TW201139376A - Carboxylic acid composition, and curable resin composition containing the carboxylic acid composition - Google Patents

Abstract

Although capable of providing light stability, a light stabilizer (HALS) involves a problem such that deterioration in heat resistance and coloring resistance is caused thereby. It is, however, necessary to use a certain amount of an HALS for the purpose of having sufficient light stability, and there is therefore a need for an HALS that has excellent heat resistance and coloring resistance. Disclosed herein is an HALS which has excellent heat resistance and coloring resistance, while exhibiting good fixability to a resin. Specifically disclosed is a carboxylic acid composition represented by formula (1). (In the formula, the plurality of Rs may be the same or different and each independently represents an alkyl group or aryl group having 1-20 carbon atoms; and the plurality of ns may be the same or different and each represents an average that is a number of 1-3.) Also specifically disclosed is a carboxylic acid composition which is obtained by a reaction between a compound represented by formula (2) and an acid anhydride having 3-22 carbon atoms.

Description

[Technical Field] The present invention relates to a m-acid composition suitable for use as an additive for plastics for electrical and electronic materials, and a composition of a curable resin containing the composition of (4) Things. [Prior Art] The plastic (including the thermosetting resin) is deteriorated by the influence of light reception. In particular, light with a large amount of energy acts on a polymer constituting a plastic (including a thermosetting resin), breaks the bond, and causes deterioration (embrittlement, coloring, etc.) to add a light stabilizer for protecting the member in such an environment. (HALS, Himdered Amine Light Stabilizer, hindered amine light stabilizer), especially for automotive parts, home appliances, office automation parts, there is a greater demand for financial support (for example, refer to the non-patent literature [), HALS P It stops the deterioration caused by ultraviolet rays and improves the weather resistance of plastics. It is said that HALS itself absorbs the wire by several shirts, but can stabilize by capturing harmful free radicals generated by ultraviolet energy. HALS are being studied for addition to various plastics, such as polypropylene (PP) or high density polyethylene (HDpE), low density polyethylene (LDPE) and other dense hydrocarbons, impact resistant polystyrene (Hips), general purpose Phenylethylenes such as polystyrene (GPPS), acrylonitrile-butadiene-styrene copolymer (ABS), poly(p-dibenzoic acid), or polypyrene ), engineering plastics such as polycarbonate (PC), polyacetal (ΡΟΜ), and polydecylamine (PA), and also added to polyurethane (PU), polyethylene (pvc), Various resins such as epoxy resin and acrylic 201139376 resin. [Non-Patent Document 1] Additive Information Network http://www.tenkazai.com/index.html [Summary of the Invention] HALS is sold on the market and has been blocked. The piperidine structure has a compound having various structures, and has a compound having various structures. Since it is required to smoothly transfer to the surface portion of the resin which causes ultraviolet deterioration according to the mechanism of action, it is generally a compound having no reactive group, and therefore, it is borrowed after overflow. The problem of discharging out of the system by volatilization or extraction. Various high molecular weight hals which are difficult to move in the system have been studied for this problem. However, although the volatilization is improved, it is difficult to exert internal mobility. In addition, although HALS can be stabilized by heat resistance and coloring resistance, it is necessary to have a certain degree of HALS excellent in coloring resistance. While imparting light stability, but contrary to the problem. However, in order to have sufficient HALS, it is necessary to have a heat resistance, ^, with the purpose of swaying - the kind of resin is better fixed, resistant to cockroaches, cockroaches. ^ 松布',,, HALS excellent in color resistance. The present invention has been completed in view of the above. The state of the art has been studied in detail, and as a result, the present invention relates to: 1) a carboxylic acid composition which is represented by the following formula 201139376

The η of the independent table is a phase (in the formula, a plurality of R may be the same or different, and an alkyl group or an aryl group having a carbon number of 1 to 20, and a plurality of the same or different average values respectively) 1 to 3); (2) A carboxylic acid composition by the following formula (2)

(3) A method for producing a carboxylic acid composition according to the above (2), characterized in that it is in the absence of a solvent or a weight of 5 Å relative to the raw material used. The reaction is carried out at 40 to 150 ° C in an organic solvent of less than %; (4) A light stabilizer composition characterized by being a carboxylic acid composition of the above (j) or (2) and an acid anhydride (5) A plastic composition comprising the carboxylic acid 201139376 as in the above (1) or (2), and/or the light stabilizer composition as in the above (4); or (2) a composition A curable resin composition containing the carboxylic acid composition of (t) above and/or a light stabilizing and curable resin as described in (4) above; (7) a cured product which is as described above (4) The curable resin composition is cured. The carboxylic acid composition of the present invention has been clarified (further, in the present specification, for the convenience of explanation, the case of the mono-carboxylic acid compound is also expressed as a dicarboxylic acid composition, and the composition of the present invention contains such a shape g) #Having the effect as a light stabilizer (HALS) can be added to various plastic materials, and in addition, it can be controlled to discharge to the system not only in the resin which can react with the carboxylic acid (or can be bonded by intermolecular force) The outer structure 'has a structure excellent in heat resistance and coloring resistance. Based on this feature, it can be used for various plastic materials and curable resin compositions. The curable resin composition of the present invention is particularly useful as a sealing material for coatings, adhesives, molded articles, semiconductors, and optical semiconductors, in a curable resin composition containing an epoxy resin which is expected to react with (4) in a system. It is used for the grain m, the semiconductor of the optical semiconductor (die b〇n-g), the material resin, the polyimide resin, and other raw materials or modifiers, plasticizers, lubricant raw materials, medical pesticide intermediates, coatings. The raw material of the resin and the coloring agent (t 〇ner) are useful for the resin, and in particular, since the carboxylic acid composition of the present invention is excellent in transparency, it is used as a curable resin composition for high-intensity white LED or photo-semiconductor sealing. The additives used are extremely useful. Further, in the description of 201139376, the term "heat resistance and coloring resistance" means that the coloring which occurs during heating is reduced. [Embodiment] The polycarboxylic acid of the present invention is represented by the following formula (1).

, gossip, there are a plurality of feet can be the same - the mountain J邗J丌τ is different, the independent table number is 1 to 20 of the yard base or aryl 'in addition, there are a plurality of η can be phase 5 or different The average value is 丨~3). The substituent R is preferably a chain or a cyclic alkyl or aryl group, and is resistant to enthalpy, ring, and diterpene: particularly preferably substituted or unsubstituted cyclohexane-fired cross-linked polycyclic burnt The benzene ring, the substituted or unsubstituted unsubstituted naphthalene ring, etc., m"), substituted or otherwise limited, for example, "the substituent is not an oxime. Give 4 to 3 yards or carbon numbers! To the carboxylic acid composition of the present invention, the straw is represented by the following formula (2). 8 201139376 H3Q ch3

(2) Manufactured by an addition reaction with an acid needle (hereinafter, the conjugate is referred to as a diol (7). The compound can be produced by a methyl group addition of a methyl group), and may also be contained. The hexahydroxyl of the raw material: the acid anhydride used for the 2,2,6,6-tetramethylpiperidine or the epoxy earth, for example, J-p-benzic anhydride, tdmellitic anhydride, Jiao"·,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Phthalic anhydride, methylhexahydroortho-benzene: 曱„, Dingyuan tetracarboxylic anhydride, bicyclo [from morphology ^:: formic acid ^ methyl bicyclo [2, 2, 1] Geng, a 2, 3 - two A compound such as a carboxylic acid anhydride or a cyclohexane-hydrazine-triterpene acid- 3,4-pin is not particularly limited as long as it is an acid needle having one or more cyclic acid anhydride structures in the molecule, and two or more kinds thereof may be mixed. Preferred anhydrides are polycarboxylic anhydrides having more than one alkyl-substituted or carboxyl-substituted or unsubstituted anhydride structure having a cyclohexane structure in the molecule. Specific examples thereof include, but are not limited to, cyclohexane tricarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, cyclohexane-hydrazine, and 2-dicarboxylic anhydride. Two or more kinds are mixed. The reaction of the acid anhydride with the diol (2) is usually an addition reaction using an acid or a base as a catalyst, and in the present invention, a particularly non-catalytic reaction is possible. 201139376 = Catalyst-based In the case, the catalyst which can be used is, for example, an acid compound such as salt-夂Ί甲韵' trifluoromethane acid, p-toluene acid, light, tri-acetic acid, tri-acetic acid, and sodium hydroxide oxidation. A metal hydroxide such as calcium oxychloride 'magnesium hydroxide, or an amine compound such as triethylamine tributylamine. The ratio of β is determined to be - A - Lu "...u is a one-month female pyridine, 1,8-diaza Miscellaneous double coat [··] eleven-7_ thin, meditate, triterpene, tetrazole and other heterocyclic compounds, tetramethyl wind oxidation record, (5) ethyl hydroxide, tetrapropyl hydroxide, four : 虱 emulsified record, trimethyl ethyl oxyhydroxide, 'trimethyl propyl oxynitride, known:, trimethyl butyl hydrogen etched _ m ^ , *, dimethyl hexadecyl hydroxide Ammonium, trioctylmethylammonium hydroxide, tetradecylammonium vapor, ammonium methylammonium chloride, tetramethylammonium tetramethylammonium acetate, trioctylmethylacetate, etc. The catalyst may be used in combination or in combination of two or more. Among them, preferred is triethylamine, pyridine or dimethylaminopyridine. The use of the catalyst I is not particularly limited to the total weight of the raw material. 1 〇〇 weight injury 'pass · preferably used 〇〇〇 i ~ 5 parts by weight as needed. The reaction is preferably no roll over 彳 # c & . The reaction of the combination 1, but an organic solvent can also be used. The amount of the organic solvent used is 0:(10)5, preferably 5 to 〇7, more preferably 0.005 to 0.5 (i.e.) relative to the total weight i'a weight ratio of the acid needle to the diol as the reaction substrate. 5〇% by weight or less). When the weight ratio is higher than the above, the progress of the reaction becomes extremely slow. Therefore, specific examples of the organic solvent that can be used are: hexane, cyclohexyl, gem, etc. Aromatic smoke compounds such as benzene and diphenylbenzene, methyl ethyl, methyl isobutyl ketone, cyclopentanone, cyclohexane, etc., ether, tetrahydrofuran: ether such as decane! Ester, butyl acetate, decyl decanoate and other ester compounds 10 201139376 and the like. The reaction temperature is not particularly limited as long as the reaction can be carried out, and is preferably 40 to 200 ° C, particularly preferably 40 to 15 (TC, particularly in the presence of an excess of an excess (exceeding the molar ratio). When the reaction is carried out in the absence of a solvent, since the acid anhydride is volatilized, it is preferably a reaction of rc or less, particularly preferably 40 to 100 ° C. Reaction ratio of the acid anhydride to the diol (2) Theoretically, it is preferably a reaction such as a molar reaction, but it may be changed as needed. That is, as will be described later, when the acid anhydride used in the curable resin composition of the present invention is the same as the acid anhydride used herein. Alternatively, the reaction may be carried out in an excess of an acid anhydride at the time of production, and at the end of the reaction of the acid anhydride with the diol (2), a mixture of the acid liver and the slow acid composition of the present invention (HALS composition). When the acid base is used as the oxime in comparison with the functional group equivalent, the cross-linked polycyclic diol is 〇〇〇ι 2 or 2, more preferably 0.01 to 1.5, based on the molar ratio thereof. Manufactured as a hardener composition by the above method from 0_01 to 1 1 〇1 In the case, it is preferably used in the range of 〇〇1 to 〇7, more preferably 〇Μ~0.5. The reaction time also depends on the reaction temperature and the amount of the catalyst, but from the viewpoint of industrial production, Long-term reaction will eliminate ', η 托 a lot of energy, so it is not good. In addition, 'short reaction time means that the reaction is imminent, and the safety is not considered. The preferred range is 丨~ u, 士^ The earthing time of 48 hours is preferably from 1 to 36 hours, more preferably from 1 to 24 hours. By neutralizing, respectively, by this, after the target reaction is completed, it is removed by washing, adsorption, etc. in the case of using a catalyst. Catalyst, distilling solvent to remove 201139376 Multi-taste of acid. In addition, when there is no catalyst reaction, the solvent is distilled off as needed, and when it is solvent-free or catalyst-free, it can be directly taken out as a product. The method is as follows: the acid anhydride and the diol (2) are directly taken out after the reaction reaction is completed under conditions of 4 〇 丨 〇 5 〇 c > c without a butterfly or a levy agent. The carboxylic acid composition of the present invention has The structure of the above formula (1) is such that "the page is not a colorless to pale yellow solid resin & (sometimes crystallizes.) In addition, when the reaction is carried out in an excess of an acid anhydride, the shape is mostly liquid. The carboxylic acid composition HALS composition of the present invention) 35 is used for stabilizing an organic material against oxidative, thermal or photoinduced disintegration. As long as the HALS composition of the present invention exerts a hardening action, such an organic material is not limited. In the present invention, the plastic or plastic material is not limited to a synthetic resin having plasticity, and refers to a synthetic or natural product, and examples thereof include the following organic hygienic knives. In the present invention, the organic material of the present invention has a polymer of a monoolefin and a diene which are hardened by heat: for example, polypropylene is used. Poly_4-Kakitan is a ruthenium, a polybutene-I, a soil 1, a polyisoprene or a poly-t-diene, an anthracene ring, a polymer of a (4), a ruthenium), such as a high-density polyethylene Rare (second grade (;: two cross-links can also be low Women of polyethylene (LDPE), 12 201139376 linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE) and the like, but are not limited thereto, may be mixed with two or more. The above polymers of monoolefins, particularly polyethylene and polypropylene, are particularly preferably produced by the following methods: a) Free radical polymerization (generally, under high temperature and high pressure). b) catalytic polymerization using a catalyst which typically contains more than one metal of Groups IVb, Vb, or VIII of the Periodic Table. The metals generally have more than one or more ligands in summer 'typically oxides, dentates, alcoholates, esters, ethers, amines, alkyls, alkenyls, and/or aromatics that can be coordinated via π- or σ _ base. The s-specific metal complex may be either a free body or may be immobilized on a substrate, typically activated magnesium hydride, titanium (niobium), aluminum oxide or cerium oxide. These catalysts may be soluble or insoluble to the polymerization medium. The catalyst may be used in the polymerization itself, and other activators may be used, typically an alkyl metal, a metal hydride, a metal alkyl-formate metal alkoxide or a metal alkyl alkane (the above metal is a cycle) Ia, Ua and/or Ilia elements of the table). The activator can be modified by conventional methods by other ester, ether, amine or oxime ether groups. The above catalysts are usually named Phillips, Standard 〇il 'Ziegler_Natta, TNZ (DuPont, DuPont), metal scent or single point catalyst (single) Site cata〗 ySt, S%). Copolymers of mono- and di-olefins with each other or with other ethylene monomers: eg ethylene/propylene copolymer, linear low density polyethylene (LldPE) and mixtures thereof with low-degree polyethylene (LDpE), propylene/丁浠一i ”Polymer, propylene/isobutylene copolymer, ethylene/butene-1 copolymer, B 13 201139376 olefin/hexene copolymer, ethylene/decylpentene copolymer, ethylene/heptene copolymer Ethylene/octene copolymer, propylene/butadiene copolymer, isobutylene/isoprene copolymer, ethylene/alkyl acrylate copolymer, ethylene/alkyl methacrylate copolymer, ethylene/vinyl acetate copolymerization And such copolymers with carbon monoxide or ethylene/acrylic acid copolymers and such salts (ionic polymers), and ethylene and propylene with dienes such as hexadiene, dicyclopentadiene or ethylene norbornene a terpolymer; and a mixture of the above copolymers and a mixture of the above-mentioned polymers of the monoolefins and diolefins, such as a polypropylene/ethylene propylene copolymer, ldpe/ethylene-vinyl acetate Vinegar copolymer (EVA), LDPE/6 - acrylic acid copolymers ... A), LLDPE / EVA, LLDPE / eaa and alternating or random polyalkylene/carbon oxide copolymers, and mixtures thereof with other polymers such as polydecylamine. a polymeric hydrocarbon resin (for example, a carbon number of 5 to 9) and such a hydrogenated modification such as a tackifier) and a mixture of a polyalkylene group and a starch. Polystyrene, poly(p-methylstyrene) Polyethylene methyl styrene. 2. Impact-resistant polystyrene (deletion), general-purpose polystyrene (Gpps). Stupid ethylene or methyl stupid ethylene and diene or acrylic acid derivatives such as Qin Ethylene / Alkyl acrylate, styrene/butadiene/saki/alkyl acrylate, styrene/butadiene/alkyl methacrylate, ^ ^ present ethylene/maleic acid', Benthene / acrylonitrile / methyl acrylate. # 々人仏日 'this ethylene copolymer and other substances such as polyacrylate, diene poly sigma or ethylene / propylene / two 201139376 ene 2L polymerization High impact resistance mixture; and block copolymer of styrene, such as styrene/butadiene/styrene, styrene/isoprene/styrene, Styrene / ethylene / butene / stupid ethylene or stupid ethylene / ethylene / propylene / styrene. Graft copolymer of styrene or α-mercapto ethylene: for example, polybutadiene grafted styrene, polybutylene Diene-styrene or polybutylene-acrylonitrile copolymer grafted styrene, polybutylene grafted styrene and acrylonitrile (or mercapto acrylonitrile), polybutadiene grafted stupid ethylene, In acrylonitrile and decyl methacrylate, polybutadiene grafted styrene and cis-butanic acid; in polybutadiene grafted styrene, acrylonitrile and maleic acid liver in polybutanol Dilute grafting of phenethyl hydrazide and cis-butyl diimide; grafting of styrene and alkyl acrylate or mercapto acrylate on polybutadiene; grafting of benzene to ethylene/propylene/ene terpolymer Ethylene and acrylonitrile, polyacrylic acid alkyl or polyalkyl methacrylate grafted styrene and acrylonitrile, acrylic acid acrylate/butadiene copolymer grafted styrene and acrylonitrile, and a mixture of a copolymer of the above-mentioned stupid ethylene or α-mercaptostyrene and a diene or an acrylic acid derivative, For example, a copolymer mixture well known as ABS-, MBS-, AS-- or AES-polymer. Halogen-containing polymers: for example, polychloroprene, gasified rubber, gasified or gas sulfonated polyethylene, copolymer of ethylene and vinyl chloride, surface gas alcohol homopolymer or copolymer, especially halogenated vinyl compound Polymers such as polystyrene (PVC), polyvinylidene gas, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene, ethylene / vinyl acetate or Partial dichloro 15 201139376 Ethylene/vinyl acetate copolymer From α, a polymer derived from an unsaturated acid and its derivatives: for example polyacrylate and polydecyl acrylate; modified with butyl acrylate to impact resistance Polymethyl methacrylate, polypropylene decylamine and polyacrylonitrile. Or a copolymer of monomers such as each other or with other unsaturated monomers, such as acrylonitrile/butadiene copolymer, acrylonitrile/alkyl acrylate copolymer, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile /halogenated ethylene copolymer or acrylonitrile / alkyl methacrylate / butadiene terpolymer. Polymers derived from unsaturated alcohols and amines or such mercapto derivatives or acetals: for example polyvinyl alcohol, polyvinyl acetate 'polyvinyl vinyl acrylate, polystyrene vinyl ester, poly-n-butene a copolymer of vinyl diacrylate, polyvinyl butyrate, polyallyl allylic acid or polyallyl melamine; and the above olefin. Homopolymers and copolymers of cyclic ethers: for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-epoxypropyl ether. Polyacetal: for example, polyoxymethylene (hydrazine) and polymethyl benzoate containing ethylene oxide as a comonomer; polyacetal modified with thermoplastic polyurethane (PU), acrylate or mbs. Polyphenylene ether and sulfide, and polyphenylene ether and styrene polymer or with the 醯月月女's composition. a hydroxyl-terminated polyether, polyester or a group of 201139376 polyisocyanuric acid corresponding to indoleamine 4, polyamine 6, 12/12, polyfluorene polybutene and as another An aliphatic or aromatic-derived polyamine decanoate of the composition and a precursor thereof. Polyamines (PA) and copolymerized decylamines derived from monoamines and di-oroxic acids and/or amines of tracism or derivatization. For example, polyamido polyamine 6/6, 6/10, 6/9, 6/12, 4/6, amine 11, and polyamine 12' are aromatic starting from meta-xylene, diamine and adipic acid. Polyamide; a polyamine produced from hexamethylenediamine and isophthalic acid and/or terephthalic acid with or without the addition of an elastomer as a modifier, such as poly 2,4,4-didecyl Hexamethylene terephthalamide or poly(m-phenylene amide); the above polyamine and polyolefin, olefin copolymer, ionic 5 compound or chemically bonded or grafted elastomer a stagnation copolymer, or a block copolymer with poly-such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamine or copolyamine modified with EPDM or ABS; and condensation during processing Polyamide (RIM polyamine). Polyurea, polyimine, polyamidimide and polybenzimidazole. Polyesters derived from dicarboxylic acids and diols and/or hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly Terephthalic acid monoterpene, 4-dihydroxydecylcyclohexyl ester and polybenzoic acid ester, and block copolymerization derived from the end group; and polycarbonate or MBS modified ester. Polycarbonate (PC) and polyester carbonate. Polysulfone, polyethersulfone and polyetherketone" aldehydes as one of the components and phenol, urea and melamine-derived crosslinked polymers as another component, such as phenol/formaldehyde resin, 17 201139376 vein/formic acid resin and melamine / Mast resin dry and non-dry acid alcohol resin. Self-saturated and unsaturated

These halogen-containing modified materials. , AK a Japanese as a cross-linked, and less flammable substituted acrylate: for example, a cross-linking acrylic resin derived from epoxy acrylate, urethane acrylate or polyesterate. 1 曰 归 polyisocyanate or epoxy resin with melamine resin, urea resin, acid acid resin, polyester resin and acrylate resin. Epoxy resin: For example, an epoxy resin composition derived from bisepoxypropyl ether or an alicyclic diepoxide. a curable resin with a phenol resin 'amine compound (amino group-containing resin), an acid anhydride, a carboxylic acid, etc.) natural polymer: for example, cellulose, rubber, gelatin, and the like, chemically modified polymeric homologous derivatives, For example, cellulose acetate, cellulose propionate and cellulose butyrate or cellulose ethers such as decyl cellulose; and rosin and derivatives thereof. Mixture of the above polymers (poly blend):

For example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS 'PC/ABS, PBTP/ABS, PC/ASA, PC/ PBT, PVC/CPE, PVC/acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6. and copolymer, PA / HDPE, PA 201139376 / pp, PA / ppo. Organic = bulk compound or as a natural and synthetic compound of the compound such as minerals? Oil, fat and €, and any weight, based on animal, vegetable and vegetable fats, oils and mash or synthetic vinegar (formula: formazan, adipate, phosphate or trimellitate) The combination of the oil and the oil:::! A mixture of oils which are typically used as a textile of fibers and as an aqueous emulsion of such materials. An aqueous emulsion of natural or synthetic rubber; for example, a natural latex of a styrene/tauadiene copolymer. The addition of the carboxylic acid composition of the present invention to the organic material as described above is not particularly limited as long as the effect can be exerted, and the weight of the organic material _ 通常 is usually added by G.G1 to 1G by weight. Jia Wei 〇〇 1~5 weight $ injury, more preferably 〇. 〇 25~3 parts by weight, especially good for 〇 milk called weight. In the present invention, it is particularly preferable to add to a curable resin composition containing an epoxy resin. The curable resin composition containing the carboxylic acid composition of the present invention is used as a coating material, an adhesive, a molded article, a semiconductor, a resin for a sealing material for an optical semiconductor, a resin for a crystal grain-forming material of a photo-semiconductor, a polyamide resin, A raw material such as a polyimide resin, a modifier, a plasticizer or a lubricant raw material, a medical pesticide (4), a raw material for a coating resin, and a resin for a toner are useful, and since the cured product has excellent transparency, it is high in brightness. It is extremely useful for white or for sealing epoxy resins used in other optical semiconductors. Hereinafter, the curable resin composition of the present invention containing the carboxylic acid composition (HALS composition) of the present invention will be disclosed. 201139376 The curable resin composition of the present invention preferably contains an epoxy resin. The epoxy resin which can be used in the curable resin composition of the present invention may be a novolak type epoxy resin, a bisphenol A type epoxy resin, a stupid epoxy resin, or a trisomethane type epoxy resin. , phenol aralkyl type epoxy resin, and the like. Specific examples thereof include bisphenol A, double g ", thiodithiophene, disulfonium, diphenol, 4,4,-bisphenol, 2,2,-bisphenol, 3,3,5 ,5,_Tetramethyl: [1,1'-biphenyl]-4,4,monodiol, dioxin, m-benzoic acid, Cai di leaven, tris(4-phenylene) Burning 'u, 2, 2 - 4 (4--phenyl) E-forms, age class (stupidated, phenyl hydrazine substituted by the hospital base, naphthalene, trans-compartment substituted, di-based benzene, di-based Naphthalene, etc. with formic acid, acetic acid, benzoic acid, benzoquinone, o-hydroxybenzaldehyde, 叙 铽 铽 rs ^ soil basic ethyl ketone, o-hydroxyacetophenone, : alkene, furfural, 4,4·-double (gas methyl)-U·-biphenyl, 4 4, bis(methoxymethyl)-1 i, 桝 poor, .^ ? . A m ^ , 联本, l,4-双 (气甲a condensed private dimer of benzene, 1,4~# (methoxymethyl)benzene, etc., and a modified product of tetramethyl bisphenol dentate bisphenols derived from alcohols A 4榭fs, 虱 虱 propyl ether, alicyclic epoxy tree ruthenium, % oxypropylamine epoxide oxygen has a structure of stone oxygen plant n oxypropyl vinegar epoxy tree , the n-type oxygen resin of the shape n (1 〇) (in the chain, ring, sister-like or such at least two 豨 状, 梯 Μ 上 上 上 上 上 结构 结构 结构 古 古The base and/or the epoxy ring is a ring-like or liquid epoxy resin, but is not limited to the solid such as the oxysporin), and the curable resin composition of the present invention is used for In the case of a light-to-skull shape, an epoxy resin which is preferably a fat or a sensible use, for example, an epoxy bis-oxygen resin having a structure (S1 1/2) is preferably used in combination with _ 曰 。. In particular, in the case of the alicyclic ring "20 201139376", it is preferably a skeleton, and particularly preferably an epoxy resin obtained by combining and having a structure of the appearance. The oxidation reaction is carried out to obtain the ruthenium ring epoxy resin, and the compound is oxidized to produce carb〇xv] by the following reaction. 4. hexyl ene acid (cyclohexene vinegarization counter: Brewing reaction of Γτ with alcohol or cyclohexane methanol and slow acid

Letter : Μ"" V°l·36 P.24G9 (198G), Τ-η (2 1 Λ 1980), etc.), or the ring-dilute season of the first genus (3) 〇 reaction (Japanese special 2 〇〇3-170059, Japan's special open 2004-262871 public 耜黧 st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st st 6—〇5 and the method disclosed in the number). The yeast 'is not particularly limited as long as it is a compound having an alcoholic base group, and examples thereof include ethylene glycol, propylene glycol, hydrazine, 3-propanediol, hydrazine, 2-butanediol, M-butanediol, and μ- Glycols such as pentanediol, hexanediol, cyclohexanol, glycerol, dihypothyridine 7 — monomethylolethane, trihydroxydecylpropane, trishydroxybutane 2 I A triol such as a monoterpene-butanediol or a tetraol such as pentaerythritol. Further, examples of the carboxylic acid include oxalic acid, maleic acid, transbutene di-n-o-benzene-carboxylic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid, but are not limited thereto. . Further, a shrinkage compound obtained by a reaction of a cyclohexenal derivative with an acetal of an alcohol can be mentioned. The reaction method can be produced by a (iv) reaction, for example, a method in which a reaction medium is subjected to azeotropic dehydration while using a solvent such as methyl bromide or diphenylbenzene (United States 21 201139376 Patent No. In the case of dissolving a polyhydric alcohol in concentrated hydrochloric acid, the reaction is carried out while slowly adding an acid (Japanese Patent Laid-Open No. 48-9659), and the reaction medium uses water (U.S. Patent No. 1). A method of using an organic solvent in the reaction medium (Japanese Patent Laid-Open Publication No. Hei 7-215979), a method of using a solid acid, and a method of using a solid acid (Japanese Patent Publication No. 2-7-230992), etc. δ is preferably a ring-shaped shrinkage structure. Specific examples of the epoxy resins include J ^$.ERL- 4221, UVR-6105, and ERL-4299 (all of them are also traded (Wang 4 is a trade name, All manufactured by D〇w Chemical Co., Ltd.) 'Cell〇Xlde 2()21P, such as (5) gt4〇i, eh_5〇, EHPE3150CE (all trade names, all manufactured by Μ&ι化学工业) and dicyclopentadiene double rings Oxide π 衣 乳化 乳化 乳化 荨 荨 荨 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( In the case of the epoxy resin of the si_〇), the compound is not particularly limited as long as it is a sputum sputum, and the compound of the structure is not particularly limited. a compound obtained by a sol-gel reaction of an apricot apricot having an epoxy propyl group and/or an epoxycyclohexyl group as an essential component, or a diarrhea oil or a polyol The class is incorporated into the structure of the molecule as a segment. Specifically, the example 'Xie. Η Η · · · International Gazette W〇2〇〇5/1〇〇 445 bulletin or Japan's special offer · 4 2008- 225472 No. (International Publication No. WO2010/026714), the chemical substance disclosed in the Japanese Patent Publication No. 2007-326988, etc. 22 201139376 These may be used alone or in combination of two or more. The curable resin composition of the present invention The hardener used in + J can be extended, for example, A compound, an unsaturated cyclic scorpion coat, an acid anhydride compound of a 0 structure, a guanamine type compound, a phenol type compound, and a carboxylic acid type compound [beta]. The specific example of the hardening|curing agent which can be used is a diamine. Didiphenylmethane, diexene, January, female, diethylenetetramine, diaminodiphenyl, isophorone diamine, dicyanosamine, linoleic acid dimer and ethylene Polyamine resin synthesized by amine, o-paraic acid anhydride, trimellitic acid, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid Needle, methyl benzoic anhydride, ceric anhydride, hexahydrophthalic anhydride, methyl hexanitro phthalic anhydride, butane tetraphthalic anhydride, bicyclo[2,2,1]heptane-2,3 -Dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexanol __丨, 3,4-tricarboxylic acid-3,4-anhydride, bisphenol A, Bisphenol F, bisphenol S, bisphenoldi, stilbene, 4,4'-diphenol, 2,2,-diphenol, 3,3,5,5,tetradecyl-hydrazine-biphenyl Base]—4,4′-diol, hydroquinone, m-diphenol, naphthalenediol , tris(4-hydroxyphenyl)decane, l5l,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthalene Phenol, diphenylbenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyphenylacetamidine, dicyclopentadiene, furfural , 4, 4, a pair of (chloromethyl)-1,1'-biphenyl, 4,4, a double (methoxyalkyl)-1,1'-biphenyl, 1,4'-double ( Polycondensate of chloropurinylbenzene, 1,4'~~bis(decyloxymethyl) phenanthrene and the like, and modified quaternary bisphenols such as tetrabromobisphenol quinone, imidazole and boron trioxide (trifluoroborane) - an amine complex, a pulse derivative, a condensate of hydrazine and anthraquinone, etc., but is not limited thereto. 23 201139376 The tetacid composition (HALS composition) of the present invention can also be used as a hardener. The materials may be used singly or in combination. In the curable resin composition of the present invention, the ratio of the epoxy resin to the hardener is preferably 〇5 to U equivalent based on 1 equivalent of the epoxy group of the entire epoxy resin (it is considered that the citric acid is monofunctional, For the functional group, it is particularly good for 〇·7 to 1.2 equivalents. When it is less than G5 equivalent with respect to i equivalent of the epoxy group, or more than 1.5 equivalents, there is a hardening μ and it is impossible to obtain good hardenability. In the curable resin composition of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of the hardening accelerator which can be used include a 2-methyl taste. Sitting, 2-phenyl (four), 2 eleven yards, Kimi, 2, seventeen, six bases, 2-phenyl- 4-methylindole, and b-butyl- 2-phenyl. Sit, a benzyl group, 2-methylimidazole, cyanocyanoethyl-2-methylimidazole, guanidino-cyanoethyl-phenylimidazole, 1-cyanoethyl _ 2 -undecylimidazole, 2, 4-diamino-6(2'-methylimidazo(1'))ethyl-symmetric trimorphine, 2,4-diamino-indole, undecylimidazole (1,))ethyl a symmetrical three-plowing, 2,4-diamino -6 (2,-ethyl-4-indolyl imidazolium (1')) ethyl-symmetric three wells, 2,4-diamino- 6 (2, - 曱基.Miwa (η) ethyl-symmetric three _•isocyano cyanide addition ^, 2 a fluorenyl 11 m salic iodo Cyanide 2:3 adduct, 2-phenyl taste Salivary isocyanurate addition product, 2-phenyl-3,5-dihydroxymethylimidazole ' 2 -phenylidene 4-hydroxyindole 5-nonanimidazole, 1-cyanoethyl-2_ Phenyl~3,5-dicyanoethoxymethyl methoxide, various kinds of imipenones and these imidazoles with phthalic acid, isophthalic acid, terephthalic acid, and Triacids, pyrophoric acid salts of polycarboxylic acids such as naphthalene dicarboxylic acid, maleic acid, oxalic acid, dicyano group 24 201139376 Diamides such as decylamine, 1,8-diazabicyclo ( 5 · 4〇) undecene-7 and other diaza compounds and such salts such as tetrasyl borate, phenol novolac, and the above polycarboxylic acids or phosphinic acid (ph〇sphinic acid) Salts, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctyldecylammonium bromide, trisuccinylphosphine, tris(tolylphosphino)phosphine, bromination a phosphine or a ruthenium compound such as tetraphenylphenanthroline tetraphenylborate, a phenol such as 2,4,6-triaminononylphenol, or an amine adduct, A metal compound such as tin octylate or the like, and a microcapsule-type hardening accelerator which is a microcapsule, and the like. The curing accelerator is used, for example, depending on transparency, curing speed, working conditions, and the like. The hardness of the obtained transparent resin composition is appropriately selected. The curing accelerator is usually used in an amount of from 0.001 to 15 parts by weight based on 1 part by weight of the epoxy resin. The curable resin composition of the present invention It may also contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include tridecyl phosphate, triethyl phosphate, tricresyl phosphate, and tris(xylylene) phosphate ( Trixylenyl phosphate )., cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, 1,3 —l,3-phenylenebis (dixylenyl phosphate), 1,4-phenylphenylbis(bis(phenylenediyl)phosphate) (l, 4-phenylenebis (dixylenyl phosphate), 4,4'-biphenyl (dixylenyl phosphate), etc. (4,4'-biphenyl (dixylenyl phosphate)), etc. 25 201139376 vinegar; 9, 10—Dihydrogen-9—anthracene-10—phosphaphenanthrene-1-indene oxide (9,10-Dihydro-9-〇xa-10-ph〇sphaphenanthrene 10-〇xide), 10(2,5 — Dimensional basis) - 10H - 9 - oxa - i 〇 - phenanthrene - phosphane - oxides; epoxides are reacted with the active hydrazines of the above phosphines Phosphorus epoxy compound, red phosphorus, etc., preferably a phosphate ester, a phosphine or an epoxy-containing compound, particularly preferably ruthenium, 3 _phenylphenylbis(bis(phenylmercapto)phosphate), 1, 4 - Phenyl bis(bis(phenylenediyl)phosphate), 4,4, biphenyl (bis(phenyldimethyl)phosphate) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound / total epoxy resin = 〇丨 ~ 〇 6 (weight ratio). If the right side is less than 0_1, the flame retardancy is insufficient. If it exceeds 〇6, it may adversely affect the hygroscopicity and dielectric properties of the carbide. Further, in the curable resin composition of the present invention, a smear agent may be added as needed. The antioxidants which can be used are phenolic, sulfur-based, and phosphorus-based antioxidants. The antioxidants may be used singly or in combination of two or more. The amount of the antioxidant used is 10 parts by weight of the resin component in the curable resin composition of the present invention, usually in parts by weight, preferably 0. 01 to 0.5 part by weight of the ? antioxidant, and for example, It is an antioxidant, a sulfur-based antioxidant, a dish-based antioxidant, and the like. Specific examples of ageing γ g pore % W phenolic antioxidants can be exemplified by: 2,6-di-tert-butyl-p-methyl, butylated-p-benzyl anisole, 2,6-di-t-butyl : p-Ethylbenzene - stearyl. (3,5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3__ _ ^ # 一二二乙一四一苯苯苯Base) propionic acid vinegar, 2,4-bis-(n-octylthio)-6-(4-diyl-hydrazino-di-tert-butylanilinyl triterpenoid, 2,4-bis[(octylthio) )methyl] 26 201139376 - monophenols such as o-nonphenol; 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2, monomethylene double (4 -ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4*-butylenebis(3-mercapto-one) 6~T-butyl phenol), triethylene glycol-double [3-(3-t-butyl _5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol - bis [3 (3,5 - tert-butyl-4-yl-phenyl)propionic acid vinegar], n,N'-hexamethylene double (3,5 - -2 -butyl- 4 - Mercapto-hydrocinnamate 2,2-Sulphur-diethyl-ethyl bis[3-(3,5-di-t-butyl-4-yl-hydroxyphenyl)propionic acid S曰]3,5-Secondyl-4-yl-benzyl Phosphonic acid-diethyl ether, 3,9-double [1,1-dimercapto-2-({-)-(3_t-butyl-4-hydroxy-5-methylphenyl)propenyloxy }Ethyl]2,4,8,1〇-tetraoxaspiro[5,5] eleven, double (3,5~3 second butyl-4) Age class; 1,1,3-tris(2-mercapto-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-dimethyl-2,4,6-tri 3,5-di-tert-butyl-4-yl-hydroxy:yl)benzene, tetra-[indenyl-3-(3',5'-di-tert-butyl-4,-phenylphenyl)propionic acid Ester] decane, bis[3,3,_bis-(4,1-hydroxy-3-trit-t-butylphenyl)butyrate]diol, iso-cyanuric acid tris(3,5-two third Butyl 4-hydroxy-hydroxyl) vinegar, i, 3,5-tris(3,5._di-t-butyl-41-diyl^> m 2,4,6_ (1H,3H,5H ) Triketone, fertility, etc. High classification. Diuryl- 3,3, monothiodipropionate, triphenyl stearyl phosphite, sulfurous antioxidant Specific examples of the agent include: dipropionate, dimyristyl-3,3, monothio-3,3-thiodipropionate, etc. Specific examples of the phosphorus-based antioxidant can be exemplified 27 201139376 Diphenylisodecyl phosphate, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl neopentyl phosphite, triphosphoric acid (2,4 Di-tert-butylphenyl) ester, bis(octadecanthino) pentaerythritol di-nanoate, bis(2,4-di-t-butylphenyl)neopentitol diphosphite, Bis (2,4-di-tert-butyl 4- 4-mercaptophenyl) bisphosphonate (cyclic neopentanetetrayl bis(2,4-di-tert-butylphenyl) phosphite), double [2_ a phosphite such as tributyl-6-indenyl_4-{2_(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite; 9,1 〇_dihydro- 9-oxa- 1〇-phosphaphenanthrene-10-oxide '10-(3,5-di-t-butyl- 4-hydroxyl

Oxygen phosphorus phenanthrene oxides, etc. - Oxa-10 - Phosphenanthrene-10 - Oxidation Dihydrogen-9 - Oxa-1 〇 - Phosphene phenanthrene - 1 〇 These antioxidants can be used alone or in combination. Particularly preferred in the present invention are phosphorus-based antioxidants.

Further, two or more of the components may be combined with the carboxylic acid of the present invention, and the following amine compounds may be mentioned. Butane tetracarboxylic acid tetrakis (1,2,2,6,6-five, 4~~ butanetetracarboxylic acid tetrakis(2,2,6,6-tetra-butanetetracarboxylic acid and 1,2,2,6 , 6-penta-hydroxyl-1,1-didecylethyl)-burning mixed acetate 'sebacic acid diyl) vinegar, bis(1-undecyloxy) carbonate, methacrylic acid —2,2,6,6 — 28 201139376 Tetramethyl- 4-piperidinyl ester, bis(2,2,6,6-tetramethyl-tetra-piperidyl) sebacate, bismuth Acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 4 _ benzoquinone oxy- 2,2,6,6-tetradecyl 0 bottom bite, 1- [2 - [3 - (3,5-di-t-butyl-tetra- 4-hydroxyphenyl)propenyloxy]ethyl]- 4 - [3 - (3,5 _ di-t-butyl- 4 - Hydroxyphenyl)propanodecyloxy]-2,2,6,6-tetradecylpiperidine, methyl methic acid-1,2,2,6,6-pentamethyl- 4 Ester, bis(1,2,2,6,6-pentamethyl-tetra-piperidinyl)[[3,5-bis(1,1-di-decylethyl)-4-hydroxybenzene Methyl]butyl ester, bis(2,2,6,6-tetradecyl-Uoctyloxy)-4-piperidinyl sebacate, hydroperoxide 1, 丨 曱 曱 乙基 乙基 与 辛 辛 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 2,6,6-tetramethylpiperidine-4-yl)aminotrimethane 2-yl)- 4,7-diazanonane-no-diamine, dibutylamine· _ 二〇井.>}, 1^'-double (2,2,6,6-tetradecyl-4_piperidinyl-1,6-hexamethylenediamine with N — (2,2,6,6 — Polycondensate of tetramethyl-4-piperidinylbutylamine, poly[[6 — (1,1,3,3-tetradecylbutyl)amine--three tillage-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene [[2,2,6,6-tetradecyl-4-piperidyl)imine a polymer of 2,2,4,4 tetramethyl- 20-(cold) ——Lauryloxycarbonyl)ethyl-7-oxa-3,2〇-aza-bispiro[5.1.11.2]hexadecane- 21-one, 0-alanine-N (2'2,6 ,6-tetradecyl-4-pyridinyl)dodecylester/tetradecyl fluorene, N-ethenyl-3-pydenyl-1-one (2,2,6,6 _四曱基—4 — 派基基) mouth bite each 2,5 —, 2,2,4,4_tetramethyl-7-oxa-3,20-aza-bispiro[5.1·11.2]hexadecane- 21-ketone 2,2,4,4—four 29 201139376 fluorenyl-21-oxa-3,2〇-diazabicyclo-[51112]-t- 20-alkane 20-dodecyl propionate/fourteen Alkyl ester, malonic acid [(4-methoxyphenyl)~~methylene]_bis(1,2,2,6,6-pentamethyl-4-piperidinyl) S曰, 2 , 2,6,6-tetradecyl- 4 piperidinol higher fatty acid ester, hydrazine, 3, 3-benzenedicarboxamide, N'N, _ double (2, 2, 6,6-tetramethyl 4 ° bottom bite base ··# hindered amine system, benzophenone (octabenzone) and other benzophenone compounds, 2-(2H-benzotriazole-2-yltetradecyl) Phenyl, 2-(2-hydroxy-5-nonylphenyl)benzotriazole, 2 [2-hydroxy- 3 - (3,4,5,6-tetrahydrophthalic imine) Methyl)-5-nonylphenyl]benzotriazole, 2_(3-t-butyl-2-hydroxy-$methylphenyl)-5-chlorobenzotriazole, 2_(2-hydroxyl _3,5-di-t-amylphenyl)benzotriazole, decyl propionate_3_(3_(2H_benzene) Reaction product of triazol-2-yl)-5-t-butyl-4-hydroxyphenyl) ester with polyethylene glycol, 2-(2H-stuppyrazole-2-yl)_6-tweldium a benzotriazole compound such as an alkyl 4-nonylphenol, a benzoate such as a 2,4-di-tert-butylphenyl benzoate-3,5-di-tert-butyl-4-hydroxyl ester Department, 2_(4,6-diphenyl-1,3,5-three-d well-2-yl)-5-[(hexyl)oxy]phenol and other three well compounds, especially preferably with piperidine A hindered amine compound of the skeleton. As the above-mentioned amine compound as a light-stable material, the commercially available product disclosed below can be used. The commercially available amine-based compound is not particularly limited, and examples thereof include TINUVIN 765, TINUVIN 770 DF, TINUVIN 144, TINUVIN 123, TINUVIN 622 LD, TINUVIN 152 'CHIMASSORB 944 manufactured by Ciba Specialty Chemicals Co., Ltd., LA-52, 30 201139376 LA 57 manufactured by ADEKA. LA-62, LA-63P, LA-77Y, LA-81, LA-82 LA-87, etc. Further, in the curable resin composition of the present invention, a binder resin may be blended as needed, and a binder resin may be mentioned. : butyraldehyde resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamine resin, polyimide resin, Although it is a polyoxyl resin, etc., it is not limited to these. The blending amount of the binder resin is preferably in the range of not impairing the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 50 parts by weight, per 1 part by weight of the resin component. It is 0.05 to 20 parts by weight. An inorganic filler may be added to the curable resin composition of the present invention as needed. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, aluminum oxide, bismuth, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, zirconia, and magnesite. a powder such as a block talc, a spinel, a titanium oxide or a talc, or a spheroidized bead or the like, but is not limited thereto. These may be used singly or in combination of two or more. The content of the inorganic filler is used in an amount of 〇% by weight to 5% by weight of the curable resin composition of the present invention. Further, a decane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate or calcium stearate, a surfactant, a dye, a pigment, an ultraviolet absorber, etc. may be added to the curable resin composition of the present invention. Various admixtures and various thermosetting resins. When the curable resin composition of the present invention is used in the case of a photo-semiconductor encapsulant, a phosphor may be added as needed. The phosphor is, for example, a person who absorbs a part of the blue light emitted from the blue LED element and emits yellow light which is wavelength-converted by 31 201139376, thereby forming white light. After the phosphor is previously dispersed in the curable resin composition, the photo-semiconductor is sealed. The phosphor is not particularly limited. A conventionally known phosphor can be used, and examples thereof include a rare earth element acid salt, a thiogalic acid salt, and a protoporic acid salt. More specifically, 'a fluorescent material such as a YAG phosphor, a TAG phosphor, a strontium silicate phosphor, a thiogallate phosphor, or a sulfide phosphor can be mentioned, for example, YAl〇3:Ce 'Y3A150丨2:Ce, Y4Al2〇9:Ce, Y202S:Eu,

Sr5(P〇4)3ci: Eu, (SrEu)O · Al2〇3, and the like. The particle diameter of the phosphor may be a particle diameter known in the art, and the average particle diameter is preferably from 1 to 25 Å " m, particularly preferably from 2 to 50 m. In the case of using these phosphors, the amount thereof is from 1 to 8 parts by weight, preferably from 5 to 60 parts by weight, per 1 part by weight of the resin component. The curable resin composition of the present invention can be obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily made into a cured product by the same method as the previously known method. For example, a method of using an epoxy resin, a hardening agent, and a hardening accelerator, a scaly compound, a binder resin, an inorganic filler, and a blending agent as needed, using an extruder, a kneader, a roller, etc. as needed may be sufficient. Mixing to uniformity to obtain a curable resin composition 'when the curable resin composition is in a liquid state' is subjected to immersion or casting to impregnate the substrate into the mold and Cast molding, hardening by heating, and in the case of a solid, 'molding after melting, or by a molding machine, etc., and hardening by heating. The curing temperature and time are carried out at 8 〇 to 2 ° C for 2 to 10 hours. The hardening method may also be performed at a high temperature, but it is preferably a stepwise heating to carry out a hardening reaction. Specifically, initial hardening is performed between 8 〇 and 15 〇C, and the stage of post-hardening is improved between IGGt and 2GGt, preferably 2 to 8 stages, more preferably 2 to 4 stages. . Further, the curable resin composition of the present invention can be dissolved in methyl benzene, xylene, acetone, ▼ ethyl ethyl ketone, methyl isobutyl ketone, dimethyl decylamine, monomethyl acetamide, N. - a solvent such as methylpyrrolidone is formed into a varnish of a curable resin composition, and is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper, and dried by heating. The obtained prepreg is hot pressed into a cured product of the curable resin composition of the present invention. The solvent at this time is usually used in an amount of 1 Torr to 7 Torr/Torr, preferably 15 to 70% by weight, based on the mixture of the hard resin composition of the present invention and the solvent. Further, an epoxy resin hardened material containing carbon fibers can be obtained by the RTM method in the state of a liquid composition.

Further, the curable resin composition of the present invention can also be used as a modifier of the film type composition. Specifically, it can be used to improve the flexibility of the B-stage or the like. The film-type resin composition can be obtained by forming the curable resin composition of the present invention into the above-mentioned curable resin composition varnish, applying it to a release film, and removing the solvent under heating. B staged, whereby a tablet-like adhesive was obtained. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like. Next, the case where the epoxy resin composition of the present invention is used as a sealing material or a crystal grain-forming material of a photo-semiconductor will be described in detail. 33 201139376 When the epoxy resin composition of the present invention is used as a sealing material or a crystal grain of a high-intensity white LED or the like, the hardener (hardening) containing the poly (IV) of the present invention is sufficiently mixed Agent composition) and epoxy resin, in addition to hardening accelerator, coupling material, antioxidant, light stabilizer and other additives, to prepare epoxy resin composition, used as sealing material or for grain bonding materials and sealing Both materials. The mixing method can be carried out by mixing or heating at a normal temperature using a kneader, a three-parent machine, a universal mixer, a planetary mixer, a homomixer, a homogenizer, a bead mill, etc. The layer is applied to sapphire, spinel, tear, and a using an adhesive/grain bonding material. The GaAs, CaP, GaA1As, GaAsp, Aica, bp, (4), thin, and _ material conductor wafers on the substrate are then formed on a lead frame or a heat sink or a package. There is also a form in which a gold wire or the like is connected in order to flow a current. In order to protect the semiconductor wafer from heat or moisture damage and to function as a lens, a sealing material such as an epoxy resin is sealed. The epoxy resin composition of the present invention can be used as the sealing material or = bonding material. In terms of the steps, it is preferred that the curable tree sap composition of the present invention is used for both the grain-forming material and the sealing material. The method of using the curable resin composition of the present invention to carry out the semiconductor wafer in the following manner: a method of coating the epoxy resin composition of the present invention by a dispenser, a pot, a mesh, or a P brush. Thereafter, the semiconductor wafer is placed and heated and hardened to cause the semiconductor wafer to be bonded. Adding air circulation, infrared, high-frequency waves and other methods. The ', ' heating condition is preferably, for example, heating at 8 〇 to 23 〇〇 c! Minutes ~ U, 34 201139376 Right. In order to reduce the internal stress generated during heat hardening, for example, it can be used in 8〇~12 (Γ:: pre-hardened 3G minutes~5 hours, with 12〇~18〇χ;, 3〇 points, ~10 hours) The method of forming the material to be sealed is to use an injection method in which a sealing material is injected into the mold frame of the substrate having the semiconductor wafer and the heat sealing is formed. And pre-injecting into the mold, the semiconductor wafer fixed on the substrate is impregnated therein, and after being heat-hardened, the compression molding method is released from the mold. The main method is as follows: a dispenser, a transfer Forming, injection molding, etc. :: Hot air circulation type, infrared ray, high frequency wave, etc. can be used. Addition: Preferably, for example, the internal stress generated during the heating and hardening of i minutes to 24 hours left under 80 to C, for example, can be 8〇~12〇下吏; pre-hardening 3. After 5 minutes, it is post-hardened under the conditions of (10) ~ aero-clock to 10 hours. Further, the thermosetting resin such as the curable resin of the present invention is available. In the use of epoxy tree to remove the Buddha Specifically, a squeegee, a paint, a coating agent, a molding material (etc.), an insulating material (including a printed circuit board, Rp, etc. for sealing (four) coating, etc.), a sealing material, and a sealing material are mentioned. For the material, the cyanate resin έΒ + & b agent for the substrate, or the additive for the addition of resin or the like to the propylene compound as a curing agent for the anti-button agent, etc., "Other adhesives such as Japanese resin, In addition to the use of medical materials and medical adhesives, it can be used for electric/vehicle use, and the like, and the use of an adhesive for electronic materials. The layer (bull~35 201139376 layer substrate interlayer adhesive, grain binder] primer, etc. each of the semiconductor w^BGA reinforcing primer, anisotropic conductive film (acf), anisotropic conductive adhesive ( ACP), etc., such as an encapsulant for encapsulation. The encapsulant can be used for filling, impregnation, or transfer molding of capacitors, electric diodes, etc. =: first = C〇B, COF'tab, etc. , for flip chip (10) P special "'QFP, BGAf assembly type when installed in the package (including plus The primer of the present invention is used for curing the curable resin composition of the present invention, and is used for various purposes represented by optical component materials. The so-called light: material Ί generally means to make visible light 'infrared, ultraviolet light, In the liquid crystal display field, the sealing material for LEDs, such as a lamp type and an SMD type, may be mentioned as a material. The substrate material, the light guide plate 'prism sheet polarizing plate' phase difference plate, the viewing angle compensation film, the adhesive, the polarizer protective film, and the like, the liquid crystal display device surrounding material 1 is used, and the color of the next-generation flat panel display is expected. PDP (Electrical Destruction Display) sealing material anti-reflection film, optical compensation film 'shell material, front glass protective film, face glass replacement material, adhesive, LED display device used = LED mold material, LED sealing material , the front glass protective film, the lead glass replacement material, the adhesive, and the plasma-addressed liquid crystal (PAW) '''''' Bias plate, phase difference plate viewing angle film, adhesive, polarizer protective film, and protective film of the front glass in the organic EL (electroluminescence) display, front glass generation 36 201139376 substitute material, adhesive And various film substrates in the field emission display (FED), the protective film of the front glass, the front glass replacement material, and the adhesive. In the field of optical recording, 'VD (disc), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase-change disc), optical disc substrate material, Optical pickup lens, protective film, sealing material, adhesive, etc. In the field of optical machines, it is a lens material for a static camera, a finder prism, a target 稜鏡, a viewfinder cover (such as and c〇ver), and a light receiving sensor portion. In addition, the camera lens and viewfinder of the camera. In addition, a projection lens, a protective film, a sealing material, an adhesive, and the like of a projection television are used. A material for a lens of a light sensing machine, a sealing material, an adhesive, a film, or the like. In the field of optical components, the fiber material, the lens, the waveguide, the sealing material of the element, the adhesive, and the like around the optical switch in the optical communication system. Optical connection peripheral fiber materials, ferrules (femUe), sealing materials, adhesives, etc. In the passive parts and optical circuit parts of the light, the lens, the waveguide, and the LED are sealed (4) and connected (4) #. Base plate around the optoelectronic integrated circuit (OEIC) A fiber, quasi-material, το parts sealing material, connector special. Lighting for optical fiber truss decorative display, light pipe, sensor for industrial use, construction, etc., and communication, and communication, and the use of optical fiber in the digital field. In the semiconductor integrated body electrical 峪 遭 遭 , , mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu mu Gear part, early engine φ ^ ^ eclipse coating, switch part, headlights, lead parts, electrical parts, various internal and external parts, drive engine, brake oil 37 201139376 can, automotive rust-proof steel plate, inner side plate (interior Panel), interior materials, security, vines, bundles, fuel tubes, automobile lamps, glass linings, and laminated glass for railway vehicles. In addition, the toughness imparting agent for structural materials of aircraft' In the field of construction, it is a material for interior decoration and processing, electric cover I, sheet, glass interlayer film, glass substitute, solar cell peripheral material. In the field, it is a coating for building (h〇use). The next-generation light and electronic functional organic material are organic EL element peripheral materials, organic light-refracting elements, f-light conversion device optical amplifying elements, optical transport The substrate, the material of the substrate around the organic solar cell, the fiber material, the sealing material of the element, the adhesive, etc. [Embodiment] Next, the present invention will be more specifically described by way of examples, and the following "parts" unless otherwise specified Share." Furthermore, the invention is not limited to the embodiments. Further, in the examples, the gel permeation chromatography (hereinafter referred to as "GPC") was measured as follows. The column is Shodex SYSTEM—21 column (Kf—8〇3L, KF—802.5 (X2 root), KF_ 802), the eluent is connected to tetrahydrofuran, the flow rate is lml/min, and the column temperature is 4〇t. The detection system was carried out with Ri (Refiectiw index), and the calibration curve used standard polystyrene manufactured by Sh〇dex. Synthesis Example 1 In a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Dean-Stark tube, a nitrogen purge was performed while adding 38 201139376 plus 140 parts of ι, 4 a ring of hexanes. Dinonyl formate (DMCD~p manufactured by Iwatani Gas Co., Ltd.), 314 parts of cyclohexanone 4-methanol, and 份.〇7 parts of tetrabutoxy titanium, reacted at 120 ° C for 1 hour, reacted at 1501 For 1 hour, react at 17 ° C for 1 hour at 190. (: The reaction was carried out while extracting the sterol formed by the reaction for 12 hours. The reaction was confirmed by gas chromatography (GC), and it was confirmed that the peak of 1,4-cyclohexanedicarboxylate was 1 The area is less than or equal to the area, and then cooled to 5 ° C. After the completion of the cooling, 347 parts of toluene is uniformly mixed, and then the reaction solution is washed three times with 80 parts of a 10% by weight aqueous sodium hydroxide solution, and further 100 parts by water. / After repeated washing with water until the wastewater becomes neutral, distilling and unreacting 3_cyclohexene-1 methanol by distillation under heating and reduced pressure by a rotary evaporator, thereby obtaining 240 parts of liquid at room temperature Diolefin compound. Synthesis Example 2 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, nitrogen gas was purged, and 15 parts of water and 95 parts of water were added, and 12 parts of phosphoric acid and 0.78 parts of phosphoric acid were added. Disodium hydrogen, 27 parts of hydrogenated tallow alkyl dithioglycolate (manufactured by LlonAkzo Co., Ltd., 5 wt% hexane solution, Ar_ 2HT-Acetate), 18 parts of toluene, 118 parts of synthesis example i The dilute hydrocarbon compound obtained in the process Mixing, thereby making the liquid in an emulsion state. The solution is heated to 5 〇〇C ' - while stirring vigorously, while adding 70% of the weight of hydrogen peroxide in the hour of i hurts in the state of 5 generations ^hour. The progress of the reaction was confirmed by gas chromatography, and it was confirmed that the raw material was 1 area% or less. 39 201139376 Then, after neutralizing the 'ai weight% aqueous sodium hydroxide solution, 25 parts by weight of 20% by weight of thiosulfuric acid was added. The aqueous solution was taken for % minutes, and it was allowed to stand still. The organic layer separated into 2 layers was taken out, and 20 parts of the active stone was added to the product (Ajinomoto Fine-Techno, manufactured by Ajinomoto Fine-Techno Co., Ltd., 衣^, CP1). 20 parts of bentonite (Bengel sh, manufactured by Hojun Co., Ltd.), and stirred for 1 hour under the official (7) t-shirt 丨 至 / / dish. The filtrate was washed with 1 liter of water for 3 times. The obtained organic layer was distilled to remove toluene, thereby obtaining 9 parts of an epoxy resin (EP-1) obtained as a liquid epoxy resin (EP-1), and the epoxy equivalent of the epoxy resin was η, yaw. 3 For flasks equipped with a blender, reflux cooling tube, and agitator While performing nitrogen purge, 15 parts of water, 19 parts of 12-tungstophosphoric acid, 1.6 parts of disodium hydrogen phosphate, and 5.4 parts of dihydrogenated tallow alkyl dimethyl ammonium acetate (manufactured by LionAkzo Co., Ltd., 50 weight) were added. The % hexane solution, the heart is called 2HT-ACetate), 160 parts of toluene, 11 parts of 3-cyclohexenecarboxylic acid-3 Cyclohexene methyl ester, and then stirred again to prepare a liquid in an emulsion state. The solution was heated to 50 ° C. While stirring vigorously, 70 parts of 35 wt% hydrogen peroxide was added in one hour. In this state, the mixture was stirred at 5 ° C for 2 hours. The progress of the reaction was confirmed by gas chromatography, and it was confirmed that the peak of the raw material was i area% or less. Then, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts by weight of a 20% by weight aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes and allowed to stand. The organic layer separated into two layers was taken out, and 4 parts of activated carbon (manufactured by Ajinomoto Fine-Techno Co., Ltd., CP1) and 40 parts of bentonite (manufactured by Hojun Co., Ltd., Bengel SH) were added thereto, and the mixture was stirred at room temperature for 1 hour. , 201139376 Transition. The obtained "卩丨(9) parts of water was subjected to 3 times of water washing and the machine layer was distilled to remove the stupidity, thereby obtaining 110 parts of liquid at room temperature: Yishuyue (EP-2). The epoxy equivalent is i3 〇g/eq. 虱Synthesis Example 4' A nitrogen purge is carried out in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, and a portion of bicyclopentadienyl dimethanol and 50 parts are added. Mixture of hydrogen phthalic anhydride and methylhexahydrophthalic anhydride: (manufactured by New Japan Physical and Chemical Co., Ltd., RIKACID ΜΗ-·, hereinafter referred to as anhydride H-1), heated under thief (4) for 1 hour, The mixture was heated and stirred at 6 ° C for 1 hour (the peak of dicyclopentadienyldiethanol was confirmed by GPC to be area / (> below), thereby obtaining a hardener composition of a mixture of 60 parts of a polycarboxylic acid and an acid anhydride. The resin obtained in the evening is a colorless liquid resin, and the purity obtained by GPC is: f 兀 carboxylic acid structure is 51 area% 'methyl hexahydrophthalic anhydride and hexahydrophthalic acid The total amount is 49% by area. In addition, the functional group equivalent is 2〇1 g/eq. _ Further, the resulting hardening 12 parts of i, 2,4-cyclohexane-formic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., Η_τΜΑη, referred to as Η 2 ) was added to make a uniform hardener composition (β — ^ ). Synthesis Example 5 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, while applying a nitrogen purge, add 1 part of the diol (7) as a main component of the hindered amine compound (by the gas phase). The purity obtained by chromatography is 9 丨 area%, and contains 5 area% of 4-hydroxy-2,2,m-tetramethylpiperidine. It is detected by the 201139376 trimethyl sulfonation treatment. Therefore, it is not the correct purity. Hereinafter, it is called D-1), a mixture of methyl hexahydrophthalic anhydride and hexahydrophthalic acid needle (manufactured by New Japan Physical and Chemical Co., Ltd., rikacid) MH700 'hereinafter referred to as an acid anhydride hi), which was heated and stirred at 5 ° C for 1 hour, and heated and stirred at 70 ° C for an hour (by GPC, the peak of the diol (2) was 1 area% or less). 120 parts of a HALS composition (F_i) containing the polycarboxylic acid (A-1) of the present invention was obtained. Light yellow liquid resin. The functional group equivalent was 185 g/eq. (The acid anhydride and the oxic acid were each monofunctional). Synthesis Example 6 Nitrogen gas was introduced in a flask equipped with a mixer, a reflux cooling tube, and a mixing device. Rinse, add 2 parts of diol (D _ 1 ), 73 parts of anhydride (Η-1), 15 parts of 1,2,4-cyclohexanetricarboxylic acid-L2-anhydride (Mitsubishi Gas Chemical, Η One TMAn) was heated and stirred at 50 ° C for 1 hour, and heated and stirred at 70 ° C for 1 hour (the peak of the diol (2) was confirmed to be 1 area% or less by GPC). Thus, 100 parts of the HALS composition (F_2) containing the polycarboxylic acid (A-2) of the present invention was obtained. The obtained resin was a pale yellow liquid resin. The functional group equivalent was 171 g/eq. Example 1 '2 and Comparative Examples 1, 2, 3, and 4, respectively, were added to the total amount of the epoxy resin and the hardener, and the polycarboxylic acid of the present invention obtained in Synthesis Examples 5 and 6 obtained in Synthesis Examples 5 and 6 was added. The hals composition (F 1 , F — 2 ), the HALS manufactured by Ciba Japan Co., Ltd. as a comparative example, the tinuvin 765, the tinuvin 770 'HALS manufactured by ADEKA Co., Ltd., LA-87, and LA-62' were used to form a curable resin composition. 42 201139376 9 Other compounds used in the curable resin composition are as follows. Further, the blending thereof is as shown below. • Epoxy resin: Epoxy resin produced in Synthesis Example 2 (ερ - 1 ) 3 3 parts of epoxy resin (ερ 2 ) produced in Synthesis Example 3 4 parts • Hardener: Hardening produced in Synthesis Example 4 Composition (β-1) 8 · 3 parts • Hardening catalyst: XC9206 manufactured by KING INDUSTRIES Co., Ltd. 3 parts (LED lighting test) The curable resin composition obtained in the examples and the comparative examples was filled to The syringe was cleaned to a surface-mounted LED package having an outer diameter of 5 mm square (having an inner diameter of 4.4 mm and an outer wall height of 1 25 mm) on which a wafer having a central emission wavelength of 465 nm was placed. The cast material was placed in a heating furnace to be hardened at 1 20 C for 1 hour, and further hardened at 15 Torr for 3 hours to obtain an LED package. The illuminance before and after reflow soldering of the obtained LED was measured simply using a light-receiving element. (The light-emitting LED emits light at a current of 30 mA at a predetermined current, and receives light by a light receiving element (Photodiode visible light BS500B, Sharp Corporation) to measure the current flowing therein as a measure of illuminance). The measurement is performed immediately after the LED is sealed, and the illuminance is measured after the reflow test, and the difference is confirmed. The results are shown in Table 1. Reflow soldering test Using a high temperature observation device (SMT scope SK-5000 Shanyang Seiko Co., Ltd. 43 201139376 Co., Ltd.). The temperature was raised from 2 5 C at 2 ° C / sec to 150 ° C, then held for 2 minutes, and then raised to 2 6 0 C ' at 2 C / sec for 1 sec. [Table 1] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 HALS composition or HALS F-1 F-2 tinuvin 765 tinuvin 77 〇 LA-87 LA-62 Initial illuminance (β Α) 34.2 34.5 33.0 32.7 32.9 34.0 Illumination after reflow soldering ___(βΑ) 31.9 32.6 29.0 27.8 27.4 29.9 Illuminance retention rate 93.3% 94.5% 87.9% 85.0% 83.3% 87.9% From the above results, the cured product containing the carboxylic acid composition of the present invention is known. The resin which is excellent in heat resistance and excellent in illuminance after reflow soldering and excellent in illuminance retention rate can provide a cured product excellent in heat resistance. The present invention has been described in detail with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention, and the present invention is based on the application of the application on January 19, 2010. Patent application (Japanese Patent Application No. 2010-008822), the entire disclosure of which is incorporated herein by reference. The present invention relates to a carboxylic acid composition and a composition containing a chemical resin which are suitable for use as an additive for plastics in electrical and electronic materials. 44 201139376 [Simple description of the diagram] None [Main component symbol description

Claims (1)

201139376 VII. Patent application scope: 1. A carboxylic acid composition, which is represented by the following formula (1) -Mountain (in the formula, a plurality of R may be the same or different, respectively, and the number of alkyl groups or aryl groups of 1 to 20 may be independently eliminated, and a plurality of n may be phase s or different average values, respectively For 丨~3). 2. A carboxylic acid composition which is represented by the following formula (2) Obtained by reacting with an anhydride having a carbon number of 3 to 22. 3_ - The manufacturing method of the carboxylic acid composition of the second application patent scope is characterized in that: the following formula (2) is made (2) The reaction is carried out at 4 〇 to 5 〇 t with an acid anhydride having a carbon number of 3 to 22 in an organic solvent having no solvent or 5 〇 46 201139376 wt% or less with respect to the raw material. A light stabilizer composition characterized by being a mixture of a carboxylic acid composition and an acid anhydride of claim No. 2 or 2. 5. A plastic composition comprising the slow acid composition of claim i or 2, and/or the light stabilizer composition of the fourth aspect of the patent application. The sclerosing resin 3, the carboxylic acid composition of the patented formula or the quinone carboxylic acid composition, and/or the light stabilizer composition and the curable resin of the fourth aspect of the patent. 6-sclerosing tree 7. A type of hardened material which is obtained by hardening a patented composition of a lipid composition. 47