WO2016125874A1 - Composition de résine thermodurcissable comprenant un composé alcool polyhydrique, un composé anhydride d'acide et une résine thermodurcissable, résine d'acide polycarboxylique, composition de résine thermodurcissable l'utilisant, et dispositif photosemi-conducteur mettant en œuvre une des compositions de résine thermodurcissable en tant que matériau d'étanchéité ou matériau réfléchissant - Google Patents

Composition de résine thermodurcissable comprenant un composé alcool polyhydrique, un composé anhydride d'acide et une résine thermodurcissable, résine d'acide polycarboxylique, composition de résine thermodurcissable l'utilisant, et dispositif photosemi-conducteur mettant en œuvre une des compositions de résine thermodurcissable en tant que matériau d'étanchéité ou matériau réfléchissant Download PDF

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WO2016125874A1
WO2016125874A1 PCT/JP2016/053430 JP2016053430W WO2016125874A1 WO 2016125874 A1 WO2016125874 A1 WO 2016125874A1 JP 2016053430 W JP2016053430 W JP 2016053430W WO 2016125874 A1 WO2016125874 A1 WO 2016125874A1
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Prior art keywords
thermosetting resin
anhydride
acid
resin composition
group
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PCT/JP2016/053430
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English (en)
Japanese (ja)
Inventor
静 青木
政隆 中西
正人 鎗田
田中　栄一
義浩 川田
直佑 谷口
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority claimed from JP2015021450A external-priority patent/JP2016141799A/ja
Priority claimed from JP2015021668A external-priority patent/JP2016141806A/ja
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to CN201680008961.4A priority Critical patent/CN107250282A/zh
Publication of WO2016125874A1 publication Critical patent/WO2016125874A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/855—Optical field-shaping means, e.g. lenses
    • H10H20/856—Reflecting means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

  • 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.
  • thermosetting resin composition 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
  • the curing agent blended in the thermosetting resin composition is also required to have high transmittance and little coloration.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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 (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 (2), wherein the heteroatom is a nitrogen atom.
  • 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).
  • 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 trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • 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.
  • R 1 and R 2 represent the same meaning as R 1 and R 2 in formula (1).
  • a plurality of R 1 and R 2 are the same. May be different.
  • 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.
  • the polyvalent carboxylic acid resin is represented by the following formula (6):
  • 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.
  • 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.
  • 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, hexahydr
  • 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.
  • Tg glass transition temperature
  • (12) 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.
  • 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.
  • 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
  • an optical semiconductor device using the thermosetting resin composition as a sealing material or a reflecting material.
  • cured material and the reactivity of resin can be provided.
  • thermosetting resin composition obtained by this invention is the schematic at the time of using the thermosetting resin composition obtained by this invention as a reflector.
  • 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.
  • A polyhydric alcohol having three or more known hydroxyl groups
  • Specific examples include trimethylolpropane, pentaerythritol, glycerol, EO-modified glycerol, PO-modified glycerol, dipentaerythritol, polyhydric alcohol represented by the following formula (5), and the like.
  • 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.
  • 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
  • R 1 represents an alkylene group having 1 to 6 carbon atoms.
  • R 1 examples 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.
  • a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.
  • a plurality of R 1 may be the same or different from each other.
  • the compounds represented by the formula (5) are preferable from the viewpoint of transparency of the cured product and gas barrier properties.
  • the polyhydric alcohol (A) to be used may be liquid or 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.
  • 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.
  • trimellitic anhydride cyclohexanetricarboxylic anhydride
  • pyromellitic anhydride hydrogenated pyromellitic anhydride
  • hexahydrophthalic anhydride hexahydrophthalic anhydride
  • methylhexahydrophthalic anhydride methylhexahydrophthalic anhydride
  • a cured product having a high crosslinking density is obtained.
  • a cured product having a high glass transition temperature can be obtained.
  • 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.
  • cyclohexanetricarboxylic acid anhydride examples include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride.
  • these acid anhydrides can be used in combination, but cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferred.
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.
  • 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.
  • thermosetting resin composition in the first invention contains a thermosetting resin (C).
  • thermosetting resin (C) examples include an epoxy resin, a phenol resin, a urea resin, a melamine resin, and an unsaturated polyester 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • triazine derivative epoxy resin examples 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.).
  • silsesquioxane compound having an epoxy group that can be used a silsesquioxane compound having two or more epoxy groups in the molecule is preferable.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • thermosetting resin composition of the first invention is represented by the following formula (10).
  • 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.
  • 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.
  • 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.
  • 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.
  • P is preferably a divalent crosslinking group defined by the following (a) or (b).
  • the substituent R 3 is a group other than a hydrogen atom in the formula (2A) described later. Is more preferable.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • a catalyst 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 hydrox
  • 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.
  • 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).
  • 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.
  • 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.
  • 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
  • the reaction temperature is preferably 30 to 200 ° C, more preferably 40 to 200 ° C, and particularly preferably 40 to 150 ° C.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • the catalyst 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.
  • the desired oligoester of the terminal carboxylic acid can be obtained by distilling off the solvent as necessary.
  • 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.
  • the crosslinking group is an alkylene group having a side chain defined by (a)
  • it shows a colorless to pale yellow solid resinous form.
  • the oligoester of the terminal carboxylic acid is in the form of a solid resin. .
  • the bridging group is a bridging group defined by (b)
  • 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.
  • 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.
  • the substituent is a methyl group or a carboxyl group. This is preferable because optical characteristics are improved.
  • 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.
  • 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) .
  • 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.
  • 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.
  • a terminal carboxylic acid oligoester represented by the following formula (2A) is used as a suitable terminal carboxylic acid oligoester in the first invention.
  • 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.
  • 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
  • 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 (
  • curing accelerators 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.
  • a phosphonium compound preferably quaternary phosphonium
  • 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.
  • 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.
  • the filler examples 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.
  • the average particle size of the white pigment is preferably in the range of 0.01 to 50 ⁇ m. If it is less than 0.01 ⁇ m, the particles tend to aggregate and the dispersibility tends to deteriorate, and if it exceeds 50 ⁇ m, 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the glass transition temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
  • 150 degreeC or less is preferable and, as for the glass transition temperature of hardened
  • 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.
  • 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.
  • 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.
  • the pressure molding may be performed under conditions of 0.01 to 10 MPa and 1 to 5 seconds.
  • 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.
  • 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.
  • the production method is not particularly limited.
  • 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.
  • 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
  • the reflective material suitably applied to the resin composition of the first invention will be described in more detail.
  • 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.
  • 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.
  • 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.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.
  • R 1 examples 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.
  • a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.
  • 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.
  • 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.
  • a plurality of R 1 and R 2 may be the same or different from each other.
  • 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.
  • the content is preferably 0.5 to 5 area%, more preferably 1 to 3 area%.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.
  • R 1 examples 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.
  • a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.
  • 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.
  • 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.
  • 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.
  • a plurality of R 1 and R 2 may be the same or different from each other.
  • 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.
  • the content is more preferably 0 to 5% by area, and further preferably 0 to 3% by area.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.
  • R 1 examples 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.
  • a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.
  • 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.
  • 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.
  • 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.
  • a plurality of R 1 and R 2 may be the same or different from each other.
  • 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.
  • the content is more preferably 0.5 to 5 area%, and further preferably 0.5 to 3 area%.
  • 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%.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.
  • R 1 examples 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.
  • a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.
  • 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.
  • 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.
  • 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.
  • a plurality of R 1 and R 2 may be the same or different from each other.
  • * 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).
  • 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.
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, respectively.
  • 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.
  • 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.
  • 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.
  • 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.
  • R 1 represents the same meaning as described above.
  • the compounds represented by the formula (5) are preferable from the viewpoint of transparency of the cured product and gas barrier properties.
  • the production of the polyvalent carboxylic acid resin of the second invention can be carried out in a solvent or without a solvent.
  • a 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.
  • 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 and ketones are preferable.
  • These solvents may be used alone or in combination of two or more.
  • 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.
  • 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.
  • 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,
  • a catalyst 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).
  • thermosetting resin composition 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.
  • calcium stearate 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.
  • 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.
  • the catalyst 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.
  • 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.
  • 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.
  • 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.
  • thermosetting resin composition suitable for kneading
  • thermosetting resin composition of the second invention is a resin composition containing the polyvalent carboxylic acid resin of the second invention and other components.
  • a curing agent for thermosetting resin can be contained in the polyvalent carboxylic acid composition of the second invention.
  • 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.
  • 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.
  • 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.
  • hexahydrophthalic anhydride and methylhexahydrophthalic anhydride have a melting point of not more than room temperature, there is a problem in molding.
  • Hydrophthalic anhydride is preferred, with cyclohexanetricarboxylic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride being more preferred.
  • cyclohexanetricarboxylic acid anhydride examples include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and cyclohexane-1,2,3-tricarboxylic acid-1,2-anhydride.
  • these acid anhydrides can be used in combination, but cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is preferred.
  • 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.
  • 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.
  • trimellitic acid trimellitic anhydride, cyclohexanetricarboxylic acid, and cyclohexanetricarboxylic anhydride
  • pyromellitic acid hydrogenated pyromellitic acid
  • pyromellitic anhydride hydrogenated pyromellitic acid
  • 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
  • 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.
  • 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.
  • a thermosetting resin such as an epoxy resin, a phenol resin, a urea resin, a melamine resin, and an unsaturated polyester 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.
  • 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.
  • 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.
  • curing may be incomplete and good cured properties may not be obtained, and coloration is likely to occur. There is also a problem.
  • 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).
  • n is 2 or more and less than 12.
  • 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 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.
  • 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.
  • 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.
  • P is preferably a divalent crosslinking group defined by the following (a) or (b).
  • the substituent R 3 is a group other than a hydrogen atom in the formula (2A) described later. Is more preferable.
  • 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.
  • 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 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.
  • 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.
  • 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 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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 second invention, a reaction without a catalyst is particularly preferable.
  • a catalyst 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 hydrox
  • 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.
  • 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).
  • 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.
  • 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.
  • 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
  • the reaction temperature is preferably 30 to 200 ° C, more preferably 40 to 200 ° C, and particularly preferably 40 to 150 ° C.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • the catalyst 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.
  • the desired oligoester of the terminal carboxylic acid can be obtained by distilling off the solvent as necessary.
  • 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.
  • the crosslinking group is an alkylene group having a side chain defined by (a)
  • it shows a colorless to pale yellow solid resinous form.
  • the oligoester of the terminal carboxylic acid is in the form of a solid resin. .
  • the bridging group is a bridging group defined by (b)
  • 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.
  • 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.
  • the substituent is a methyl group or a carboxyl group. This is preferable because optical characteristics are improved.
  • 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.
  • 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) .
  • 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.
  • 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.
  • a terminal carboxylic acid oligoester represented by the following formula (2A) is used as a suitable terminal carboxylic acid oligoester in the second invention.
  • 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.
  • 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. .
  • 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
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the glass transition temperature (Tg) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
  • 150 degreeC or less is preferable and, as for the glass transition temperature (Tg) of hardened
  • 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.
  • thermosetting resin composition of the second invention can be molded under pressure (tablet) at room temperature of 0 to 30 ° C. before heat molding.
  • the pressure molding may be performed under conditions of 0.01 to 10 MPa and 1 to 5 seconds.
  • 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.
  • 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.
  • the production method is not particularly limited.
  • 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.
  • 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
  • the reflective material suitably applied to the resin composition of the second invention will be described in more detail.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.)
  • 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.
  • Table 1-2 The unit of the amount of each component in Table 1-2 is parts by weight.
  • thermosetting resin composition About the resin composition of each Example, DMA, TMA, and the transmittance
  • 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. .
  • thermosetting resin composition of the first invention has a feature of low volatilization at the time of curing.
  • GPC gel permeation chromatography
  • ICI viscosity ICI viscosity
  • softening point ICI viscosity
  • 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)
  • a standard polystyrene made by Shodex was used for the calibration curve.
  • 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.
  • the melt viscosity in the cone plate method at an ICI viscosity of 150 ° C. was measured.
  • Softening point Measured by a method according to JIS K-7234.
  • 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., Spaincid) 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.
  • MH-T methyl ethyl ketone
  • 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.
  • 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).
  • 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
  • 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.
  • less coloring can increase the transmittance when used as a sealing material, and can increase the reflectance when used as a reflecting material.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine thermodurcissable comprenant un composé alcool polyhydrique (A) ayant trois groupes hydroxyle ou plus, un composé anhydride d'acide (B), et une résine thermodurcissable (C), une composition de résine thermodurcissable caractérisée en ce qu'elle comprend un acide polycarboxylique (A) représenté par la formule (1) ci-dessous, la viscosité ICI cône-plaque étant comprise entre 0,01 Pa∙s et 10 Pa∙s dans une plage de 100 à 200 °C, et un dispositif photosemi-conducteur mettant en œuvre l'une des compositions de résine thermodurcissable en tant que matériau d'étanchéité ou matériau réfléchissant. (Dans la formule (1), R1 représente un groupe alkylène en C1-6, et R2 représente un atome d'hydrogène, ou un groupe alkyle en C1-6, ou un groupe carboxyle. Dans la formule (1), R1 et R2, dont il existe des pluralités, peuvent être identiques ou différents l'un de l'autre.)
PCT/JP2016/053430 2015-02-05 2016-02-04 Composition de résine thermodurcissable comprenant un composé alcool polyhydrique, un composé anhydride d'acide et une résine thermodurcissable, résine d'acide polycarboxylique, composition de résine thermodurcissable l'utilisant, et dispositif photosemi-conducteur mettant en œuvre une des compositions de résine thermodurcissable en tant que matériau d'étanchéité ou matériau réfléchissant Ceased WO2016125874A1 (fr)

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CN201680008961.4A CN107250282A (zh) 2015-02-05 2016-02-04 含有多元醇化合物、酸酐化合物和热固化性树脂的热固化性树脂组合物及多元羧酸树脂、以及使用了其的热固化性树脂组合物、以及使用了前述热固化性树脂组合物中的任一种作为封装材料或者反射材料的光半导体装置

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JP2015021450A JP2016141799A (ja) 2015-02-05 2015-02-05 多価アルコール化合物、酸無水物化合物及び熱硬化性樹脂を含有する熱硬化性樹脂組成物、およびその熱硬化性樹脂組成物を封止材あるいは反射材として使用した光半導体装置
JP2015021668A JP2016141806A (ja) 2015-02-05 2015-02-05 多価カルボン酸樹脂、それを用いた熱硬化性樹脂組成物、およびその熱硬化性樹脂組成物を封止材あるいは反射材として使用した光半導体装置
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JP2015-021668 2015-02-05

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JPH01193317A (ja) * 1987-11-27 1989-08-03 Enichem Sintesi Spa 熱硬化性液状組成物
JPH03121155A (ja) * 1989-10-04 1991-05-23 New Japan Chem Co Ltd エポキシ樹脂組成物
JP2001059017A (ja) * 1999-08-24 2001-03-06 Nitto Denko Corp 流延用エポキシ樹脂組成物
JP2007099901A (ja) * 2005-10-04 2007-04-19 Nippon Steel Chem Co Ltd エポキシ樹脂及びエポキシ樹脂組成物
WO2008142931A1 (fr) * 2007-05-17 2008-11-27 Nitto Denko Corporation Composition de résine époxy pour une encapsulation de dispositifs semi-conducteurs optiques, corps durci de celle-ci, et dispositif semi-conducteur optique utilisant la composition de résine époxy
WO2014050978A1 (fr) * 2012-09-27 2014-04-03 日本化薬株式会社 Résine d'acide polycarboxylique et composition de résine époxy
US20140128511A1 (en) * 2009-04-03 2014-05-08 Ccp Composites Us Llc Thermosetting Compositions Containing Isocyanurate Rings
JP2015096602A (ja) * 2013-10-07 2015-05-21 株式会社ダイセル 硬化性エポキシ樹脂組成物
WO2016013257A1 (fr) * 2014-07-24 2016-01-28 日本化薬株式会社 Acide polycarboxylique, composition d'acide polycarboxylique, composition de résine époxy et composition de résine thermodurcissable contenant chacune ledit acide polycarboxylique, produits durcis desdites compositions, et dispositif à semi-conducteur optique

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JPS51124197A (en) * 1975-04-22 1976-10-29 Dainippon Ink & Chem Inc A resin composition
JPH01193317A (ja) * 1987-11-27 1989-08-03 Enichem Sintesi Spa 熱硬化性液状組成物
JPH03121155A (ja) * 1989-10-04 1991-05-23 New Japan Chem Co Ltd エポキシ樹脂組成物
JP2001059017A (ja) * 1999-08-24 2001-03-06 Nitto Denko Corp 流延用エポキシ樹脂組成物
JP2007099901A (ja) * 2005-10-04 2007-04-19 Nippon Steel Chem Co Ltd エポキシ樹脂及びエポキシ樹脂組成物
WO2008142931A1 (fr) * 2007-05-17 2008-11-27 Nitto Denko Corporation Composition de résine époxy pour une encapsulation de dispositifs semi-conducteurs optiques, corps durci de celle-ci, et dispositif semi-conducteur optique utilisant la composition de résine époxy
US20140128511A1 (en) * 2009-04-03 2014-05-08 Ccp Composites Us Llc Thermosetting Compositions Containing Isocyanurate Rings
WO2014050978A1 (fr) * 2012-09-27 2014-04-03 日本化薬株式会社 Résine d'acide polycarboxylique et composition de résine époxy
JP2015096602A (ja) * 2013-10-07 2015-05-21 株式会社ダイセル 硬化性エポキシ樹脂組成物
WO2016013257A1 (fr) * 2014-07-24 2016-01-28 日本化薬株式会社 Acide polycarboxylique, composition d'acide polycarboxylique, composition de résine époxy et composition de résine thermodurcissable contenant chacune ledit acide polycarboxylique, produits durcis desdites compositions, et dispositif à semi-conducteur optique

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