TW201219426A - Polyvalent carboxylic acid composition, curing agent composition, and curable resin composition containing polyvalent carboxylic acid composition or curing agent composition as curing agent for epoxy resin - Google Patents

Abstract

Disclosed are a polyvalent carboxylic acid composition and a curing agent composition, each of which reduces the volatilization of a curing agent at the time of curing, and also gives a cured material having excellent heat resistance, optical properties, and moldability. Also disclosed is a curable resin composition containing the polyvalent carboxylic acid composition or curing agent composition. The curable polyvalent carboxylic acid composition and curing agent composition each contain a polyvalent carboxylic acid resin obtained by a reaction between bis(dimethylol)dialkyl ether and an acid anhydride.

Description

201219426 VI. Description of the Invention: [Technical Field] The present invention relates to a polycarboxylic acid composition suitable for use in electrical and electronic materials, a hardener composition, and a composition comprising the same or a hardener composition A curable resin composition of a hardener of an epoxy resin. [Prior Art] Polyoxic acid has high thermal stability, good electrical properties, chemical resistance, etc., and has excellent properties such as formation of a condensate or a reactivity as a crosslinking agent or a condensing agent. It has received much attention as a raw material for polymer manufacturing and has been widely used.

Vi 乃日&#;别〇##, 3% oxy-resin resin composition has been used as a resin with excellent heat resistance, 笙A, 埯^, civil, automotive, aircraft: or 'in recent years, The use in the field of optoelectronics has received attention. The use of electrical wiring (electdc W-) signal transmission, in order to gradually embarrass: a high degree of information and a large amount of information smoothly transmitted and processed, and LE search, therefore, in the field of optical components such as optical waveguides, blue and optical semiconductors, ΦΦ彳畧Η Μ Α It is expected to develop a resin composition which supplies a cured product excellent in the formation of the moon. Through the semiconductor related materials / mobile power $, # % 7 S,,, is used as a camera with light, thin, ^ plasma TV, lightweight notebook computer and other short and small electronic equipment The epoxy resin is used as a sealing material. The four electronic machines are required to have very high characteristics as a sealing material. 4' In the field of light semi-conductor sealing, with the complicated and diversified packaging of 201219426 in recent years, it is more like a forming method by transfer molding, especially in the cutting-edge field. A molding method using a liquid curable resin composition is preferably used. In the case of such an epoxy resin curing agent for such a liquid composition, an amine compound or the like can be mentioned, but the amine compound is difficult to use due to serious coloring. The use of an amine resin or a multi-repulsive resin as an epoxy resin hardener can also provide a cured product which is excellent in knowledge. However, since the shape is solid, it is difficult to use a liquid composition. Therefore, in general, in the above-mentioned field, a hardener of an acid field compound oxygen resin is used, and in particular, an acid field hardened material formed of a saturated hydrocarbon is used for a large amount of light, and the like. Formic acid needle, hexahydro-o-benzene-... Hanging as methyltetrahydro-o-fluorene net-formaldehyde anhydride, tetrahydro-o-benzene-type anhydride, which is used for the treatment of uric anhydride. Liquid methyl octahydro-o-benzate-formic acid liver 1-based tetrahydrophthalic anhydride, etc. However, when the above alicyclic acid anhydride is used as a hardener, the petrochemical agent is partially cleaved due to a high vapor pressure. Hair, so ^ used as a hardener for epoxy resin and (d) put the system for thermal hardening:, - material is sent to the big milk, so that harmful substances are released into the atmosphere: lead to dyeing, adverse effects on the human body, and虞 虞 虞 虞 虞 虞 虞 虞 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Hardened property of performance. The hardening agent of the former hardener is used to seal the LED, especially

S 201219426 is SMD (SurfaceMountDeviee) fl is more significant, because the amount of resin used is small, so due to the previous volatilization problem caused by the depression, in severe cases, the problem of line exposure n due to solder reflow, cracks, If it is peeled off, etc., and the hardening is not sufficient, there is a problem that it is difficult to withstand long-time lighting. Furthermore, in recent years, with the expansion of the LED market, there is a need for a led packaging system that improves mass production. For example, there are liquid transfer molding or shrink forming. These molding methods which use a high-temperature mold to heat-harden a liquid thermosetting resin are useful because they have a short molding time and high productivity. Moreover, if this molding method is used, an arbitrary shape can be given. However, regarding the conventional transparent sealing resin for LEDs, the molding is very difficult, and voids or unfilled portions are generated. When the mold is released, the cured product is deformed and damaged, and there are many problems in the mold release property (patent) Document 3). Therefore, the research will begin with the problem of the durability of the poly-two, the introduction of the table...w modified epoxy tree wax and so on.

The introduction of the table has a Shixia oxygen skeleton (specifically, a resin having W is used as a sealing material (Patent Document 4). Moon wood) Light is more = pass!: Guide... Oxygen skeleton resin is more epoxy than _ light More stable. Therefore, when it is used for LE, the oxygen resin is more excellent in the case of the sealing material of t on the LED wafer. However, the conductivity of the lead is higher than that of the epoxy resin, and the resistance to sulfur and other toxic gases: = lipid and cyclopolymer "tree wax or poly" modified epoxy resin as the second use shape, although the LED chip The coloring of the upper color in the seal material is not a problem', but the following question is asked: 201219426 Question: The silver component plated on the metal lead frame of the component in the LED package body (silver plating is performed to increase the reflectance) Discoloration or blackening due to corrosive gases' ultimately degrades the performance of LED products. There is a demand for a curable resin composition having a structure which is free from the above-mentioned corrosion-resistant gas, and which is a sealing material having high durability against light and heat. Patent Document 1 Patent Document 2 Patent Document 3 曰本特开2003-277473号 曰本特开2008- 063 3 33 曰本特开2010-100793号 Patent Document 4: International Publication No. 2〇〇5/ SUMMARY OF THE INVENTION [Invention] The present invention has been developed in view of the problems of the prior art described above, and its object is to provide a volatilization agent for reducing J/hardening, and further supplying heat, optical properties, and formability. A multi-repulsive composition and a hardener composition of an excellent cured product. Further, the purpose of the present invention is to provide a curable resin composition containing the polycarboxylic acid composition or the hardener, which is a hardener for an epoxy resin. The present inventors have completed the present invention in view of the above. The present invention relates to: [1] a polycarboxylic acid tree represented by the following formula (1): a hardener composition, a mixture of a lipid and an acid anhydride,

S 6 201219426

(1) represents a hydrogen atom (in the formula, a plurality of R and Q existing independently or an alkyl group having 1 to 15 carbon atoms, a carboxyl group); [2] a hardener group of [1], which has more than one existence Each of Q is independently selected from the group consisting of a hydrogen atom's sulfhydryl group and one of the treason groups (but only the compound in which Q is a hydrogen atom) [3] - the hardening of the above [1] or [2] The method for producing a composition is a solvent-free or organic compound in an amount of 5% by weight or less based on the raw material to be used, and 40 to 15 (TC is used to react the above raw materials to obtain hydrazine [4] a polycarboxylic acid. The composition is a mixture of a polyvalent carboxylic acid resin represented by the above formula (1) and a carboxylic acid having two or more functional groups; [5] a polyvalent carboxylic acid composition according to the above [4], wherein the above-mentioned two or more functionalized oxic acids The viscosity of the resin is 10000 Pa·s or less at 251. [6] The polycarboxylic acid composition according to [4] or [5] above, wherein in the above formula (1), a plurality of Q existing are independently selected. Any one of a hydrogen atom, a methyl group, or a carboxyl group (except for a compound in which all q is a hydrogen atom, except for 201219426); m one of the above [4] [6] The method for producing a polyvalent carboxylic acid composition according to any one of [6], which is in the form of a solvent-free or organic solvent in an amount of 5% by weight or less based on the raw material to be used, and is 40 to 15 Torr. [8] The method for producing a multi-repulsive acid composition according to the above [7], wherein the molar ratio of the reaction of the bis(monohydroxyindenyl)dialkyl ether of the starting material with the acid hydrazine is relative to a hydroxy oxime of bis(dihydroxymethyl)dialkyl ether, the carboxylic anhydride group being 1 〇~1 〇〇 mol; [9] a curable resin composition containing the above [丨] to [3] The hardening agent composition of any one of the above-mentioned [4] to [6], and the epoxy resin composition of the above [9], wherein the above-mentioned ring Oxygen resin alicyclic epoxy resin; [11] - The hardened material is cured by the hardening resin of the above [9] or the above [1〇]. x The polybasic acid composition or hardening of the present invention The agent composition is used as a hardener for a ring grease, especially a hardening furnace containing a poly (IV) resin, and the product is usually used to harden the epoxy resin. The temperature region has a very low degree of volatility. It is also excellent in formability and can supply stones with excellent optical properties.

S 8 201219426 Compound. The polyvalent carboxylic acid composition or the curing agent composition of the present invention is used as a raw material for a coating material, an adhesive, a molded article, a semiconductor, a sealing material for a photo-semiconductor, a resin for a photo-semiconductor, or a polyimide resin. The modifier, the plasticizer, the lubricant raw material, the pharmaceutical pesticide intermediate, the coating resin raw material, and the toner resin are useful 'in particular, because the above polycarboxylic acid composition or hardener composition is relative to the cyclic resin Since the hardening ability and the cured product obtained therefrom are excellent in transparency, it is extremely useful as a curing agent for an epoxy resin for sealing an optical semiconductor such as a high-brightness white LED. [Embodiment] The polycarboxylic acid composition or the hardener composition of the present invention contains a polyvalent carboxylic acid resin obtained by a reaction of bis(dimethylol)dialkyl ether with a specific acid anhydride (hereinafter, referred to as The polybasic acid-reducing resin of the invention is not particularly limited as long as it has an ether bond in the molecule, and is specifically a tetraol compound of the following formula as a bis(dihydroxyindenyl)dialkyl ether. (2) the structure listed,

Hc\ JOH

RR (2) 201219426 A compound of this structure can be produced by the dimerization of a triol compound which is a right-handed reaction of an aldol-cannium by an aldehyde compound and formaldehyde (AMol~~ Cannizzar〇) Reacti〇n) and synthesized. Specifically, 2 can be exemplified by 2, 2, a bis(dihydroxymethyl)dipropyl ether, 2,2,bis(dihydroxymethyl)diethyl ether, 2,2,_bis (dihydroxyl) Divalent ether, 2,2-bis(mono- &methyl)dipentyl sulphate, 2,2,-bis(dimethyl)dihexyl bond, etc. It is produced by an addition reaction of an acid anhydride with a bis(dimethyl)dialkyl group. The acid anhydride is a liver having a saturated hydrocarbon structure, and 5' can be exemplified by: hexahydrophthalic anhydride, methylhexahydrophthalic acid liver, bicyclo[2,2, π Gengyuan-2,3-di Formic acid needle, fluorenylbicyclo[2,2,1]g-burning 2,3-dicarboxylic acid liver, cycloheximide m4_tricarboxylic acid-3'4 if, etc. can also be used together, and hexaphthalene benzene alone can be used. The condition of dicarboxylic acid is not good. In the present invention, it is particularly preferred that the acid field is substituted by a burnt group and/or a cyclohexanyl structure having a reductive group in the substituent, and specifically, a cycloheximide tricarboxylic acid-3'4_ liver or a methyl group is exemplified. Hexahydrophthalic anhydride. Here, it is also possible to use hexahydrophthalic acid and, more preferably, singly or in combination with u, 4 -% hexanetricarboxylic acid _ 3,4- hydride and methyl hexahydrophthalic anhydride. The reaction of the acid gf with the bis(dimethyl)dialkyl group is usually an addition reaction of an acid or a solvent, but it is particularly preferred in the present invention to be a catalyst-free reaction. 2 When using a catalyst, as a catalyst that can be used, for example, acidity such as acid, disulfuric acid, methic acid, sultanic acid, p-toluene, acid, nitro-diacetic acid, trichloroacetic acid, etc. Compound, sodium hydroxide, hydrogen

S 10 201219426 Potassium, calcium hydroxide and hydrogen are produced as μxiong & _ emulsified town 4 metal lanthanum oxide, triethylamine, tripropylamine, tributylamine and other amine-based octagonal 匕 物, pyridine, diterpenes Heterocyclic compounds such as arylaminopyridine, 1,8-nitrobicyclo[5.4.G]-deca- 7-thin, (tetra), tri-salt, and tetra-supplement, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Tetrapropyl hydroxide, tetrabutyl sulphate, trimethylethyl hydride, gas oxidized dimercaptopropyl ketone, Lantian Τ'» Α, dimethyl butyl ammonium hydride Trimethyl cetyl sulfonium oxide, trioctylmethyl ammonium oxide II, vaporized tetradecyl ammonium, tetramethyl sulfonium bromide, moth tetramethyl phthyl, tetramethyl ammonium hexaphosphate, trioctyl acetyl acetate Four grades of salt such as methylammonium. These catalysts may be used in combination or in combination of two or more kinds, preferably triethylamine "bite, dimercaptoamine group. The use of the catalyst is not particularly limited, and it is usually preferably 0.001 to 5 parts by weight, based on the total weight of the raw material i (9) by weight. In the present reaction, a solvent-free reaction is preferred, but an organic solvent can also be used in an amount relative to the total amount of the acid anhydride of the reaction substrate and the bis(dimethyl group) dialkyl group. The weight ratio is 0.005 to 1, preferably 〇5 〇·7', more preferably 0.005 to 0.5 (i.e., 50% by weight or less). In the case where the ratio is more than one, the reaction is extremely slow, so it is not preferable. Specific examples of the organic solvent that can be used include an aromatic hydrocarbon compound such as hexane, cyclohexane or heptane, such as benzene or benzene, and methyl ethyl ketone oxime isobutyl ketone. Ketones such as pentanone and cyclohexanone, mysteries such as diethyl ether and flavonoid, and ethyl acetate, butyl acetate, and decyl methacrylate. Further, in the present invention, an acid anhydride or a liquid carboxylic acid resin (or compound) may be used instead of the solvent. 201219426 Here, a method of obtaining the polycarboxylic acid composition of the present invention will be described. As described above, a liquid polyvalent carboxylic acid resin can be used as the substitute solvent, and the liquid carboxylic acid resin is a carboxylic acid resin having two or more functional groups from the viewpoint of curing property and viscosity adjustment, and preferably has a carboxylic acid resin at 25 〇c. 〇〇〇〇Pa.s below the viscosity of the eve of the rebellion 1st tree month. Specifically, it is preferably a reaction product of an acid anhydride and a methanol-modified polyoxo compound as described above. The methanol-modified poly-heavy-oxygen compound can be synthesized, for example, by the method described in JP-A-2007-508424. As a commercially available compound, D〇wc〇rning 5562 (manufactured by Dow Corning Toray), χ22-160- AS, KF-6001 KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), XF42 B0970 (manufactured by Momentive), silaplane FM—4411, FM — 4421, FM — 4425, etc. In the present invention, a compound having a weight average molecular weight of 5 Å to 1 Torr is more preferably used, more preferably 600 to 6,000, and particularly preferably 600 to 2 Å. Also, the optimum range is 600 to 1500. Specifically, a compound of the structure represented by the following formula (3) ch3 -Si-o- (3) is preferable, and particularly, the repeating unit n is preferably from -130, more preferably from 3 to 5 to 80, particularly preferably For 3 5 to 25. Again, the best range

12 S 201219426 is 3.5~丨7.0〇 The reaction temperature is preferably 40 to 200 ° C, and particularly preferably 40 to 15 ° t. In particular, in the case where the reaction is carried out without a solvent, the reaction of (10) t or less is preferable because of the volatilization of the acid anhydride, and particularly preferably 4 g to (10). The reaction of c. If the reaction temperature is too low, there is a problem that it takes time before the reaction, and if the reaction temperature is too high, there is a possibility that the reaction other than the target becomes a coloring. In addition, the 'reaction method' can be carried out by heating or maintaining a certain temperature in an acid anhydride - a method of slowly or splitting the addition of a double (dimethyl group) second-compartment test, and can also be added after the addition. The reaction is carried out at a temperature. In particular, when the reaction is carried out without a solvent, it is preferred to carry out the above method in terms of safety. Thus, the reaction can be carried out under the following conditions to obtain the polyvalent decanoic acid composition of the present invention, and after obtaining the polyhydric carboxylic acid resin of the present invention, it can be mixed with the liquid polycarboxylic acid as the present invention. ~ A tribute to the ruthenium carboxylic acid composition. It is theoretically preferable to adjust the functional group equivalent to the equimolar or the reaction of the upper and lower sides of the base of the U. Yan Wen. For example, when the acid anhydride is set to 1, the red group of bis(dihydroxydecyl)dialkyl ether is 〇.9 to 1.1, preferably 0.9 to 1.05 equivalent. On the other hand, when the hydroxyl group of the bis(dimethyl)monoalkyl ether is set to 1, it is preferred to use the hydroxyl group relative to the bis(dihydroxymethyl)dialkyl ether. The molar carboxylic anhydride group became 1.0~1〇n^w ^ 耳 ear in the manner of adjusting the reaction time of the Moer 201219426 ratio. In the polycarboxylic acid composition of the present invention, the ratio of the polycarboxylic acid ester of the present invention is relative to that of the multi-reading acid resin and the above-mentioned a 2 acid-reducing compound. B 罝 罝 ' is a Buley weight 0 / 〇, preferably 丄 ~ 20% by weight. Here, the method of obtaining the hardener composition of the present invention is said to be a month; ^ the hardener composition of the present invention In the case where the acid needle used is the same as the acid sulphate used in this ', when the force is produced, the reaction is carried out in the excess acid oxime. When the reaction of the acid Sf with the bis(dimethyl)dialkyl ether is completed A mixture of an acid if and a polydecanoic acid of the present invention (a hardener composition) can also be obtained. In this case, it is preferred because the excess acid liver also replaces the solvent of the reaction. In the case of the hardener composition used in the form, it is preferred to compare the specific reaction ratio with the functional group equivalent thereof, and when the acid anhydride is set to 1, the molar ratio is double (dihydroxyindole). The hydroxyl group of the dialkyl ether is preferably in the range of 0.001 to 0.9, more preferably The range of 01 8·8 is more preferably in the range of 〇〇1 to 〇7, and particularly preferably in the range of 〇〇1 to 〇.4. Here, the polycarboxylate of the present invention can also be obtained under the following conditions. After the acid resin, it is mixed with an acid anhydride to form a hardener composition of the present invention. That is, when the polycarboxylic acid resin of the present invention is used as a hardening agent for an epoxy resin, especially when it is used as a liquid composition. It can be mixed with an acid needle to form a hardener composition of the present invention. An acid anhydride which can be used is an acid needle which does not have an aromatic ring in its structure and has a saturated ring structure of 14 201219426. Specifically, it can be cited as six gas. Phthalic anhydride-based hexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[m]heptane: 2,3-dicarboxylic anhydride, fluorenylbicyclo[2'2'i]heptane-2, 3-dicarboxylic acid needle, % hexane-1,3,4-tricarboxylic acid-3,4-anhydride, etc. In the hardener composition of the present invention, the multi-repulsive resin of the present invention: the ratio is relatively The total amount of the above acid anhydride and the polycarboxylic acid resin is reset, and is 5 to 80% by weight, preferably 5 to 65% by weight. The reaction time is also determined by the reaction temperature and the contact temperature. Media and other decisions, but from the point of view of industrial production, the county 0 main pq + e also, long-term reaction due to the consumption of a large amount of energy, and therefore owe. And too short reaction time means that the reaction is severe, safety In terms of the preferred range, it is 48 hours, more than ~36 hours, more preferably i-24 hours. After the reaction is finished, in the case of using the catalyst, respectively, by neutralization, = washing , money ^ _ medium and solvent solvent frequency ^ ^ in the reaction without catalyst, depending on the need to go to the solvent, and then two or two, no catalyst, can not be particularly purified and straight: take out, form制品 The most suitable manufacturing method is 无 without catalyst, ^ ^ ^ ^ ^ 40 ~ loot: make the anhydride, " under the shape of the warranty, in the law. - alcohol reaction, directly after the reaction, after the end

In this way, the eve of the sorcerer's ^ DO color ~ 々 ~ (five): The moon's moon (4) tree material often shows the color of the ~ ~ color solid resin (sometimes crystallized). In the case of the reaction of phthalic anhydride, there are many cases in which the excess is in the form of a heart, and the liquid is not in the form of a liquid. Preferably, 15 201219426 is a polycarboxylic acid resin composed of at least one methyl group or a plurality of groups, preferably more than a plurality of Q, independently selected from the group consisting of nitrogen atom, methyl group, and ruthenium. The polyvalent carboxylic acid resin which is any one (except for the case where only Q is a compound of a gas atom) is preferably a polybasic acid resin composed only of a methyl group and/or a slow group. ^ Especially in the present invention Preferably, the polyvalent carboxylic acid resin is used in the form of a liquid, and is preferably a hardener composition composed of a mixture of a multi-reading resin and a sour liver, or a mixture of a S-acid resin and a liquid tickic acid. The form of the polyvalent carboxylic acid composition is used. When the polycarboxylic acid resin of the present invention is obtained as a solid, it is preferably mixed with (4) or liquid (tetra) acid at a temperature of 15 passages or less and used for compatibility. The curable resin composition contains the hardener composition of the present invention or In the case where the carboxylic acid composition is used as the curing agent, the content of the elemental retinoic resin of the present invention in the curable resin composition is usually 0.02 to 〇5 in terms of a weight ratio with respect to the resin component 1, preferably. The reason for 〇〇2~〇〇 is that if the weight ratio is less than 0.02', the mold release from the mold is deteriorated. If the weight ratio exceeds 0.5, the fluidity at room temperature becomes too low. It is difficult to use it. The polycarboxylic acid composition and the hardener composition of the present invention are excellent in transparency. Therefore, they are used as a curing agent for epoxy resins, coating materials, adhesives, molded articles, and semiconductor resins for sealing materials for optical semiconductors. For the use of a resin for a die-bonding material of a photo-semiconductor, a polyamide or a polyimide resin, a modifier, a plasticizer or a lubricant raw material, a pharmaceutical pesticide intermediate, a resin for a coating resin, and a toner. The tree is useful and useful, especially as a hardener for epoxy resins.

In the case of 16 S 201219426, it is excellent in the hardening ability and the transparency of the obtained cured product is excellent. Therefore, it is extremely useful as a curing agent for epoxy resin which is used for a light semiconductor sealing such as a high-brightness white LED. Hereinafter, the curable resin composition of the present invention comprising the polyvalent carboxylic acid composition or the curing agent composition of the present invention will be described. The present curing agent composition may also contain a curing catalyst, an additive or an inorganic filler as described below. Hereinafter, the curable resin composition of the present invention comprising the polyvalent carboxylic acid composition or the curing agent composition of the present invention is contained. The curable resin composition of the present invention may contain an epoxy resin. Base-[1,1'-biphenyl]-4,4'-monodiol, hydroquinone, alcohol, tris(4-hydroxyphenyl)methane, u, 2,2-four can be used in the present invention Examples of the epoxy resin in the curable resin composition include an acid varnish type epoxy resin, a double 35A type epoxy resin, a biphenyl type epoxy resin, a triphenyldecane type epoxy resin, and a phenol aralkyl group. Type epoxy resin, etc. Specific examples thereof include bisphenol A, bisphenol s, thiodiphenol, bismuth phenol, bisphenol, 4, 4, monophenol, 2,2'-biphenol, 3, 3, and 5, 5, - four armor}, bisexual, naphthalene quaternary (4-hydroxyphenyl) yinyuan (4) (benzene age, benzene, phthalocyanine, phthalocyanine, phthalic acid, hydroxybenzaldehyde, o-hydroxyl Benzaldehyde, p-hydroxyphenylacetamidine, o-hydroxyphenyl dipyridyl naphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde,

Equivalent bisphenols, epoxy propyl ethers derived from alcohols, tetrabromobisphenol 〖Do not, alicyclic 17 201219426 Epoxy tree, epoxy, sesquiterpene oxygen tree Lunar oxime, epoxy propyl ester epoxy tree ring-shaped 'ladder' or the series of milk resin (a mixture of structures having a mixed structure of P 4 ^ or more in a chain structure) and a & It is not limited to these, such as air propyl and / solid or liquid epoxide fresh, " epoxy resin; In particular, in the case of hardening the present invention, it is preferred that the 舆m ruthenium is used for optical use of an oxygen resin, preferably with abundance: a wide resin or an epoxy group-containing polysulfide == oxygen: fat In the case, it is preferred to have an oxidized ruthenium of an epoxy group in the skeleton, and more preferably an epoxy resin obtained by a oximation reaction of a compound having a cyclohexene structure. The alicyclic epoxy resin, It can be exemplified by the deuteration reaction of the cyclohexenecarboxylic acid 'alcohol' with the alcoholic scent, or the cyclohexyl ester (the esterification reaction of 1 τ drunk with the carboxylic acid) ρ 44^Γ〇Ω V〇1·36 P-24〇9(198〇)'Tetrahedron Letter ρ· 75 (1980), etc.), or hexamethylene furfural, the first family of eight: -ion) (曰本特开2〇〇3一17〇) 〇59========================================================================================================== Obtained by oxidation, etc. = = 'As long as it is a compound having an alcoholic base group, there is no particular limitation'. Ethylene glycol, propylene glycol, ... Glycol, hydrazine, 2-butanediol, 'butanol, 1> 5-pentanediol, hydrazine, 6-hexanediol, cyclohexanedimethanol, etc.: alcohols glycerol, trimethylmethyl Ethylene, Sanjing, Methylamine, Sanjing, Dip, 2-Methyl-i,4-butanediol, etc., neopentyl alcohol, etc.

S 18 201219426 Alcohols, etc. Further, it is not limited to those of citric acid, butadiic acid, phthalic acid, acid, isophthalic acid, and hexanic acid; and dicarboxylic acid and trans-formic acid.夂, 环 院 院 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二As a reaction method, a cellulization reaction can be produced, for example, a method of removing a solvent such as toluene or xylene in a medium (U.S. Patent No. 2), in concentrated hydrochloric acid. After the alcohol, the method of slowly adding the side of the mixture to carry out the reaction is carried out (the method of using the water in the reaction medium) (U.S. Patent No. 3092640); use in the reaction medium A method of using an organic solvent (Japanese Patent Laid-Open Publication No. Hei 7-215979); a method using a solid acid catalyst (Japanese Patent Laid-Open Publication No. Hei 20-23-23992). A cyclic acetal structure is preferred in terms of structural stability. Further, an alicyclic polyene oxide such as vinylcyclohexene or limonene, dicyclopentadiene, monopentylene, methyl dicyclopentadiene, dicyclohexene or octadiene may be oxidized. Adults and so on. Specific examples of such epoxy resins include ERL·-422 1 and ERL·4299 (all of which are trade names, all manufactured by Dow Chemical), EPOLEAD GT401, EHPE3150, and EHPE3150CE (all of which are trade names, all of which are Daicel). Chemical industry manufacturing, and dicyclopentadiene diepoxide temple, but not limited to these (Reference: General Epoxy Resin, Basic Section I, p76-85). These may be used singly or in combination of two or more. 201219426 The epoxy resin having a sesquisoid structure is not particularly limited as long as it is an organic core m having an epoxy ring structure, and in the present invention, /, Oxygen cyclohexyl alkoxy 7 is a compound obtained by a sol-gel reaction of a raw material. As for the eight-body and S, the Japanese Patent Publication No. 2004-256009, the Japanese Patent Publication No. 2-346144, and the International Publication No. 2004/072150 'Japan Special Employment No. 8747, International Publication No. 2006/ 〇03990 No. 2, Japanese Patent Publication No. 2_- 1() 4248, International Publication No. 7/59〇9, Japanese Patent Laid-Open No. 2GG4__1() 849, Japanese Patent Laid-Open No. 359933, and International Publications A sesquiterpoxy-type organopolyoxane having a three-dimensionally expanded network structure as described in Japanese Laid-Open Patent Publication No. Hei. The structure of the sesquitercene gas is not particularly limited, but since the simple three-dimensional network structure is made of money, the (four) compound is harder than the present invention, and it is particularly preferable to have the poly stone in the U. The above-mentioned sesquiterpene oxide, structural block structure obtained by the gel-gel reaction. As a manufacturing method of such a compound, the manufacturing method and structure as described in International Publication No. 2010/026714 are mentioned. In the curable resin composition of the present invention, the polybasic acid-reducing composition or the hardener composition of the present invention may be used in combination with other hardeners. When used in combination, the ratio of the multi-enzyme resin of the present invention to all the hardeners is preferably 2 g% by weight, more preferably 30% by weight or more. Examples of the curing agent which can be used in combination with the polyvalent tick acid resin of the present invention include an amine compound, an acid needle compound having an unsaturated ring structure, and a brewing amine system:

S 20 201219426 A compound, a quinone compound, a drum acid compound, and the like. Specific examples of the hardener which can be used include diaminodiphenylmethane, di-extension ethyltriamine, tri-extension ethyltetramine, diaminodiphenylsulfone, isophora-diamine, and second atmosphere. Polydiamine resin synthesized from dimeramide and linoleic acid and polydiamine resin synthesized from ethyl diamine, phthalic anhydride, trimellitic anhydride, dihydroartanic acid, maleic anhydride, Tetrahydrophthalic anhydride, methyltetrahydron-dodecanoic acid needle, Nadie methyl anhydride, benzoic acid anhydride, hexa- phthalic anhydride, decyl hexahydrophthalic acid Anhydride, butane tetracarboxylic acid needle, bicyclo[2,2,1]heptane-2,3-diphthalic anhydride, methylbicycloheptane-2,3-diphthalic anhydride, cyclohexane-1,3,4 Tricarboxylic acid _3,4-anhydride, double a, bisphenol F, bisphenol S, bismuth bisphenol, bisphenol, 4,4, bisphenol, 2,2, bisphenol, 3'3 ',5,5,tetramethyl-[1,1,biphenyl]-4,4,-diol, p-diphenol, resorcinol, naphthalenediol, tris-(4-hydroxybenzene) Methane, m2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl group) Phenol 'naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyl Acetophenone, dicyclopentadiene, furfural, 4,4, a double (gas methyl)-1,1,biphenyl, 4,4-bis(methoxymethyl)-u,-linked a polycondensate of benzene, p p bis(chloroindenyl)benzene, 1,4, bis(decyloxy)benzene, and the like, and a modified bisphenol or imidazole such as tetrabromobisphenol A And a boron trifluoride amine complex, an anthracene derivative, a condensate of a olefin and a phenol, etc., but it is not limited to these. These may be used alone or in combination of two or more. In the curable resin composition of the present invention, the ratio of the hardener to the epoxy resin is equivalent to the epoxy group equivalent of the entire epoxy resin, preferably 〇曰5 21 201219426 1 · 5 equivalents (the carboxylic acid is set It is monofunctional, and the acid anhydride is made into a hydrazine functional group, and it is especially preferably 0.5 to 1.2 equivalent. When the equivalent of the epoxy group is less than 5 equivalents or more than 1.5 equivalents, the hardening is incomplete and good hardening properties are not obtained. In the curable resin composition of the present invention, a hardening accelerator and a curing agent may be used in combination. Specific examples of the hardening accelerator which can be used include 2-methylimidazole, 2-phenylimidazole, 2-|--imidazole, and 2-|-heptylimidazole 2 -phenyl- 4 —Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-mercaptoimidazole, cyanoethyl-2-mercaptoimidazole, 1-cyanoethyl-2-phenylimidazole, 1 —Cyanoethyl- 2,11-imidazolium, 2,4-diamino- 6 (2'-methylimidazolium (1,)) ethyl---Sansui well, 2,4-diamino- 6 (2'-undecyl imidazolidinyl--three-till, 2,4-diamino-6(2,-ethyl-4-methylimidazolium (1,)) ethyl--three wells, 2, 4-diamino- 6 (2'-nonyl imidazolium ethyl one homotrioxane _ iso-cyanuric acid adduct, 2 monomethylimidazoisocyanuric acid 2:3 adduct, 2 —Phenyl imidazole iso-cyanuric acid adduct, 2-phenyl- 3,5-di-methyl-methyl. Sodium, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1- Various flavors of cyanoethyl-2-phenyl- 3,5-dicyanoethoxymethyl imipenoids, and the likes of phthalic acid and isophthalic acid and isophthalic acid a salt of a polycarboxylic acid such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid or oxalic acid, or a guanamine such as dicyanodiamine. a diazonium compound such as 8-diazinobicyclo(5.4.0)-carbon-7-ene and a salt such as tetraphenylborate or a phenol novolac, and the above polycarboxylic acid or phosphinic acid ( Phosphate acid) salts, tetrabutylammonium bromide, cetyltrimethylammonium bromide, > stinky

22 S 201219426 =—octyl sulfonium sulphate, triphenylphosphine, tris(methylphenyl)phosphine, evolution tetraphenylphosphine, tetraphenylphosphine tetraphenylborate, etc. Phosphides or phosphonates, one or two A phenol such as an aminomethylphenol, an amine adduct, a metal compound such as tin octylate, or the like, and a microcapsule-type hardening accelerator obtained by using the curing accelerator as a microcapsule. Which of these curing accelerators is used is appropriately selected depending on the properties required for the transparent resin composition obtained by, for example, transparency, curing rate, operating conditions and the like. The hardening accelerator is used in a range of usually from 1 to 15 parts by weight based on the weight of the epoxy resin i 〇 。. The curable resin composition of the present invention may further contain a phosphorus-containing compound as a component imparting flame retardancy. The phosphorus-containing compound may be reactive or may be added. Specific examples of the phosphorus-containing compound include trimethyl sulphate, triethyl phosphate, tricresyl phosphate, tris(diphenylene) phosphate, tolyldiphenyl phosphate, and phenylphosphine phenyl 2,6. - bis(xylene) vinegar, 1,3 -phenylene bis(di(xylylene) phosphate), 1,4 phenylphenyl bis(xylylene phosphate), 4,4' biphenyl Phosphate (di(xylylene) phosphate), 9,10-dihydro- 9-oxa-10-filled phenanthrene-10-oxide ^"❹一口丨!!}^!·. — oxa — 10 — phosphaphenanthrene — 10 — oxide) '10(2,5-dihydroxyphenyl)-10H-9-oxa-l-phosphonium-phenanthr #10-oxide (10 — (2,5 — Dihydroxyphenyl) — 10H — 9 — oxa — 10 — phosphaphenanthrene — 10—oxide) A phosphorus-containing epoxy compound such as phosphine, which is obtained by reacting an epoxy resin with an active hydrogen of the above phosphine; Ester, phosphine or phosphorus-containing epoxy compound 'is especially 1,3 -phenylene bis(xylylene) phthalate), fluorene, 4-phenylene bis(sodium succinate) Xylene) ester, 4,4, a biphenyl (di(diphenylene) ester) or a ring-containing oxide 23 201219426. The content of phosphorus compounds is higher than human = 01 ~ f) 6 曰, It is a phosphorus compound/all epoxy resin °·1 0.6 (weight 1 ratio). If the husband violates ^, Α Λ < 禾达 ο.1, the flame retardancy is not sufficient, if it exceeds 0.6 ', there is a hardened material. The possibility of the wetness and the dielectric properties may be adversely affected. Further, in the curable resin composition of the present invention, an antioxidant may be added as needed. The antioxidant which can be used in the preparation of the resin may be exemplified. The antioxidant is used alone or in combination of two or more. The antioxidant is used in an amount of 1 to 0 parts by weight based on the resin component in the curable resin composition of the present invention. The amount of the antioxidant is preferably 0.01 to 0.5 parts by weight. Examples of the antioxidant include, for example, an age-based antioxidant, a sulfur-based antioxidant, a condensed antioxidant, etc. As a specific example of the anti-oxidant, It can be exemplified by 2,6-di-tert-butyl-p-butyl butyl butyl group Di-tert-butyl-p-ethylphenol, stearyl-gluten-(3,5-di-t-butyl-tetra- 4-hydroxyphenyl)propionate, isooctyl-3 _(3,5-di Tert-butyl-4-hydroxyphenyl)propionate, 2,4-di-mono(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-i,3 , 5 - San Geng' 2,4_bis[(octylthio)methyl]-o-cresol and other monophenols; 2,2,monodecyl bis (4-indolyl-6-t-butyl) Phenol), 2,2·-methylenebis(4-ethyl-6-t-butylphenol), 4,4-thiobis(3-methyl-6-t-butylphenol) 4, 4, monobutylene (3-fluorenyl-6-tert-butylphenol), triethylene glycol-bis[3 - (3 - 2 -butyl-5-indenyl-4-hydroxyphenyl) Acid ester], 1,6-hexanediol-bis[3 - (3,5-di-t-butyl-4-cyclohydroxyphenyl)propionate], n, n, /, methylene double (3 , 5-two second butyl _4 mono-based phenyl propyl amide, 2, 2

S 24 201219426—Sulfur-diethyl-ethyl bis[3—(3 5—a =-di-butyl-4-hydroxyphenyl)propanol], 3,5-di-tert-butyl-4 - Λ some Λ J丞4 hydroxy 卞 膦 膦 膦 膦 一 一 一 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Surface - ς - methyl phenyl) propionate oxime λ λ1_248 soil semi-ethylene burst J 2 '4,8,10-tetraoxaspiro[5,5] eleven, double (3,5 - two Third butyl-4, fluorenyl benzyl hexanoate, about bisphenols; 1,1,3-tris(2-indolyl-4) 钸 ς Τ丞 Τ丞 4 包基五—Third butyl phenyl” butadiene, 1,3,5 —trimethyl—246 — : ί35 — — β — “+ ', 〇 卩, 5 第三 butyl butyl 4-hydroxyl group) Benzene, tetrakis[methylene-3-(3,5,2-di-tert-butyl-4,-hydroxyphenyl)propionic acid vinegar], bismuth, bis[3,3,-bis-(4, once —-3,-t-butylphenyl)acid]dicool,:- λ*· -- -- w a J ^Sa —(3,5-one second butyl-4-hydroxybenzyl)_ Heterodimeric decanoic acid, 1,3,5 — ·=("3,51— · flute-τι λ 5 ~y5 ^ A second butyl- 4, monohydroxybenzyl) _ three-plowed 2,4,6- (1H,3H,5H) triketone, tocopherol and other high molecular phenols. Specific examples of the sulfur-based antioxidant include 3,3·-thiodipropionic acid dilaurin S曰3, 3 thiodipropionic acid dimyristyl ester, and 3,3'-thiodipropionic acid di-hard. Lipid esters, etc. Specific examples of the scaly antioxidant include triphenyl phosphite, sulfonium sulfonate, phenyl diisoindole sulphate, and tris(nonylphenyl) sulfite. Diisodecyl neopentyl alcohol phosphite, tris(2,4-dibutyl butyl phenyl) phosphite, cyclic bis(octadecyl) pentaerythritol phosphite (Cyclic neopentanetetraylbis (Cyclic neopentanetetraylbis) Octadecyl)phosphite), cyclic bis(2,4-di-tert-butylphenyl)neopentitol phosphite, cyclic bis(2,4-dibutylbutyl-4-indenylphenyl) Neopentyl phosphite phosphite, hydrogen bisphosphite [2 - second butyl ~ 6 - methyl - 4 - {2 - (octadecyloxycarbonyl) ethyl} stupid 25 201219426 base] vinegar and other phosphorous acid Ester; 9,1 〇~2& oxide, 10-(3 5 — _wind oxa 〇 〇 磷 磷 磷 - - - - - - - - - - - 经 - - 经 经 - - - - - ) ) ) ) ) ~. - 9,10-dihydro-9-oxo oxide, 10-decyloxyphosphorus oxide, and the like. L, phenanthrene ~ 10 Oxide, etc. These antioxidants can be used alone. In particular, in the present invention, it is also possible to combine two or more kinds of them into a dish-based antioxidant. Further, in the hardening of the present invention, it is also possible to add a sturdy sputum agent to the composition of the sputum. As a light stabilizer, it is considered to be a hindered amine light stabilizer, especially HALS. HALS, there is no special limit to 'as a representative, one earth amine · 丄, 3, 5 - three wells · N, N, a pair (2, 2, 6, 6 - four two two bottom bite a polycondensate of hexamethylenediamine and n-(m-tetrakisyl-4-(4-yl)butylamine, dimethyl-petroethyl)-4-thiol ―2,2,M—Tetramethyl ♦ Qiang, poly... ~ (1,1,3,3-tetradecylbutyl)amine 1^5—three wells—2,4—diyl}{ (2'2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene U2,2,6'6-tetramethyl-4-piperidinyl)imine}] , bis(1 2 2,6 6-pentamethyl~4-piperidinyl)[[3,5-bis(M-dimethylethyl)-4-hydroxyphenyl]indolyl]butylpropane Acid ester, bis(2,2,6,6-tetramethyl-4(piperidinyl), oxime oxime 'bis(1,2,2,6,6-pentamethyl- 4- 〇 bottom ° Alkalic acid vinegar, bis(octyloxy-2,2,6,6-tetramethyl- 4 - fluorene base) azelaic acid vinegar, 2 - (3'5 a second butyl- 4 Monobenzyl (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, etc., of benzyl))-n-butylmalonate. HALS can be used alone or in combination of two or more.

S 201219426 Further, in the curable resin composition of the present invention, an adhesive resin may be added as needed. As the viscous + % | Μ | τ / ~ part of the tree, the butadiene resin, acetal resin, acrylic resin, iS g · tree such as % 虱 nylon resin, NBR - phenol system Resin, epoxy - NBR system, polyamine resin, polyimide resin, polyoxyn resin, etc. 'but are not limited thereto. The blending amount of the adhesive resin is preferably a range of flame retardancy and heat resistance of the non-destructive hardened material, and is 16/>1!» /im Λ to the range with respect to the hardening property. The cutting is usually carried out using 0.05 to 5 parts by weight, preferably 0.05 to 20 parts by weight. In the curable resin composition of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include crystalline vermiculite, molten vermiculite, alumina, vermiculite, calcium niobate, calcium carbonate, niobium carbide, tantalum nitride, niobium, oxidized, olivine, and talc. a carcass such as spinel, titanium dioxide or talc, or a granule formed by spheroidizing the particles, etc., but is not limited to square, and black. 5 Xuan and other filling materials can be used alone or in combination of two or more. The content of the inorganic filler is from 0 to 95% by weight in the curable resin composition of the present invention. Further, in the curable resin composition of the present invention, a decane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate or calcium stearate, a surfactant, a dye, a pigment, and an external line may be added. Various preparation agents such as absorbents and various thermosetting resins. When the curable resin composition of the present invention is used for a photo-semiconductor encapsulant, a phosphor may be added as needed. A fluorescent system, for example, has the effect of forming white light by absorbing a portion of the blue light emitted from the blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in the curable resin composition in advance, the photo-semiconductor is sealed. 27 201219426 The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include a rare earth element aluminate and a thiogallate salt; More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, an orthophthalate phosphor, a thiopentate phosphor, or a sulfide phosphor may be mentioned, and YA1〇3 may also be mentioned: Ce, Y3Al5〇i2: Ce, Y4Al2〇9: Ce, Y2O2S · Eu, Sr5(P〇4)3C1: Eu, (SrEu)O · Al2〇3, and the like. The particle diameter of the related phosphor is a particle diameter known in the art, and the average particle diameter is preferably from i to 25 〇em, particularly preferably from 2 to 5 〇 ym. In the case of using these phosphors, the amount thereof is from 1 to 8 parts by weight, and preferably from 5 to 60 parts by weight, based on 1 part by weight of the above resin component. The curable resin composition of the present invention is obtained by borrowing, knife, and sputum. The curable resin composition of the present invention can be easily formed into a cured product by the same method as previously known. For example, the following method may be used: an epoxy resin and a hardener of the present invention, and optionally a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent, if necessary, using an extrusion crucible, a kneader, a roll, or the like. When it is sufficiently mixed until it is uniform, a curable resin composition is obtained. When the curable resin composition is in a liquid state, it is filled (p (ming) or material, impregnated into a substrate, and composed of a curable resin. The mold of the distributor is cast and molded and hardened by heating. When the curable resin composition is solid, the mold is molded by casting, or molded by using a transfer molding machine, and the like. It is hardened by heating. The curing temperature and time are '80~20 (rc, 2, the method of hardening and hardening, it can be solidified once at a certain temperature, but it is preferable to gradually heat up and harden the reaction. Specifically Talk

S 28 201219426 Initial hardening is carried out at l〇〇°C~20 (post-hardening between TCs. The stage of hardening is preferably divided into 2 to 8 stages for temperature rise, more preferably 2 stages. The curable resin composition of the present invention is dissolved in toluene, xylene, acetone, mercaptoethyl ketone, decyl isobutyl ketone, dimethylformamide, dimercaptoacetamide, N-decylpyrrolidine A curable resin composition varnish is formed by a solvent such as a ketone, and is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a preform (prepreg) The preform is subjected to hot press forming, whereby a cured product of the curable resin composition of the present invention can be formed. At this time, the agent is used in the mixture of the curable resin composition of the present invention and the solvent = The amount is usually from 1 to 70% by weight, preferably from 15 to 7% by weight. Further, the liquid composition can also directly obtain a ring-hardened product containing carbon fibers by RTM. The curable resin composition is used as a bismuth type composition The modifier of the substance may be used in particular in the case of improving the flexibility or the like in the step B. The film-type resin composition is obtained by using the curable resin composition of the present invention as a curable resin composition varnish. The form is applied to a release film and the solvent is removed by heating, and then B is obtained as a sheet-like carrier. The 兮H d # edge layer. The chip-like connector can be used as a multilayer substrate or the like. The interlayer between the layers is described in detail as a case where the curable resin composition of the present invention is used as a photo-semiconductor (tetra) material or a die-bonding material. The curable resin composition of the present invention is used as a high-brightness white color! 29 201219426 In the case of a sealing material or a die bonding material of a photo-semiconductor, the crucible composition or the polycarboxylic acid composition containing the polycarboxylic acid resin of the present invention, and a hardening accelerator other than the epoxy resin, coupling A material such as a material antioxidant or a light stabilizer is sufficiently mixed to prepare a curable resin composition, which is used as a sealing material or both for a die bonding material and a sealing material. Using a kneader, a three-roll mill, a universal mixer, a planetary mixer, a homogenous mixer, a homogenous disperser, and a bead mill are equal to normal temperature or heating mixing. Optical semiconductor components such as local brightness white LEDs are usually made of an adhesive. (Crystalline material) GaAs, GaP, GaA丨As, GaAsp, inp, etc. laminated on substrates such as sapphire, spinel, sic, &

A semiconductor wafer such as InN AIN or InGaN is connected to a lead frame or a heat radiating plate or a package to form a current flowing therethrough. Therefore, a wire such as a gold wire is also connected. In order to prevent the heat or moisture from damaging the semiconductor wafer and causing it to function as a lens, it is sealed with a sealing material such as an epoxy resin. The curable resin composition of the present invention can be used as the above-mentioned sealing material or die-bonding material. In the step, it is preferred to use the curable resin composition of the present invention for both the die bonding material and the sealing material. By using the curable resin composition of the present invention to bond a semiconductor wafer to a substrate, the semiconductor wafer can be placed and heat-hardened by applying a curable resin composition of the present invention to a small-filled or screen-printing method. Next, the semiconductor wafer can be heated by a method such as hot air loop type, infrared ray, high frequency, etc. The heating condition is, for example, preferably 80 to 23 (TC, i minutes to 24 hours or so.

S 30 201219426 Internal stress generated during heat hardening, for example, after pre-hardening under conditions of 8 〇 to izu 匕, 3 〇 minutes to 5 hours, at 12 〇 to 18 代, 3 〇 minutes to 10 hours After the hardening. In the molding method of the blade sealing material, an injection method in which a sealing material is injected into a mold to which a semiconductor wafer is fixed is inserted, and then heat-hardened and molded is formed; a sealing material is previously injected into the mold to be fixed to the substrate. After the semiconductor wafer is immersed therein and heat-hardened, the compression molding method such as demolding from the mold is performed. As the injection method, a dispenser, a transfer molding, and an injection molding can be cited. For heating, hot air loop type, infrared light, high frequency, etc. can be used. The heating conditions are, for example, preferably from 80 to 23 Torr, from 1 minute to 24 hours. In order to reduce the internal stress generated during heat hardening, for example, after pre-hardening under conditions of 8 〇 to WC for 30 minutes to 5 hours, post-hardening is carried out under conditions of (3) to 18 〇C '30 minutes to 1Q hours. . Further, the curable resin composition of the present invention can be used for a general use of an epoxy resin/thermosetting resin, specifically, an adhesive, a coating agent, a molding material (including a sheet, a film, a book, etc.). In addition to the sealing material, the insulating material: a printed circuit board, a wire coating, or the like may be used, or a composition of a sulphuric acid vinegar resin for a substrate or a resist may be used. An additive added to another resin such as an acrylic vinegar-based resin as a chemical agent is used as an adhesive agent. In addition to civil engineering, construction, automotive, general use, and medical adhesives, an adhesive for electronic materials may also be mentioned. /Specialized, as an adhesive for electronic materials', it can be mentioned as a layer (buUd) 31 201219426 A layer of a multilayer substrate such as a substrate is indirectly b. An adhesive for a conductor, a BGA is strong... An underfill such as an underfill is barely used. An adhesive for mounting such as a ruthenium filler, an anisotropic conductive film, or an anisotropic conductive paste (ACP). Light 2: Two sealants, for example, capacitors, transistors, diodes, hair (four) seals, 'IC, LSI, etc., dipping, transfer, and 'C' or LSI class C〇B , COF, TAB, etc. used in the dressing = seal: crystallized " used, underfill 'qfp, bga and csp, the seal of women's wear (including reinforcing underfill). The present invention obtained by curing the curable composition of the present invention can be used for various materials represented by optical member materials. The term "light = material" generally refers to a material used for the purpose of passing visible light, infrared rays, ultraviolet rays, X-rays, and '4 prior to passing through the material. More specifically, in addition to the sealing material for LEDs such as a lamp type or an SMD type, it may be mentioned. Examples of the liquid crystal display device such as a substrate material in the field of a liquid crystal display, a light guide plate, a lens, a polarizing plate, a phase difference plate, a viewing angle correction film, an adhesive, and a liquid crystal film such as a polarizing film can be used. In addition, I cite the sealing material for the color of the lower-generation flat panel display, the anti-reflection film 'optical correction film, the outer casing material, the front film glass, the front plate glass substitute material, and the adhesive'. The molding material of the LED used in the display device, the sealing material of the coffee, the protective film of the front glass, the replacement material of the front glass, and the adhesive, and the substrate of the electropolymerization solution Ba (PALC) Material 'light guide plate, prism sheet' deflecting plate, phase difference plate, field of view 3 minus angle> positive film, adhesive, polarizing element protective film', and the front plate glass in organic EL (electroluminescence) display

S 32 201219426 Protective film, front glass substitute material, and adhesive, and various film substrates in the field emission display (FED), a protective film for the front glass, a front glass substitute material, and an adhesive. In the field of optical recording, VD (disc), CD/CD-R0M, CD-R/RW, dvd_r/Dvd-ram, MO/MD, PD (phase change disc), optical disc substrate material, optical disc player A pickup lens, a protective tape, a sealing material, an adhesive, and the like. The lens material for a static camera can be cited in the field of optical equipment, such as a hall, a device, a target, a viewfinder cover, and a light-receiving sensor. Further, a photographic lens and a viewfinder of a video camera can be cited. ^: List the projection lens, protective film, and sealing material of the projection TV: the connector j and the like. Examples of X's include a lens material for a light sensing device, a sealing material, a connector, a film, and the like. In the field of optical components, the fiber materials, lenses, waveguides, sealing materials for components, adhesives, etc., which are surrounded by optical switches of the optical communication system, are listed as optical fiber materials and ferrules around the optical connector. Seal (four), and then feed. In the light (4) member and the optical circuit member, the sealing material of the mirror, the waveguide, the LED, the sealing material of the CCD, and the sealing material of the CCD can be cited as the substrate material around the photoelectron integrated circuit, the sealing material of the fiber component, and the adhesive. Wait. In the field of (4), it can be listed as: 传 传, 1 illuminator for illumination, f-light tube, etc., sensor type for industrial use, device dioxin, etc., and digital LSI and super LSIM field for communication infrastructure and home use. Among the materials surrounding the body circuit, a resist material for micro-etching technology can be cited. In the field of automobiles and transport aircraft, the reflector lamps of steam (4) can be cited (ia...e thin (4), shaft 33 201219426 bearing retainer headlights, engine internal components, corrosion resistant sleeves, switch parts, sides - end Wire harnesses and fuel hose towel materials can be used as a substitute for multi-layer glass for railway vehicles. In addition, it is a kind of structural glass of the aircraft. Also, the structural materials of the aircraft: two raw materials: pre-agent, engine peripheral components, protection - End set. In the field of construction, it can be used to display the interior of the touch, the processing materials, the lampshade, the sheet, the glass, the glass, the glass, the solar cell, and the solar cell. The film for coating, as a material for the next-generation optical and electronic device, includes an organic EL element peripheral material, an organic light refractive element, an optical amplifying element of an optical-to-optical conversion device, an optical calculus element, and a substrate material surrounding the organic solar cell. Fibrous material, sealing material of the element, adhesive, etc. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, and the following description refers to the weight unless otherwise specified. Further, the present invention is not limited to the embodiments.

Further, in the examples, the measurement by a gel permeation chromatography (hereinafter referred to as "GPC") is as follows. The column is made of Sh〇dex SYSTEM—21 column (KF—803L, KF—802.5 (χ2), KF—802), and the washing liquid is connected with tetrahydrofuran at a flow rate of 1 ml/min and the column temperature is 40 C. 'The test was performed on RI (Reflective Index) and the calibration curve was made using standard polystyrene manufactured by Shodex. In addition, the functional group equivalent is calculated based on the ratio calculated by GPC.

S 34 201219426 A value obtained by setting the carboxylic acid and the acid anhydride to 1 equivalent. Example 1 A nitrogen purge was carried out on a flask equipped with a stirrer, a reflux cooling tube, and a stirring apparatus, and 2,2,-bis(dihydroxymethyl)dipropyl ether (manufactured by Perstorp) was added at room temperature. , Di-ΤΜΡ) 1 part, methyl hexahydrophthalic anhydride (hereinafter referred to as acid anhydride Hi) 95 parts, hexahydrophthalic anhydride (hereinafter referred to as anhydride H2) 5 parts, and at 80 ° C The mixture was heated and stirred for 8 hours, whereby 11 parts of a hardener composition (B1) containing the polycarboxylic acid resin (A1) of the present invention and an acid anhydride (H1, H2) was obtained. The obtained product was a colorless liquid resin. The viscosity at 25 ° C is 120 Pa·s. Further, as a raw material, 2,2,-bis(dihydroxymethyl)dipropyl ether and an acid anhydride are reacted at the molar ratio relative to each other, 2,2 bis(monomethylol)dipropyl ether. The hydroxyl group is 1 mole and the carboxylic anhydride group is 3.9 moles. Example 2 An acid anhydride (H1) was added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring apparatus while adding a volume of an acid anhydride (H1), and the temperature was raised to 9 Torr (>c, and then added 2 times in 2 hours. 2,-bis(dihydroxymethyl)dipropyl ether (manufactured by Perst〇rp, Di-TMP) 1 part, and then directly mixed with thief for 5 hours, thereby obtaining a polycarboxylic acid resin containing the present invention (A2) 110 parts of the hardener composition (B2) with an acid anhydride (Hi). The obtained resin is a colorless liquid resin. The viscosity at 25 ° C is 118 Pa·s. Further, as a raw material 2, 2, _ The molar ratio of bis(dihydroxymethyl)dipropyl ether to the anhydride is hydroxy oxime relative to 2,2,_bis(dihydroxymethyl)dipropyl ether, and the carboxylic anhydride group is 37. Example 3 35 201219426 Adding an acid anhydride (Η 1 ) to a flask containing a stirrer, a reflux cooling tube, and a mixing device while adding an acid anhydride (Η 1 ) 168 parts, methanol modified poly-stone oxygen (manufactured by Shin-Etsu Chemical Co., Ltd., X— 22 — 160 — AS, the following general formula (3)) 488 parts 'react at 70 ° C for 8 hours, thereby forming a liquid carboxylic acid (hereinafter referred to as After C 1 ) (viscosity at 25 ° C is 1050 mPa · s), after heating to 90 ° C, add 6.8 parts of anhydride (Η1 ) and stir for 30 minutes, then add 2, 2 in 2 minutes in 30 minutes. 'One double (dimethyl) dipropyl (manufactured by Perst rp, Di- ΤΜΡ) 6.26 parts, heated and stirred directly at 90 ° C for 5 hours, thereby obtaining a polycarboxylic acid resin (A2) containing the present invention 679 parts of a polycarboxylic acid composition (B3) with a liquid polycarboxylic acid (C1). The obtained resin is a colorless liquid resin, and has a viscosity of 2960 mPa·s at 25 ° C. Further, it becomes a raw material 2 , 2, a double (dihydroxymethyl) dipropyl ether and an anhydride in the reaction of the molar ratio relative to 2, 2, a double (dihydroxymethyl) dipropyl ether hydroxyl 1 molar, carboxy The anhydride group was 1.0 mole.

In the above formula, 'η represents the average number of repetitions' and the value of η calculated based on the measurement results of the gel permeation chromatograph is about 8.6. Example 4 An acid anhydride (Η1) was added to a flask equipped with a stirrer, a reflux cooling tube, and a mixing device while adding an acid anhydride (Η1) 2 0 1 _ 6 parts, methanol modified polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-160) -AS) 488 parts, 2,2'-bis(di-pyridyl)dipropyl shim (manufactured by perst〇rp, Di-TMP) 12.5 parts,

S 36 201219426 8 0 ° C reaction for 8 hours, thereby obtaining 702.1 parts of the polycarboxylic acid composition (B4) containing the polyvalent carboxylic acid resin (A2) of the present invention and the liquid polycarboxylic acid (C1). The obtained resin was a colorless liquid resin. The viscosity at 25 ° C is 2880 mPa·s. Furthermore, the molar ratio of 2,2'-bis(dihydroxyindenyl)dipropyl ether to the acid anhydride in the reaction is relative to 2,2'-di(dihydroxymethyl)dipropyl ether. The hydroxyl group is 1 mole and the carboxylic anhydride group is 1.0 mole. Synthesis Example 1 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was carried out while adding 丨, 4-cyclohexane diacetate (Nippon Chemical and Chemical Manufacturing Co., Ltd. 'SKY-CDM) 1 aliquot, anhydride (hi) One part was heated and mixed at 60 ° C for 4 hours to obtain a comparative hardener composition (b5 ). Synthesis Example 2 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 1 part of 1,6-hexanediol and 1 part of hydrazine were added while heating with nitrogen gas at 60 ° C. After mixing for 4 hours, 110 parts of the hardener composition (B6) for comparative use was obtained. Synthesis Example 3 &amp; A flask equipped with a stirrer, a reflux cooling tube, and a stirring device was subjected to nitrogen rinsing while adding water hydrazine, cyclohexenyl fluorenylcyclohexene decanoic acid hydrazine, 14 parts, 12 - 1 part of phosphotungstic acid, 1 · 5 parts of sodium tungstate, 1.5 parts of disodium hydrogen phosphate, # y y ^, and 50% of xylene solution of trioctyl ammonium acetate. For K parts, the solution was warmed to 45 ° C, and 35 parts of hydrazine/hydrazine was added for 20 minutes. <110 parts of hydrogenated hydrogenated water were kept at 45j: 5t and stirred for 12 hours. 37 201219426 .. After neutralizing with a 1 weight 〇/〇 gas oxidized steel aqueous solution, 20 weights were added. /. 25 parts of an aqueous solution of sodium thiosulfate was given for 3 minutes and allowed to stand. The organic layer separated into two layers was extracted, and activated carbon (manufactured by Fine-Techno, CP1), 5 parts, and montmorillonite (manufactured by Kunipia F) were added thereto, and after three hours at room temperature (four), the mixture was subjected to hydrazine. The obtained mash was washed with water 10 G injury 3 : owed, and the obtained organic layer was made to be toluene', thereby obtaining 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylformate (EP1) 111 copies. The epoxy equivalent of the obtained epoxy resin was /eq. The viscosity at 25 ° C is 2l! mPa · s (E-type viscometer). Synthesis Example 4 106 parts of 10,000-(3,4 epoxycyclohexyl)ethyltrimethoxy decane and a methyl phenyl group of a decyl alcohol terminal having a weight average molecular weight of 17 Å (measured by Gpc) were added to a reaction vessel. 234 parts of hydrazine oil (calculated as a decyl alcohol equivalent of 85 Å, calculated by using 1/2 of the weight average molecular weight measured by GPC), and 18 parts of a potassium oxynitride (KOH) methanol solution, and the bath temperature was set to 75. Hey, and warm up. After the temperature was raised, the reaction was carried out under reflux for 8 hours. Then, after adding 305 parts of methanol, 86.4 parts of decyl alcohol/gluten solution (concentration: 50% by weight) of distilled water was added dropwise thereto over 60 minutes, and refluxed at 75°C under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous solution of dihydrogen phosphate, and then methanol was recovered at 8 〇t to recover about 9 〇 0 / Torr. 38 parts of decyl isobutyl ketone was added and washed three times with 200 parts of water. Then, the solvent was removed from the organic phase at 1,001 by a rotary evaporator under reduced pressure, whereby 300 parts of an epoxy resin (EP2) having a decane structure was obtained. The obtained compound had an epoxy equivalent of 729 g / eq., a weight average molecular weight of 22 Å, and a colorless and transparent appearance.

38 S 201219426 Synthesis Example 5 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a nitrogen purge was carried out while adding dimethyl 4-methylcyclohexanedicarboxylate (DMCD-p), 14 parts, 314 parts of cyclohexene _ 4-sterol, 07 parts of tetrabutoxytitanium hydride, reacted at 120 ° C for 1 hour, reacted at i50 «t for 1 hour, and reacted at 170 ° C for 1 hour at 19 ° C After reacting for 12 hours, the reaction was carried out while removing the methanol formed by the reaction, and then it was cooled to 5 Torr. After the completion of the cooling, 347 parts of toluene was added and homogenized, and then washed with water of 80 parts of a 1% by weight aqueous solution of sodium hydroxide three times, and further washed with water i00 parts/time until the wastewater became neutral, using a rotary evaporator. Diphenylbenzene and unreacted cyclohexene-tetradecyl alcohol are distilled off under heating and reduced pressure, whereby bis(3-cyclohexenylmethyl)=1,4-cyclohexanedicarboxylic acid is obtained as a main component. It is 240 parts of a compound (D-1) which is liquid at normal temperature. Synthesis Example 6 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 95 parts of 12-phosphonium tungstate, 78 parts of diammonium hydride, and 37 parts of trioctyl acetate were added while performing gas-air washing. 2.7 parts of ammonium 5G% dimethyl benzene solution, 180 parts of benzene, and 8 parts of compound (D-丨) ι obtained in Synthesis Example 5, the solution was heated to 6 (TC-surface was stirred vigorously and added at t hour 35 70% by weight of hydrogen peroxide water 'directly to 6 Torr. Stir for 13 hours. Confirmation of the progress of the reaction by gas chromatography. The result indicates that the spike of the raw material disappeared. Then, after neutralizing with an aqueous solution of i% by weight of sodium hydroxide, Add 2 parts by weight of 2Q% by weight aqueous sodium thiosulfate solution, (4) for 30 minutes, and let stand. Extract and separate into two layers of organic layer, and add activated carbon (Aji_QtQFine-Techn(^ 39 201219426 & CP 1 ) 2〇 2, part of bentonite (manufactured by H〇Jun, Bengel SH), and filtered after stirring for 1 hour. The obtained filtrate was washed with water 3 times in water, and the product was distilled off from the obtained organic layer. This is obtained at room temperature: liquid epoxy resin (EP3) U9 parts The epoxy equivalent of the obtained epoxy resin was 207 g/eq. at 25 χ: the viscosity was 92 〇〇mPa·s (E-type viscometer). &quot; Synthesis Example 7 In the hardener composition (B2) 5 parts After adding 2 parts of mercaptoethyl ketone and uniformly dissolving, methyl hexaphthalene phthalic anhydride remaining excessively with the added methyl ethyl ketone was removed at 100 to 150 ° C using a rotary evaporator ( H1) (In the case where no mercapto hexahydrophthalic anhydride is not eluted, the nitrogen gas is supplied under heating and reduced pressure for 40 minutes to sufficiently remove the acid anhydride), thereby obtaining 16.2 parts of the polyfluorene carboxylic acid resin (A2). The resin is in the form of a colorless solid resin. The softening point of the obtained resin (according to JIS K-7234) is 90.1 C, and the melt viscosity at 150 C is 〇.64 Pa · s. The carboxylic acid resin is higher than 90 C or higher. At the temperature, the fluidity is very low and the operation is difficult. The melt viscosity of the wood melt viscosity at 150 °C is one of the melt viscosity measurement machines: the ICI high temperature viscosity meter (RESEARCH EQUIPMENT (Manufactured by LONDON) LTD.)

Cone No. (cone number): 4 (measurement range is 〇~4 〇〇pa · s) Examples 5 and 6, Comparative Example 1 The hardener composition of the present invention obtained by Example 2 (bi, B2) was used. ), the comparative example uses an acid anhydride (HI) as a hardener, and an epoxy resin (Ερι)

S 40 201219426 As an epoxy resin, cetyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25 % methanol solution, hereinafter referred to as κ 1 ) is used as a hardening accelerator, as shown in the following table. The blending ratio (parts by weight) shown in Fig. 1 was prepared and defoamed for 20 minutes to obtain a curable resin composition of the present invention or comparatively. The obtained curable resin composition was subjected to a volatilization test according to the following points, and the results are shown in Table 1. Further, the hardening conditions were pre-hardened under conditions of 120 ° C for X 2 hours, and then hardened under conditions of i50 〇 c x 5 hours. (Volatilization Test) After the vacuum defoaming of 20 knives in the curable resin composition obtained in the examples and the comparative examples was carried out, the glass substrate was formed into a barrier by heat-resistant tape so as to be 3 mm × 20 mm × 1 mm in height. Cast slowly on the top. After accurately measuring the weight of the cast resin, the cast molding was cured under the above conditions. The weight of the cured product obtained in this manner was measured, and it was confirmed that the weight at the time of hardening was 3: reduction (hardening of the examples and the comparative examples was hardened in the same manner in the same manner) [Table 1] Item Example 5 Example 6 Comparative Example 1 Ring 1 L Resin EP1 13.0 13.0 13.0 Composition Hardener Hardener Composition B1 18.5 B2 18.4 Anhydride H1 16.8 Hardening Accelerator Quaternary Money Salt K1 0.01 0.01 0.01 ,, - Hazelnut Volatilization Test Weight Reduction Brother 3.9% 3.2% 9.8% 41 201219426 When Comparative Examples 5 and 6 and Comparative Example 1 were compared, it was confirmed that the amount of volatilization of the curable resin composition of the present invention was small. Example 7, Comparative Examples 2 and 3 The epoxy resins (EP1, Ep3) obtained in Synthesis Examples 3 and 6 were used as an epoxy resin, and the hardener composition (B2) obtained in Example 2 was used for synthesis. The hardener composition (B5, b6) obtained in Examples 1 and 2 was used as a hardener, and a quaternary phosphonium salt (manufactured by Sakamoto Chemical Industry, hishic〇lin PX4MP, hereinafter referred to as K2) was used as a hardening accelerator, and the following table was used. The β-wean ratio (parts by weight) shown in 2 was blended and defoamed for 2 minutes to obtain a curable resin composition of the present invention or comparatively. * The obtained curable resin composition was slowly cast and molded into a test piece mold to be pre-hardened under the conditions of l2Q &lt;t χ3 hours, and then hardened under the condition of TC x 1 hour. A variety of test hardened materials were obtained. The following cured heat transmittance test was carried out for every 4 π temple cured product. The results - and shown in Table 2 below (heat resistance transmittance test) heat resistance test conditions: at 15 〇 The thickness of the tank is placed in the tank of t, measured by the thickness of 8 mm, and converted to a transmittance of 1.0 mm. The rate of change is measured by a spectrophotometer.

42 S 201219426 [Table 2] Item Example 7 Comparative Example 2 Comparative Example 3 Composition of epoxy resin ΕΡ1 6.0 6.0 6.0 ΕΡ3 4.0 4.0 4.0 Hardener hardener composition Β2 11.5 Β5 11.5 Β6 11.5 Hardening accelerator quaternary salt Κ2 0.02 — 0.02 0.02 Result and heat transmittance transmittance retention rate 62% 57% 52% Example 8, Comparative Example 4, 5 Epoxy resin (EP2) obtained in Synthesis Example 4 was used as an epoxy resin The hardener composition (B2) obtained in Example 2, and the hardener composition (B5, B6) obtained in Synthesis Examples 1 and 2 were used as a hardener, and a quaternary salt was used (manufactured by Sakamoto Chemical Industry, HISHICOLIN PX4MP). Hereinafter, referred to as K2) as a hardening accelerator, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (manufactured by Ciba Japan, TINUVIN 770DF, hereinafter referred to as hindered amine L1) is used. As an additive, and using 4,4-butylidene bis(3 fluorenyl-6-t-butylphenyl-ditridecyl phosphite) (manufactured by ADEKA, Adekastab 260 ' hereinafter referred to as phosphorus-containing compound l2 ) as a phosphorus compound, as shown in Table 3 below. The blending ratio (parts by weight) was formulated and defoamed for 20 minutes to obtain a curable resin composition of the present invention or comparatively used. The known curable resin composition was slowly cast and molded into a test piece mold, and the (4) molded product was pre-cured under conditions of 12 Torr for 3 hours, and then hardened under an hour condition to obtain various tests. Hardened material. The obtained cured product was subjected to the following heat resistance transmittance test. The results of 43 201219426 are shown together in the following table (heat resistance transmittance test). Heat resistance test conditions: 15 (in the box of rc, 9, *, sheet size. The thickness of 0 Smm is measured. The rate was measured by a spectrophotometer at a transmittance of 40 〇 nm. The rate of change was calculated. [Table 3]

From the above results, it is clear that the curable resin composition using the hardener composition of the present invention has optical properties excellent in heat resistance. Example 9, Comparative Examples 6, 7, and 8 The epoxy resin (Ep2) obtained in Synthesis Example 4 was used as an epoxy resin, and the hardener composition (B1) obtained in Example 、 was used in Synthesis Example 1. The hardener composition (B5, B6) and the acid anhydride (hi) obtained in 2 are used as a hardener, (K2) is used as a hardening accelerator, and (acetamidine) is used as an additive, and the blending ratio shown in Table 4 below is used. The parts by weight were formulated and defoamed for 20 minutes to obtain a curable resin composition of the present invention or comparatively.

44 S

Hardened under 150 Cxi hours' to obtain various test hard 201219426 molds

The imine film is sufficiently cured to suppress volatilization.) In the following hardness and heat resistance (Tg), 醯 (hardness) is placed on the surface of the mold to remove various kinds of hardness.

Xiao's A is based on JIS K 7215 "Durometer Hardness Test Method"

Xiao's D According to JIS K 721 5 "Test Method for Hardness of Plastic Durometer" (Heat Resistance (Tg)) The curable resin composition obtained in the examples and the comparative examples was cast into a Teflon (registered trademark). The manufactured 5 mm tube was hardened under the above conditions to obtain a test piece. The test piece was used to carry out a heat resistance test under the conditions shown below. The measurement conditions were dynamic viscoelasticity tester: TA-made by instrument, DMA-2940. Temperature range: 4 (TC~250〇C) Heating rate: 2°C/min. Test piece size: Use 2mm 1 5mm cut. 45 201219426 [Table 4] Item Comparative Example 6 Example 9 Comparative Example 7 Comparative Example 8 Composition of cyclic blush EP2 7.3 7.3 7.3 7.3 Hardener Hardener Composition B1 1.8 B5 1.8 B6 1.8 Anhydride HI 1.7 Hardening Accelerator Grade IV Town Salt K? 0.02 0.02 0.02 0.02 Additive hindered amine LI 0.015 0.015 0.015 0.015 Result Hardness A &gt;90 &gt;90 &gt;90 77 Xiao's D 62 62 46 _ Heat resistance TMA (Tg) °c 63 67~1 58 From the above results, it is clear that the curable resin composition containing the hardener composition of the present invention is maintained as compared with the cured product of Comparative Example 6 using an acid anhydride Η1 which is generally used as a curing agent for an epoxy resin. Tg or hardness, and further exhibits the remarkable effect of soaring heat resistance. On the other hand, it can be seen that Comparative Example 6 of Comparative Example 7 and Comparative Example 8 and Comparative Example 6 using an acid anhydride 通常1 which is generally used as a curing agent for an epoxy resin Hardened The performance was greatly lowered in any of hardness and heat resistance. (Examples 10 to 11 and Comparative Example 9) The polyvalent tickic acid compositions β 3 and β obtained in Examples 3 and 4 were used. 4. The C1 in Example 3 was separately synthesized to obtain c1, and zinc 2-ethylhexanoate (hereinafter referred to as Κ3) was used as a curing accelerator, and the composition ratio shown in Table 5 was used to form a curable resin. The object was then subjected to vacuum defoaming for 2 minutes. (A) The LED lighting test was filled in a syringe and cast by a precision ejection device.

S 46 201219426 The outer diameter of a light-emitting element having an emission wavelength of 465 nm is a 5 mm square surface-shaped LED package (having an inner diameter of 4.4 mm and an outer wall height of 1.25 mm). Thereafter, the hardening treatment was performed for 1 hour at 12 (rc), and further hardening treatment was performed at 150 ° C for 3 hours to obtain a led for lighting test. The lighting test was performed at a current of 11.5 times the 20 mA of the predetermined current. The lighting test was performed as follows. As a measurement item, the illuminance before and after lighting after 40 hours and after 8 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated. Table $. Lighting detailed conditions Illumination wavelength: Center emission wavelength, 465nm Drive mode: Constant current mode, using 230mA (light-emitting element gauge is 20 m A), three lights in series (n = 3 average) drive Environment: Lighting at 2 5 °C, 65% wet heat engine: illuminance after 40 hours, after 80 hours and illuminance retention rate (B) Gas permeability test (corrosion gas permeability test): Filled in syringe The surface mount type LED package (having an inner diameter of 4.4 mm and an outer wall height of 125 mm) having a 5 mm square outer diameter of a wafer having a center emission wavelength of 465 nm was cast by a precision discharge device. In a heating furnace, 12 (TC was subjected to a hardening treatment for 1 hour) and further hardened at 150 ° C for 3 hours to prepare an LED package. The LED package was placed in an etching gas under the following conditions, and observed. Color change of the part of the silver-plated lead frame inside the seal. Determination of the condition rot # gas: 20% aqueous solution of ammonium sulfide (in the case of sulfur component reacts with silver 47 201219426 'turns black')

Contact method: the container of the aqueous solution of sulfuric acid and the above-mentioned LE are simultaneously present in the wide-mouth glass voyage, and the cover of the wide-mouthed glass bottle is covered in the garbage bottle, and the vulcanized recording gas and the LED package are volatilized under the sealed condition. Contact for 1 hour. Corrosion determination: Judgment is made based on the black lead (so-called blackening) of the lead frame inside the LED package. [table 5]

According to the above results, it is clear that the multi-dimensional acid-reducing resin of the present invention and the curable resin composition of the product are excellent in the illuminance test illuminance retention, and the gas permeation resistance can be obtained without discoloring the lead frame. Excellent results. The present invention has been described in detail with reference to the preferred embodiments of the invention. Furthermore, the present application is based on this patent application (Japanese Patent Application No. 2G1G_ 149471) filed on Jun. 3, 2010, the entire disclosure of which is incorporated herein by reference. .

48 S 201219426 [Simple description of the diagram] Benefits &lt; *», [Key component symbol description] None 49

Claims (1)

201219426 VII. Patent application scope: 1. A hardener composition which is a mixture of a polycarboxylic acid resin and an acid anhydride represented by the following formula (1). Or a carbon number of 1 to 15, a carboxyl group, a carboxyl group). 2. The hardener composition according to claim 2, wherein in the formula (1), the plurality of Q present independently are independently selected from the group consisting of a hydrogen atom, a sulfhydryl group, and a carboxyl group (but Except for the case where only Q compounds are all hydrogen atoms). 3. - The scope of the patent towel is the first! The method for producing a hardener composition according to the item or the second item is obtained by reacting the raw material in a solvent of no solvent or in an organic solvent of 5% by weight or less based on the raw material to be used, in the range of 4 G to 15 g. A multi-component m acid composition which is a mixture of a polybasic acid resin represented by the formula (1) and a carboxylic acid having two or more functional groups. 5. The polybasic acid composition of claim 4, wherein the viscosity of the carboxylic acid resin having two or more functional groups is 25 or less 〇〇〇〇pa·s or less. 6. In the case of the diversified (four) composition of the fourth or fifth item of the patent money, in the formula: (1), the plurality of enthalpy of existence are independent and are selected from the group consisting of a hydrogen atom, a methyl group and a few groups. ―The person to go (except for the case where only Q is a compound of a hydrogen atom). The method for producing a multi-component of any one of claims 4 to 6 of the invention, which is in the form of a solvent-free or organic solvent of 50% by weight or less relative to the raw material used. The solvent is obtained by reacting the raw material in a solvent of 4 Torr to 15 liters. 8. The method for producing a polycarboxylic acid composition according to claim 7, wherein the molar ratio of the bis(dihydroxyindenyl)dialkyl ether of the starting material to the anhydride is relative to bis (dihydroxyl) Methyl)dialkyl ether hydroxy oxime, carboxylic anhydride group is 1. 〇~1 〇〇 Mo Er. A hardening resin composition containing the hardener composition of any one of the above claims or the scope of claims 4 to 6 in the cup _ τδ -V ^ * negative疋 carboxylic acid composition and epoxy resin. /· For example, the hardening resin composition of the ninth patent scope of the third patent, which is an alicyclic epoxy resin. 11. A kind of hardened material, a gentleman is made of a cured resin composition of the ninth or tenth item of the patent application. 51