TWI743364B - Triazine compound, curable composition, method for producing hardened product, and hardened product - Google Patents

Abstract

Provides a triazine compound that has excellent solubility in p-toluene or dimethylformamide, and can obtain a curable composition with excellent ultraviolet absorbing ability, a curable composition containing the triazine compound, a method for manufacturing the cured product, and curing Things. A triazine compound, which is formed by linking three aromatic groups substituted by a hydroxyl group at the 2nd position with a triazine ring, and one or two of the three aromatic groups are selected from acrylic groups and methyl groups. An aromatic group of at least one group of an acrylic group, an epoxy group, and an allyl group.

Description

Triazine compound, curable composition, method for producing hardened product and hardened product

The present invention relates to a triazine compound, a curable composition, a method for producing a hardened product, and the hardened product. More specifically, it relates to the excellent solubility of p-toluene or dimethylformamide, and excellent ultraviolet rays can be obtained. A triazine compound of a curable composition with absorption capacity, a curable composition containing the triazine compound, a method for producing a cured product, and a cured product.

Curable compositions used for sealing materials, adhesives, paints, etc. that bond the transparent substrate to the adherend are required to have various properties such as curability, adhesiveness, and coating processability. The use of an organic resin composition for the curable composition is preferable in terms of ease of processing, but when exposed to ultraviolet rays, the organic resin will be accelerated by its discoloration or resin embrittlement. Therefore, various ultraviolet absorbers have been developed so far, and studies have been conducted to impart excellent weather resistance to organic resins.

For example, in Patent Document 1, it is proposed to form a hard coat layer of a benzotriazole-based compound containing a UV absorber having a radically polymerizable (meth)acrylic functional group on a substrate film. Weather-resistant hard coat film. According to Patent Document 1, a large amount of ultraviolet absorber can be contained without impairing the hardness of the hard coat layer, and a hard coat layer having both high hardness and excellent ultraviolet absorber can be obtained.

In addition, Patent Document 2 proposes a hard coat film produced using a curable composition containing a triazine-based ultraviolet absorber having a (meth)acryloyl group. According to Patent Document 2, a hard coat film having excellent ultraviolet curability, hardness, and adhesion to the substrate can be obtained. [Prior Technical Documents] [Patent Documents]

[Patent Document 1]: Japanese Patent Application Publication No. 2007-230093 　　 [Patent Document 2]: Japanese Patent Application Publication No. 2013-203758

[The problem to be solved by the invention]

However, the benzotriazole-based ultraviolet absorber used in Patent Document 1 is not satisfactory in terms of its absorption wavelength and absorption capacity. In addition, the photocurable composition proposed in Patent Document 2 has insufficient moldability of the cured film, and there is a problem that a film with a uniform thickness cannot be produced stably.

Therefore, the object of the present invention is to provide a triazine compound which is a curable composition with excellent solubility in p-toluene or dimethylformamide, and a curable composition with excellent ultraviolet absorption ability, a curable composition containing it, and The manufacturing method of the hardened object and the hardened object. [Means to solve the problem]

The inventors of the present invention have worked hard to solve the above-mentioned problems and found that if three aromatic groups substituted by a hydroxyl group at position 2 are connected to the triazine ring, one or two of the three aromatic groups A triazine compound containing an acrylic group, a methacrylic group, an epoxy group, or an aromatic group of an allyl group can overcome the above-mentioned problems and complete the present invention.

That is, the triazine compound of the present invention is characterized in that it is formed by linking three aromatic groups substituted by a hydroxyl group at position 2 with a triazine ring, and one or two of the aforementioned three aromatic groups, It is an aromatic group having at least one group selected from the group consisting of an acrylic group, a methacrylic group, an epoxy group, and an allyl group.

(通式(1)中，X表示碳原子數1~20之直鏈或具有分支之烷基、丙烯酸基或甲基丙烯酸基，烷基之一部分的氫原子被丙烯酸基、甲基丙烯酸基、環氧基，或烯丙基取代之基，R¹ 表示X，或直鏈或具有分支之碳原子數1~10之烷基，R² 表示直鏈或具有分支之碳原子數1~10之烷基，R³ ~R¹¹ 各自獨立表示氫原子、羥基、鹵素原子、碳原子數1~20之烷基、碳原子數2~20之烯基、碳原子數1~20之烷氧基、碳原子數6~20之芳基，全部之烷基、烯基、烷氧基，係直鏈或可具有分支，碳鏈之一部分，可被羰基、醯亞胺基、醯胺鍵或氧原子取代，碳鏈之氫原子，可被羥基取代)表示者，特佳為下述通式(2)

(通式(2)中，R¹² 表示碳原子數1~8之烷基，或下述式(3)

(式(3)中，R¹ ’表示碳原子數1~8之烷基)表示之基，R¹³ 及R¹⁴ 表示氫原子或甲基)表示者。Among the triazine compounds of the present invention, the following general formula (1) is preferred

(In the general formula (1), X represents a linear or branched alkyl group with 1 to 20 carbon atoms, an acrylic group or a methacrylic group, and a part of the hydrogen atom of the alkyl group is Epoxy group, or allyl group substituted, R ¹ represents X, or linear or branched alkyl with 1 to 10 carbon atoms, R ² represents linear or branched with 1 to 10 carbon atoms Alkyl group, R ³ ~ R ¹¹ each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, Aryl groups with 6 to 20 carbon atoms, all alkyl groups, alkenyl groups, and alkoxy groups, linear or branched, part of the carbon chain, can be bonded by carbonyl, imino, amide or oxygen atoms Substitution, the hydrogen atom of the carbon chain may be substituted by a hydroxyl group) is represented by the following general formula (2)

(In the general formula (2), R ¹² represents an alkyl group with 1 to 8 carbon atoms, or the following formula (3)

(In formula (3), R ¹ ′ represents an alkyl group having 1 to 8 carbon atoms) represents a group, and R ¹³ and R ¹⁴ represent a hydrogen atom or a methyl group).

The curable composition of the present invention is characterized by containing 0.001 to 20 parts by mass of the triazine compound of the present invention relative to 100 parts by mass of the total of the curable monomer, the curable oligomer, and the curable polymer .

The curable composition of the present invention preferably further contains 0.1 to 10 parts by mass of a polymerization initiator. The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.

The method for producing a cured product of the present invention is characterized by irradiating the curable composition of the present invention with light or heating at 50 to 200°C.

The cured product of the present invention is characterized by using the curable composition of the present invention. [Effects of Invention]

According to the present invention, it is possible to provide a triazine compound which is a curable composition with excellent solubility of p-toluene or dimethylformamide, and a curable composition with excellent ultraviolet absorption ability, a curable composition containing the triazine compound, and a cured product thereof. Manufacturing method and its hardened product. The curable composition of the present invention is excellent in the formability of coating films or films, and can produce coating films or films stably.

Hereinafter, embodiments of the present invention will be described in detail. The triazine compound of the present invention is a novel compound, which is useful as an ultraviolet absorber. The triazine compound of the present invention is formed by linking three aromatic groups substituted by a hydroxyl group at position 2 with a triazine ring, and one or two of these three aromatic groups are selected from acrylic groups. At least one type of aromatic group from the group consisting of methacrylic group, epoxy group, and allyl group.

In the triazine compound of the present invention, the aromatic group includes, for example, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.

表示之化合物。The triazine compound of the present invention is preferably the following general formula (1)

Represents the compound.

Here, in the general formula (1), X represents a linear or branched alkyl group with 1 to 20 carbon atoms, an acrylic group or a methacrylic group, and a part of the hydrogen atom of the alkyl group is replaced by an acrylic group or methacrylic acid group. Group, epoxy group, or allyl-substituted group, R ¹ represents X or an alkyl group with ^{1 to 10 carbon atoms, R 2} represents an alkyl group with 1 to 10 carbon atoms, and R ³ to R ¹¹ are each independently Represents hydrogen atom, hydroxyl group, halogen atom, C1-C20 alkyl group, C2-C20 alkenyl group, C1-C20 alkoxy group, C6-C20 aryl group. Part or all of the alkyl, alkenyl, and alkoxy groups may be linear or branched. A part of the carbon chain may be substituted by a carbonyl group, an imino group, an amide bond or an oxygen atom. The hydrogen atom of the carbon chain, Can be substituted by hydroxyl.

X in the general formula (1), a linear or branched alkyl group with 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Base, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1,2-dimethylpropyl, n-hexyl, cyclohexyl, 1,3 -Dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n-heptyl, 2-heptyl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl, tert-octyl, 2-ethylhexyl, 2-methylhexyl, 2-propane Hexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-decyl Trialkyl, isotridecyl, n-tetradecyl, isotetradecyl, n-pentadecyl, isopentadecyl, n-hexadecyl, isohexadecyl, n -Heptadecyl, isoheptadecyl, n-octadecyl, isoctadecyl, n-nonadecyl, isnonadecyl, n-eicosyl, isoeicosyl Wait.

In the general formula (1), ^{the alkyl group having 1 to 10 carbon atoms represented by R 1} and R ² may be linear or branched, for example, methyl, ethyl, propyl, 2-propynyl , Butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, decyl, etc.

In the general formula (1), ^{the halogen atom represented by R 3} to R ¹¹ includes, for example, a fluorine atom, a bromine atom, and a chlorine atom.

In the general formula (1), R ³ to R ¹¹ represent alkyl groups having 1 to 20 carbon atoms. In addition to the above alkyl groups, undecyl, dodecyl, tridecyl, tetradecyl Alkyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, etc.

In the general formula (1), ^{the alkenyl groups having 2 to 20 carbon atoms represented by R 3} to R ¹¹ include vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1 -Butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentene Group, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, etc.

In the general formula (1), ^{the alkoxy groups with 1 to 20 carbon atoms represented by R 3} to R ¹¹ include, for example, methoxy, ethoxy, iso-propoxy, butoxy, and sec-butoxy Group, tert-butoxy, iso-butoxy, pentyloxy, iso-pentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy , 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, 1-octyloxy, iso-octyloxy, tert-octyloxy and so on.

In the general formula (1), ^{the aryl groups with 6 to 20 carbon atoms represented by R 3} to R ¹¹ include, for example, phenyl, naphthyl, anthryl, phenanthryl, stilbene, indenyl, and 2-methylbenzene Group, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4- iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 4- Stearyl phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4- Dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert- Butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-pentylphenyl, 2,5-di-tert-octylphenyl, 2,4-diiso Propylphenylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl)-4-yl, 2,4,5-trimethylphenyl, ferrocene, etc.

Specific examples of the triazine compound represented by the general formula (1) include the following compounds, but the triazine compound of the present invention is not limited to these compounds.

R ¹² may be an alkyl group with 1 to 8 carbon atoms, or a group represented by the following formula (3), R ¹³ represents an alkyl group with 1 to 4 carbon atoms, and R ¹³ to R ¹⁵ represent a hydrogen atom or a methyl group. R ¹⁶ represents an alkyl group or phenyl group having 1 to 8 carbon atoms.

式(3)中，R¹ ’可列舉碳原子數1~8之烷基。

In the formula (3), R ¹ ′ can be an alkyl group having 1 to 8 carbon atoms.

表示之化合物。此處，通式(2)中，R¹² 為碳原子數1~8之烷基、上述式(3)表示之基，R¹³ 及R¹⁴ 為氫原子或甲基。Among the triazine compounds of the present invention, in terms of compatibility with curable components, heat resistance, volatility resistance, and weather resistance, the following general formula (2) is more preferable

Represents the compound. Here, in the general formula (2), R ¹² is an alkyl group having 1 to 8 carbon atoms, the group represented by the above formula (3), and R ¹³ and R ¹⁴ are hydrogen atoms or methyl groups.

The method for producing the triazine compound represented by the general formula (1) or the general formula (2) is not particularly limited, and can be synthesized by a method in ordinary organic synthesis. In addition, as the purification method, methods using distillation, recrystallization, reprecipitation, filtering materials, and adsorbents can be suitably used.

Next, the curable composition of the present invention will be explained. The curable composition of the present invention contains the triazine compound of the present invention. In the curable composition of the present invention, the blending amount of the triazine compound of the present invention is 0.001-20 relative to the total 100 parts by mass of the curable monomer, the curable oligomer, and the curable polymer. The parts by mass are preferably 0.002-10 parts by mass, more preferably 0.03-10 parts by mass from the viewpoint of compatibility with curable components, heat resistance, weather resistance, and volatility resistance. When the blending amount is less than 0.001, the heat resistance and weather resistance may be insufficient, and when it exceeds 20 parts by mass, the compatibility with the curable component may deteriorate.

In the curable composition of the present invention, the curable monomer, curable oligomer, and curable polymer preferably have one or more radically polymerizable functional groups, and examples thereof include one or more (methyl ) Acrylic functional groups, such as (meth)acrylic acid groups.

所表示之基。In the curable composition of the present invention, the (meth)acryloyloxy group represents the following formula (4)

The base expressed.

In the formula (4), R ¹⁷ represents a hydrogen atom or a methyl group, when R ¹⁷ is a methyl group, it is a methacryloxy group, and when R ¹⁷ is a hydrogen atom, it is an acryloxy group.

The curable monomer, curable oligomer, and curable polymer are preferably those obtained by using a (meth)acrylate compound. (Meth)acrylate compounds, for example, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylate )Tridecyl acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Isostearyl ester, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, (meth)acrylate Base) methoxyethyl acrylate, butoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, methyl tetrahydrofuran (meth)acrylate, glycidyl (meth)acrylate , 2-hydroxy-3-phenoxypropyl (meth)acrylate, nonylphenoxyethyl tetrahydrofuran methyl (meth)acrylate, caprolactone modified methyl tetrahydrofuran (meth)acrylate, (formaldehyde) Base) diethylaminoethyl acrylate; 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6- Hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2- Alkyl glycol di(meth)acrylates such as ethyl-1,3-propanediol di(meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth) Polyoxyalkyl ether di(meth)acrylates such as acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.; nor camphor Alkyl dimethanol diacrylate, norbornane diethanol di(meth)acrylate, diol bis (methyl) obtained by adding 2 moles of ethylene oxide or propylene oxide to norbornane dimethanol Acrylate, 5-ethyl-5-hydroxymethyl-β,β-dimethyl-1-1,3-dioxane-2-ethanol diacrylate, tricyclodecane dimethanol bis(methyl) Acrylic acid ester, tricyclodecane diethanol di(meth)acrylate, and tricyclodecane dimethanol addition of ethylene oxide or propylene oxide 2 mol of glycol di(meth)acrylate , Pentacyclopentadecane dimethanol di(meth)acrylate, Pentacyclopentadecane diethanol di(meth)acrylate, Pentacyclopentadecane dimethanol addition to ethylene oxide or propylene oxide 2 Diol bis(meth)acrylate obtained by moles, diethanol bis(meth)acrylate obtained by adding 2 moles of ethylene oxide or propylene oxide to pentacyclopentadecane diethanol Diol bis(meth)acrylates with alicyclic structure; isocyanuric acid bis(2-propylene oxyethyl) hydroxyethyl, isocyanuric acid bis(2-acrylic acid) (Oxypropyl) hydroxypropyl, bis(2-propenoxybutyl) hydroxybutyl isocyanurate, bis(2-methacryloxyethyl) hydroxyethyl isocyanurate , Bis(2-methacryloxypropyl) hydroxypropyl isocyanurate, bis(2-methacryloxybutyl) hydroxybutyl isocyanurate, isocyanuric acid Ginseng cyanurate (2-propylene oxyethyl) ester, ginseng isocyanurate (2-acryloxy propyl) ester, ginseng isocyanurate (2-acryloxy butyl) ) Ester, ginseng isocyanurate (2-methacryloxyethyl) ester, ginseng isocyanurate (2-methacryloxypropyl) ester, ginseng isocyanurate ( 2-methacryloxybutyl) ester, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, ethylene oxide Modified phosphoric acid (meth)acrylate, ethylene oxide modified alkylated phosphoric acid (meth)acrylate, urethane (meth)acrylate, polyfunctional urethane (meth) Acrylate, epoxy (meth)acrylate, urethane (meth)acrylate with polyether skeleton, urethane (meth)acrylate with polyester skeleton, polycarbonate skeleton Polyester (meth)acrylate obtained by esterifying (meth)acrylic acid with urethane (meth)acrylate polyol, and esterification of (meth)acrylic acid with polyether skeleton polyol Polyether (meth)acrylate and the like obtained by chemical conversion.

The above-mentioned urethane (meth)acrylate is a compound having one acryloyl or methacryloyl group and more than one urethane bond (-NHCOO-). In addition, the aforementioned urethane (meth)acrylate is, for example, a reaction product of polyols, polyisocyanates, and (meth)acrylate having a hydroxyl group. Here, the polyols include ethylene glycol, 1,4-butanediol, neopentyl glycol, polycaprolactone polyol, polyester polyol, polycarbonate diol, polytetramethylene glycol, etc. . In addition, examples of polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like. Furthermore, the (meth)acrylate having a hydroxyl group includes 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylic acid Esters, ε-caprolactone adducts of 2-hydroxyethyl (meth)acrylate, etc.

The polyfunctional urethane (meth)acrylate is a compound having a plurality of acrylic or methacrylic groups and one or more urethane bonds (-NHCOO-). In addition, the above-mentioned polyfunctional urethane (meth)acrylate is, for example, a reaction product of a polyfunctional (meth)acrylate having a hydroxyl group and a polyisocyanate. Here, the polyfunctional (meth)acrylate having a hydroxyl group includes, for example, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and the like. On the other hand, as polyisocyanates, toluene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned.

The epoxy (meth)acrylate is, for example, a reaction product of a polyepoxy compound and (meth)acrylic acid. Here, the polyepoxy compound is preferably a polyglycidyl compound. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, phenol methane type epoxy resin, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether can be mentioned. Glyceryl ether, trimethylolpropane polyglycidyl ether, etc.

In the curable composition of the present invention, the content of curable monomer, curable oligomer, and curable polymer is preferably 80~ 95% by mass, more preferably 90 to 95% by mass.

The manufacturing method of the cured product of the present invention is performed by irradiating the curable composition of the present invention with light or heating at 50 to 200°C. For example, the curing method of the curable composition includes a one-liquid curing type, a two-liquid curing type using a curing agent, and an active energy ray curing type that is cured by irradiation with ultraviolet rays or ionizing radiation. The curable composition of the present invention is preferably an ultraviolet curable composition.

The curable composition of the present invention preferably contains one or more polymerization initiators. The polymerization initiator can be used in the curable composition of the present invention as long as it initiates polymerization of curable monomers, curable oligomers, and curable polymers.

The polymerization initiator includes, for example, a photopolymerization initiator, a thermal polymerization initiator, and the like, but the present invention is not limited to this example. These polymerization initiators can be used individually or in combination. Furthermore, those having two properties, such as those that act as thermal polymerization initiators among the photopolymerization initiators, or those that act as photopolymerization initiators among the thermal polymerization initiators, can be irradiated with light or heated, Harden the molding material.

Examples of the photopolymerization initiator include the following compounds. (1) Benzophenone derivatives: for example, benzophenone, O-benzyl benzoic acid methyl ester, 4-benzyl-4'-methyl benzophenone, dibenzyl ketone, fennel Ketones and so on.

(2) Acetophenone derivatives: For example, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropanebenzene, 2,2-dimethoxy-1,2- Diphenylethane-1-one (for example, IRGACURE 651 manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone (for example, IRGACURE 184 manufactured by BASF, Esacure KS300 manufactured by DKSH Japan), 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinopropan-1-one (for example, IRGACURE 907 manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxyl -2-Methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one (for example, IRGACURE 127 manufactured by BASF Corporation), methyl phenylglyoxylate, and the like.

(3) Thioxanthone derivatives: for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, two Ethyl thioxanthone and so on.

(4) Benzophenone derivatives: for example, Benzophenone, Benzophenone dimethyl ketal, benzyl-β-methoxyethyl acetal and the like can be mentioned.

(5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropane-1-one (for example, DAROCURE 1173 manufactured by BASF), etc. .

(6) Oxime compounds: For example, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2 -(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzyl)oxime, 1,3-diphenylpropanetrione-2-(O -Ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzyl)oxime 1,2-octanedione, 1-(4-(phenylthio) )-2-(O-benzyloxime)] ethyl ketone (for example, IRGACURE OXE01 manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzyloxime)-9H-carbazole- 3-yl]-1-(O-acetyloxime) (for example, IRGACURE OXE02 manufactured by BASF Corporation) and the like.

(7) α-Hydroxy ketone compounds: For example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2 -Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanyl)-benzyl]phenyl}-2 -Methyl propane, etc.

(8) α-Aminoalkylphenone compounds: For example, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (for example, BASF Corporation System, IRGACURE 369), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one (such as BASF System, IRGACURE 379) and so on.

(9) Phosphine oxide compounds: For example, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (for example, manufactured by BASF Corporation, IRGACURE 819), bis(2,6-di Methoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (for example, manufactured by BASF Corporation, DAROCURE TPO) and so on.

(10) Titanocene compounds: for example, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)benzene Base) Titanium (manufactured by Ciba Specialty Chemicals, IRGACURE 784) and the like.

Thermal polymerization initiators, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azo Bis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleronitrile), 2,2'-azobis[2-(2-methylpropionamidine) dihydrochloride , Benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, 2,2'-azobis(2-methylpropionic acid ) Dimethyl, dicumyl peroxide, 1,1-bis(tert-butylperoxy) 3,3,5-trimethylcyclohexane, caproic acid tert-butylperoxy -2-ethyl ester, potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, dicyandiamine, p-cyclohexyl toluenesulfonate, diphenyl(methyl)aluminum tetrafluoroborate, etc.

The content of the polymerization initiator in the curable composition of the present invention is preferably 0.1-10 parts by mass relative to the total of 100 parts by mass of the curable monomer, curable oligomer, and curable polymer , It is more preferably 0.1 to 5 parts by mass, and still more preferably 0.1 to 1 parts by mass. If it is less than 0.1 parts by mass, the curing may be insufficient, and if it exceeds 10 parts by mass, the physical properties of the cured product may be adversely affected.

In the curable composition of the present invention, a curing accelerator (sensitizer) may be added together with the polymerization initiator. Hardening accelerators that can be added, for example, triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylamino Amines such as isoamyl benzoate and ethyl p-dimethylaminobenzoate, hydrogen donors such as 2-mercaptobenzothiazole, and pigment sensitizers such as xanthene, thioxanthene, coumarin, Thiocoumarin and so on.

The blending amount of the curing accelerator is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1 parts by mass relative to the total of 100 parts by mass of the curable monomer, curable oligomer, and curable polymer share.

The light source of the active light when curing the curable composition of the present invention by photopolymerization can be one that emits light with a wavelength of 300 to 450 nm, for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be used.

The method of blending the triazine compound of the present invention into the curable composition is not particularly limited, and a known blending technique of resin additives can be used. For example, the method of adding the curable component of the curable composition to the polymerization system in advance at the time of polymerization, the method of adding during the polymerization, and the method of adding after the polymerization can be used. In addition, when blending the curable composition after polymerization, mixing with powder or pellets of the polymer obtained by the polymerization and kneading with a processing machine such as an extruder can be used to make the curable composition of the present invention a parent. The method of blending the material with the curable composition, etc. The type of processing equipment used, processing temperature, cooling conditions after processing, etc. can also be used without special restrictions, and mixing conditions can be appropriately selected so that the physical properties of the obtained resin become suitable for the intended use. In addition, the curable composition of the present invention may be blended into the curable composition alone or by coating other resin additives or fillers to form particles.

The polymerization tank used in the polymerization reaction may be directly used as a continuous reaction tank in an existing polymerization equipment, and the present invention is not particularly limited to the size, shape, material, etc. of the conventional polymerization equipment.

The preferred molecular weight of the curable component obtained by polymerization varies depending on the application, but when used as a coating film, the weight average molecular weight measured by GPC is preferably 5,000 to 150,000, more preferably 10,000 to 100,000 The scope. When the weight-average molecular weight of the curable component is less than 5,000, the strength or durability of the molded body may be lacking. If it is more than 150,000, the processability may be reduced.

The curable composition of the present invention may optionally contain known resin additives (such as phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, other antioxidants, Hindered amine compounds, ultraviolet absorbers, flame retardants, flame retardant additives, lubricants, fillers, hydrotalcites, fatty acid metal salts, antistatic agents, fluorescent whitening agents, which are different from the triazine compound of the present invention, Pigments, dyes, etc.).

Phenolic antioxidants, for example, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2' -Methylene bis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2'-thio Diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylhydrosulfanylmethyl) Phenol, 2,2'-isobutylene bis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide, 2,2'-oxamide-bis [Ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3-(3',5'-di-tert-butyl -4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxy- Phenylpropionic acid and C13-15 alkyl ester, 2,5-di-tert-pentylhydroquinone, hindered phenol polymer (trade name "AO.OH.98" manufactured by ADEKA PALMAROLE), 2,2' -Methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl) acrylic acid Yl)-4-methylphenyl ester, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate , 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f][ 1,3,2]-dioxaphosphepin, hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis[ Monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate) calcium salt, 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2 The reaction product of (3H)-benzofuranone and o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-tri (Azin-2-ylamino)phenol, DL-a-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-( 4'-Hydroxy-3'-tert-butyl-phenyl)butyric acid)diol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-dec Octaalkoxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxy Benzyl Group) phosphonate, tridecyl-3,5-tert-butyl-4-hydroxybenzylthio acetate, thiodiethylene bis[(3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate), 4,4'-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-bis(3,5-bis- tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis( 4-hydroxy-3-tert-butylphenyl)butyric acid) glycol ester, 4,4'-butylene bis (2,6-di-tert-butylphenol), 4,4'-butylene bis (6-tert-butyl-3-methylphenol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 1,1,3-ginseng (2-methyl -4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl) Phenyl) phenyl) terephthalate, 1,3,5-ginseng (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1, 3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-ginseng (3,5-di-tert-butyl-4 -Hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-ginseng [(3,5-di-tert-butyl-4-hydroxyphenyl)propanoxyethyl] Isocyanurate, Si[methylene-3-(3',5'-tert-tributyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4- Methyl-6-(2-propenyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5 -Methylhydrocinnamyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[β-(3 -tert-butyl-4-hydroxy-5-methylphenyl)propionate], stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate , Palmyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl amide, myristyl-3-(3,5-di-tert-butyl-4-hydroxyl Phenyl) propionate, lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, etc. 3-(3,5-dialkyl-4- Hydroxyphenyl) propionic acid derivatives and the like. The blending amount when blending the phenolic antioxidant is 0.001 to 5 parts by mass, more preferably 0.03 to 3 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Phosphorus antioxidants include, for example, triphenyl phosphite, diisooctyl phosphite, seven (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, and diisooctyl phosphite. Octyl phenyl ester, diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, ginseng (dipropylene glycol) phosphite, dioleyl hydrogen phosphite , Trilauryl trithiophosphite, bis(tridecyl) phosphite, ginseng (isodecyl) phosphite, ginseng (tridecyl) phosphite, diphenyldecyl phosphite, Dinonylphenyl bis(nonylphenyl) phosphite, poly(dipropylene glycol) phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, ginseng nonyl phenyl phosphite, ginseng (2,4- Di-tert-butylphenyl) phosphite, ginseng (2,4-di-tert-butyl-5-methylphenyl) phosphite, ginseng (2-tert-butyl-4-(3 -tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tris(decyl)phosphite, octyl diphenyl phosphite, diphosphite (Decyl) monophenyl ester, mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite , Phosphite bis(2,4-di-tert-butyl-6-methylphenyl) ethyl ester, tetra(tridecyl)isopropylene diphenol diphosphite, tetra(tridecyl) )-4,4'-n-butylene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-gin (2-methyl 4-hydroxy-5-tert-butylphenyl) butane triphosphite, diphosphonite (2,4-di-tert-butylphenyl) diphenyl ester, 9,10-di Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorous acid (1-methyl-1-propenyl-3-ylidene) ginseng (1,1-dimethylethyl)-5 -Methyl-4,1-phenylene)hexatridecyl ester, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite Ester, phosphorous acid 2,2'-methylene bis(4,6-di-tert-butylphenyl)-octadecyl ester, 2,2'-ethylene bis(4,6-di-tert -Butylphenyl) fluorophosphite, 4,4'-butylene bis(3-methyl-6-tert-butylphenyl di-tridecyl) phosphite, ginseng (2-(( 2,4,8,10-tetra-tert-butyl dibenzo[d,f][1,3,2]dioxaphosphaheptin-6-yl)oxy]ethyl)amine, 3 ,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 2,4,6-tri -tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly4,4'-isopropylidene diol C12-15 alcohol phosphite, bis(di Isodecyl) pentaerythritol diphosphite, bis(tridecyl)pentaerythritol di Phosphite, bis(octadecyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite , Bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Bis(2,4-dicumylphenyl) pentaerythritol diphosphite and the like. The blending amount when the phosphorus antioxidant is blended is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Thioether antioxidants, for example, tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C12/C14)thiopropionate) Oxy]5-tert-butylphenyl) sulfide, di-tridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, Dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl/stearylthiodipropionate, 4,4' -Thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), distearyl-disulfide. The blending amount when the thioether antioxidant is blended is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone) and other 2-hydroxybenzophenones. Ketones; 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy- 3,5-Di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole Azole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazole Phenol), 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2-[2-hydroxy-3-(2-propenyloxy Ethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloxyethyl)-5-tert-butylphenyl]benzotriazole Azole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2- Methacryloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloxyethyl)benzene Yl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy- 3-tert-pentyl-5-(2-methacryloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methyl Allyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloxymethyl)phenyl]benzotriazole, 2- [2-Hydroxy-4-(3-methacryloxy-2-hydroxypropyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloxypropyl) 2-(2-hydroxyphenyl)benzotriazoles such as phenyl)benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert- Butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl(3,5-di-tert-butyl-4-hydroxy)benzoate, dodecane Base (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecane Base (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenate Benzoates such as alkyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2'-ethoxy aniline, 2-ethoxy- 4'-Lauryl oxaniline and other substituted oxanilines; ethyl-α-cyano-β,β-diphenyl acrylate, methyl-2 -Cyanoacrylates such as cyano-3-methyl-3-(p-methoxyphenyl) acrylate; various metal salts or metal clamp compounds, especially nickel and chromium salts, or Clamp compound class and so on. The blending amount when blending the ultraviolet absorber is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Hindered amine compounds, for example, stearic acid 2,2,6,6-tetramethyl-4-piperidinate, stearic acid 1,2,2,6,6-pentamethyl-4-piperidinate , 2,2,6,6-tetramethyl-4-piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, si(2, 2,6,6-Tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylic acid ester, Si (1,2,2,6,6-pentamethyl-4- Piperidinyl)-1,2,3,4-butane tetracarboxylic acid ester, bis(2,2,6,6-tetramethyl-4-piperidinyl)･bis(tridecyl)-1 ,2,3,4-Butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-bis(tridecyl)-1,2,3 ,4-Butane tetracarboxylic acid ester, bis(1,2,2,4,4-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl 4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane/2,4-dichloro-6-morpholinyl-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine poly Condensate, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s -Triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(1, 2,2,6,6-Pentamethyl-4-piperidinyl)amino)-s-triazine-6-yl)-1,5,8-12-tetraazadodecane, 1,6 ,11-Shen [2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl] Aminoundecane, 1,6,11-gin[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino) )-s-Triazine-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidinyl}sebacate, double {4-(2,2,6,6-Tetramethyl-1-undecyloxy)piperidinyl)carbonate and the like. The blending amount when the hindered amine compound is blended is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Nucleating agents, for example, sodium-2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate, lithium-2,2'-methylene bis(4,6- Di-tert-butylphenyl) phosphate, aluminum hydroxy bis[2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate], sodium benzoate, 4-tert- Butylbenzoic acid aluminum salt, sodium adipate and 2 sodium bicyclo[2.2.1] heptane-2,3-dicarboxylate and other carboxylic acid metal salts; dibenzylidene sorbitol, bis(methyl sulfide) Poly(benzyl)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, and bis(dimethylbenzylidene)sorbitol, etc. Alcohol derivatives; N,N',N"-[2-methylcyclohexyl]-1,2,3-propane tricarboxamide, N,N',N"-tricyclohexyl-1,3, Amine compounds such as 5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide, 1,3,5-tris(dimethylisopropylamino)benzene, etc. The blending amount when blending the nucleating agent is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Flame retardants include, for example, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl phosphate-2,6-dixylene phosphate, resorcinol bis (Diphenyl phosphate), (1-methylethylene)-4,1-phenylene tetraphenyl diphosphate, 1,3-phenylene tetrakis (2,6-dimethylphenyl) ) Phosphate, ADEKA Co., Ltd. product name "Adekastab FP-500", "Adekastab FP-600", "Adekastab FP-800" aromatic phosphate; divinyl phenylphosphonate, phenylphosphonic acid two Phosphonates of allyl ester, phenylphosphonic acid (1-butenyl ester), etc.; phenyl diphenyl hypophosphite, methyl diphenyl hypophosphite, 9,10-dihydro-9-oxa-10 -Phosphoric acid esters such as phosphaphenanthrene-10-oxide derivatives; phosphazene compounds such as bis(2-allylphenoxy) phosphazene, xylenol-based phosphazene; melamine phosphate, pyrocarbon Melamine phosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, vinyl benzyl compounds containing phosphorus and phosphorus-based flame retardants such as red phosphorus; Metal hydroxides such as magnesium hydroxide and aluminum hydroxide; brominated bisphenol A epoxy resin, brominated phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromobenzene) Group), ethylene bis-tetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclodecane Dioxane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-ginseng (tribromophenoxy)-1,3,5-triazine, Bromine of tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate, and brominated styrene Department of flame retardant, etc. These flame retardants are preferably used in combination with anti-dripping agents such as fluororesin or flame retardant additives such as polyols and hydrotalcite. The blending amount at the time of blending the flame retardant is 1-100 parts by mass, more preferably 10-70 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

The lubricant is added for the purpose of imparting lubricity to the surface of the molded body and improving the effect of preventing damage. Examples of lubricants include unsaturated fatty acid amides such as oleamide and mustard amide; saturated fatty acid amides such as behenyl amide and stearyl amide; butyl stearate, stearyl alcohol, and stearyl amine. Acid monoglyceride, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hardened castor oil, stearylamine, oleamide, ethylene distearylamine Wait. These can be used singly or in combination of two or more. The blending amount when the lubricant is blended is 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Hydrotalcite is a compound salt compound composed of magnesium, aluminum, hydroxyl, carbonic acid group, and arbitrary crystal water, which is known as a natural product or a synthetic product. Examples of the compound salt compound include a part of magnesium or aluminum with alkali metal or zinc and other metals. The substituent or the hydroxyl group or the carbonic acid group is substituted with another anionic group. Specifically, for example, the metal of the hydrotalcite represented by the following general formula (5) may be substituted with an alkali metal. In addition, for Al-Li hydrotalcites, a compound represented by the following general formula (6) can also be used.

此處，通式(5)中，x1及x2分別表示滿足下述式 　　0≦x2/x1＜10，2≦x1+x2≦20 　　表示之條件的數，p表示0或正數。

Here, in the general formula (5), x1 and x2 respectively represent numbers satisfying the conditions represented by the following formula 0≦x2/x1<10, 2≦x1+x2≦20, and p represents 0 or a positive number.

此處，通式(6)中，A^q- 表示q價之陰離子，p表示0或正數。

Here, in the general formula (6), A ^q- represents a q-valent anion, and p represents 0 or a positive number.

In addition, the carbonate anions in the hydrotalcites may be partially substituted by other anions.

Hydrotalcites can be those that dehydrate crystal water, or they can be organic sulfonic acids made of higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and alkali metal dodecylbenzenesulfonic acid salts. Coated with metal salt, higher fatty acid amide, higher fatty acid ester or wax.

Hydrotalcites can be natural or synthetic products. The method for synthesizing the compound includes Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Application Publication No. 61- Known methods described in Bulletin No. 174270, Japanese Patent Application Laid-Open No. 5-179052, etc. In addition, the aforementioned hydrotalcites can be used without being restricted by their crystal structure, crystal particles, and the like. The blending amount when the hydrotalcite is blended is 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

Examples of antistatic agents include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, and anionic Anionic antistatic agents such as alkyl sulfonate, higher alcohol sulfate ester salt, higher alcohol ethylene oxide adduct sulfate ester salt, higher alcohol ethylene oxide adduct phosphate ester salt, etc.; polyhydric alcohol fatty acid ester , Polyglycol phosphate, polyoxyethylene alkyl allyl ether and other non-ionic antistatic agents; amphoteric alkyl betaines such as alkyl dimethyl amino acetic acid betaine; imidazoline amphoteric active agent Amphiphilic antistatic agent. The antistatic agent can be used alone or in combination with two or more antistatic agents. The blending amount when the antistatic agent is blended is 0.03 to 2 parts by mass, more preferably 0.1 to 0.8 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

The pigments can also use commercially available pigments, such as Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

Fluorescent whitening agent refers to a compound that absorbs ultraviolet rays from sunlight or artificial light and converts it into violet to blue visible light to radiate fluorescence to promote the whiteness or blue tone of the formed body. Examples of the fluorescent whitening agent include benzoxazole-based compounds C.I. Fluorescent Brightner 184; coumarin-based compounds C.I. Fluorescent Brightner 52; diaminostilbene disulfonic acid-based compounds C.I. Fluorescent Brightner 24, 85, 71, and the like. The blending amount when the fluorescent whitening agent is used is 0.00001 to 0.1 parts by mass, more preferably 0.00005 to 0.05 parts by mass relative to 100 parts by mass of the curable component of the curable composition of the present invention.

The dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro Dyes such as dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, etc., and these can also be used in a mixture of plural kinds.

The curable composition of the present invention can be molded using a known molding method. For example, injection molding method, extrusion molding method, blow molding method, vacuum molding method, inflation molding method, calender molding method, slush molding method, dipping method can be used. Molding method, foam molding method, etc. to obtain molded products.

The curable composition of the present invention is particularly suitable for use in the formation of electrical/electronic materials such as semiconductor integrated circuits, optical components or liquid crystal panels, adhesive sheets used when bonding various light sources or diffusers, and organic thin films. Materials, printing inks, paints, coating materials such as various coating agents, vehicles, building materials, sealing materials, etc. [Example]

Hereinafter, examples are used to illustrate the present invention in more detail. However, the present invention is not limited in any way by the following examples.

[Production Example 1] Compound No. 1 was synthesized according to the following reaction diagram. The manufacturing example will be described in order.

(1) Intermediate 1 is manufactured in a 2L 5-necked eggplant flask, and 4,4',4"-(1,3,5-triazine-2,4,6-triyl) ginseng (2- Methylbenzene-1,3-diol) 100g (0.22mol), n-hexyl bromide 72.3g (0.44mol), potassium hydroxide 30.3g (0.22mol), dimethylformamide 270g, and n- 270g of decane, heated to 100°C, stirred for 6 hours for reaction. After the reaction, cooled to 80°C, added formic acid for neutralization, and heated up to 130°C. Desolventizer was removed by drying under reduced pressure and cooled to room temperature. The resultant was obtained. The product was washed with methanol and toluene, purified by silica gel chromatography, and further dried at 75°C using a vacuum dryer to obtain 21.8 g of yellow powder. 1H-NMR confirmed that the obtained yellow powder was Intermediate 1. Analysis The results are shown in Table 1.

1H-NMR(DMSO-d6)

1H-NMR(DMSO-d6)

(2) Production of Intermediate 2 "In a 2L 5-necked eggplant flask, 86.2g of Intermediate 1, 0.25g (6.2mmol) of sodium hydroxide, and 185g of cyclohexanone were added to each. After the temperature was raised to 140°C, the pressure was reduced to 30 kPa while stirring, and reflux dehydration was performed until water ceased to distill. After that, 13.9 g (0.16 mol) of ethylene carbonate was added to the reaction system, and the mixture was stirred for 17 hours to perform the reaction. After the reaction, it was cooled to 70°C, and formic acid was added for neutralization. Add methanol/distilled water=5/1 solvent to the system and stir for a period of time to precipitate solids. It was filtered and washed with methanol. It was dried in a vacuum dryer at 75° C., and dried under total reduced pressure to obtain 100.5 g of orange powder. It was confirmed that the obtained product was Intermediate 2 using 1H-NMR. The analysis results are shown in Table 2.

1H-NMR(DMSO-d6)

1H-NMR(DMSO-d6)

(3) Compound No.1 was manufactured in a 2L 5-necked eggplant flask, each of which was added Intermediate 2 (90.0g), 0.8g (0.80mmol) of 4-methoxyphenol, and p-toluenesulfonic acid monohydrate 2.3 g (12.0 mmol), 19.3 g (0.22 mol) of methacrylic acid, and 200 g of o-xylene were heated to 145° C., and the reaction was carried out by stirring for 10 hours while performing normal pressure reflux dehydration using a Dean-Stark apparatus. After completion of the reaction, it was cooled to 80°C, 100 g of distilled water was added, and it was cooled to room temperature while stirring to precipitate the reaction product. The precipitate was separated by filtration and washed with methanol. The obtained crude crystals were crystallized with methyl ethyl ketone/ethanol-2/1 solvent, and then dried at 130° C. under total reduced pressure with a vacuum dryer to obtain 58.3 g of yellow powder. It was confirmed that the obtained product was compound No. 1 using 1H-NMR. The analysis results are shown in Table 3.

1H-NMR(CDCl3)

1H-NMR(CDCl3)

[Examples 1 to 3, Comparative Examples 1 to 4] In a 100 mL four-necked eggplant-shaped flask, 5.0 g (49.9 mmol) of methyl methacrylate (MMA) and 0.33 g of azobisisobutyronitrile ( 30mol%/MMA ratio) and the composition of the ultraviolet absorber (UVA) and the solvent described in Table 4, stirred at room temperature. After stirring, bubbling was performed with nitrogen for 20 minutes, and then degassed. In addition, the values in parentheses in the columns of ultraviolet absorbers and solvents in Table 4 are the parts of each component relative to 100 parts by mass of MMA.

Next, the 4-neck eggplant-shaped flask was heated in an oil bath at 86°C, and the reaction was carried out for the time shown in Table 4. After the reaction, the 4-neck flask was taken out from the oil bath and cooled to room temperature. Next, while stirring the reacted composition, it was dropped into 200 mL of methanol to precipitate the polymer. The polymer was separated by filtration, washed with methanol, and dried to obtain a polymer.

Add 3 mL of tetrahydrofuran and 2 or 3 spoons of the resulting polymer to a glass vial, and stir while applying ultrasonic waves to dissolve the polymer. Using high-speed liquid chromatography (HPLC), the molecular weight of the polymer was determined under the following conditions.

(Measurement conditions) 　　 device: high-speed liquid chromatography (manufactured by JASCO Corporation) 　　 column: GPC KF-805L (manufactured by Showa Denko Co., Ltd.) 　　developing solvent: tetrahydrofuran flow rate: 0.50mL/min 　　 column temperature: 40°C 　　 detector ：RI 　　 Injection volume: 100μL

From the perspective of Comparative Example 3, when the comparative compound was used, the molecular weights Mn and Mw were both larger than those of Comparative Examples 1 and 2 in which the ultraviolet absorber was not blended, and it was confirmed that a high-molecular-weight body was formed. The formation of high-molecular-weight bodies makes it difficult to adjust the film thickness of the coating film or the film, which greatly impairs the formability.

In Comparative Example 4, the composition became gel-like in 15 minutes after the start of the reaction and could not be stirred, so the reaction was terminated at this point in time. Although the polymer was obtained as a yellow powder when washed with methanol, it could not be dissolved in DMF and could not be measured by gel permeation chromatography (GPC).

In contrast, from Examples 1 to 3, it can be confirmed that when the triazine compound of the present invention is used, there is no problem with the solubility of the solvent, and the influence on the polymerization of PMMA is small.

In addition, the compound No. 1 of the present invention and the comparative compound No. 2 having the following structure were dissolved in chloroform, and the UV absorbance was measured. The UV absorbance spectrum of compound No. 1 is shown in FIG. 1 and the UV absorbance spectrum of comparative compound No. 2 is shown in FIG. 2. From Figure 1, the compound of Compound No. 1 also has absorption capacity in the UV-B region (wavelength 280-315nm), and can shield ultraviolet light with a low addition amount. On the other hand, it can be seen from FIG. 2 that only one comparative compound No. 2 having an aromatic group with a hydroxyl group at the No. 2 position has insufficient ultraviolet absorption performance in a wavelength region greater than 300 nm.

From the above point of view, by using the compound of the present invention, it is possible to provide a curable composition with excellent ultraviolet absorption capacity and good moldability.

[Figure 1] A graph showing the ultraviolet absorption spectrum of Compound No. 1 of the triazine compound of the present invention.　　[Figure 2] shows the ultraviolet absorption spectrum of Comparative Compound No.2.

Claims (8)

A triazine compound with the following general formula (2)

(In the general formula (2), R ¹² represents an alkyl group with 1 to 8 carbon atoms, or the following formula (3)

(In the formula (3), R ^{1 'carbon} atoms of the alkyl group having 1 to 8) represents the group, R ¹³ and R ¹⁴ represents a hydrogen atom or a methyl group). A curable composition characterized by containing 0.001 to 20 parts by mass of triazine as in claim 1 relative to 100 parts by mass of the total of curable monomers, curable oligomers, and curable polymers Compound. The curable composition of claim 2, which further contains 0.1-10 parts by mass of a polymerization initiator. The curable composition according to claim 3, wherein the polymerization initiator is a photopolymerization initiator. The curable composition according to claim 3, wherein the polymerization initiator is a thermal polymerization initiator. A method for manufacturing a hardened object, characterized by irradiating a hardened composition as in Claim 4 with light to form a hardened object. A method for manufacturing a hardened object, characterized by heating the hardenable composition as claimed in claim 5 at 50 to 200°C to form the hardened object. A hardened product characterized by using the hardenable composition according to any one of Claims 2 to 5.

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