were measured as follows.
1) GPC
The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., the detection was performed by RI (Reflective index), and a standard polystyrene made by Shodex was used for the calibration curve. Further, the functional group equivalent was calculated from the ratio calculated from GPC, and the value was determined with 1 equivalent each of carboxylic acid and acid anhydride.
2) The melt viscosity in the cone plate method at an ICI viscosity of 150 ° C. was measured.
3) Softening point It measured by the method according to JIS K-7234.

（式（１５）中、＊印はその場所で結合していることを意味する。）
また、得られたＧＰＣチャートを下記に示す。

Synthesis example 1 (curing agent A-1 for thermosetting resin)
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 75.1 parts ditrimethylolpropane (manufactured by Perstorp), methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MHT) ) 131.2 parts, 47.9 parts of glutaric anhydride and 254.2 parts of methyl ethyl ketone (MEK) were added, followed by heating and stirring at 80 ° C. for 9 hours to obtain a MEK solution of the compound represented by formula (15). It was. Thereafter, the solvent was removed at 150 ° C. for 1 hour to obtain a curing agent for thermosetting resin.
The obtained curing agent was colorless and solid. The functional group equivalent was 214 g / eq. Met. The ICI viscosity was 0.62 Pa · s at 150 ° C. The softening point was 74.9 ° C.

(In the formula (15), * means that the bond is made at that place.)
Moreover, the obtained GPC chart is shown below.

Preparation of thermosetting light reflecting resin composition (Example 1)
Using TEPIC-S (Nissan Chemical Co., Ltd. triglycidyl isocyanurate) and Hishicolin PX-4MP (Nihon Kagaku Kogyo Co., Ltd. curing catalyst), each component was blended according to the blending table shown in Table 1, and mixed with a mixer. After sufficiently kneading, the mixture was melt-kneaded under a predetermined condition with a mixing roll, cooled, and pulverized to prepare the thermosetting resin composition of Example 1. In addition, the unit of the compounding quantity of each component in Table 1 is parts by weight, and the blank represents that the component is not used.

Evaluation of thermosetting resin composition About the resin composition of each Example, DMA, TMA, and the transmittance | permeability of hardened | cured material were measured with the method shown below. The results are shown in Table 1.

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

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

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

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

  The thermosetting resin curing agent of the present invention has a low melt viscosity and excellent moldability, and the thermosetting resin composition using the thermosetting resin curing agent has a sufficiently high glass transition temperature and is colored. Therefore, the thermosetting resin composition of the present invention is useful as an optical semiconductor sealing material or a light reflecting material. A sufficiently high glass transition temperature is important for formability and reliability. In addition, less coloring can increase the transmittance when used as a sealing material, and can increase the reflectance when used as a reflecting material.

Claims (9)

The hardening | curing agent for thermosetting resins containing the polyhydric carboxylic acid represented by following formula (1a).

Formula (1a) _in, P 1 to P ₄ each represent an organic group containing a carboxyl group of a hydroxyl group or 1 to 15 carbon atoms. In the formula (1a), a plurality of P _{1 to} P ₄ may be the same or different, but in the plurality of P _{1 to} P ₄ , at least one of the following formulas (1b) or ( 1c).

In the formulas (1a) to (1c), an asterisk (*) means binding at that position.
In formula (1b), R ₂ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group.
In formula (1c), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in formula (1c), a plurality of R ₃ may be the same It can be different. The thermosetting resin curing agent, wherein at least one of P _{1 to} P ₄ of the thermosetting resin curing agent according to claim 1 is represented by the following formula.

In formula (1c), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m represents an integer and represents 1 to 9, and in formula (1c), a plurality of R ₃ may be the same It can be different. The curing agent for thermosetting resins according to claim 1, and trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride Contains one or more compounds selected from acid, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethyl glutaric acid A curing agent for a thermosetting resin, characterized in that the curing agent for a thermosetting resin according to claim 1: (trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid) Acid anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, One or more selected from ruhexahydrophthalic anhydride, glutaric anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, glutaric acid, and diethyl glutaric acid The curing agent for thermosetting resin, wherein the compound) is in a weight ratio of 99: 1 to 10:90. The curing agent for thermosetting resins according to claim 3, wherein the ICI cone plate viscosity is in the range of 0.01 Pa · s to 10 Pa · s in the range of 100 to 200 ° C. The hardening agent for thermosetting resins according to any one of claims 3 and 4, wherein a softening point is in a range of 20 ° C to 150 ° C. The thermosetting resin composition whose glass transition temperature (Tg) of the hardened | cured material of the thermosetting resin composition containing the hardening | curing agent for thermosetting resins as described in any one of Claims 1-5 is 30 degreeC or more. object. Hardened | cured material formed by thermosetting the thermosetting resin composition of Claim 6. An optical semiconductor device sealed with the cured product according to claim 7. An optical semiconductor device using the cured product according to claim 7 as a reflective material.