WO2016125874A1

WO2016125874A1 - Thermosetting resin composition including polyhydric alcohol compound, acid anhydride compound and thermosetting resin, polycarboxylic acid resin, thermosetting resin composition using same, and photosemiconductor device using either one of the thermosetting resin compositions as sealing material or reflective material

Info

Publication number: WO2016125874A1
Application number: PCT/JP2016/053430
Authority: WO
Inventors: 静青木; 政隆中西; 正人鎗田; 田中　栄一; 義浩川田; 直佑谷口
Original assignee: 日本化薬株式会社
Priority date: 2015-02-05
Filing date: 2016-02-04
Publication date: 2016-08-11
Also published as: TW201702298A; CN107250282A

Abstract

Provided are a thermosetting resin composition including a polyhydric alcohol compound (A) with three or more hydroxyl groups, an acid anhydride compound (B), and a thermosetting resin (C), a thermoset resin composition characterized by including a polycarboxylic acid (A) represented by formula (1) below, wherein the ICI cone-plate viscosity is within a range from 0.01 Pa∙s to 10 Pa∙s in a 100-200°C range, and a photosemiconductor device using either one of the thermosetting resin compositions as a sealing material or reflective material. (In formula (1), R¹ represents a 1-6C alkylene group, and R² represents a hydrogen atom, or a 1-6C alkyl group, or a carboxyl group. In formula (1), R¹ and R², pluralities of which exist, may be identical to or different from one another.)

Description

Any of a thermosetting resin composition containing a polyhydric alcohol compound, an acid anhydride compound and a thermosetting resin, a polycarboxylic acid resin, a thermosetting resin composition using the same, and the thermosetting resin composition Optical semiconductor device using one of them as sealing material or reflecting material

The first of the present invention (hereinafter referred to as the first invention) is a curing agent for a thermosetting resin, which can suppress the volatilization amount at the time of curing, and is less colored to a cured product, and a thermosetting resin using the same The present invention relates to a composition and an optical semiconductor device using such a thermosetting resin composition as a sealing material or a reflecting material. The second of the present invention (hereinafter referred to as the second invention) can sufficiently increase the glass transition temperature of the cured product, has excellent moldability, and has little coloration to the cured product. The present invention relates to a thermosetting resin composition using the same, and an optical semiconductor device using the thermosetting resin composition as a sealing material or a reflecting material.

When the thermosetting resin composition is used as a semiconductor sealing material or as a semiconductor reflector, if the thermosetting resin composition contains a highly volatile material, the Since the material is volatilized, voids are generated and the reliability may be lowered, or the equivalent ratio may be shifted to lower the cured physical properties. In addition, since there is a problem of odor during handling, it is desirable that the resin composition has a small amount of volatilization. Further, materials that have a long pot life and are difficult to be colored are required as semiconductor sealing materials and reflecting materials. And since the illuminance of an optical semiconductor will fall if the thermosetting resin composition absorbs the light which an optical semiconductor emits, the thermosetting resin composition has a high transmittance | permeability and a thing with little coloring is desirable. 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 more, and from the viewpoint of moldability, the softening point and viscosity of the curing agent are within a certain range. It is important to be.

Acid anhydrides used as curing agents for thermosetting resins have been used for optical semiconductor sealing and the like because of their excellent heat resistance and transparency. However, because of its high volatility and low melting point, a thermosetting resin composition containing only an acid anhydride as a curing agent for a thermosetting resin has reduced physical properties and odor due to volatilization of the acid anhydride. There was a problem. Furthermore, since it 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.

International Publication No. 2005/049597 International Publication No. 2005/121202

The first object of the present invention is to provide a thermosetting resin composition that can sufficiently increase the glass transition temperature of a cured product, has a small amount of volatilization during curing, and has little coloration to the cured product, and such thermosetting properties. The object is to provide a semiconductor device using a resin composition as a sealing material or a reflecting material.
In addition, the second object of the present invention is to sufficiently increase the glass transition temperature of the cured product, excellent in moldability, and less colored to the cured product, and a thermosetting resin composition using the same. And a semiconductor device using such a thermosetting resin composition as a sealing material or a reflecting material.

The first invention is to contain a polyhydric alcohol having 3 or more hydroxyl groups in the curable resin composition, thereby suppressing the volatilization amount at the time of curing, excellent moldability, and being less colored when made into a cured product. Is found.
In addition, in the second invention, the curable resin composition has a specific viscosity, a polyvalent carboxylic acid having an isocyanuric ring represented by the following formula (1), and the following formulas (1a) and / or (1b). ) By containing a polyvalent carboxylic acid resin containing the compound represented by a certain ratio, it has a sufficient glass transition temperature when made into a cured product, has excellent moldability, and is colored when made into a cured product. It has been found that there are few.

That is, the present invention relates to the following (1) to (16).
(1) A thermosetting resin composition containing a polyhydric alcohol compound (A) having three or more hydroxyl groups, an acid anhydride compound (B), and a thermosetting resin (C).
(2) The thermosetting resin composition according to (1), wherein the polyhydric alcohol compound (A) having three or more hydroxyl groups has a cyclic structure containing one or more heteroatoms in the molecule.
(3) The thermosetting resin composition according to (2), wherein the heteroatom is a nitrogen atom.
(4) The thermosetting resin composition according to (1), wherein the polyhydric alcohol compound (A) having three or more hydroxyl groups is a polyhydric alcohol compound represented by the following formula (5).

(In Formula (5), R ¹ represents an alkylene group having 1 to 6 carbon atoms. In Formula (5), a plurality of R ¹ may be the same or different.)
(5) The acid anhydride compound (B) is trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. The thermosetting resin composition according to any one of (1) to (4), which is one or more compounds selected from:
(6) The thermosetting resin composition according to any one of (1) to (5), wherein the thermosetting resin (C) is an epoxy resin.
(7) Following formula (1)

(In the formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group. R ¹ and R ² may be the same or different.)
Containing 70% by area or more in the measurement of gel permeation chromatography, polyvalent carboxylic acid (A1) represented by
The following formula (1a)

(In formula (1a), R ¹ and R ² represent the same meaning as R ¹ and R ^{2 in} formula (1). In formula (1a), a plurality of R ¹ and R ² are the same. May be different.)
And / or the following formula (1b)

(In the formula ^{^{(1b), R 1, R}} 2 is Formula (1) ^{^R} 1, ^R ² the same meaning represents the. Formula in in ^{^{(1b), R 1, R}} 2 existing in plural in the same May be different.)
A thermosetting resin composition containing a polyvalent carboxylic acid resin containing 0.5 to 10 area% of a carboxylic acid (A3) represented by the formula (1) as measured by gel permeation chromatography.
(8) The polyvalent carboxylic acid resin is represented by the following formula (6):

(In formula (6), R ² represents the same meaning as R ² in formula (1).)
(7) The thermosetting resin composition according to (7), which is a polyvalent carboxylic acid resin containing 5 to 20 area% of an acid anhydride represented by formula (1) as measured by gel permeation chromatography.
(9) The polyvalent carboxylic acid resin is a compound obtained by reacting the compound represented by the formula (1) with the compound represented by the formula (6) described in (8), The thermosetting property according to (7), which is a polyvalent carboxylic acid resin containing 0.5 to 10 area% of a high molecular weight compound having a retention time shorter than that of the compound represented by the formula (1) in the measurement of the association chromatography Resin composition.
(10) The thermosetting resin composition according to any one of (7) to (9), wherein the softening point is in the range of 20 ° C to 150 ° C.
(11) The polyvalent carboxylic resin and trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride Product, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride, one or more compounds selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid , Hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are a total of one or more compounds. 1% by weight to 9% in the curable resin composition It occupies wt%, (7) The thermosetting resin composition according to any one of - (10).
(12) The thermosetting resin composition according to any one of (7) to (11), which contains a thermosetting resin.
(13) The thermosetting resin composition according to (12), wherein a glass transition temperature (Tg) of a cured product obtained by curing the thermosetting resin composition is 30 ° C. or higher.
(14) A cured product obtained by thermosetting the thermosetting resin composition according to any one of (1) to (6), (12) and (13).
(15) An optical semiconductor device sealed with the cured product according to (14).
(16) An optical semiconductor device using the cured product according to (14) as a reflector.

According to the first invention, a thermosetting resin composition that suppresses the volatilization amount at the time of curing, has excellent moldability, and has little coloration when made into a cured product, and the thermosetting resin composition as a sealing material or a reflective material The optical semiconductor device used as can be provided.
Further, according to the second invention, a polyvalent carboxylic acid resin having a sufficient glass transition temperature of the cured product, excellent moldability, and less colored when made into a cured product, and a thermosetting resin composition using the same And an optical semiconductor device using the thermosetting resin composition as a sealing material or a reflecting material. 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.

It is the schematic at the time of using the thermosetting resin composition obtained by this invention as a reflector.

The first invention will be described in detail below.

The thermosetting resin composition of 1st invention contains the polyhydric alcohol (A) which has 3 or more of hydroxyl groups, It is characterized by the above-mentioned.
In the first invention, if it is a polyhydric alcohol having three or more known hydroxyl groups, it is possible to obtain a composition in which the volatilization amount during curing is suppressed even when used in combination with the acid anhydride (B). It becomes possible. Specific examples include trimethylolpropane, pentaerythritol, glycerol, EO-modified glycerol, PO-modified glycerol, dipentaerythritol, polyhydric alcohol represented by the following formula (5), and the like. Especially, it is preferable to provide the cyclic structure containing a hetero atom in a molecule | numerator, and especially the alcohol represented by following formula (5) is preferable from the amount of volatilization at the time of hardening being suppressed, and being excellent in handling with solid.

Thus, by using the polyhydric alcohol (A) having three or more hydroxyl groups, even when there is no curing accelerator, the amount of volatilization at the time of curing can be suppressed, and the addition amount of the curing accelerator can be reduced. Since it can implement | achieve, while being able to obtain the resin composition which suppresses coloring property, it becomes possible to implement | achieve the thermosetting resin composition with a long pot life.

In the formula (5), R ¹ represents an alkylene group having 1 to 6 carbon atoms.

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

In Formula (5), a plurality of R ¹ may be the same or different from each other.

Among the compounds represented by the formula (5), the compounds represented by the following formulas (7) to (9) are preferable from the viewpoint of transparency of the cured product and gas barrier properties.

In the first invention, the polyhydric alcohol (A) to be used may be liquid or solid. When the polyhydric alcohol is solid, the softening point is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, and particularly preferably 120 ° C. or lower. This is because if the softening point is higher than 180 ° C., the curing reaction proceeds rapidly during kneading, and a sufficiently uniform composition cannot be obtained.

In the first invention, the polyhydric alcohol (A) used has a functional group equivalent of 250 g / eq. Or less, preferably 240 g / eq. The following is more preferable. By being in such a range, it becomes possible to obtain a cured product having excellent heat resistance.

The ratio of the polyhydric alcohol compound (A) having 3 or more hydroxyl groups to the acid anhydride in the thermosetting resin composition of the first invention is from 0.1 to 0.1 mol of acid anhydride per 1 mol of hydroxyl group of the polyhydric alcohol. It is preferably 100 moles. If the acid anhydride is less than 0.1 mol, the glass transition temperature will not be sufficiently high, and if the acid anhydride is more than 100 mol, the volatile matter will increase and a sufficient effect may not be obtained. More preferably, the acid anhydride is 0.5 to 10 moles per mole of the hydroxyl group of the polyhydric alcohol.

The thermosetting resin composition of the first invention contains an acid anhydride compound (B). The acid anhydride compound (B) used has a functional group equivalent of 250 g / eq. Or less, preferably 240 g / eq. The following is more preferable. By being in such a range, it becomes possible to obtain a cured product having excellent heat resistance.

Suitable acid anhydride compounds (B) include trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. One type or two or more types of compounds selected may be mentioned.

In the presence of trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride, a cured product having a high crosslinking density is obtained. A cured product having a high glass transition temperature can be obtained.

Of trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride, cyclohexanetricarboxylic acid is difficult to color. Acid anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferred, and cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are more preferred.

Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride. In the first invention, these acid anhydrides can be used in combination, but cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferred.

Furthermore, among these, a compound represented by the following formula (6) is preferable.

In the formula (6), R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.

Of the compounds represented by the formula (6), compounds represented by the following (2) to (4) are particularly preferred.

One or more acid anhydrides selected from trimellitic anhydride, cyclohexanetricarboxylic acid anhydride, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride Is preferably 0.1 to 10 mol of acid anhydride with respect to 1 mol of hydroxyl group of the polyhydric alcohol compound (A) having 3 or more hydroxyl groups. If the acid anhydride is less than 0.1 mol, the glass transition temperature will not be sufficiently high, and if the acid anhydride is more than 10 mol, the volatile matter will increase and there is a possibility that a sufficient effect will not be obtained. More preferably, the acid anhydride is 0.5 to 5 moles per mole of the hydroxyl group of the polyhydric alcohol.

The thermosetting resin composition in the first invention contains a thermosetting resin (C). Examples of the thermosetting resin (C) include an epoxy resin, a phenol resin, a urea resin, a melamine resin, and an unsaturated polyester resin. In the first invention, it is desirable to use an epoxy resin.

The epoxy resin can be used without any particular limitation as long as it is usually blended as a conventional thermosetting resin composition or epoxy resin composition. 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 triazine derivative epoxy resins such as nurate and silsesquioxane compounds having an epoxy group, and these may be used alone or in combination of two or more. Among these epoxy resins, since those having high heat resistance and light resistance are preferred, specifically, from the viewpoint of melt viscosity, coloring of the resulting cured product and glass transition temperature, etc., it does not contain an aromatic ring, Preference is given to triazine derivative epoxy resins such as glycidyl ether type epoxy resins, alicyclic epoxy resins, diglycidyl isocyanurates, triglycidyl isocyanurates, and silsesquioxane compounds having an epoxy group.

Examples of alicyclic epoxy resins include 1,2: 8,9-diepoxy limonene, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, (3,4-epoxycyclohexyl) methyl-3, 4-epoxycyclohexylcarboxylate, bis- (3,4-epoxycyclohexyl) adipate, bis- (3,4-epoxycyclohexylmethylene) adipate, bis- (2,3-epoxycyclopentyl) ether, (2,3-epoxy And compounds having at least one 4- to 7-membered cyclic aliphatic group in the molecule and at least one epoxy group in the molecule, such as -6-methylcyclohexylmethyl) adipate and dicyclopentadiene dioxide. It is done. As such an alicyclic epoxy resin, an alicyclic epoxy resin having two or more epoxy groups in the molecule is preferable. An alicyclic epoxy resin having two or more epoxy groups in the molecule is available as a commercial product, for example, Celoxide 8000, Celoxide 2021P, Celoxide 2081, EHPE 3150 (all manufactured by Daicel Corporation) and the like. It is done.

Examples of the triazine derivative epoxy resin include 1,3,5-tris (oxiranylmethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. These triazine derivative epoxy resins are commercially available, and examples thereof include TEPIC-S, TEPIC-L, TEPIC-VL, TEPIC-PAS B22, and TEPIC-UC (all manufactured by Nissan Chemical Co., Ltd.).

Further, as the silsesquioxane compound having an epoxy group that can be used, a silsesquioxane compound having two or more epoxy groups in the molecule is preferable. As the silsesquioxane compound having two or more epoxy groups in the molecule, the skeleton is not particularly limited. For example, a glycidyl group and a siloxane structure having a chain structure, a cyclic structure, a ladder structure, or a mixed structure of at least two of them can be used. And / or an epoxy resin having an epoxycyclohexane structure.

Specific examples of the silsesquioxane compound having two or more epoxy groups in the molecule include, for example, a cage silsesquioxane having an epoxy ring described in Japanese Patent Laid-Open No. 2005-263869, and Japanese Patent Laid-Open No. 2008-2008. An alicyclic epoxy group-containing silicone resin described in Japanese Patent No. 248169, and an organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in Japanese Patent Application Laid-Open No. 2008-19422 are used. can do. These silsesquioxane compounds having two or more epoxy groups in the molecule are commercially available, and are cyclic siloxanes having two or more epoxy groups in the molecule, trade name “X-40-2670”. (Shin-Etsu Chemical Co., Ltd.).

The compounding ratio of the epoxy resin and the acid anhydride compound (B) is such that the carboxyl group generated by the reaction of the acid anhydride group with the hydroxyl group is 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin. It is preferable to carry out the reaction so as to achieve a ratio, and particularly preferable to carry out the reaction so that the amount is 0.5 to 1.2 equivalent. When the carboxyl group is less than 0.5 equivalent relative to 1 equivalent of the epoxy group, or when the carboxyl group exceeds 1.5 equivalent, curing may be incomplete and good cured properties may not be obtained. In addition, there is a problem that it becomes easy to color.

In addition, the thermosetting resin composition can contain various components as other components. The carboxylic acid that can be contained as a component of the thermosetting resin composition of the first invention can be used without particular limitation as long as it is a known carboxylic acid. Specifically, in the presence of trimellitic acid, cyclohexanetricarboxylic acid, pyromellitic acid, and hydrogenated pyromellitic 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. Of trimellitic acid, cyclohexanetricarboxylic acid, pyromellitic acid, and hydrogenated pyromellitic acid, cyclohexanetricarboxylic acid and hydrogenated pyromellitic acid are preferable from the viewpoint of difficulty in coloring.

When the above carboxylic acid is contained in the thermosetting resin composition, the total of one or more compounds selected from trimellitic acid, cyclohexanetricarboxylic acid, pyromellitic acid and hydrogenated pyromellitic acid is thermosetting. The proportion of the conductive resin composition is 1% to 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 becomes high and handling becomes difficult. More preferably, it is 10 to 60% by weight, and still more preferably 20 to 50% by weight.

In the thermosetting resin composition of the first invention, the polyhydric alcohol compound (A) having three or more hydroxyl groups as the weight ratio: (trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic acid One or more compounds selected from anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride ) Is preferably 99: 1 to 1:99, more preferably 90:10 to 10:90, and particularly preferably 50:50 to 10:90. 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 polyhydric alcohol compound (A) having three or more hydroxyl groups, trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl The total proportion of one or more compounds selected from hexahydrophthalic anhydride is preferably 1% by weight to 90% by weight in the thermosetting resin composition. 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.

Furthermore, the oligoester of the terminal carboxylic acid that can be contained in the thermosetting resin composition of the first invention is represented by the following formula (10).

(Wherein a plurality of P are residues of a polyhydric alcohol having 2 to 20 carbon atoms which may contain 0 to 6 oxygen, nitrogen 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 less than 12.)

A specific structural formula is a compound having the structure of formula (10) and 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 represented by the formula (10) is a compound obtained by an esterification reaction of a bi- to hexafunctional polyhydric 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 represented by the formula (10), 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), and is preferably a branched cross-linking group or a cycloalkyl group. In particular, P is preferably a divalent crosslinking group defined by the following (a) or (b).
(A) a chain alkyl chain having a branched structure having 6 to 20 carbon atoms, the chain alkyl chain having a linear main chain having 3 to 12 carbon atoms and 2 to 4 side chains; And at least one of the side chains has a bridging group having 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. Cross-linking group.
However, when P is (b), it is preferable that when the linking group R is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent R ³ is a group other than a hydrogen atom in the formula (2A) described later. Is more preferable.

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 preferred oligoester of a terminal carboxylic acid in the first invention can be obtained by addition reaction of a bi- to hexafunctional polyhydric alcohol having 6 or more carbon atoms and a saturated aliphatic cyclic acid anhydride.
The oligoester of the terminal carboxylic acid in the first invention may be a composition containing two kinds of oligoesters of the 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.

The bi- to hexafunctional polyhydric alcohol having 6 or more carbon atoms used for the synthesis of the oligoester of the terminal carboxylic acid in the first invention is specifically a hydroxyl group at the end of the bridging group P in the formula (10). And an oligoester of a terminal carboxylic acid marked with.
In the formula (10), the crosslinkable group represented by P is preferably a divalent crosslinkable group defined by the above (a) or (b), and will be specifically described below.
The divalent crosslinking group defined in (a) is a divalent chain alkyl chain obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure having 6 to 20 carbon atoms. 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 with oxygen atoms on both sides of P in the formula (10) 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 bridging group having a linear main chain having 3 to 12 carbon atoms and 2 to 4 side chains, and at least one of the side chains having 2 to 10 carbon atoms. Can 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. The 2 to 4 side chains are preferably branched from carbon atoms having different main chains.

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 the raw material, polyhydric alcohols having at least two side chains and at least two of which are side chains having 2 to 4 carbon atoms are preferred.
Among such skeletons, particularly preferred polyhydric alcohols 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.

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

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

In the formula, a plurality of R 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 first 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.

The amount of the catalyst used is not particularly limited, but it is usually preferable to use 0.001 to 5 parts by weight, if necessary, with respect to 100 parts by weight of the total weight of the raw materials.
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 to 0.5 part (that is, 50% by 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. In view of the reaction time, the reaction temperature is preferably 30 to 200 ° C, more preferably 40 to 200 ° C, and particularly preferably 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.
The specific charging ratio of the two at the time of reaction is such that the polyhydric alcohol is equivalent to 0.001 to 2 equivalents in terms of the hydroxyl group equivalent to 1 equivalent of the acid anhydride group in terms of the functional group 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 first invention, the obtained terminal carboxylic acid oligoester is preferably solid, and in order to obtain a solid resinous terminal carboxylic acid oligoester, ideally an equimolar equivalent or more of polyhydric alcohol However, fluidity is important because of the addition of filler, and in order to secure this fluidity, some balance is lost in the range where the solids are maintained (softening point of 50 ° C or higher). It doesn't matter.
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 great deal of energy. An excessively short reaction time means that the reaction is abrupt and is not preferable from the viewpoint of safety. A 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.

After completion of the reaction, when a catalyst is used, 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.

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 terminal carboxylic acid oligoester 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 the first invention, since the optimum method of using the thermosetting resin composition containing the oligoester of the terminal carboxylic acid is molding by transfer, the oligoester of the terminal carboxylic acid is in the form of a solid resin. .

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, the compound having a methyl group or a carboxyl group as the substituent is less colored and the optical properties are improved.

In the compound of the crosslinking 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 first invention is a cycloalkane skeleton or norbornane skeleton having 4 to 10 carbon atoms, the substituent is preferably a formula having a methyl group or a carboxyl group, or both ( A composition containing an oligoester of terminal carboxylic acid 9) 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 (9) in which the substituent is not a hydrogen atom is preferred. The remainder is an oligoester of a terminal carboxylic acid of the following formula (2A) in which R ³ is a hydrogen atom.

As a suitable terminal carboxylic acid oligoester in the first 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), for the reasons described above, an alkyl group or a carboxyl group in which R ³ has 1 to 3 carbon atoms can be suitably used.
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, other curing agents that can be used in combination include, for example, amine compounds, acid anhydride compounds having an unsaturated ring structure, acid anhydrides having an organosiloxane skeleton, amide compounds, phenol compounds, and carboxylic acid compounds. Etc. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and phthalic anhydride, pyromellitic anhydride. Acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2 , 1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic 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.

A hardening accelerator can be added to the curable resin composition of 1st invention as needed. Curing accelerators 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, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole imidazoles, and imidazoles with phthalic acid, isophthalic acid, terephthalic acid , Salts with oligoesters of terminal carboxylic acids such as trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7 and their tetrafes Salts such as ruborates and phenol novolaks, 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, microcapsule-type curing accelerators in which these curing accelerators are microcapsules, and carbonyl compound zinc complexes. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as heat resistance, curing speed, and working conditions. As a thing preferable in 1st invention, a phosphonium compound (preferably quaternary phosphonium) or a zinc stearate is mentioned.
The curing accelerator is usually used in an amount of 0.001 to 15 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the epoxy resin.

If necessary, as additives other than those mentioned above, commonly used additives for epoxy resins such as pigments, dyes, fluorescent brighteners, reinforcing materials, fillers, white pigments, nucleating agents, interfaces An activator, a plasticizer, a viscosity modifier, a fluidity modifier, a flame retardant, an antioxidant, an ultraviolet absorber, and a light stabilizer may be added.

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

The white pigment described above is not particularly limited, and for example, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, basic zinc carbonate, kaolin, calcium carbonate, and the like can be used. The white pigment may be a hollow particle. Moreover, you may surface-treat with a silicon compound, an aluminum compound, organic substance etc. suitably with respect to a white pigment. These may be used alone or in combination of two or more. The average particle size of the white pigment is preferably in the range of 0.01 to 50 μm. If it is less than 0.01 μm, the particles tend to aggregate and the dispersibility tends to deteriorate, and if it exceeds 50 μm, the reflective properties of the cured product tend not to be sufficiently obtained. The average particle diameter can be measured using, for example, a laser diffraction / scattering particle size distribution meter. In the first invention, it is preferable to use titanium oxide, particularly titanium dioxide powder. This is because whiteness, light reflectivity, and hiding power are high, dispersibility stability is excellent, and availability is easy. The crystal form of titanium oxide is not particularly limited, and may be a rutile type, anatase type, or a mixture of both, but the anatase type has a photocatalytic function and deteriorates the resin. In the first invention, the rutile type is preferable.

Further, the content of the white pigment is in the range of 10 to 95% by weight, more preferably 50 to 95% with respect to the entire resin composition. If the total content is less than 10% by weight, the light reflection characteristics of the cured product tend not to be obtained sufficiently, and if it exceeds 95% by weight, the moldability of the resin composition tends to be poor, and the substrate tends to be difficult to produce. It is in.

In the thermosetting resin composition of the first invention, it is usually preferable that the ICI cone plate viscosity is 0.01 to 10 Pa · s in the range of 100 to 200 ° C. If it is less than 0.01 Pa · s, burrs may be easily generated. On the other hand, if it is greater than 10 Pa · s, the productivity may decrease. In the present embodiment, the ICI viscosity of the thermosetting resin composition at 150 ° C. is preferably 0.01 Pa · s to 10 Pa · s, and more preferably 0.05 Pa · s to 5 Pa · s. In the thermosetting resin composition of the first invention, when the ICI cone plate viscosity is 0.01 to 10 Pa · s in the range of 100 to 200 ° C., and a high viscosity liquid or solid at room temperature, the conventional acid In the case of an anhydride curing agent, kneading, which was impossible without pretreatment such as prepolymerization, can be performed without pretreatment, which is preferable. Moreover, since the thermosetting resin composition after kneading is solid at room temperature, it is also characterized in that it can be easily molded as a tablet. And adjusting to the said range means that when a filler such as an inorganic filler is blended, the composition becomes solid at room temperature (25 ° C.), so that molding becomes easy, and since there are few volatile components, there are problems such as voids. This is preferable because it can be effectively prevented.

In the thermosetting resin composition of the first invention, since defects such as voids can be effectively prevented as compared with the case where a normal acid anhydride is used, molding becomes easy.

Further, the thermosetting resin composition of the first invention desirably has a softening point in the range of 20 ° C to 150 ° C. More specifically, it is preferably in the range of 30 ° C. to 130 ° C., more preferably in the range of 40 ° C. to 120 ° C. By adjusting to this range, various components can be easily stirred and mixed with a mixer, etc., and further kneaded or melt kneaded with a mixing roll, extruder, kneader, roll, extruder, etc., cooled, pulverized It becomes possible to do.

The glass transition temperature of the cured product is preferably 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 first invention can be obtained by uniformly dispersing and mixing the various components described above. The method is not particularly limited. Can be mentioned. The conditions for kneading or melt-kneading may be determined depending on the types and amounts of the components, and are not particularly limited. However, kneading at 20 to 200 ° C. for 5 to 40 minutes is more preferable. When the kneading temperature is less than 20 ° C., the dispersibility of each component is lowered and it is difficult to sufficiently knead, and when the temperature is higher than 200 ° C., the crosslinking reaction of the resin composition proceeds rapidly. The resin composition may be cured.

The thermosetting resin composition of the first invention is preferably capable of being pressed (tablet) at room temperature of 0 to 30 ° C. before heat molding. For example, the pressure molding may be performed under conditions of 0.01 to 10 MPa and 1 to 5 seconds. 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 first invention is useful in applications such as optical semiconductor sealing materials and optical semiconductor reflectors that require high glass transition temperatures and high transmittance.

In the case of use for light reflection, the production method is not particularly limited. For example, it is preferable to produce the thermosetting resin composition of the first invention by transfer molding. The thermosetting resin composition of the first invention is poured into a mold and, for example, cured for 60 to 800 seconds under conditions of a mold temperature of 150 to 190 ° C. and a molding pressure of 2 to 20 MPa, and then taken out from the mold. And heat curing at an after-cure temperature of 150 ° C. to 180 ° C. for 1 to 3 hours.

(Semiconductor device)
In the semiconductor device of the first invention, as a specific example of a typical structure, as described in International Publication No. 2012-124147, a light reflection preventing member having a cylindrical hollow portion is disposed on a substrate, An optical semiconductor element is disposed on the substrate in the internal space of the cylindrical 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.

The reflective material suitably applied to the resin composition of the first invention will be described in more detail. In the reflective material obtained by molding, discoloration due to thermal deterioration is suppressed. The reflective material can be used as an LED reflector for an LED lighting apparatus such as an LED bulb. The reflective material obtained from the thermosetting resin composition of the first invention can constitute an inexpensive LED reflector having a long lifetime.

FIG. 1 shows an example of an LED lighting device using a reflective material obtained by molding a thermosetting resin composition. This reflector is the LED reflector 1. The reflective material is formed in a frame shape, and has a recess 2 and a hole 3 at the center. The recess 2 is provided as an inclined surface. The wall surface of the recess 2 serves as a reflecting surface that reflects light. The hole 3 is provided at the bottom of the recess 2 so as to penetrate the LED reflector 1. A lead frame 4 on which an LED 5 as a light emitting element is mounted is fitted in the hole 3. The lead frame 4 may be provided with wiring for supplying electricity to the LED 5. The light emitting surface side (upper part in the figure) of the recess 2 is covered with a transparent cover 6. Thereby, LED5 is protected. The cover 6 is joined to the LED reflector 1 at the opening edge of the recess 2. The LED reflector 1 functions as a reflector for efficiently reflecting the light emitted from the LED 5. The shape of the LED reflector 1 is not limited to the shape shown in FIG. 1, and can be appropriately designed in consideration of the light quantity, color, directivity characteristics, and the like of the mounted LED 5. With the thermosetting resin composition for light reflectors described above, since the moldability is good, it is possible to easily obtain a molded body having a desired shape.

Subsequently, the second invention will be described in detail.

The thermosetting resin composition of the second invention is obtained by gel permeation chromatography (hereinafter, referred to as polyvalent carboxylic acid (A1) having an isocyanuric ring represented by the following formula (1) from the viewpoint of increasing the glass transition temperature. It is characterized by containing a carboxylic acid resin containing 70% by area or more as measured by GPC). Here, it is preferable to contain 75 area% or more, and it is more preferable that it is 80 area% or more. Although an upper limit is not specifically limited, For example, what is necessary is just 99.9 area% or less.

In the formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.

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

Among R ² , a methyl group and a carboxyl group are preferable, and the thermosetting resin composition containing the polyvalent carboxylic acid (A1) has a viewpoint that the viscosity at room temperature (25 ° C.) does not increase excessively, A methyl group is preferable from the viewpoint of transparency, and a carboxyl group is particularly preferable from the viewpoint of gas barrier properties, high glass transition temperature (Tg), and hardness of the resulting cured product.

In the formula (1), a plurality of R ¹ and R ² may be the same or different from each other.

The thermosetting resin composition of the second invention is represented by the following formula (1a) from the viewpoint of enhancing the reliability and cured physical properties of a member such as a sealing material or a light reflecting material using the thermosetting resin composition. The ratio of the total amount of the polycarboxylic acid (A2) and / or the carboxylic acid (A3) represented by the following formula (1b) in the polyvalent carboxylic acid resin is 0.5 to 10 area% in the GPC measurement. It contains a carboxylic acid resin. Here, the content is preferably 0.5 to 5 area%, more preferably 1 to 3 area%.

In the formula (1a), R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.

Among R ² , a methyl group and a carboxyl group are preferable, and a viewpoint that the viscosity at room temperature (25 ° C.) of the thermosetting resin composition containing a polyvalent carboxylic acid resin does not increase too much and the transparency of the resulting cured product are obtained. From the viewpoint of the above, a methyl group is preferable, and a carboxyl group is particularly preferable from the viewpoint of gas barrier properties, high glass transition temperature (Tg), and hardness of the obtained cured product.

In the formula (1a), a plurality of R ¹ and R ² may be the same or different from each other.

In the thermosetting resin composition of the second invention, the proportion of the polyvalent carboxylic acid (A2) represented by the formula (1a) in the polyvalent carboxylic acid resin is 0 to 10% by area in GPC measurement. It is preferable to contain a carboxylic acid resin. Here, the content is more preferably 0 to 5% by area, and further preferably 0 to 3% by area.

In formula (1b), R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.

In the formula (1b), a plurality of R ¹ and R ² may be the same or different from each other.

In the thermosetting resin composition of the second invention, the ratio of the polyvalent carboxylic acid (A2) represented by the above formula (1b) in the polyvalent carboxylic acid resin is 0.5 to 10 area in GPC measurement. % Carboxylic acid resin is preferably contained. Here, the content is more preferably 0.5 to 5 area%, and further preferably 0.5 to 3 area%.

The thermosetting resin composition of the second invention has a large total amount of the high molecular weight mixture represented by the polyvalent carboxylic acids (A4) to (A6) represented by the following formulas (1c) to (1e). It is preferable to contain a carboxylic acid resin whose proportion in the polyvalent carboxylic acid resin is 0.5 to 15 area% in the GPC measurement. Here, the content is more preferably 0.5 to 10 area%, and further preferably 1 to 5 area%.

In the formulas (1c) to (1e), R ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.

In the formulas (1c) to (1e), a plurality of R ¹ and R ² may be the same or different from each other.

In the formula (1c), * represents a hydroxyl group, a residue obtained by reacting a hydroxyl group present in the above formulas (1a) to (1b) with a carboxyl group present in the above formulas (1) and (1a) to (1b), or The hydroxyl group present in the formula (6) represents a residue obtained by reacting with the carboxyl group present in the formula (1) and the formulas (1a) to (1b).

The high molecular weight substance (A4) is eluted with a shorter retention time than the compound represented by the formula (1) in the GPC retention time.
The compound obtained by reacting the compound represented by the formula (1) with the compound represented by the formula (6), wherein the retention time in the measurement of gel permeation chromatography is the formula (1). A polyvalent carboxylic acid resin containing 0.5 to 10 area% of a high molecular weight compound shorter than the compound represented by

The thermosetting resin composition of the second invention is a carboxylic acid resin in which the proportion of the acid anhydride represented by the following formula (6) in the polyvalent carboxylic acid resin is 5 to 20 area% in the GPC measurement. It is preferable to contain. Here, the content is preferably 5 to 15% by area.

In formula (6), R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, respectively.

The polyvalent carboxylic resin of the second invention is obtained by an addition reaction between a trishydroxyalkyl compound isocyanurate represented by the following formula (5) and a carboxylic acid anhydride compound represented by the following formula (6). be able to.

In formula (5), R ¹ represents the same meaning as described above.

The production of the polyvalent carboxylic acid resin of the second invention can be carried out in a solvent or without a solvent. As the solvent, any solvent that does not react with the trishydroxyalkyl compound of isocyanuric acid represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6) 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. When the solvent is used, the amount used is 0.1% relative to a total of 100 parts by mass of the trishydroxyalkyl compound isocyanurate represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6). 5 to 300 parts by mass are preferred.

Since the polyvalent carboxylic acid resin of the second invention is often solid at room temperature (25 ° C.), it is preferably synthesized in a solvent from the viewpoint of workability.

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

When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.
The amount used in the case of using a catalyst is 0. 0 with respect to a total of 100 parts by mass of the trishydroxyalkyl compound isocyanurate represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6). 05 to 10 parts by mass are preferred.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. At this time, it is preferable to avoid using an alcoholic solvent such as methanol or ethanol or water because it reacts with an unreacted carboxylic acid anhydride compound represented by the formula (6).

In the second invention, in the cured product of the obtained thermosetting resin composition, from the viewpoint of improving transparency and heat-resistant transparency, zinc carboxylate such as zinc octylate can be preferably used as a catalyst, From the viewpoint of reducing the coloration of the resulting polyvalent carboxylic acid resin or thermosetting resin composition, it is preferable to carry out the reaction 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 resin of the second 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 performed in two or more stages. For example, the reaction may be performed 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 a polyvalent carboxylic acid resin 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 resin and / or thermosetting resin composition is left as it is. It can also be used as a curing accelerator for epoxy resin compositions containing.
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 resin of the second 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 resin of the second 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 resin of the second invention, excellent durability can be realized and a thermosetting resin composition suitable for kneading can be obtained.

The thermosetting resin composition of the second invention is a resin composition containing the polyvalent carboxylic acid resin of the second invention and other components. In the polyvalent carboxylic acid composition of the second invention, a curing agent for thermosetting resin can be contained. Suitable curing agents for thermosetting resins include trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyro Examples thereof include one or more compounds selected from merit acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methyl In the presence of hexahydrophthalic anhydride, a cured product having a high crosslinking density can be obtained, so that a cured product having a high glass transition temperature can be obtained. However, carboxylic acids such as trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, and hydrogenated pyromellitic acid anhydride or An acid anhydride has a high softening point or melting point because it has crystallinity, and a specific melting point is 150 ° C. to 300 ° C., which may cause a problem in molding. On the other hand, since hexahydrophthalic anhydride and methylhexahydrophthalic anhydride have a melting point of not more than room temperature, there is a problem in molding. Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride, and Among the methylhexahydrophthalic anhydrides, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, hydrogenated pyromellitic acid, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahexan anhydride are difficult to color. Hydrophthalic anhydride is preferred, with cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride being more preferred.
Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride. In the second 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, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride, and The total of one or more compounds selected from methylhexahydrophthalic anhydride preferably accounts for 1% to 90% by weight in the thermosetting resin composition. If it is lower than 1% by weight, the glass transition temperature will not be sufficiently high. If it is higher than 90% by weight, the melting point will be high and handling may be difficult. More preferably, it is 10 to 60% by weight, and still more preferably 20 to 50% by weight.

Further, in the thermosetting resin composition of the second invention, the polyvalent carboxylic acid (A1) represented by the above formula (1) and trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride Of one or more compounds selected from products, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride The functional group equivalent in the mixture is 250 g / eq. Or less, preferably 240 g / eq. The following is more preferable. By being in this range, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic acid The effect of the compound amount of one or more compounds selected from anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride is effectively exhibited, and a cured product having excellent heat resistance can be obtained. Become.

The weight ratio is the polyvalent carboxylic acid (A1) represented by the above formula (1): (trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated 1 or 2 or more compounds selected from pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride) are 99; 1 to 10:90 90:10 to 20:80 is more preferable, and 80:20 to 50:50 is particularly 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.

The thermosetting resin composition of the second invention includes the polyvalent carboxylic acid resin of the second invention, trimellitic acid, trimellitic acid anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid anhydride, pyromellitic acid, water Contains one or more compounds selected from the group consisting of pyromellitic acid anhydride, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Trimellitic acid, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride The total of one or more compounds selected from It is preferable to account for 1 wt% to 90 wt% in the thermosetting resin composition. 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.

The thermosetting resin composition in the second invention is preferably 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 invention, it is desirable to use an epoxy resin.

The epoxy resin can be used without any particular limitation as long as it is usually blended as a conventional thermosetting resin composition or epoxy resin composition. 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 second invention is such that the active group 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. (Acid 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.

Moreover, the oligoester of the terminal carboxylic acid that can be contained as a component of the curing agent for the thermosetting resin of the second invention is represented by the following formula (10).

Specific structural formula is a compound having the structure of the following formula (10) and 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.

The particularly preferred oligoester of the terminal carboxylic acid in the second invention can be obtained by addition reaction of a bi- to hexafunctional polyhydric alcohol having 6 or more carbon atoms and a saturated aliphatic cyclic acid anhydride.
The oligoester of the terminal carboxylic acid in the second invention may be a composition containing two oligoesters of the 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 bi- to hexafunctional polyhydric alcohol having 6 or more carbon atoms used for the synthesis of the terminal carboxylic acid oligoester in the second invention is specifically a hydroxyl group at the end of the bridging group P in the formula (10). And an oligoester of a terminal carboxylic acid marked with.
In the formula (10), the crosslinkable group represented by P is preferably a divalent crosslinkable group defined by the above (a) or (b), and will be specifically described below.
The divalent crosslinking group defined in (a) is a divalent chain alkyl chain obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure having 6 to 20 carbon atoms. 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).

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 second 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.

The reaction ratio between the acid anhydride and the polyhydric alcohol is theoretically preferably equimolar, but can be changed as necessary.
The specific charging ratio of the two at the time of reaction is such that the polyhydric alcohol is equivalent to 0.001 to 2 equivalents in terms of the hydroxyl group equivalent to 1 equivalent of the acid anhydride group in terms of the functional group 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 second invention, the obtained terminal carboxylic acid oligoester is preferably solid, and in order to obtain a solid resinous terminal carboxylic acid oligoester, ideally an equimolar equivalent or more of polyhydric alcohol However, fluidity is important because of the addition of filler, and in order to secure this fluidity, some balance is lost in the range where the solids are maintained (softening point of 50 ° C or higher). It doesn't matter.
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.

Usually, when the crosslinking group is an alkylene group having a side chain defined by (a), it shows a colorless to pale yellow solid resinous form.
In the second invention, since the optimum method of using the thermosetting resin composition containing the oligoester of the terminal carboxylic acid is molding by transfer, the oligoester of the terminal carboxylic acid is in the form of a solid resin. .

That is, when the terminal carboxylic acid oligoester composition of the second invention is a cycloalkane skeleton or a norbornane skeleton having 4 to 10 carbon atoms, the substituent is preferably a formula having a methyl group or a carboxyl group, or both ( The composition containing the oligoester of terminal carboxylic acid of 10) is preferable. 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 (10), 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 a suitable terminal carboxylic acid oligoester in the second invention, a terminal carboxylic acid oligoester represented by the following formula (2A) is used.

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 anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic 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.

A curing accelerator can be added to the thermosetting resin composition of the second invention as necessary. Curing accelerators 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, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole imidazoles, and imidazoles with phthalic acid, isophthalic acid, terephthalic acid , Salts with oligoesters of terminal carboxylic acids such as trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7 and their tetrafes Salts such as ruborate and phenol novolac, oligoesters of the above 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, microcapsule-type curing accelerators in which these curing accelerators are microcapsules, and carbonyl compound zinc complexes. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, heat-resistant colorability, curing speed, and working conditions. Preferred examples of the second invention include phosphonium compounds (more preferably quaternary phosphonium) and zinc stearate.
The curing accelerator is usually used in an amount of 0.001 to 15 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the epoxy resin.

In the thermosetting resin composition of the second invention, it is desirable that the ICI cone plate viscosity of the curing agent for the thermosetting resin under a high temperature condition during molding is higher than that of a conventional acid anhydride curing agent, etc. Specifically, it is desirable that the pressure is 0.01 to 10 Pa · s within the range of 100 to 200 ° C. which is the molding temperature range. If it is less than 0.01 Pa · s, burrs are likely to occur. On the other hand, if it is greater than 10 Pa · s, the productivity may decrease.
In this embodiment, the ICI viscosity of the thermosetting resin curing agent at 150 ° C. is preferably 0.01 Pa · s to 10 Pa · s, more preferably 0.05 Pa · s to 5 Pa · s. .
By adjusting to the said range, it becomes solid at normal temperature (25 degreeC), shaping | molding becomes easy, and malfunctions, such as a void, can be prevented effectively. Further, since it is solid at room temperature, kneading, which is impossible without pretreatment such as prepolymerization in the case of liquid, is possible without pretreatment, and since it is solid, it is easy to mold as a tablet. Furthermore, by setting to such a low-viscosity thermosetting resin composition, each component that has been conventionally difficult to knead due to its crystallinity has a high softening point or melting point, and is sufficiently melted and dispersed in the curing agent. Therefore, the crystals are broken and are sufficiently kneaded with the epoxy resin as the main agent, so that each component is effectively arranged and a cured product having excellent physical properties can be obtained.

The thermosetting resin composition of the second invention preferably has a softening point of 20 to 150 ° C, more preferably in the range of 30 ° C to 130 ° C, and in the range of 40 ° C to 120 ° C. More preferably, it is 50 to 130 ° C.
By adjusting to this range, various components can be easily stirred and mixed with a mixer, etc., and further kneaded or melt kneaded with a mixing roll, extruder, kneader, roll, extruder, etc., cooled, pulverized It becomes possible to do.

The glass transition temperature (Tg) of the cured product is desirably higher than the molding temperature. If the glass transition temperature (Tg) of the cured product is equal to or lower than the molding temperature, the cured product in the mold is in a low elastic rubber state, so the rubber-like cured product is taken out of the mold, and the ejector is removed. When pushing, there is a possibility that a problem may occur due to deformation. Specifically, the glass transition temperature (Tg) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
Here, in 2nd invention, 150 degreeC or less is preferable and, as for the glass transition temperature (Tg) of hardened | cured material, 140 degreeC or less is more preferable.

The thermosetting resin composition of the second invention can be obtained by uniformly dispersing and mixing the various components described above. The method is not particularly limited. Can be mentioned. The conditions for kneading or melt-kneading may be determined depending on the types and amounts of the components, and are not particularly limited. However, kneading at 20 to 100 ° C. for 5 to 40 minutes is more preferable. 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 second invention can be molded under pressure (tablet) at room temperature of 0 to 30 ° C. before heat molding. For example, the pressure molding may be performed under conditions of 0.01 to 10 MPa and 1 to 5 seconds. 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 second invention is useful in applications such as optical semiconductor sealing materials and optical semiconductor reflectors that require high glass transition temperatures and high transmittance.

In the case of using for light reflection, the production method is not particularly limited. For example, it is preferable to produce the thermosetting resin composition of the second invention by transfer molding. The thermosetting resin composition of the second invention is injected into a mold and, for example, cured for 60 to 800 seconds under conditions of a mold temperature of 150 to 190 ° C. and a molding pressure of 2 to 20 MPa, and then taken out from the mold. The composition is heat-cured at an after-cure temperature of 150 ° C. to 180 ° C. for 1 to 3 hours.

(Semiconductor device)
The semiconductor device of the second invention, when a specific example is illustrated with respect to a typical structure, arranges a light reflection preventing member having a cylindrical hollow portion on a substrate as described in International Publication No. 2012/124147, An optical semiconductor element is disposed on the substrate in the internal space of the cylindrical 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.

The reflective material suitably applied to the resin composition of the second invention will be described in more detail. In the reflective material obtained by molding, discoloration due to thermal deterioration is suppressed. The reflective material can be used as an LED reflector for an LED lighting apparatus such as an LED bulb. The reflective material obtained from the thermosetting resin composition of the second invention can constitute an inexpensive LED reflector having a long lifetime.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the following description.

First, the first invention will be described in detail by way of examples.

Preparation of thermosetting light reflecting resin composition (Examples 1-1 to 1-2, Comparative Examples 1-1 to 1-2)
EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), THEIC-G (polyhydric alcohol compound manufactured by Shikoku Kasei Kogyo Co., Ltd.), Ricacid MH-T (curing agent for epoxy resin manufactured by Shin Nippon Chemical Co., Ltd.) Using Hishicolin PX-4MP (a curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), the respective components were blended according to the blending table shown in Table 1-1, and Examples 1-1 to 1-2 and Comparative Example 1- 1 to 1-2 thermosetting resin compositions were prepared. In Table 1-1, the unit of the blending amount of each component is parts by weight, and the blank indicates that the component is not used.

Preparation of thermosetting light reflecting resin composition (Examples 1-3 to 1-4)
EHPE-3150 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), ditrimethylolpropane (polyhydric alcohol compound manufactured by Perstorp Japan Co., Ltd.), Rikacid MH-T (curing agent for epoxy resin manufactured by Shin Nippon Chemical Co., Ltd.) Each component was blended according to the blending table shown in Table 1-2 using Hishicolin PX-4MP (a curing catalyst manufactured by Nippon Chemical Industry Co., Ltd.), and the thermosetting resins of Examples 1-3 to 1-4 A composition was prepared. The unit of the amount of each component in Table 1-2 is parts by weight.

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 1-1.

(A) Differential thermal-thermogravimetric simultaneous measurement (TG / DTA)
About the differential thermal-thermogravimetric simultaneous measurement (TG / DTA), it measured on the following conditions using the differential thermal calorific value simultaneous measuring apparatus (SII nanotechnology Co., Ltd. Exstar TG / DTA7200).
(Measurement condition)
Measurement temperature: 40 ° C to 150 ° C
Temperature increase rate: 20 ° C./min Retention time: 150 ° C. for 1 hour Flow gas: Nitrogen gas Flow rate: 200 ml / min Pan: Aluminum sample amount: 4-6 mg

In addition, Examples 1 to 4 and Comparative Examples 1 and 2 in Table 1-1 and Table 1-2 below represent Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2, respectively. .

From the above results, it can be seen that the thermosetting resin composition of the first invention has a feature of low volatilization at the time of curing.

Subsequently, the second invention will be described in detail by way of examples.

Here, 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 coupled 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 Measured by a method according to JIS K-7234.

Synthesis Example 2-1 (Curing Agent A-1 for Thermosetting Resin)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 261.2 parts of tris (2-hydroxyethyl) isocyanurate while purging with nitrogen, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Corporation) (Licacid MH-T) 504.6 parts and MEK 766.0 parts were added, and a MEK solution containing the compound was obtained by heating and stirring at 70 ° C. for 7 hours. Thereto, 153.2 parts of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH-T) was added, and the mixture was heated and stirred at 70 ° C. for 1 hour. Thereafter, the temperature was raised from 70 ° C. to 150 ° C. in about 1 hour, and the solvent was removed under the conditions of 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 232 g / eq. Met. The ICI viscosity was 0.38 Pa · s at 150 ° C. The softening point was 82.6 ° C.
Further, the GPC area ratio was 81.1% for the 3-substituted product as the main component, 3.04% for the 2-substituted product, and 1.04% for the 1-substituted product.

Synthesis Example 2-2 (Curing Agent A-2 for Thermosetting Resin)
7840 parts of isocyanuric acid tris (2-hydroxyethyl), methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid) while purging with nitrogen in a reaction vessel equipped with a stirrer, reflux condenser, and stirrer 15140 parts of (MH-T) and 23000 parts of methyl ethyl ketone (MEK) were added, and a MEK solution containing the compound was obtained by heating and stirring at 70 ° C. for 7 hours. To the place where the temperature of the MEK solution was lowered to room temperature, 4600 parts of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MHT) was added, and the mixture was heated and stirred at 40 ° C. for 1 hour. Thereafter, the temperature was gradually raised from 40 ° C. to 150 ° C. under reduced pressure over about 5 hours, and the solvent was removed under the conditions of 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 234 g / eq. Met. The ICI viscosity was 0.40 Pa · s at 150 ° C. The softening point was 82.9 ° C.
The GPC area ratio was 82.59% for the 3-substituted product, which was the main component, 0.00% for the 2-substituted product, and 1.25% for the 1-substituted product.

Examples 1-2 in Table 2-1 above show the results of GPC analysis of the curing agents obtained in Synthesis Examples 2-1 and 2-2, respectively. In Table 2-1, the mono-substituted product is obtained by replacing one compound of the formula (5) with the compound of the formula (6), and the 2-substituted product is represented by the formula (5). The compound is a compound in which two compounds are substituted with the compound of the above formula (6), and the 3-substituent represents a compound in which three compounds of the above formula (5) are substituted with the compound of the above formula (6).

According to the second invention, a polyvalent carboxylic acid resin that provides a cured product having excellent moldability, less coloration when cured into a cured product, and a sufficient glass transition temperature, a thermosetting resin composition using the same, and An optical semiconductor device using the thermosetting resin composition as a sealing material or a reflecting material can be provided. Furthermore, by suppressing the softening point of the polyvalent carboxylic acid resin or the thermosetting resin composition using the same, the handling of the thermosetting resin composition is facilitated and sufficient kneading is possible, resulting in cured physical properties. It is possible to provide a cured product that is excellent in. Moreover, the thermosetting resin composition excellent also in the reactivity of resin, and the hardened | cured material excellent in toughness can be provided.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese patent applications (Japanese Patent Application Nos. 2015-021450 and 2015-021668) filed on Feb. 5, 2015, which are incorporated by reference in their entirety. Also, all references cited herein are incorporated as a whole.

The curing agent for thermosetting resins of the first invention has a low volatility and excellent moldability, and the thermosetting resin composition using the curing agent for thermosetting resins has a sufficiently high glass transition temperature. The thermosetting resin composition of the first invention is useful as a sealing material for optical semiconductors or a material for light reflecting materials because it gives a cured product with little coloring. A sufficiently high glass transition temperature is important for formability and reliability. Further, when used as a reflective material, the reflectance can be increased.

The curing agent for thermosetting resins of the second invention has a low melt viscosity and excellent moldability, and the thermosetting resin composition using the curing agent for thermosetting resins has a sufficient glass transition temperature. The thermosetting resin composition of the second invention is useful as a sealing material for an optical semiconductor or a material for a light reflecting material because it gives a cured product that is high and less colored. 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.

1 LED reflector, 2 reflector, 3 holes, 4 lead frame, 5 LED, 6 cover

Claims

A thermosetting resin composition containing a polyhydric alcohol compound (A) having three or more hydroxyl groups, an acid anhydride compound (B), and a thermosetting resin (C).
The thermosetting resin composition according to claim 1, wherein the polyhydric alcohol compound (A) having three or more hydroxyl groups has a cyclic structure containing one or more heteroatoms in the molecule.
The thermosetting resin composition according to claim 2, wherein the heteroatom is a nitrogen atom.
The thermosetting resin composition according to claim 1, wherein the polyhydric alcohol compound (A) having three or more hydroxyl groups is a polyhydric alcohol compound represented by the following formula (5).

(In Formula (5), R 1 represents an alkylene group having 1 to 6 carbon atoms. In Formula (5), a plurality of R 1 may be the same or different.)
The acid anhydride compound (B) is selected from trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermosetting resin composition is one or more compounds.
The thermosetting resin composition according to any one of claims 1 to 5, wherein the thermosetting resin (C) is an epoxy resin.
Following formula (1)

(In the formula (1), R 1 represents an alkylene group having 1 to 6 carbon atoms, and R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group. R 1 and R 2 may be the same or different.)
Containing 70% by area or more in the measurement of gel permeation chromatography, polyvalent carboxylic acid (A1) represented by
The following formula (1a)

(In formula (1a), R 1 and R 2 represent the same meaning as R 1 and R 2 in formula (1). In formula (1a), a plurality of R 1 and R 2 are the same. May be different.)
And / or the following formula (1b)

(In the formula (1b), R 1, R 2 is Formula (1) R 1, R 2 the same meaning represents the. Formula in in (1b), R 1, R 2 existing in plural in the same May be different.)
A thermosetting resin composition containing a polyvalent carboxylic acid resin containing 0.5 to 10 area% of a carboxylic acid (A3) represented by the formula (1) as measured by gel permeation chromatography.
The polyvalent carboxylic acid resin is represented by the following formula (6).

(In formula (6), R 2 represents the same meaning as R 2 in formula (1).)
The thermosetting resin composition according to claim 7, which is a polyvalent carboxylic acid resin containing 5 to 20% by area of an acid anhydride represented by the following formula as measured by gel permeation chromatography.
The polyvalent carboxylic acid resin is a compound obtained by reacting the compound represented by the formula (1) with the compound represented by the formula (6) according to claim 8, and the gel permeation chromatography The thermosetting resin composition according to claim 7, which is a polyvalent carboxylic acid resin containing 0.5 to 10 area% of a high molecular weight product whose retention time is shorter than that of the compound represented by the formula (1) in the measurement of .
The thermosetting resin composition according to any one of claims 7 to 9, wherein the softening point is in the range of 20 ° C to 150 ° C.
Trivalent acid, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, chlorohexanetricarboxylic acid anhydride, pyromellitic acid, hydrogenated pyromellitic acid, pyromellitic acid anhydride, hydrogenated pyromellitic acid anhydride, Contains one or more compounds selected from hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic anhydride, pyromellitic acid, water The thermosetting property is a total of one or two or more compounds selected from an added pyromellitic acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. 1% to 90% by weight in the resin composition Occupied, the thermosetting resin composition according to any one of claims 7-10.
The thermosetting resin composition according to any one of claims 7 to 11, which contains a thermosetting resin.
The thermosetting resin composition according to claim 12, wherein a glass transition temperature (Tg) of a cured product obtained by curing the thermosetting resin composition is 30 ° C or higher.
A cured product obtained by thermosetting the thermosetting resin composition according to any one of claims 1 to 6, 12, and 13.
An optical semiconductor device sealed with the cured product according to claim 14.
An optical semiconductor device using the cured product according to claim 14 as a reflector.