JP5656213B2 - Carboxylic acid composition and curable resin composition containing the carboxylic acid composition - Google Patents

Description

  The present invention relates to a carboxylic acid composition as an additive for plastics suitable for electrical and electronic materials and optical applications, and a curable resin composition containing the carboxylic acid composition.

Plastic (including thermosetting resin) deteriorates due to the influence of light. In particular, light having large energy acts on a polymer constituting a plastic (including a thermosetting resin), breaks a bond, and induces deterioration (embrittlement, coloring, etc.).
In order to protect components from such an environment, a light stabilizer (HALS) is added, and there is a great need for improving weather resistance especially for automobile parts, home appliances and OA parts.
HALS prevents deterioration due to ultraviolet rays and improves the weather resistance of plastics. HALS itself absorbs little ultraviolet light, but is said to be stabilized by scavenging harmful free radicals generated by ultraviolet energy.

  For this reason, HALS is not only a variety of plastics, such as polyolefins such as PP, HDPE and LDPE, styrenes such as HIPS, GPPS and ABS, engineering plastics such as PBT, PET, PC, POM and PA, as well as PU, PVC. Addition to various resins such as epoxy resins and acrylic resins has been studied.

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HALS has various structures other than the hindered piperidine structure, but its action mechanism requires a smooth transition to the resin surface where UV degradation occurs. A compound that does not have a sex group is common, and therefore, after bleeding out, there is a problem that it volatilizes or is extracted out of the system by extraction. In order to solve such a problem, various types of high molecular weight HALS that are difficult to move in the system have been studied. However, although the volatilization is improved, there is a problem that the movement inside is difficult and the characteristics are not easily obtained.
Moreover, although the light stability can be imparted by HALS, there is a problem that the thermal colorability deteriorates. However, in order to have sufficient light stability, a certain amount of HALS is required, and therefore HALS excellent in heat-resistant coloring property is required.
The present invention has been made to solve such problems, and an object of the present invention is to provide HALS that has good fixability to a resin and is excellent in heat-resistant coloring.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
Following formula (1)

（式中、複数存在するＲ、ｎはそれぞれ独立して、Ｒは炭素数１〜２０のアルキル基またはアリール基を表す。またｎは平均値であり１〜３である。）で表されるカルボン酸組成物、
（２）
下記式（２）

(In the formula, a plurality of R and n are each independently R represents an alkyl group or an aryl group having 1 to 20 carbon atoms, and n is an average value and is 1 to 3). A carboxylic acid composition,
(2)
Following formula (2)

と炭素数３〜２２の酸無水物との反応により得られるカルボン酸組成物、
（３）
無溶剤、もしくは使用する原料に対し、５０重量％以下の有機溶剤中、４０〜１５０℃で反応させることを特徴とする前項（２）に記載のカルボン酸組成物の製造方法、
（４）
前項（１）または（２）に記載のカルボン酸組成物と酸無水物との混合物であることを特徴とするＨＡＬＳ組成物、
（５）
前項（１）または（２）に記載のカルボン酸組成物、および／または前項（４）に記載のＨＡＬＳ組成物を含有するプラスチック、
（６）
前項（１）または（２）に記載のカルボン酸組成物、および／または前項（４）に記載のＨＡＬＳ組成物を含有する硬化性樹脂組成物、
（７）
前項（６）に記載の硬化性樹脂組成物を硬化してなる硬化物、
に関する。

And a carboxylic acid composition obtained by reaction of a C3-22 acid anhydride,
(3)
The method for producing a carboxylic acid composition according to item (2) above, wherein the reaction is carried out at 40 to 150 ° C. in an organic solvent of 50% by weight or less with respect to a solvent-free or raw material to be used,
(4)
A HALS composition, which is a mixture of the carboxylic acid composition according to (1) or (2) and an acid anhydride;
(5)
A plastic containing the carboxylic acid composition according to (1) or (2) above and / or the HALS composition according to (4) above,
(6)
A curable resin composition comprising the carboxylic acid composition according to (1) or (2) above and / or the HALS composition according to (4) above;
(7)
Hardened | cured material formed by hardening | curing curable resin composition of previous clause (6),
About.

  Carboxylic acid composition of the present invention (In the present specification, for the sake of convenience, a single carboxylic acid compound is also expressed as a carboxylic acid composition, and the carboxylic acid composition of the present invention includes such an embodiment. ) Has an effect as a light stabilizer (HALS), and can be added to various plastic materials, and in a resin that can react with carboxylic acid (or can be bonded by intermolecular force). In addition to being a structure that can control the discharge of water, it has a structure excellent in heat-resistant colorability, and thus is useful for various plastic materials and curable resin compositions. The curable resin composition of the present invention is particularly useful in a curable resin composition containing an epoxy resin that can be expected to react with a carboxylic acid in the system, and is used as a paint, an adhesive, a molded article, a semiconductor, and an optical semiconductor. Useful as raw materials and modifiers for encapsulants, optical semiconductor die bond materials, polyimide resins, plasticizers, lubricating oil raw materials, pharmaceutical and agrochemical intermediates, paint resin raw materials, and toner resins However, since the carboxylic acid composition of the present invention is particularly excellent in transparency, it is extremely useful as an additive for a high-brightness white LED or a curable resin composition for sealing an optical semiconductor.

（式中、複数存在するＲ、ｎはそれぞれ独立して、Ｒは炭素数１〜２０のアルキル基またはアリール基を表す。またｎは平均値であり１〜３である。）で表される。
置換基Ｒは鎖状、あるいは環状のアルキル基、もしくはアリール基が好ましく、耐熱性、耐光性の観点から置換／あるいは非置換のシクロヘキサン環、ベンゼン環、架橋多環式アルキル環（ノルボルネン環やトリシクロデカン環）、ナフタレン環などが特に好ましい。 The polyvalent carboxylic acid of the present invention has the following formula (1)

(In the formula, a plurality of R and n are each independently R represents an alkyl group or an aryl group having 1 to 20 carbon atoms, and n is an average value and is 1 to 3). .
The substituent R is preferably a chain or cyclic alkyl group or an aryl group. From the viewpoint of heat resistance and light resistance, a substituted / unsubstituted cyclohexane ring, benzene ring, bridged polycyclic alkyl ring (norbornene ring or tricyclic ring) is preferred. Cyclodecane ring) and naphthalene ring are particularly preferred.

で表される化合物と酸無水物との付加反応により製造される（以下、前記式（２）の化合物をジオール（２）と称す。本化合物は４−ヒドロキシ−２，２，６，６−テトラメチルピペリジンのエチレンオキサイド付加により製造することができ、原料の４−ヒドロキシ−２，２，６，６−テトラメチルピペリジンや、エチレンオキサイドがさらに付加した物を含んでも構わない。）。使用できる酸無水物としては、例えば無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ［２，２，１］ヘプタン−２，３−ジカルボン酸無水物、メチルビシクロ［２，２，１］ヘプタン−２，３−ジカルボン酸無水物、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物などの化合物が挙げられるが、分子内に一つ以上の環状酸無水物構造を有する酸無水物であれば特に限定されず、２種類以上を混合しても構わない。
好ましい酸無水物としてはシクロヘキサン構造を有するアルキル置換あるいはカルボキシル基による置換、もしくは無置換の酸無水物構造を分子内に１つ以上有する多価カルボン酸無水物であり、具体的には１，２，４−シクロヘキサントリカルボン酸−１，２−無水物、４−メチルシクロヘキサン−１，２−ジカルボン酸無水物、シクロヘキサン−１，２−ジカルボン酸無水物などが挙げられるがこれに限らず、２種類以上を混合しても構わない。 The carboxylic acid composition of the present invention has the following formula (2)

(Hereinafter, the compound of the formula (2) is referred to as diol (2). This compound is 4-hydroxy-2,2,6,6- It can be produced by addition of tetramethylpiperidine with ethylene oxide, and may include 4-hydroxy-2,2,6,6-tetramethylpiperidine as a raw material or a product further added with ethylene oxide. Examples of acid anhydrides that can be used include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride. Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- Examples of the compound include dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and any acid anhydride having one or more cyclic acid anhydride structures in the molecule. It does not specifically limit and you may mix 2 or more types.
Preferred acid anhydrides are polyvalent carboxylic acid anhydrides having one or more alkyl-substituted, carboxyl-substituted, or unsubstituted acid anhydride structures in the molecule having a cyclohexane structure. , 4-cyclohexanetricarboxylic acid-1,2-anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, etc. The above may be mixed.

The reaction between the acid anhydride and the diol (2) is generally an addition reaction using an acid or a base as a catalyst, but in the present invention, a reaction without a catalyst is particularly preferable.
When a catalyst is used, examples of the catalyst that can be used include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, hydroxide Metal hydroxides such as potassium, calcium hydroxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7 -Heterocyclic compounds such as ene, imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethyl Ammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, A quaternary ammonium salt such as trioctylmethylammonium acetate can be used. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

  The amount of the catalyst used is not particularly limited, but is preferably 0.001 to 5 parts by weight based on the total weight of the raw material of 100 parts by weight.

  In this reaction, a reaction without a solvent is preferable, but an organic solvent may be used. The amount of the organic solvent used is 0.005 to 1, preferably 0.005 to 0.7, more preferably 0.005, in a weight ratio with respect to the total amount 1 of the acid anhydride and diol as reaction substrates. ˜0.5 (ie 50% by weight or less). When the weight ratio exceeds 1, the progress of the reaction is extremely slow, which is not preferable. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, diethyl ether , Ethers such as tetrahydrofuran and dioxane, and ester compounds such as ethyl acetate, butyl acetate and methyl formate can be used.

  The reaction temperature is preferably 40 to 200 ° C, particularly preferably 40 to 150 ° C. In particular, when this reaction is carried out in the presence of an excess (amount ratio exceeding equimolar) of an acid anhydride and without a solvent, the reaction at 100 ° C. or lower is preferred because of the volatilization of the acid anhydride. The reaction at is particularly preferred.

The reaction ratio between the acid anhydride and the diol (2) is theoretically preferably an equimolar reaction, but can be changed as necessary. That is, as will be described later, when the acid anhydride used in the curable resin composition of the present invention and the acid anhydride used here are the same, the reaction is carried out in an excess of acid anhydride at the time of production. When the reaction between the anhydride and the diol (2) is completed, a mixture (HALS composition) of the acid anhydride and the carboxylic acid composition of the present invention may be used.
As a specific reaction ratio, the functional group equivalent is compared, and when the acid anhydride is 1, the cross-linked polycyclic diols are 0.001 to 2, more preferably 0.01 to 1.5 by the molar ratio. More preferably, it is 0.01-1.1. When manufacturing a hardening | curing agent composition as mentioned above, it is preferable to use in the range of 0.01-0.7, More preferably, 0.01-0.5.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a large amount of energy. An excessively short reaction time means that the reaction is abrupt and is not preferable from the viewpoint of safety. A preferred range is 1 to 48 hours, preferably 1 to 36 hours, and more preferably 1 to 24 hours.

  When a catalyst is used after completion of the reaction, the catalyst is removed by neutralization, water washing, adsorption, etc., and the solvent is distilled off to obtain the desired polyvalent carboxylic acid. In the case of a reaction without a catalyst, the product can be obtained by removing the solvent as necessary, and in the case of a solvent-free or catalyst-free reaction, taking it out as it is.

The most preferred production method is a method in which the acid anhydride and the diol (2) are reacted at 40 to 150 ° C. under non-catalytic and solvent-free conditions, and taken out as they are after completion of the reaction.
The carboxylic acid composition of the present invention thus obtained has the structure of the above formula (1) and usually shows a colorless to pale yellow solid resinous form (which may crystallize in some cases). In addition, when reacted in an excess of acid anhydride, the shape often shows a liquid state.

  The carboxylic acid composition (or HALS composition) of the present invention is suitable for stabilizing organic materials against oxidation, heat or light induced decay. Examples of such materials are:

Monoolefin and diolefin polymers:
For example, polypropylene (PP), polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, cycloolefin, cyclopentene, norbornene polymer, polyethylene (which may be non-crosslinked or crosslinked), for example Examples include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and branched low density polyethylene (BLDPE). However, the present invention is not limited thereto, and two or more types may be mixed. .
The aforementioned monoolefin polymers, especially polyethylene and polypropylene, are particularly preferably produced by the following method: a) radical polymerization (usually under high temperature and pressure).
b) Catalytic polymerization using a catalyst that usually contains one or more metals from groups IVb, Vb, VIb or VIII of the periodic table. These metals are usually one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, which may be π (pi)-or σ (sigma) -coordinated. It has alkenyl and / or aryl. These metal complexes may be free or fixed on a substrate, typically activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst can be used by itself in the polymerization, and other activators, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes can be used (see above metals). Is an element of group Ia, IIa and / or IIIa of the periodic table). The activator may be modified by conventional methods with other ester, ether, amine or silyl ether groups. Such catalyst systems are usually named Philips, Standard Oil Indiana, Ziegler Natta, TNZ (DuPont), metallocene or single site catalyst (SSC).

Copolymers of monoolefins with diolefins or with other vinyl monomers:
For example, ethylene / propylene copolymer, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / butene-1 copolymer, propylene / isobutylene copolymer, ethylene / butene-1 copolymer, ethylene / hexene copolymer , Ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, ethylene / vinyl acetate copolymer and their monoxide Copolymers with carbon or ethylene / acrylic acid copolymers and their salts (ionomers), and ethylene Terpolymers of propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene norbornene; and mixtures of the above copolymers with each other and with the polymers listed in the monoolefin and diolefin polymers such as polypropylene / ethylene propylene copolymers, LDPE / ethylene -Vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and their mixtures with other polymers such as polyamides.

Hydrocarbon resins (for example having 5 to 9 carbon atoms) and their hydrogenated modifications (for example tackifiers) and mixtures of polyalkylenes and starch.

Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene). For example, high impact polystyrene (HIPS), general purpose polystyrene (GPPS).

Copolymers of styrene or α-methylstyrene with diene or acrylic derivatives:
For example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; styrene copolymers and other polymers such as poly High impact mixtures with acrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / Propylene / styrene.

Styrene or α-methylstyrene graft copolymer:
For example, styrene for polybutadiene, styrene for polybutadiene-styrene or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) for polybutadiene, styrene, acrylonitrile and methyl methacrylate for polybutadiene, styrene and maleic anhydride for polybutadiene; styrene for polybutadiene, Acrylonitrile and maleic anhydride; polybutadiene with styrene and maleimide; polybutadiene with styrene and alkyl acrylate or methacrylate; ethylene / propylene / diene terpolymer with styrene and acrylonitrile, polyalkyl acrylate or polyalkyl methacrylate with styrene and acrylonitrile, acrylate / Tadiene copolymers known as styrene and acrylonitrile, and mixtures thereof with the copolymers listed in the above-mentioned copolymers of styrene or α-methylstyrene with diene or acrylic derivatives, eg ABS-, MBS-, ASA- or AES-polymers Copolymer mixture.

Halogen-containing polymer:
For example, polychloroprene, chlorinated rubber, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride (PVC), Polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

Polymers derived from α, β-unsaturated acids and derivatives thereof:
For example, polyacrylates and polymethacrylates; polymethylmethacrylate, polyacrylamide and polyacrylonitrile modified to impact resistance with butyl acrylate. Or copolymers of these monomers with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers. .

Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals:
For example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyrate, polyallyl phthalate or polyallyl melamine; copolymers with the aforementioned olefins.

Homopolymers and copolymers of cyclic ethers:
For example, polyalkylene glycol, polyethylene oxide, polypropylene oxide or a copolymer of these with bisglycidyl ether.

Polyacetal:
For example, polyoxymethylene containing polyoxymethylene (POM) and ethylene oxide as comonomers; polyacetal modified with thermoplastic polyurethane (PU), acrylate or MBS.

Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxide and styrene polymers or polyamides.

Polyurethanes derived from polyethers, polyesters or polybutadienes containing hydroxy end groups as one component and aliphatic or aromatic polyisocyanates as the other component and precursors thereof.

Polyamides (PA) and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams. For example, aroma starting from polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene, diamine and adipic acid Polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid with or without elastomer as a modifier, such as poly-2,4,4-trimethylhexamethylene terephthalamide Or poly-m-phenylene isophthalamide; the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers, or polyethers such as polyethylene glycol, polypropylene glycol or polytetramethyle. Block copolymers of glycol; as well as EPDM polyamides or modified with or ABS copolyamide; and processing polyamides condensed during (RIM polyamide systems).

Polyurea, polyimide, polyamideimide and polybenzimidazole.

Polyesters or corresponding lactones derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-1,4-dimethylol-cyclohexane terephthalate and polyhydroxybenzoate and hydroxy Block copolyetheresters derived from terminal polyethers; and polyesters modified with polycarbonate or MBS.

Polycarbonate (PC) and polyester carbonate.

Polysulfone, polyethersulfone and polyetherketone.

Crosslinked polymers derived from aldehyde as one component and phenol, urea and melamine as another component, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

Dry and non-dry alkyd resins.

Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and vinyl compounds as crosslinkers, and their halogen-containing modifications with low flammability.

Substituted acrylic ester:
For example, crosslinkable acrylic resins derived from epoxy acrylate, urethane acrylate or polyester acrylate.

Alkyd resin, polyester resin and acrylate resin crosslinked with melamine resin, urea resin, polyisocyanate or epoxy resin.

Epoxy resin:
For example, an epoxy resin composition derived from bisglycidyl ether or an alicyclic diepoxide. Curable resin with phenolic resin, amine compound (amino group-containing resin), acid anhydride, carboxylic acids, etc.

Natural polymer:
For example, cellulose, gum, gelatin and chemically modified polymer homologue derivatives thereof such as cellulose acetate, cellulose propionate and cellulose butyrate or cellulose ethers such as methylcellulose; and rosin and derivatives thereof.

Mixture of the aforementioned polymers (polyblend):
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 / heat Plastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.

Natural and synthetic organic materials that are pure monomeric compounds or mixtures of such compounds:
For example, the above oils, fats and waxes based on mineral oils, animal and vegetable fats, oils and waxes or synthetic esters (eg phthalates, adipates, phosphates or trimellitates) and mixtures of synthetic esters and mineral oils mixed in any weight ratio The material is typically used as a fiber spinning oil and as an aqueous emulsion of such material.

Aqueous emulsion of natural or synthetic rubber:
For example, natural latex of carboxylated styrene / butadiene copolymer.

  The resin composition of the present invention is 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.025 to 3 parts by weight, and still more preferably 100 parts by weight of the plastic material as described above. Is added at 0.025 to 1 part by weight.

  In this invention, addition to the curable resin composition containing an epoxy resin is preferable. The curable resin composition containing the carboxylic acid composition of the present invention includes paints, adhesives, molded articles, semiconductors, optical semiconductor encapsulant resins, optical semiconductor die bond material resins, polyamide resins, polyimide resins, and the like. Are useful as raw materials and modifiers, plasticizers and lubricating oil raw materials, pharmaceutical and agrochemical intermediates, paint resin raw materials, and toner resins. It is extremely useful as an epoxy resin used for optical semiconductor sealing.

Hereinafter, the curable resin composition of the present invention containing the carboxylic acid composition (HALS composition) of the present invention will be described.
The curable resin composition of the present invention preferably contains an epoxy resin.

  Examples of the epoxy resin that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, epoxy resin having siloxane structure (Si-O) (chain, cyclic, ladder, or a mixture of at least two of them) Glycidyl group and / or epoxycyclohexane in siloxane structure Include solid or liquid epoxy resin having an epoxy resin) or the like having a concrete, but not limited thereto.

In particular, when the curable resin composition of the present invention is used for optical applications, an alicyclic epoxy resin or an epoxy resin having a siloxane structure (Si-O), such as an epoxy group-containing silicone resin, preferably an epoxy having a silsesquioxane structure Use in combination with a resin is preferred. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These alicyclic epoxy resins include esterification reaction of cyclohexene carboxylic acid with alcohols or esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) )), Or Tyschenko reaction of cyclohexene aldehyde (method described in JP 2003-170059 A, JP 2004-262871 A, etc.), and transesterification of cyclohexene carboxylic acid ester (JP A And a compound obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Application Publication No. 2006-052187.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diols, diols such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc. And tetraols. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), A method using an organic solvent (Japanese Patent Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

In particular, in the case of an epoxy resin having a siloxane structure (Si-O), it is not particularly limited as long as it is a compound having a siloxane structure, and various silane coupling agents (coupling agents having a glycidyl group and / or an epoxycyclohexane group are essential). And a compound obtained by a sol-gel reaction with a component) and having a structure in which silicone oil or polyhydric alcohols are incorporated into the molecule as a segment.
Specific examples thereof include compounds described in republished patents WO2005 / 100445, Japanese Patent Application No. 2008-225472, and Japanese Patent Application Laid-Open No. 2007-326988.
These may be used alone or in combination of two or more.

  Examples of the curing agent that can be used in the curable resin composition of the present invention include amine compounds, acid anhydride compounds having an unsaturated ring structure, amide compounds, phenol compounds, and carboxylic acid compounds. . Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, Bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid- 3, -Anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1, 1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols ( Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, , 4'-bis (chloromethyl) benzene, polycondensates with 1,4'-bis (methoxymethyl) benzene, and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane -Examples include, but are not limited to, amine complexes, guanidine derivatives, and condensates of terpenes and phenols. In some cases, the carboxylic acid composition (HALS composition) of the present invention may be used as a curing agent. 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 epoxy resin to the curing agent is 0.5 to 1.5 equivalents based on 1 equivalent of the epoxy groups of all epoxy resins (monofunctional carboxylic acid, 1 acid anhydride). It is considered to be organoleptic), particularly preferably 0.7 to 1.2 equivalents. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  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 curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2 ′ -Methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxy Various imidazoles of methylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, Salts with polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7 and their tetraphs Salts such as nylborate and phenol novolac, salts with the above polycarboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (tolyl) phosphine Phosphines and phosphonium compounds such as tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and curing thereof Examples thereof include a microcapsule-type curing accelerator having a microcapsule as an accelerator. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

  The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, you may add antioxidant to the curable resin composition of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part of resin components in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part.

  Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) ethyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

  Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.

  These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Further, the curable resin composition of the present invention may be used in combination with another light stabilizer in combination with the carboxylic acid composition of the present invention.
Examples of the light stabilizer that can be used in combination include the following amine compounds.
For example, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl ) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis ( 2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetramethyl-4-piperidyl methacrylate Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2 , 6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2 , 2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decanedioic acid bi (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ″, N ″ ′ -Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane- 1,10-diamine, dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- ( 2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-Diyl] [(2,2 , 6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and 4-hydroxy-2,2,6 , 6-Tetramethyl-1-piperidineethanol polymer, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa-3,20-diazadispiro [5.1 11.2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1 -(2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [5,1,11,2] Heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -heneicosane-20- Propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6 Hindered amines such as 1,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) , Benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) Enol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2 -(3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl-3- ( Reaction product of 3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl) -6-dodecyl- Benzotriazole compounds such as 4-methylphenol, 2,4-di-tert-butyl Benzoates such as phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy ] Triazine-based compounds such as phenol and the like can be mentioned, and hindered amine-based compounds having a piperidine skeleton are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  Furthermore, binder resin can also be mix | blended with the curable resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

  An inorganic filler can be added to the curable resin composition of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.

When using the curable resin composition of this invention for an optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y Examples include ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) 3 Cl: Eu, (SrEu) O.Al ₂ O _{3, and the} like. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part of the resin component, Preferably it is 5-60 weight part.

  The curable resin composition of this invention is obtained by mixing each component uniformly. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are thoroughly mixed using an extruder, kneader, roll, etc. as necessary until uniform. If the curable resin composition is in liquid form, potting or casting, impregnating the base material, pouring the curable resin composition into a mold, casting, curing by heating, or solid In this case, there is a method of molding by using a casting after melting or a transfer molding machine and further curing by heating. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, it can be hardened at a high temperature at a stretch, but it is preferable to raise the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 80 and 150 ° C., and post-curing is performed between 100 and 200 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

  Further, the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, glass fiber, A prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heat-dried is subjected to hot press molding to obtain a cured product of the curable resin composition of the present invention. can do. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

  Moreover, the curable resin composition of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B stage. Such a film-type resin composition is formed by applying the curable resin composition of the present invention on the release film as the curable resin composition varnish, removing the solvent under heating, and then performing B-stage. To obtain a sheet-like adhesive. This 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 an optical semiconductor sealing material or die bonding material will be described in detail.

  When the epoxy resin composition of the present invention is used as a sealing material for an optical semiconductor such as a high-intensity white LED, or a die bond material, a curing agent (curing agent composition) containing the polyvalent carboxylic acid of the present invention, Prepare an epoxy resin composition by thoroughly mixing additives such as curing accelerators, coupling materials, antioxidants, light stabilizers, etc., in addition to epoxy resins, and seal them as sealing materials or die bond materials. Used for both materials. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

  Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and to play a role of a lens. The epoxy resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.

As a method of adhering a semiconductor chip to a substrate using the curable resin composition of the present invention, the epoxy resin composition of the present invention is applied by a dispenser, potting, or screen printing, and then the semiconductor chip is placed and heat cured. The semiconductor chip can be bonded. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
For example, the heating condition is preferably 80 to 230 ° C. and about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. For example, the heating condition is preferably 80 to 230 ° C. and about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

  Furthermore, the curable resin composition of the present invention can be used for general applications in which thermosetting resins such as epoxy resins are used. Specifically, adhesives, paints, coating agents, molding materials (sheets) , Film, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, and acrylate esters as resist curing agents Examples thereof include additives to other resins and the like.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

  The cured product of the present invention obtained by curing the curable resin composition of the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a polarizer protective film in the liquid crystal display field. Also, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, LED display devices, which are expected as next-generation flat panel displays LED mold material, LED sealing material, front glass protective film, front glass substitute material, adhesive, and substrate material in plasma addressed liquid crystal (PALC) display, light guide plate, prism sheet, deflection plate, Retardation plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various films in field emission display (FED) Board, front Protective film of glass, front glass substitute material, an adhesive. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. In the examples, the measurement of gel permeation chromatography (hereinafter referred to as “GPC”) is as follows.
The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., the detection was performed by RI (Reflective index), and a standard polystyrene made by Shodex was used for the calibration curve.

Synthesis example 1
A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, and 140 parts of dimethyl 1,4-cyclohexanedicarboxylate (DMCD-p manufactured by Iwatani Gas Co., Ltd.), cyclohexene-4-methanol 314 And 0.07 part of tetrabutoxytitanium were added, and the reaction was carried out at 120 ° C. for 1 hour, 150 ° C. for 1 hour, 170 ° C. for 1 hour, and 190 ° C. for 12 hours while removing methanol produced by the reaction. When the progress of the reaction was confirmed by gas chromatography (GC), it was confirmed that the peak of dimethyl 1,4-cyclohexanedicarboxylate was 1% by area or less, and then cooled to 50 ° C.
After cooling, 347 parts of toluene was added and homogenized, and then the reaction solution was washed 3 times with 80 parts of a 10 wt% aqueous sodium hydroxide solution, and further washed with water until the wastewater became neutral at 100 parts / time of water. Then, 240 parts of a liquid diolefin compound was obtained at room temperature by distilling off toluene and unreacted 3-cyclohexene-1-methanol under reduced pressure by heating with a rotary evaporator.

Synthesis example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 of disodium hydrogen phosphate, di-tallow alkyldimethylammonium acetate while purging with nitrogen. 7 parts (50% by weight lion solution manufactured by Lion Akzo, Acquard 2HT Acetate), 180 parts of toluene, 118 parts of the diolefin compound obtained in Synthesis Example 1 were added, and the mixture was stirred again to obtain a liquid in an emulsion state. The temperature of this solution was raised to 50 ° C., and 70 parts of 35 wt% hydrogen peroxide water was added over 1 hour while stirring vigorously, and the mixture was stirred at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by gas chromatography, the raw material peak was 1 area% or less.
Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of activated carbon (CP1 manufactured by Ajinomoto Fine Techno) and 20 parts of bentonite (Bengel SH manufactured by Hojun) were added thereto, and the mixture was stirred for 1 hour at room temperature and then filtered. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 119 parts of a liquid epoxy resin (EP-1) at room temperature. The epoxy equivalent of the obtained epoxy resin was 217 g / eq. Met.

Synthesis example 3
4. A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 1.9 parts of 12-tungstophosphoric acid, 1.6 sodium disodium hydrogen phosphate, di-tallow alkyldimethylammonium acetate 4 parts (50% by weight hexane solution manufactured by Lion Akzo, Acquard 2HT Acetate), 160 parts of toluene, 110 parts of 3-cyclohexenecarboxylic acid 3-cyclohexene methyl ester were added, and the mixture was stirred again to obtain a liquid in an emulsion state. The temperature of the solution was raised to 50 ° C., and 70 parts of 35 wt% hydrogen peroxide water was added over 1 hour while stirring vigorously, and the mixture was stirred at 50 ° C. for 20 hours. When the progress of the reaction was confirmed by gas chromatography, the raw material peak was 1 area% or less.
Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 40 parts of activated carbon (CP1 manufactured by Ajinomoto Fine-Techno) and 40 parts of bentonite (Bengel SH manufactured by Hojun) were added thereto, and the mixture was stirred for 1 hour at room temperature and then filtered. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 110 parts of a liquid epoxy resin (EP-2) at room temperature. The epoxy equivalent of the obtained epoxy resin is 130 g / eq. Met.

Synthesis example 4
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 10 parts of dicyclopentadiene dimethanol, a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (Shin Nippon Rika ( Co., Ltd., Rikacid MH-700, hereinafter referred to as “anhydride H-1” is added, and the mixture is heated and stirred at 40 ° C. for 1 hour at 60 ° C. for 1 hour (by GPC, the peak of dicyclopentadienedimethanol) Was found to be 1 area% or less.), 60 parts of a curing agent composition which was a mixture of polycarboxylic acid and acid anhydride was obtained.
The obtained resin was a colorless liquid resin, and the purity by GPC was 51 area% for the structure of polycarboxylic acid, and the total amount of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride was 49 area%. . The functional group equivalent was 201 g / eq. Met.
Furthermore, 12 parts of 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (hereinafter referred to as H-TMAn, hereinafter referred to as H-2) manufactured by Mitsubishi Gas Chemical Co., Ltd. was added to the obtained curing agent composition. It was set as the uniform hardening | curing agent composition (B-1).

Synthesis example 5
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and a hindered amine compound containing diol (2) as a main component (purity of 91 area% by gas chromatography, 4-hydroxy-2 , 2,6,6-tetramethylpiperidine is contained in an area of 5% by area and is not accurate because it is detected by trimethylsilylation treatment, hereinafter referred to as D-1.) 10 parts, methylhexahydrophthalic anhydride 100 parts of a mixture of the product and hexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH700, hereinafter referred to as acid anhydride H1) is added, and the mixture is heated and stirred at 50 ° C for 1 hour and at 70 ° C for 1 hour (The peak of the diol (2) was confirmed to be 1 area% or less by GPC.) Thereby, 120 parts of HALS composition (F-1) containing the polyvalent carboxylic acid (A-1) of the present invention was obtained. The obtained resin was a pale yellow liquid resin. Functional group equivalent is 185 g / eq. (Acid anhydride and carboxylic acid are considered to be monofunctional each).

Synthesis Example 6
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, and 12 parts of diol (D-1), 73 parts of acid anhydride (H-1), 1,2,4-cyclohexanetricarboxylic acid -1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd.) 15 parts was added, and the mixture was heated and stirred at 50 ° C. for 1 hour and 70 ° C. for 1 hour (the peak of diol (2) was 1% by GPC. Confirmed that :) As a result, 100 parts of a HALS composition (F-2) containing the polyvalent carboxylic acid (A-2) of the present invention was obtained. The obtained resin was a pale yellow liquid resin. Functional group equivalent is 171 g / eq. Met.

Examples 1 and 2, Comparative Examples 1, 2, 3, 4,
HALS composition (F-1, F-2) containing the polyvalent carboxylic acid of the present invention obtained in Synthesis Examples 5 and 6, as comparative examples, HALS: tinuvin 765, tinuvin 770 manufactured by Ciba Japan, HALS manufactured by Adeka: LA -87 and LA-62 were added at 2000 ppm to the total amount of epoxy resin and curing agent, respectively, to prepare a curable resin composition.
Other compounds used in the curable resin composition are as follows. The blending ratio is as shown below.
·Epoxy resin:
Epoxy resin (EP-1) produced in Synthesis Example 2 3.3 parts
4.9 parts of epoxy resin (EP-2) produced in Synthesis Example 3 Curing agent:
8.3 parts of curing agent composition (B-1) produced in Synthesis Example 4 and curing catalyst:
King Industries XC9206 0.03 part

(LED lighting test)
The curable resin compositions obtained in Examples and Comparative Examples were filled into syringes, and a precision discharge device was used to mount an outer diameter 5 mm square surface mount LED package (inner diameter 4.4 mm, The outer wall height was 1.25 mm). The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours, and an LED package was prepared. About the obtained LED, the illuminance before and after the reflow was simply measured using a light receiving element. (Under light shielding, the prepared LED was made to emit light at a specified current of 30 mA, received by a light receiving element (Photodiode visible light BS500B manufactured by Sharp), and the current value flowing there was used as a measure of illuminance.) The measurement was performed for the illuminance immediately after LED sealing and after the reflow test, and the difference was confirmed. The results are shown in Table 1.
Reflow test Using a high-temperature observation device (SMT scope SK-5000 Sanyo Seiko Co., Ltd.).
The temperature was raised from 25 ° C. to 150 ° C. at a rate of 2 ° C./second, then held for 2 minutes, further raised to 260 ° C. at 2 ° C./second, and held for 10 seconds.

  From the above results, the cured product containing the carboxylic acid composition of the present invention is not only excellent in the initial illuminance, but also is a resin excellent in illuminance after reflow and its illuminance retention, and a cured product excellent in heat resistance. I can give you.

Claims (7)

Following formula (1)

(Wherein, there exist a plurality of R, n are each independently, R represents an alkyl group or an aryl group having 1 to 20 carbon atoms. The n is 1 to 3 in value.) Carboxylic acid represented by A carboxylic acid composition comprising one or more of the following. Following formula (2)

The carboxylic acid composition obtained by addition reaction with the diol represented by these, and a C3-C22 acid anhydride. 3. The method for producing a carboxylic acid composition according to claim 2, wherein the reaction is carried out at 40 to 150 [deg.] C. in a solvent-free or raw material used in an organic solvent of 50% by weight or less. A HALS composition, which is a mixture of the carboxylic acid composition according to claim 1 or 2 and an acid anhydride. A plastic containing the carboxylic acid composition according to claim 1 and / or the HALS composition according to claim 4. A curable resin composition containing the carboxylic acid composition according to claim 1 and / or the HALS composition according to claim 4. A cured product obtained by curing the curable resin composition according to claim 6.