JP5640319B2 - Curing agent for thermosetting resin, thermosetting resin composition, cured product, and semiconductor device - Google Patents

Description

  The present invention relates to a curing agent for a thermosetting resin, a thermosetting resin composition, a cured product, and a semiconductor device.

  In addition to being used as a curing agent for epoxy resins, acid anhydrides are used as raw materials for reacting with diamines to obtain polyimide compounds. Acid anhydrides are inexpensive and have excellent transparency, electrical insulation, chemical resistance, moisture resistance, adhesion, etc., electrical insulation materials, semiconductor device materials, optical semiconductor sealing materials, adhesive materials, paint materials, etc. It is used for various purposes.

  As acid anhydrides, intermolecular condensates of carboxylic acid compounds are also known. For example, a polycarboxylic acid anhydride obtained by an intermolecular dehydration condensation reaction of an aliphatic dicarboxylic acid exhibits excellent flexibility and thermal shock properties, and can be used alone or in combination with other acid anhydrides for powder coatings and Used as a curing agent for casting resins. So far, intermolecular condensates of aliphatic dicarboxylic acids such as polyazeline acid and polysebacic anhydride have been used for thermosetting resins such as epoxy resin curing agents, melamine resin curing accelerators, acrylic powder coating curing agents, etc. Commercially available as a curing agent. Patent Document 1 below also proposes a film using a high-purity, high-molecular-weight acid anhydride resin having an average molecular weight exceeding 20000 obtained by condensing aliphatic and aromatic dicarboxylic acids between molecules. ing.

  On the other hand, an acid anhydride used as a raw material for a polyimide compound is an aromatic or condensed carboxylic acid in the molecule because of an essential characteristic of forming an imide bond with a diamine compound and forming a skeleton that becomes a main chain. Linear and cycloaliphatic tetracarboxylic anhydrides are usually used.

JP 63-258924 A

  An epoxy resin molding material is used as a semiconductor sealing material. However, when an optical semiconductor is sealed, the cured product needs to have sufficient transparency. Therefore, it is desirable that the curing agent blended in the material for such use is less colored. On the other hand, the molding material is required to be able to form a cured product having a high glass transition temperature from the viewpoint of heat resistance and releasability of the molded body. In addition, the melting point and viscosity of the curing agent blended in the molding material are important characteristics that are largely related to the fluidity, moldability, workability, storage stability, and freedom of blending design of the material.

  The acid anhydrides that have been put to practical use as curing agents for epoxy resins are not as diverse as the curing agents for epoxy resins such as polyamines, phenol novolacs, and imidazole curing agents. As a result, the glass transition temperature of the molded product after curing cannot be sufficiently increased, and when the molded product is released from the mold, an external mold release agent or a release sheet is used. It was necessary to assist.

  Since tetracarboxylic acid anhydrides are often high melting points (150 ° C. or higher), it is difficult to apply to applications other than those used as raw materials for polyimide compounds. Furthermore, since the application is very limited, it is disadvantageous in terms of cost.

  The conventional intermolecular condensate of the carboxylic acid compound has not been actively designed as a curing agent to be blended in the transparent sealing material, and its use has been limited.

  The present invention is capable of sufficiently increasing the glass transition temperature of a cured product, and further sufficiently curing the cured product, a thermosetting resin curing agent, a thermosetting resin composition using the same, and a method for producing the same. The purpose is to provide. Another object of the present invention is to provide a cured product obtained by curing such a thermosetting resin composition and a semiconductor device encapsulated thereby.

  In order to solve the above problems, the curing agent for thermosetting resin of the present invention is (A) a monocarboxylic acid compound having one carboxyl group represented by the following general formula (1), or the following general formula (1). And a polycarboxylic acid condensation product obtained by a condensation reaction of a monocarboxylic acid compound having one carboxyl group represented by formula (2) and a polycarboxylic acid compound having three or more carboxyl groups represented by the following general formula (2): And (B) one or more polyvalent carboxylic acid compounds having three or more carboxyl groups represented by the following general formula (2).

［一般式（１）中、Ｒ^１は、炭素数４〜１５の１価の脂環式炭化水素基、炭素数２〜１５の１価の複素環基、直鎖状若しくは分岐状の炭素数２〜１５の１価の飽和炭化水素基、又は、直鎖状若しくは分岐状の炭素数２〜１５の１価の不飽和炭化水素基を示す。ただし、いずれの基も置換基として下記一般式（１−１）で表される基又は下記式（１−２）で表される基を有していてもよい。

（一般式（１−１）中、Ｒ^１１は、炭素数１〜５０の直鎖状若しくは分岐状の飽和炭化水素基、又は、直鎖状若しくは分岐状の炭素数２〜１５の１価の不飽和炭化水素基を示す。］

［一般式（２）中、ｎは３以上の整数を示し、Ｒ^２は、炭素数３〜１５の脂環式炭化水素基若しくは炭素数２〜１５の複素環基を含む、ｎ価の有機基を示す。］

[In General Formula (1), R ¹ is a monovalent alicyclic hydrocarbon group having 4 to 15 carbon atoms, a monovalent heterocyclic group having 2 to 15 carbon atoms, or a linear or branched carbon number. A monovalent unsaturated hydrocarbon group having 2 to 15 monovalent saturated hydrocarbon groups or a linear or branched monovalent unsaturated hydrocarbon group having 2 to 15 carbon atoms is shown. However, any group may have a group represented by the following general formula (1-1) or a group represented by the following formula (1-2) as a substituent.

(In the general formula (1-1), R ¹¹ represents a linear or branched saturated hydrocarbon group having 1 to 50 carbon atoms, or a linear or branched monovalent monovalent group having 2 to 15 carbon atoms. Represents an unsaturated hydrocarbon group.]

[In General Formula (2), n represents an integer of 3 or more, and R ² represents an n-valent organic compound containing an alicyclic hydrocarbon group having 3 to 15 carbon atoms or a heterocyclic group having 2 to 15 carbon atoms. Indicates a group. ]

  The curing agent for a thermosetting resin of the present invention contains at least one of the (A) polyvalent carboxylic acid condensate and the (B) polyvalent carboxylic acid compound, thereby The compatibility is excellent, the glass transition temperature Tg of the cured product can be sufficiently increased, and coloring to the cured product can be sufficiently small. According to the curing agent for a thermosetting resin of the present invention, it is possible to obtain a cured product having excellent transparency and high Tg by blending with the thermosetting resin composition.

  From the viewpoint of increasing Tg at the time of curing, the curing agent for thermosetting resin of the present invention includes a monocarboxylic acid compound having one carboxyl group represented by the above general formula (1) and the following general formula (2-1). It is preferable that the polycarboxylic acid condensate represented by the following general formula (3) obtained by the condensation reaction of the tricarboxylic acid compound represented by

［一般式（２−１）及び（３）中、Ｒ^３は、炭素数３〜１５の脂環式炭化水素基若しくは炭素数２〜１５の複素環基を含む、３価の有機基を示す。］

[In General Formulas (2-1) and (3), R ³ represents a trivalent organic group containing an alicyclic hydrocarbon group having 3 to 15 carbon atoms or a heterocyclic group having 2 to 15 carbon atoms. . ]

  Moreover, the hardening | curing agent for thermosetting resins of this invention is the following general formula (3-1) obtained by condensation reaction of hydrogenated trimellitic anhydride and the isocyanuric acid derivative represented by the following general formula (2-2). It is preferable that the polycarboxylic acid condensate represented by this is included.

［一般式（２−２）及び（３−１）中、Ｒ^２１は、炭素数１〜１５の１価の脂環式炭化水素基、炭素数２〜１５の１価の複素環基、直鎖状若しくは分岐状の炭素数２〜１５の１価の飽和炭化水素基、又は、直鎖状若しくは分岐状の炭素数２〜１５の１価の不飽和炭化水素基を示す。］

[In General Formulas (2-2) and (3-1), R ²¹ represents a monovalent alicyclic hydrocarbon group having 1 to 15 carbon atoms, a monovalent heterocyclic group having 2 to 15 carbon atoms, A linear or branched monovalent saturated hydrocarbon group having 2 to 15 carbon atoms or a linear or branched monovalent unsaturated hydrocarbon group having 2 to 15 carbon atoms is shown. ]

  Moreover, the hardening | curing agent for thermosetting resins of this invention contains the polyhydric carboxylic acid condensate represented by following formula (3-2) obtained by the condensation reaction between two molecules of hydrogenated trimellitic anhydride. be able to. In this case, Tg can be made higher.

  Moreover, it is preferable that the hardening | curing agent for thermosetting resins of this invention further contains the acid anhydride formed by (C) polyhydric carboxylic acid compound ring-closing condensation in a molecule | numerator.

  The curing agent for thermosetting resin of the present invention can be a curing agent for epoxy resin.

  Moreover, it is preferable that the hardening | curing agent for thermosetting resins of this invention contains the said polyhydric carboxylic acid condensate whose number average molecular weight Mn is 300-20000. In this case, the fluidity at the time of transfer molding can be further improved.

  Moreover, it is preferable that the hardening | curing agent for thermosetting resins of this invention contains the said polyhydric carboxylic acid condensate which exists in the range of 10-30000 mPa * s in the range of ICI cone plate viscosity of 100-150 degreeC. In this case, the generation of burrs during transfer molding can be more effectively suppressed.

  Moreover, it is preferable that the hardening | curing agent for thermosetting resins of this invention contains the said polyhydric carboxylic acid condensate which has a softening point in the range of 20-200 degreeC. In this case, the fluidity at the time of transfer molding can be further improved.

  The present invention also provides a thermosetting resin composition comprising a thermosetting resin and the thermosetting resin curing agent of the present invention. According to the thermosetting resin composition of the present invention, it is possible to obtain a cured product having excellent transparency and high Tg by containing the curing agent for thermosetting resin of the present invention. Moreover, according to the thermosetting resin composition of this invention, it becomes possible to improve the mold release property of the hardened | cured material obtained by making it harden | cure in a shaping | molding die.

  In the thermosetting resin composition of the present invention, the thermosetting resin can include an epoxy resin having at least two epoxy groups.

The thermosetting resin composition of the present invention has a glass transition temperature of Tg ₁ (° C.) of a cured product obtained by thermosetting at a temperature HC (° C.) on a substrate or in a mold. In addition, it is preferable that Tg ₁ -HC is 10 ° C. or higher. According to such a thermosetting resin composition, it is possible to obtain a cured product having a glass transition temperature higher by 10 ° C. or more than the temperature at which the cured product is released from the mold such as a mold, The self-release of the cured product becomes possible.

  The present invention also provides curing for a thermosetting resin containing one or more of the (A) polyvalent carboxylic acid condensate and the (B) polyvalent carboxylic acid compound and the (C) acid anhydride. A method for producing an agent, comprising: melting and mixing one or more of the (A) polyvalent carboxylic acid condensate and the (B) polyvalent carboxylic acid compound and the (C) acid anhydride. The manufacturing method of the hardening | curing agent for thermosetting resins which has this is provided.

  The present invention also provides a cured product obtained by thermosetting the thermosetting resin composition of the present invention. The cured product of the present invention can have both a high glass transition temperature and transparency.

  The present invention also provides a semiconductor device sealed with the cured product of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the glass transition temperature of hardened | cured material can fully be raised, and also the hardening | curing agent for thermosetting resins with few coloring to hardened | cured material, a thermosetting resin composition using the same, and its manufacturing method And the hardened | cured material which hardened this thermosetting resin composition, and the semiconductor device sealed by it can be provided.

1 is a schematic end view showing an embodiment of an optical semiconductor device.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.

(Curing agent for thermosetting resin)
First, (A) polyvalent carboxylic acid condensate used in the present invention will be described. In this specification, the “polyvalent carboxylic acid condensate” means that a carboxylic acid compound having a carboxyl group is dehydrated and condensed between two or more molecules, and each carboxyl group is intermolecularly dehydrated. Refers to a condensate formed by forming an acid anhydride bond.

  In contrast, in this specification, “an acid anhydride formed by ring-closing condensation of a polyvalent carboxylic acid” means, for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride It refers to an acid anhydride in which two carboxyl groups are dehydrated and condensed in the molecule, such as hexahydrophthalic anhydride, and is distinguished from a “polyvalent carboxylic acid condensate”.

  The (A) polyvalent carboxylic acid condensate used in the present invention is a monocarboxylic acid compound having one carboxyl group represented by the following general formula (1) or one represented by the following general formula (1) It is a polyvalent carboxylic acid condensate obtained by a condensation reaction of a monocarboxylic acid compound having a carboxyl group and a polyvalent carboxylic acid compound having three or more carboxyl groups represented by the following general formula (2).

［一般式（１）中、Ｒ^１は、炭素数４〜１５の１価の脂環式炭化水素基、炭素数２〜１５の１価の複素環基、直鎖状若しくは分岐状の炭素数２〜１５の１価の飽和炭化水素基、又は、直鎖状若しくは分岐状の炭素数２〜１５の１価の不飽和炭化水素基を示す。ただし、いずれの基も置換基として下記一般式（１−１）で表される基又は下記式（１−２）で表される基を有していてもよい。

（一般式（１−１）中、Ｒ^１１は、炭素数１〜５０の直鎖状若しくは分岐状の飽和炭化水素基、又は、直鎖状若しくは分岐状の炭素数２〜１５の１価の不飽和炭化水素基を示す。］

［一般式（２）中、ｎは３以上の整数を示し、Ｒ^２は、炭素数３〜１５の脂環式炭化水素基若しくは炭素数２〜１５の複素環基を含む、ｎ価の有機基を示す。］

[In General Formula (1), R ¹ is a monovalent alicyclic hydrocarbon group having 4 to 15 carbon atoms, a monovalent heterocyclic group having 2 to 15 carbon atoms, or a linear or branched carbon number. A monovalent unsaturated hydrocarbon group having 2 to 15 monovalent saturated hydrocarbon groups or a linear or branched monovalent unsaturated hydrocarbon group having 2 to 15 carbon atoms is shown. However, any group may have a group represented by the following general formula (1-1) or a group represented by the following formula (1-2) as a substituent.

(In the general formula (1-1), R ¹¹ represents a linear or branched saturated hydrocarbon group having 1 to 50 carbon atoms, or a linear or branched monovalent monovalent group having 2 to 15 carbon atoms. Represents an unsaturated hydrocarbon group.]

[In General Formula (2), n represents an integer of 3 or more, and R ² represents an n-valent organic compound containing an alicyclic hydrocarbon group having 3 to 15 carbon atoms or a heterocyclic group having 2 to 15 carbon atoms. Indicates a group. ]

  Examples of the monocarboxylic acid compound having one carboxyl group represented by the following general formula (1) include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, and hydrogenated naphthalene. And monocarboxylic acids such as hydrogenated biphenyl and derivatives thereof. These monocarboxylic acid compounds are preferably those having a boiling point higher than the reaction temperature for condensation between molecules. Among the above compounds, from the viewpoint of being inexpensive, monocarboxylic acid of cyclohexane and its derivative is desirable, and hydrogenated trimellitic anhydride is particularly desirable.

As the polyvalent carboxylic acid compound having three or more carboxyl groups represented by the general formula (2), for example, R ^{2 in} the formula is an isocyanuric ring, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclohexane. Examples thereof include cyclic aliphatic groups such as pentadiene, adamantane, hydrogenated naphthalene, and hydrogenated biphenyl, and trisiloxane compounds in which n is 3. When the polyvalent carboxylic acid condensate obtained by reacting such a compound is used as a curing agent for an epoxy resin, it is easy to obtain a transparent cured product.

  Examples of the (A) polycarboxylic acid condensate used in the present invention include a monocarboxylic acid compound having one carboxyl group represented by the general formula (1) and a tricarboxylic acid represented by the following general formula (2-1). A polyvalent carboxylic acid condensate represented by the following general formula (3) obtained by a condensation reaction of an acid compound is preferred.

［一般式（２−１）及び（３）中、Ｒ^３は、炭素数３〜１５の脂環式炭化水素基若しくは炭素数２〜１５の複素環基を含む、３価の有機基を示す。］

[In General Formulas (2-1) and (3), R ³ represents a trivalent organic group containing an alicyclic hydrocarbon group having 3 to 15 carbon atoms or a heterocyclic group having 2 to 15 carbon atoms. . ]

  In particular, a polyvalent carboxylic acid represented by the following general formula (3-1) obtained by a condensation reaction of hydrogenated trimellitic anhydride and an isocyanuric acid derivative represented by the following general formula (2-2) Condensates are preferred.

［一般式（２−２）及び（３−１）中、Ｒ^２１は、炭素数１〜１５の１価の脂環式炭化水素基、炭素数２〜１５の１価の複素環基、直鎖状若しくは分岐状の炭素数２〜１５の１価の飽和炭化水素基、又は、直鎖状若しくは分岐状の炭素数２〜１５の１価の不飽和炭化水素基を示す。］

[In General Formulas (2-2) and (3-1), R ²¹ represents a monovalent alicyclic hydrocarbon group having 1 to 15 carbon atoms, a monovalent heterocyclic group having 2 to 15 carbon atoms, A linear or branched monovalent saturated hydrocarbon group having 2 to 15 carbon atoms or a linear or branched monovalent unsaturated hydrocarbon group having 2 to 15 carbon atoms is shown. ]

  The polyvalent carboxylic acid condensate obtained from the monocarboxylic acid compound and the tricarboxylic acid compound can be obtained, for example, by reacting 3 equivalents of the monocarboxylic acid compound with 1 equivalent of the tricarboxylic acid compound.

  The thermosetting resin curing agent of the present invention is a monocarboxylic acid compound molecule obtained as a by-product when the polyvalent carboxylic acid condensate obtained from the above-described monocarboxylic acid compound and tricarboxylic acid compound is produced. You may contain the polyhydric carboxylic acid condensate obtained from this. Examples of such a polyvalent carboxylic acid condensate include a polyvalent carboxylic acid condensate represented by the following formula (3-2) obtained by a condensation reaction between two molecules of hydrogenated trimellitic anhydride. It is done.

  The curing agent for thermosetting resin of the present invention is a polycarboxylic acid condensate obtained by a condensation reaction of a monocarboxylic acid compound having one carboxyl group represented by the general formula (1). The polyvalent carboxylic acid condensate represented by (3-2) can be included.

  (A) The polycarboxylic acid condensate preferably has a number average molecular weight Mn of 300 to 20000. In addition, the number average molecular weight Mn refers to the polystyrene conversion value obtained by gel permeation chromatography. When the number average molecular weight Mn of the polyvalent carboxylic acid condensate is smaller than 300, the ICI corn plate viscosity tends to be low, and when it is larger than 20000, the ICI corn plate viscosity tends to be high. There is a tendency for compatibility with epoxy resins and other resins to decrease.

  The (A) polyvalent carboxylic acid condensate preferably has an ICI cone plate viscosity in the range of 10 to 30000 mPa · s in the range of 100 to 150 ° C. By adding a polyvalent carboxylic acid condensate having an ICI cone plate viscosity in the range of 10 to 30000 mPa · s in the range of 100 to 150 ° C., for example, the occurrence of resin burrs in epoxy resin molding materials for transfer molding can be reduced. The effect that the moldability of a thermosetting resin composition etc. is improved can be acquired. The ICI corn plate viscosity of the polyvalent carboxylic acid condensate is that of Research Equipment (London) LTD. It is determined by an ICI cone plate viscometer manufactured by the manufacturer.

  Next, a method for synthesizing (A) the polyvalent carboxylic acid condensate will be described. As a synthesis method of the polyvalent carboxylic acid condensate, for example, the monocarboxylic acid compound represented by the above general formula (1), or the monocarboxylic acid compound represented by the above general formula (1) and the above general formula ( Examples thereof include a method in which acetic anhydride in which the polyvalent carboxylic acid compound represented by 2) is soluble is condensed while deaceticating and dehydrating.

  Specifically, for example, a raw material, a monocarboxylic acid compound, or a tricarboxylic acid compound and a monocarboxylic acid compound are refluxed in acetic anhydride and an organic base for 5 to 30 minutes in a nitrogen atmosphere, and then the temperature is increased. Is increased to 180 ° C., and the condensation reaction proceeds by distilling off acetic acid and water produced by the reaction in an open system under a nitrogen stream. Examples of the organic base include propionic anhydride, acetyl chloride, aliphatic acid chloride, and trimethylamine. And when a volatile component is no longer observed, polycondensed carboxylic acid condensate can be obtained by melt condensation at a temperature of 180 ° C. for 3 hours, more preferably for 1 hour while reducing the pressure in the reaction vessel. .

  The polyvalent carboxylic acid condensate obtained above may be purified by recrystallization using an aprotic solvent such as acetic anhydride, or may be purified using a reprecipitation method.

  The (A) polyvalent carboxylic acid condensate is preferably synthesized by selecting a combination that does not change color after the dehydration condensation reaction from the above monocarboxylic acid compound and polyvalent carboxylic acid compound. .

As (B) polyvalent carboxylic acid compound used in the present invention, for example, R ^{2 in} the formula is an isocyanuric ring, cyclohexane, cycloheptane, cyclooctane, norbornene, dicyclopentadiene, adamantane, hydrogenated naphthalene, hydrogenated Examples thereof include cyclic aliphatic groups such as biphenyl, and tricarboxylic acid compounds which are cyclic siloxanes and n is 3. (B) Hydrogenated trimellitic acid is particularly preferable as the polyvalent carboxylic acid compound.

  The curing agent for thermosetting resins of the present invention can further contain (C) an acid anhydride formed by ring-closing condensation of a polyvalent carboxylic acid compound in the molecule. According to the curing agent for an acid anhydride-based thermosetting resin of this embodiment, the heat-resistant coloring property in a high-temperature environment is excellent as compared with the conventional curing agent for an acid anhydride-based thermosetting resin. Moreover, as for the content rate of (C) component in the hardening | curing agent for thermosetting resins of this embodiment, 1-100 mass parts is preferable with respect to a total of 100 mass parts of (A) component and (B) component.

  (C) As an acid anhydride formed by ring-closing condensation of a polyvalent carboxylic acid compound in a molecule, for example, it is generally used in an epoxy resin molding material for sealing electronic parts and an epoxy resin molding material for sealing optical semiconductors. And those that react with epoxy resins. It is preferable to use the acid anhydride (C) that is relatively uncolored. Examples of such anhydrides include acid anhydrides obtained by ring-closing condensation of polycarboxylic acids and isocyanuric acid. Derivatives, phenolic compounds and the like.

  Examples of acid anhydrides formed by polycyclic carboxylic acid ring-closing condensation include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, anhydrous Examples thereof include methyl nadic acid, anhydrous nadic acid, glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

  Examples of the isocyanuric acid derivatives include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3- Carboxypropyl) isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate and the like.

  Among the above acid anhydrides, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, anhydrous Diethyl glutaric acid and 1,3,5-tris (3-carboxypropyl) isocyanurate are preferably used.

  The acid anhydride having an aromatic ring, such as trimellitic anhydride and pyromellitic anhydride, is preferably one in which all of the unsaturated bonds of the aromatic ring are hydrogenated.

  (C) An acid anhydride may be used individually by 1 type, or may be used together 2 or more types.

  The acid anhydride (C) preferably has a molecular weight of about 100 to 400, and is preferably colorless or light yellow.

  Moreover, the acid anhydride generally used as a raw material of a polyimide resin may be used for (C) acid anhydride.

  (C) The curing agent for thermosetting resin of the present embodiment further containing an acid anhydride comprises (A) a polyvalent carboxylic acid condensate and / or (B) a polyvalent carboxylic acid compound, and (C) an acid anhydride. It can manufacture by mixing a thing (mixing process). For example, after mixing (A) component and / or (B) component and (C) component using a well-known mixer, this embodiment is further knead | mixed with a 3 roll mill, an extruder, etc. as needed. The thermosetting resin curing agent can be obtained as a mixture. From the viewpoint of obtaining a cured product such as an epoxy resin having transparency, the mixture preferably has translucency.

  In this embodiment, it is preferable that (A) polyvalent carboxylic acid condensate and / or (B) polyvalent carboxylic acid compound and (C) acid anhydride have compatibility. “Compatibility” means that component (A) or component (B) has an affinity with other components (A), (B) or (C) and exists as a uniform solution or mixture. means.

  More specifically, for example, the component (A) and / or the component (B) and the component (C) are mixed at a weight ratio of 1/1, and these components are completely dissolved at 120 ° C., followed by stirring. About the liquid mixture obtained by performing, when leaving still for 30 minutes and taking out a part of liquid mixture and visually observing, it means the state which can be confirmed as a transparent liquid with no isolation | separation between components.

  In this specification, such a state is referred to as “soluble”, and the case where the components are separated and become an opaque liquid is referred to as “insoluble”. Combinations of components (A) and / or (B) and (C), which are soluble in each other but require a long time to dissolve, require more heat energy for heating over a long period of time, This is disadvantageous in terms of productivity and cost.

  Moreover, in the said mixing process, it is preferable to obtain the mixture which does not have the cloudiness by a precipitate from a viewpoint of suppressing the increase in the viscosity resulting from generation | occurrence | production of a precipitate. Note that “white turbidity due to precipitates” indicates that there is no scattering of electromagnetic waves in the visible light region. More specifically, it indicates that there is no fine particle having a scattering center that causes Rayleigh scattering, Mie scattering, and diffraction scattering phenomenon of light.

  As a mixing process which can suppress generation | occurrence | production of a deposit, for example, (A) component and / or (B) component are 100 mass parts in total, and (C) component 1-100 mass parts is made into the container made from heat-resistant glass. Examples of the method include weighing and heating the container in a temperature range of 35 to 180 ° C. using a heater using a fluid such as silicone oil or water as a medium. The heating method is not limited to the above method, and a known method such as thermocouple or electromagnetic wave irradiation can be used, and ultrasonic wave or the like may be irradiated to promote dissolution. The mixing step is preferably melt mixing in a state where the material can flow.

  Although the curing agent for thermosetting resins of the present invention can be suitably used as a curing agent for epoxy resins, it is a thermosetting resin for the purpose of increasing the glass transition temperature of the cured product or polymer compound. It can also be used by mixing with a certain phenol resin, urethane resin, acrylate resin, silicone resin or the like.

  Moreover, the hardening | curing agent containing 1 or more types of the (A) component and (B) component which concerns on this invention mentioned above, and the said (C) component as needed is a polyimide, polyamide, a polyamideimide, a polyurethane amideimide. It can also be used as a cross-linking material for thermoplastic resins such as polyamide and polyester.

(Thermosetting resin composition)
The thermosetting resin composition of the present invention contains a thermosetting resin and the curing agent for thermosetting resin of the present invention.

  Examples of the thermosetting resin include an epoxy resin having at least two epoxy groups, an acrylic resin, and a silicone resin.

  As an epoxy resin, what is generally used with the epoxy resin molding material for electronic component sealing can be used. Specifically, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins and other phenols and aldehyde novolak resins epoxidized, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted bisphenols, etc. Glycidylamine type epoxy resin obtained by reaction of polyamine such as glycidyl ether, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, linear aliphatic epoxy resin and alicyclic epoxy obtained by oxidizing olefin bond with peracid such as peracetic acid Examples thereof include resins. These can be used alone or in combination of two or more.

  The epoxy resin is preferably relatively uncolored, and examples of such an epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl isocyanurate, and triglycidyl isocyanate. Nurate, 1,3-cyclohexanedicarboxylic acid including 1,2-cyclohexanedicarboxylic acid, dicarboxylic acid diglycidyl ester derived from 1,4-cyclohexanedicarboxylic acid; phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Diglycidyl esters of dicarboxylic acids such as methyltetrahydrophthalic acid, nadic acid, and methylnadic acid; glycidyl esters such as nuclear hydrogenated trimellitic acid and nuclear hydrogenated pyromellitic acid having an alicyclic structure in which the aromatic ring is hydrogenated Tel and the like.

  In addition, polyorganosiloxane having an epoxy group whose main chain is a silicone skeleton produced by heating and hydrolyzing and condensing a silane compound in the presence of an organic solvent, an organic base and water is also included. It is done.

  Furthermore, an epoxy resin having a chemical structure represented by the following general formula (4), which is a copolymer composed of a glycidyl methacrylate monomer and a monomer polymerizable with the glycidyl methacrylate monomer, can be used.

（式中、Ｒ^４１はグリシジル基を示し、Ｒ^４２及びＲ^４３はそれぞれ独立に、水素原子、又は炭素数１〜６の飽和若しくは不飽和の一価の炭化水素基を示し、Ｒ^４４は一価の飽和炭化水素基を示し、ｐ及びｑは正の整数を示す。）

^{(Wherein, R 41} represents a glycidyl ^group, each ^{R 42} and ^{R 43} independently represent a hydrogen atom, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon ^{atoms, R 44} in one A saturated saturated hydrocarbon group, and p and q are positive integers.)

  The blending ratio of the epoxy resin and the curing agent for thermosetting resin of the present invention in the thermosetting resin composition (hereinafter referred to as epoxy resin composition) of the present embodiment containing an epoxy resin as the thermosetting resin is the epoxy resin. It is preferable that an active group (an acid anhydride group or a hydroxyl group) in a curing agent capable of reacting with the epoxy group is 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group therein. When the ratio of the active group is less than 0.5 with respect to 1 equivalent of epoxy group, the curing rate of the epoxy resin composition becomes slow and the glass transition temperature of the resulting cured product may be lowered, which is sufficient. May not provide a sufficient elastic modulus. On the other hand, when the ratio of the active group exceeds 1.2 equivalents, the strength after curing may decrease.

  A curing catalyst may be further added to the epoxy resin composition from the viewpoint of improving curability. The curing catalyst is not particularly limited, and examples thereof include tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, tri-2,4,6-dimethylaminomethylphenol. Imidazoles such as 2-ethyl-4-methylimidazole, 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n -Phosphorus compounds such as butylphosphonium-tetrafluoroborate and tetra-n-butylphosphonium-tetraphenylborate, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination of two or more. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles, and phosphorus compounds.

  The content of the curing catalyst in the epoxy resin composition is preferably 0.01 to 8.0% by mass and more preferably 0.1 to 3.0% by mass with respect to the epoxy resin. When the content of the curing accelerator relative to the epoxy resin is less than 0.01% by mass, a sufficient curing acceleration effect may not be obtained. On the other hand, when the content exceeds 8.0% by mass, the resulting cured product is discolored. May be.

  The epoxy resin composition of the present embodiment is preferably used as a transparent resin material, but can be functionalized by containing an inorganic filler, a white pigment, and an inorganic phosphor as necessary. For example, the epoxy resin composition of the present embodiment can be used as a thermosetting resin composition for light reflection by adding a white pigment.

  When used as a transparent resin material, it is necessary that the cured product obtained by the thermosetting reaction has transparency, and it is desirable that the light transmittance in the visible light region from the ultraviolet light having a wavelength of 350 to 800 nm is sufficiently high. In the present embodiment, the light transmittance for predetermined light having a wavelength of 350 to 800 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. Moreover, when a transparent resin material is a use of the transparent sealing resin for optical semiconductors, it is preferable that hardened | cured material shows said light transmittance with respect to the light of wavelength 460nm.

  On the other hand, when used as a thermosetting resin composition for light reflection, a cured product obtained by a thermosetting reaction needs to have a sufficiently high light reflectance in a wavelength region from visible light to near ultraviolet light. In this case, the reflectance with respect to predetermined light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

  The thermosetting resin composition of the present invention and the cured product thereof are used in various applications such as electrical insulating materials, optical semiconductor sealing materials, adhesive materials, paint materials and molding materials that require high transparency and heat resistance. Is possible.

(Cured product)
The cured product of the present invention is obtained by thermosetting the thermosetting resin composition of the present invention. Hereinafter, the hardened | cured material which concerns on suitable embodiment of this invention, and the method of obtaining it are demonstrated.

  The cured product according to the present embodiment is produced by subjecting the above-described epoxy resin composition according to the present invention to transfer molding, compression molding, liquid injection molding, or potting molding. The above molding method is usually used for inserting a lead frame, a ceramic substrate, an organic substrate, or the like as a base material to form a desired cured product on the base material.

  In the above method, for example, after molding using a heated mold, it is further post-cured to obtain a desired cured product. In this method, the higher the temperature condition during molding, the faster the curing.

  However, when the molding temperature is increased, the melt viscosity of the molding material tends to decrease accordingly, and this causes the molten resin to protrude into the gap between the upper mold and the lower mold and become burrs. Conditions where burrs are likely to occur are not preferable because a resin stain occurs at an unintended location on the substrate, and a step of removing this by washing is required, resulting in loss of productivity.

  When the glass transition temperature of the cured product is lower than the molding temperature, the cured product is in a rubber state with low elasticity immediately after molding. When the rubber-like cured product is released from the mold, it is necessary to apply an excessive release force by an ejector provided in the mold. At this time, if the cured product has poor elasticity, there is a risk of problems such as deformation and destruction.

  From the viewpoint of suppressing the above problems, it is desirable that the melt viscosity of the epoxy resin composition under a high temperature condition during molding is higher than that in the case of using a conventional acid anhydride curing agent. It is desirable to make the transition temperature sufficiently higher than the molding temperature.

  In this embodiment, from the viewpoint of obtaining a burr reduction effect, the ICI cone plate viscosity of the epoxy resin composition at 150 ° C. is preferably greater than 10 mPa · s, more preferably greater than 50 mPa · s, and 100 mmPa More preferably, it is larger than s.

Further, from the viewpoint of improving the mold releasability of the cured product, the glass transition temperature of the cured product obtained when thermally cured at a temperature HC (° C.) on the substrate or in the mold is Tg ₁ (° C.). Tg ₁ -HC is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and further preferably 50 ° C. or higher.

  According to the curing agent for thermosetting resin of the present invention, when the thermosetting temperature is 150 ° C., the temperature difference between the glass transition temperature and the thermosetting temperature of the cured product can be set to the above temperature or more. Moreover, the temperature difference between the glass transition temperature of the cured product and the temperature at the time of releasing the cured product can be set to the above temperature or more.

(Semiconductor device)
The semiconductor device of the present invention is sealed with a cured product of the thermosetting resin composition of the present invention. A semiconductor device according to a preferred embodiment of the present invention will be described. FIG. 1 is a schematic end view of a chip-type light emitting diode which is an optical semiconductor device. The light emitting diode 100 includes a light emitting diode element 105 as a light emitting element, and an optically transparent sealing material 110 provided so as to seal the light emitting diode element 105. The light emitting diode element 105 is disposed at the bottom of the cavity portion 102 formed by the case member 107. The light emitting diode element 105 is electrically connected to the lead frame 101a via a connection layer 120 made of a conductive paste or the like, and is electrically connected to the lead frame 101b via a wire 108.

  The sealing material 110 which is an optical member in the light emitting diode 100 mainly serves to protect the light emitting diode element 105 from the outside air and to contain (carry) a phosphor. The sealing material 110 includes a cured product of the thermosetting resin composition of the present invention. In order to obtain the sealing material 110, first, a solution-like resin composition is poured into the cavity portion 102 and filled. Next, if necessary, various additives such as phosphors are added to the thermosetting resin composition, and then the thermosetting resin composition is subjected to heat treatment, thereby thermosetting the thermosetting resin. In this way, the sealing material 110 which is a cured product of the thermosetting resin composition of the present invention is obtained, and the light emitting diode 100 is completed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited to these Examples.

<Preparation of polyvalent carboxylic acid condensate>
(Polyvalent carboxylic acid condensate A1)
In a reaction vessel, 170 g of C3CIC acid (1,3,5-tris (3-carboxypropyl) isocyanurate, manufactured by Shikoku Kasei Co., Ltd.) and 261 g of hydrogenated trimellitic anhydride (produced by Mitsubishi Gas Chemical Co., Ltd.) in acetic anhydride. The mixture was refluxed at a temperature of 130 ° C. for 30 minutes in a nitrogen atmosphere. Thereafter, the temperature in the system was raised to 180 ° C., and acetic acid and water produced by the reaction were distilled off in an open system under a nitrogen stream. When no volatile components were observed, the reaction vessel was decompressed and heated at 150 ° C. for 3 hours for melt condensation to obtain a polyvalent carboxylic acid condensate.

(Polyvalent carboxylic acid condensate A2)
In the reaction vessel, 261 g of hydrogenated trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company) was refluxed in acetic anhydride at a temperature of 130 ° C. for 30 minutes in a nitrogen atmosphere. Thereafter, the temperature in the system was raised to 180 ° C., and acetic acid and water produced by the reaction were distilled off in an open system under a nitrogen stream. When no volatile components were observed, the reaction vessel was decompressed and heated at 150 ° C. for 3 hours for melt condensation to obtain a polyvalent carboxylic acid condensate.

(Polyvalent carboxylic acid condensate B1)
In a reaction vessel, 168 g of trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 166 g of benzenetricarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were refluxed in acetic anhydride at a temperature of 130 ° C. for 60 minutes. Thereafter, the temperature in the system was raised to 180 ° C., and acetic acid and water produced by the reaction were distilled off in an open system under a nitrogen stream. When no volatile components were observed, the reaction vessel was decompressed and heated at 150 ° C. for 3 hours for melt condensation to obtain a polyvalent carboxylic acid condensate.

<Characteristic evaluation of polyvalent carboxylic acid condensate>
Regarding the polyvalent carboxylic acid condensates A1 to A2 and B1, the number average molecular weight, ICI cone plate viscosity, softening point and appearance were evaluated by the following methods. The evaluation results are shown in Table 1.

[Number average molecular weight]
The number average molecular weight Mn of the condensate was measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. The Mn is GPC as a pump (L-6200 manufactured by Hitachi, Ltd.), column (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation, trade name), detector (manufactured by Hitachi, Ltd.). L-3300RI type) was used, and tetrahydrofuran was used as an eluent, and the temperature was 30 ° C. and the flow rate was 1.0 ml / min.

[ICI cone plate viscosity]
The viscosity of the condensate was measured by Research Equipment (London) LTD. Using an ICI corn plate viscometer made at 150 ° C.

[Softening point and appearance]
About the softening point, the obtained condensate was heated on the hotplate and the change of the property was confirmed visually and evaluated. About the external appearance, the property and transparency in 25 degreeC were confirmed visually and evaluated.

<Preparation of epoxy resin composition>
Example 1
First, 54 parts by mass of the polyvalent carboxylic acid condensate A1 and 62 parts by mass of hexahydrophthalic anhydride are melt-mixed with stirring at 120 ° C. until completely compatible, and cured for an acid anhydride epoxy resin. An agent was obtained.

  Next, after melt-mixing 100 parts by weight of triglycidyl isocyanurate as an epoxy resin and completely mixed with stirring at 120 ° C. until complete compatibility, the heating was stopped and the temperature was higher than 80 ° C. When the temperature decreased to a low temperature, 1.0 part by mass of tetra-n-butylphosphonium-0,0-diethylphosphorodithioate was added as a curing catalyst and further stirred to obtain a light-transmitting epoxy resin composition.

  The compatibility between the curing agents at 120 ° C. and the compatibility between the epoxy resin and the curing agent at 120 ° C. were visually confirmed and evaluated.

(Example 2)
First, 44 parts by mass of the polyvalent carboxylic acid condensate A2 and 62 parts by mass of hexahydrophthalic anhydride are melt-mixed with stirring at 120 ° C. until they are completely mixed. A curing agent was obtained.

  Next, after melt-mixing 100 parts by weight of triglycidyl isocyanurate as an epoxy resin and completely mixed with stirring at 120 ° C. until complete compatibility, the heating was stopped and the temperature was higher than 80 ° C. When the temperature decreased to a low temperature, 1.0 part by mass of tetra-n-butylphosphonium-0,0-diethylphosphorodithioate was added as a curing catalyst and further stirred to obtain a light-transmitting epoxy resin composition.

( Reference Example 3)
First, 35 parts by mass of hydrogenated trimellitic acid and 62 parts by mass of hexahydrophthalic anhydride are melt-mixed with stirring at 120 ° C. until completely compatible, and an acid anhydride type epoxy resin curing agent. Got.

  Next, after melt-mixing 100 parts by weight of triglycidyl isocyanurate as an epoxy resin and completely mixed with stirring at 120 ° C. until complete compatibility, the heating was stopped and the temperature was higher than 80 ° C. When the temperature decreased to a low temperature, 1.0 part by mass of tetra-n-butylphosphonium-0,0-diethylphosphorodithioate was added as a curing catalyst and further stirred to obtain a light-transmitting epoxy resin composition.

(Comparative Example 1)
First, 66 parts by mass of the polyvalent carboxylic acid condensate B1 and 62 parts by mass of hexahydrophthalic anhydride were stirred at 120 ° C., but they were not compatible. Further, 100 parts by mass of triglycidyl isocyanurate as an epoxy resin was added thereto and stirred at 120 ° C., but they were not compatible.

  When the epoxy resin composition obtained above was cured at 180 ° C., it was not uniformly cured.

(Comparative Example 2)
After melt-mixing 139 parts by weight of hexahydrophthalic anhydride and 100 parts by weight of triglycidyl isocyanurate as an epoxy resin at 120 ° C. until they are completely compatible, heating is stopped and the temperature is lowered to a temperature lower than 80 ° C. As a curing catalyst, 1.0 part by mass of tetra-n-butylphosphonium-0,0-diethylphosphorodithioate was added as a curing catalyst and further stirred to obtain a translucent epoxy resin composition.

<Characteristic evaluation of epoxy resin composition>
The epoxy resin composition obtained above and its cured product were evaluated by the following various characteristic tests. The evaluation results are shown in Table 2.

[Transparency and color]
About transparency and a color, the obtained hardened | cured material confirmed visually and evaluated.

[Light transmission test]
Each of the translucent epoxy resin compositions obtained above was heated at 100 ° C. for 4 hours and then post-cured at 150 ° C. for 2 hours to prepare a test piece having a thickness of 1.0 mm. The light transmittance at a wavelength of 460 nm was measured with a −750 type (manufactured by JASCO Corporation).

[Glass-transition temperature]
Each of the translucent epoxy resin compositions obtained above was filled in a mold heated to a temperature of 180 ° C. (a mold having a cavity with dimensions of 19 mm × 3 mm × 3 mm), and the molding pressure was 6.9 MPa. Transfer molded. In this way, a test piece having a shape of 19 mm × 3 mm × 3 mm was produced. About these test pieces, the glass transition temperature was calculated | required from the bending point of the linear expansion curve measured on the conditions of a temperature increase rate of 5 degrees C / min using the Rigaku Denki thermomechanical analyzer (TAS-100).

<Evaluation of transfer moldability of epoxy resin composition>
The epoxy resin composition obtained above was filled in a mold heated to a temperature of 150 ° C., and transfer molded under conditions of a molding pressure of 6.9 MPa. The mold used was a mold that was entirely chrome plated and provided with an ejector. The releasability when the molded body (cured product) was released from the mold was evaluated according to the following criteria.
[Releasability]
Good: Can be easily removed from the mold without destroying or deforming the cured product.
Defective: The cured product is difficult to remove from the mold, and if it is forcibly removed, the cured product is broken or deformed.

  As shown in Table 1, an isocyanuric acid derivative having three carboxyl groups and a hydrogenated trimellitic anhydride are heated and reacted while deacetic acid to give a colorless transparent solid condensate (polyvalent carboxylic acid condensate). A1) was obtained, and this condensate was confirmed to be compatible with hexahydrophthalic anhydride. Moreover, it was confirmed that the polyvalent carboxylic acid condensate B1 obtained by the condensation reaction of hydrogenated trimellitic anhydride is also colorless and transparent and exhibits compatibility with hexahydrophthalic anhydride. Further, as shown in Table 2, a mixture of the polyvalent carboxylic acid condensate A1 or polyvalent carboxylic acid condensate B1 and hexahydrophthalic anhydride is a polyfunctional epoxy resin such as triglycidyl isocyanurate. It was confirmed that they were compatible. Moreover, according to the epoxy resin composition of Example 1 or 2 which mix | blended polyvalent carboxylic acid condensate A1 or polyvalent carboxylic acid condensate A2, it is 20 degreeC or more high temperature rather than hardening conditions by thermosetting. It was confirmed that a translucent cured product having a glass transition temperature and excellent translucency can be obtained. Furthermore, it was found that the epoxy resin compositions of Examples 1 and 2 have good mold releasability during transfer molding, and the molded product can be easily released using an ejector.

In addition, the epoxy resin composition of Reference Example 3 blended with hydrogenated trimellitic acid also has a glass transition temperature that is 20 ° C. or more higher than the curing conditions by thermosetting, and is excellent in translucency. It was confirmed that a translucent cured product was obtained. Further, it was found that the mold releasability at the time of transfer molding was good, and the molded body could be easily released using an ejector.

  On the other hand, the polyvalent carboxylic acid condensate B1, which is a wholly aromatic polyvalent carboxylic acid condensate, has low transparency and becomes cloudy when melt-mixed with hexahydrophthalic anhydride. And in the epoxy resin composition of the comparative example 1 which mix | blended polyhydric carboxylic acid condensate B1, uniform hardened | cured material was not able to be obtained. The epoxy resin composition of Comparative Example 2 was very difficult to remove from the mold because it was in close contact with the mold after curing and the elasticity of the cured product was poor.

DESCRIPTION OF SYMBOLS 100 ... Light emitting diode, 101a, b ... Lead frame, 102 ... Cavity part, 105 ... Light emitting diode element, 107 ... Case member, 108 ... Wire, 110 ... Sealing material, 120 ... Connection layer.

Claims (14)

It is represented by the following general formula (3) obtained by a condensation reaction of a monocarboxylic acid compound having one carboxyl group represented by the following general formula (1) and a tricarboxylic acid compound represented by the following general formula (2-1). A curing agent for a thermosetting resin, which contains a polyvalent carboxylic acid condensate.

[In General Formula (1), R ¹ is a monovalent alicyclic hydrocarbon group having 4 to 15 carbon atoms, a monovalent heterocyclic group having 2 to 15 carbon atoms, or a linear or branched carbon number. A monovalent unsaturated hydrocarbon group having 2 to 15 monovalent saturated hydrocarbon groups or a linear or branched monovalent unsaturated hydrocarbon group having 2 to 15 carbon atoms is shown. However, any group may have a group represented by the following general formula (1-1) or a group represented by the following formula (1-2) as a substituent.

(In the general formula (1-1), R ¹¹ represents a linear or branched saturated hydrocarbon group having 1 to 50 carbon atoms, or a linear or branched monovalent monovalent group having 2 to 15 carbon atoms. Represents an unsaturated hydrocarbon group.)]

[In General Formulas (2-1) and (3), R ³ represents a trivalent organic group containing an alicyclic hydrocarbon group having 3 to 15 carbon atoms or a heterocyclic group having 2 to 15 carbon atoms. . ] Including a polyvalent carboxylic acid condensate represented by the following general formula (3-1) obtained by a condensation reaction of a hydrogenated trimellitic anhydride and an isocyanuric acid derivative represented by the following general formula (2-2), Curing agent for thermosetting resin.

[In General Formulas (2-2) and (3-1), R ²¹ represents a monovalent alicyclic hydrocarbon group having 1 to 15 carbon atoms, a monovalent heterocyclic group having 2 to 15 carbon atoms, A linear or branched monovalent saturated hydrocarbon group having 2 to 15 carbon atoms or a linear or branched monovalent unsaturated hydrocarbon group having 2 to 15 carbon atoms is shown. ] The hardening | curing agent for thermosetting resins containing the polyhydric carboxylic acid condensate represented by the following formula (3-2) obtained by the condensation reaction between two molecules of hydrogenated trimellitic anhydride.

  The hardening | curing agent for thermosetting resins as described in any one of Claims 1-3 containing the said polyhydric carboxylic acid condensate whose number average molecular weight Mn is 300-20000. The curing for thermosetting resin according to any one of claims 1 to 4 , comprising the polyvalent carboxylic acid condensate having an ICI cone plate viscosity in the range of 10 to 30,000 mPa · s in the range of 100 to 150 ° C. Agent. The hardening | curing agent for thermosetting resins as described in any one of Claims 1-5 containing the said polyhydric carboxylic acid condensate which has a softening point in the range of 20-200 degreeC. (C) The curing agent for thermosetting resins according to any one of claims 1 to 6 , further comprising an acid anhydride formed by ring-closing condensation of the polyvalent carboxylic acid compound in the molecule. The curing agent for thermosetting resins according to any one of claims 1 to 7 , which is a curing agent for epoxy resins. The thermosetting resin composition containing a thermosetting resin and the hardening | curing agent for thermosetting resins as described in any one of Claims 1-8 . The thermosetting resin composition according to claim 9 , wherein the thermosetting resin includes an epoxy resin having at least two epoxy groups. Tg ₁ -HC is 10 ° C. or higher, when Tg ₁ (° C.) is the glass transition temperature of the cured product obtained when thermally cured at a temperature HC (° C.) on the substrate or in the mold. The thermosetting resin composition according to claim 9 or 10 . A method for producing a curing agent for a thermosetting resin according to claim 7 , comprising:
The manufacturing method of the hardening | curing agent for thermosetting resins which has the process of melt-mixing the said polyhydric carboxylic acid condensate and the said (C) acid anhydride. Hardened | cured material formed by thermosetting the thermosetting resin composition as described in any one of Claims 9-11 . A semiconductor device sealed with the cured product according to claim 13 .

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