CN110678448A - Triazine compound, curable composition, method for producing cured product, and cured product thereof - Google Patents
Triazine compound, curable composition, method for producing cured product, and cured product thereof Download PDFInfo
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- CN110678448A CN110678448A CN201880033157.0A CN201880033157A CN110678448A CN 110678448 A CN110678448 A CN 110678448A CN 201880033157 A CN201880033157 A CN 201880033157A CN 110678448 A CN110678448 A CN 110678448A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
Abstract
Disclosed is a triazine compound which has excellent solubility in toluene or dimethylformamide and can give a curable composition having excellent ultraviolet absorption ability, a curable composition containing the triazine compound, a method for producing a cured product of the curable composition, and a cured product of the curable composition. A triazine compound in which 3 aromatic groups substituted with a hydroxyl group at the 2-position are linked to a triazine ring, and 1 or 2 of the 3 aromatic groups are aromatic groups having at least 1 group selected from the group consisting of an acrylic group, a methacrylic group, an epoxy group and an allyl group.
Description
Technical Field
The present invention relates to a triazine compound, a curable composition, a method for producing a cured product, and a cured product thereof, and more particularly, to a triazine compound which has excellent solubility in toluene or dimethylformamide and can give a curable composition having excellent ultraviolet absorption ability, a curable composition containing the triazine compound, a method for producing a cured product thereof, and a cured product thereof.
Background
Curable compositions such as adhesives and paints that can be used for sealing materials and bonding transparent substrates to adherends are required to have various properties such as curability, adhesiveness, and coating processability. When an organic resin composition is used as the curable composition, it is preferable in terms of ease of processing, but deterioration such as discoloration or embrittlement of the organic resin is promoted when the composition is exposed to ultraviolet light. Therefore, various ultraviolet absorbers have been developed so far, and studies have been made to impart excellent weather resistance to organic resins.
For example, patent document 1 proposes a weather-resistant hard coat film in which a hard coat layer containing an ultraviolet absorber having a radically polymerizable (meth) acrylic functional group, for example, a benzotriazole-based compound, is formed on a base film. According to patent document 1, a large amount of the 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.
Further, 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 coating film having excellent ultraviolet curability and excellent hardness and adhesion to a substrate can be obtained.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007-230093
Patent document 2: japanese patent laid-open publication No. 2013-203758
Disclosure of Invention
Problems to be solved by the invention
However, the benzotriazole-based ultraviolet absorbers used in patent document 1 are unsatisfactory in both absorption wavelength and absorption capacity. Further, the photocurable composition proposed in patent document 2 has a problem that the moldability of the cured film is insufficient, and a film having a uniform thickness cannot be stably produced.
Accordingly, an object of the present invention is to provide a triazine compound which has excellent solubility in toluene or dimethylformamide and can give a curable composition having excellent ultraviolet absorbability, a curable composition containing the triazine compound, a method for producing a cured product of the curable composition, and a cured product of the curable composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a triazine compound in which 3 aromatic groups substituted with a hydroxyl group at the 2-position are linked to a triazine ring and 1 or 2 of the 3 aromatic groups are aromatic groups containing an acrylic group, a methacrylic group, an epoxy group or an allyl group, and have completed the present invention.
That is, the triazine compound of the present invention is characterized in that 3 aromatic groups substituted with a hydroxyl group at the 2-position are linked to the triazine ring, and 1 or 2 of the 3 aromatic groups are aromatic groups having at least 1 group selected from the group consisting of an acrylic group, a methacrylic group, an epoxy group, and an allyl group.
Among the triazine compounds of the present invention, those represented by the following general formula (1) are preferred
(in the general formula (1), X represents a C1-20 linear or branched alkyl group, an acrylic group, a methacrylic group, or a group in which a hydrogen atom of a part of the alkyl group is substituted with an acrylic group, a methacrylic group, or an epoxy groupRadicals or allyl-substituted radicals, R1X, or a linear or branched alkyl group having 1 to 10 carbon atoms, R2Represents a straight-chain or branched alkyl group having 1 to 10 carbon atoms, R3～R11Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, all of the alkyl groups, alkenyl groups, and alkoxy groups are optionally straight-chain or branched, a part of the carbon chain is optionally substituted with a carbonyl group, an imide group, an amide bond, or an oxygen atom, and a hydrogen atom of the carbon chain is optionally substituted with a hydroxyl group), and particularly preferably a compound represented by the following general formula (2)
(in the general formula (2), R12Represents an alkyl group having 1 to 8 carbon atoms or a group represented by the following formula (3), R13And R14Represents a hydrogen atom or a methyl group).
(in the formula (3), R1’Represents an alkyl group having 1 to 8 carbon atoms).
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 per 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, and 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 the curable composition at 50 to 200 ℃.
The cured product of the present invention is characterized by being obtained by using the curable composition of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a triazine compound which has excellent solubility in toluene or dimethylformamide and can give a curable composition having excellent ultraviolet absorbability, a curable composition containing the triazine compound, a method for producing a cured product of the curable composition, and a cured product of the curable composition can be provided. The curable composition of the present invention has excellent moldability into a coating film or film, and can stably produce a coating film or film.
Drawings
FIG. 1 is a diagram showing an ultraviolet absorption spectrum of Compound No.1 of the triazine compound of the present invention.
FIG. 2 is a graph showing an ultraviolet absorption spectrum of comparative Compound No. 2.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The triazine compound of the present invention is a novel compound, which is a compound useful as an ultraviolet absorber. The triazine compound of the present invention is a triazine compound in which 3 aromatic groups substituted with a hydroxyl group at the 2-position are linked to a triazine ring, and 1 or 2 of the 3 aromatic groups are aromatic groups having at least 1 group selected from the group consisting of an acrylic group, a methacrylic group, an epoxy group, and an allyl group.
In the triazine compound of the present invention, examples of the aromatic group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like.
The triazine compound of the present invention is preferably a compound represented by the following general formula (1).
In the general formula (1), X represents a C1-20 linear or branched alkyl group, an acrylic group, a methacrylic group, or a group in which a hydrogen atom of a part of the alkyl group is substituted with an acrylic group, a methacrylic group, an epoxy group or an allyl group, and R is1X or an alkyl group having 1 to 10 carbon atoms, R2Represents an alkyl group having 1 to 10 carbon atoms, R3～R11Each independently represents a hydrogen atom or a hydroxyl groupA halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Some or all of the alkyl, alkenyl and alkoxy groups are optionally straight-chain or branched, some of the carbon chains are optionally substituted by carbonyl, imide, amide or oxygen atoms, and the hydrogen atoms of the carbon chains are optionally substituted by hydroxyl groups.
Examples of the linear or branched alkyl group having 1 to 20 carbon atoms for X in the general formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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-propylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, N-dodecyl, isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, isotetradecyl, n-pentadecyl, iso-pentadecyl, n-hexadecyl, iso-hexadecyl, n-heptadecyl, iso-heptadecyl, n-octadecyl, iso-octadecyl, n-nonadecyl, iso-nonadecyl, n-eicosyl, iso-eicosyl, and the like.
In the general formula (1), R1And R2The alkyl group having 1 to 10 carbon atoms is optionally a straight chain or branched one, and examples thereof include a methyl group, an ethyl group, a propyl group, a 2-propynyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, and a decyl group.
In the general formula (1), as R3～R11Examples of the halogen atom include a fluorine atom, a bromine atom, and a chlorine atom.
In the general formula (1), R3～R11Examples of the alkyl group having 1 to 20 carbon atoms include, in addition to the above alkyl groups, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecylAlkyl, eicosyl, and the like.
In the general formula (1), as R3～R11Examples of the alkenyl group having 2 to 20 carbon atoms 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-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl and the like.
In the general formula (1), as R3～R11Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy, and tert-octyloxy.
In the general formula (1), as R3～R11Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 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-octylphenyl, 2, 4-diisopropylphenylphenyl, 4-cyclohexylphenyl, (1, 1' -biphenyl) -4-yl, 2,4, 5-trimethylphenyl, ferrocenyl and the like.
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.
R12Examples thereof include C1-8 alkyl groups or groups represented by the following formula (3), R13Represents an alkyl group having 1 to 4 carbon atoms, R13～R15Represents a hydrogen atom or a methyl group, R16Represents an alkyl group having 1 to 8 carbon atoms or a phenyl group.
In the formula (3), R1’Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms.
Among the triazine compounds of the present invention, compounds represented by the following general formula (2) are more preferable from the viewpoint of compatibility with curable components, heat resistance, volatility resistance, and weather resistance.
Here, in the general formula (2), R12Is an alkyl group having 1 to 8 carbon atoms, a group represented by the formula (3), R13And R14Is a hydrogen atom or a methyl group.
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 general organic synthesis. In addition, as a purification method, a method using distillation, recrystallization, reprecipitation, a filter material, or an adsorbent can be suitably used.
Next, the curable composition of the present invention will be described. The curable composition of the present invention contains the triazine compound of the present invention. In the curable composition of the present invention, the amount of the triazine compound of the present invention is 0.001 to 20 parts by mass relative to 100 parts by mass of the total of the curable monomer, the curable oligomer, and the curable polymer, and is preferably 0.002 to 10 parts by mass, more preferably 0.03 to 10 parts by mass, from the viewpoint of compatibility with the curable component, heat resistance, weather resistance, and volatility resistance. When the 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 be deteriorated.
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 those having one or more (meth) acrylic functional groups, for example, (meth) acryloyl groups.
In the curable composition of the present invention, the (meth) acryloyloxy group means a group represented by the following formula (4).
In the formula (4), R17Represents a hydrogen atom or a methyl group, R17When it is methyl, it is methacryloyloxy, R17And a hydrogen atom is an acryloyloxy group.
The curable monomer, curable oligomer, and curable polymer are preferably those using a (meth) acrylate compound. Examples of the (meth) acrylate compound include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, tetrahydrofurylmethyl (meth) acrylate, glycidyl (meth) acrylate, and mixtures thereof, 2-hydroxy-3-phenoxypropyl (meth) acrylate, nonylphenoxyethyltetrahydrofuran methyl (meth) acrylate, caprolactone-modified tetrahydrofuran methyl (meth) acrylate, diethylaminoethyl (meth) acrylate; alkyl diol di (meth) acrylates such as 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, and 2-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate; polyoxyalkyl ether di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate; norbornanedimethanol diacrylate, norbornanedimethanol di (meth) acrylate, diol di (meth) acrylate obtained by adding ethylene oxide or propylene oxide to norbornanedimethanol in an amount of 2 moles, 5-ethyl-5-hydroxymethyl-beta, beta-dimethyl-1, 3-dioxane-2-ethanol diacrylate, tricyclodecanedimethanol di (meth) acrylate, tricyclodecanediethanol di (meth) acrylate, diol di (meth) acrylate obtained by adding ethylene oxide or propylene oxide to tricyclodecanedimethanol in an amount of 2 moles, pentacyclopentadecane dimethanol di (meth) acrylate, pentacyclopentadecane diethanol di (meth) acrylate, diol di (meth) acrylate obtained by adding ethylene oxide or propylene oxide to pentacyclopentadecane dimethanol in an amount of 2 moles, Diol di (meth) acrylates having an alicyclic structure such as diol di (meth) acrylates obtained by adding 2 moles of ethylene oxide or propylene oxide to pentacyclopentadecane diethanol; bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxypropyl isocyanurate, bis (2-acryloyloxybutyl) hydroxybutyl isocyanurate, bis (2-methacryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-methacryloyloxypropyl) hydroxypropyl isocyanurate, bis (2-methacryloyloxybutyl) hydroxybutyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, tris (2-acryloyloxybutyl) isocyanurate, tris (2-methacryloyloxyethyl) isocyanurate, tris (2-methacryloyloxypropyl) isocyanurate, tris (2-methacryloyloxybutyl) isocyanurate, tris (2-methacryloyloxypropyl) isocyanurate, bis (2-acryloyloxypropyl) isocyanurate, bis (2-acryloyloxybutyl, Tris (2-methacryloyloxybutyl) isocyanurate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, poly (meth) acrylate of dipentaerythritol, 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 having a polyether skeleton, urethane (meth) acrylate having a polyester skeleton, polyester (meth) acrylate obtained by esterifying (meth) acrylic acid with a polyol of urethane (meth) acrylate having a polycarbonate skeleton, polyether (meth) acrylate obtained by esterifying (meth) acrylic acid with a polyol having a polyether skeleton, and the like.
The urethane (meth) acrylate is a compound having one acryloyl group or methacryloyl group and having one or more urethane bonds (-NHCOO-). The urethane (meth) acrylate is a reaction product of a polyol, a polyisocyanate, and a (meth) acrylate having a hydroxyl group, for example. Examples of the polyhydric alcohol include ethylene glycol, 1, 4-butanediol, neopentyl glycol, polycaprolactone polyol, polyester polyol, polycarbonate diol, and polytetramethylene glycol. Further, examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, and 4, 4' -diphenylmethane diisocyanate. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, and an epsilon-caprolactone adduct of 2-hydroxyethyl (meth) acrylate.
The polyfunctional urethane (meth) acrylate is a compound having a plurality of acryloyl groups or methacryloyl groups and having one or more urethane bonds (-NHCOO-). The polyfunctional urethane (meth) acrylate is, for example, a reaction product of a polyfunctional (meth) acrylate having a hydroxyl group and a polyisocyanate. Examples of the polyfunctional (meth) acrylate having a hydroxyl group include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate. On the other hand, as the polyisocyanate, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like can be cited.
The epoxy (meth) acrylate is, for example, a reactant of a polyepoxy compound and (meth) acrylic acid. The polyepoxide is preferably a polyglycidyl compound. Specific examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, triphenol methane type epoxy resins, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether and the like.
In the curable composition of the present invention, the content of the curable monomer, the curable oligomer, and the curable polymer is preferably 80 to 95% by mass, and more preferably 90 to 95% by mass, based on the solid content (component other than the solvent) of the curable composition.
The method for producing a cured product of the present invention is carried out by irradiating the curable composition of the present invention with light or heating the curable composition at 50 to 200 ℃. Examples of the curing method of the curable composition include a one-pack curing type, a two-pack curing type using a curing agent, and an active energy ray curing type in which curing is performed by irradiation with ultraviolet rays or ionizing radiation. In the curable composition of the present invention, ultraviolet-curable type is preferable.
The curable composition of the present invention preferably contains one or more polymerization initiators. The polymerization initiator may be used in the curable composition of the present invention as long as it can initiate polymerization of the curable monomer, curable oligomer, or curable polymer.
Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, but the present invention is not limited to these examples. These polymerization initiators may be used alone or in combination. The molding material can be cured by light irradiation or heating by using a material having two properties, such as a photopolymerization initiator acting as a thermal polymerization initiator or a photopolymerization initiator acting as a thermal polymerization initiator.
Examples of the photopolymerization initiator include the following compounds.
(1) Benzophenone derivatives: examples thereof include benzophenone, methyl O-benzoylbenzoate, 4-benzoyl-4' -methylbenzophenone, dibenzylketone and fluorenone.
(2) Acetophenone derivatives: examples thereof include 2, 2' -diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2-dimethoxy-1, 2-diphenylethan-1-one (for example, IRGACURE 651 manufactured by BASF Corp.), 1-hydroxycyclohexylphenyl ketone (for example, Esacure KS300 manufactured by BASF Corp.), 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (for example, IRGACURE 907 manufactured by BASF Corp.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl ] -phenyl } -2-methylpropan-1-one (for example, IRGACURE 907 manufactured by BASF Corp., IRGACURE 127), methyl phenylglyoxylate, and the like.
(3) Thioxanthone derivatives: examples thereof include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone and diethylthioxanthone.
(4) Benzil derivatives: examples thereof include benzil, benzil dimethyl ketal, and benzil- β -methoxyacetal.
(5) Benzoin derivatives: examples thereof include benzoin, benzoin methyl ether, and 2-hydroxy-2-methyl-1-phenylpropan-1-one (e.g., DAROCURE 1173 manufactured by BASF corporation).
(6) Oxime-based compound: examples thereof include 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-benzoyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime 1, 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl oxime) ] ethanone (e.g., IRGACURE OXE01, manufactured by BASF Co., Ltd.), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3H-carbazol -yl ] -1- (O-acetyloxime) (e.g., IRGACURE OXE02, manufactured by BASF corporation), and the like.
(7) α -hydroxyketone compound: examples thereof include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) -benzyl ] phenyl } -2-methylpropane.
(8) α -aminoalkylphenone-based compound: examples thereof include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (e.g., IRGACURE 369 manufactured by BASF corporation) and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (e.g., IRGACURE 379 manufactured by BASF corporation).
(9) Phosphine oxide-based compound: examples thereof include bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (e.g., IRGACURE 819 manufactured by BASF), bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (e.g., DAROCURE TPO manufactured by BASF).
(10) Titanocene compound: examples thereof include bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (IRGACURE 784, product of Ciba Specialty Chemicals).
Examples of the thermal polymerization initiator include 2,2 '-azobis (isobutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (2-methylbutyronitrile), 4' -azobis (4-cyanovaleronitrile), 2 '-azobis [2- (2-methylpropionamidine) dihydrochloride, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dimethyl 2, 2' -azobis (2-methylpropionate), diisopropylphenyl peroxide, 1-bis (tert-butylperoxy) 3,3, 5-trimethylcyclohexane, tert-butylperoxy-2-ethyl hexanoate, potassium persulfate, ammonium persulfate, sodium persulfate, and the like, Hydrogen peroxide, dicyandiamide, cyclohexyl p-toluenesulfonate, diphenyl (methyl) sulfonium tetrafluoroborate and the like.
The content of the polymerization initiator in the curable composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total of the curable monomer, the curable oligomer, and the curable polymer. When the amount is less than 0.1 part by mass, curing may be insufficient, and when 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. Examples of the curing accelerator that can be added include amines such as triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, isoamyl p-dimethylaminobenzoate, and ethyl p-dimethylaminobenzoate, hydrogen donors such as 2-mercaptobenzothiazole, and pigment sensitizers such as xanthene, thioxanthene, coumarin, and thiocoumarin.
The amount of the curing accelerator to be blended is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass, based on 100 parts by mass of the total of the curable monomer, the curable oligomer and the curable polymer.
As a light source of active light for curing the curable composition of the present invention by photopolymerization, those emitting light with a wavelength of 300 to 450nm, for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, and the like can be used.
The method for blending the triazine compound of the present invention into the curable composition is not particularly limited, and a known blending technique of a resin additive can be used. For example, a method of adding the curable component of the curable composition to the polymerization system in advance at the time of polymerization, a method of adding the curable component during the polymerization, and a method of adding the curable component after the polymerization can be used. In addition, when the curable composition is compounded after polymerization, there may be mentioned a method of mixing the composition with a powder or a pellet of a polymer obtained by polymerization and kneading the mixture by using a processing machine such as an extruder, a method of compounding the curable composition of the present invention into a curable composition after using the curable composition as a master batch, and the like. The type of processing machine used, the processing temperature, the cooling conditions after processing, and the like may be used without particular limitation, and the mixing conditions may be appropriately selected so that the physical properties of the obtained resin can be suitable for the user. The curable composition of the present invention may be blended alone or may be blended into a particulate form by coating with other resin additives, fillers, or the like.
The polymerization vessel used for the polymerization reaction may be a continuous reaction vessel used in conventional polymerization facilities, and the size, shape, material and the like of conventional polymerization facilities are not particularly limited in the present invention.
The preferred molecular weight of the curable component obtained by polymerization may vary depending on the application, but when used as a coating film, the weight average molecular weight measured by GPC is preferably in the range of 5 to 15 ten thousand, more preferably 1 to 10 ten thousand. When the weight average molecular weight of the curable component is less than 5 thousand, the strength or durability of the molded article may be poor, and the processability may be lowered when 15 ten thousand or more.
The curable composition of the present invention may optionally contain known resin additives (for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, another antioxidant, a hindered amine compound, an ultraviolet absorber different from the triazine compound of the present invention, a flame retardant aid, a lubricant, a filler, hydrotalcite, a fatty acid metal salt, an antistatic agent, a fluorescent whitening agent, a pigment, a dye, etc.) within a range in which the effects of the present invention are not significantly impaired.
Examples of the phenol-based antioxidant include 2, 6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4, 6-dimethylphenol, styrenated phenol, 2 ' -methylenebis (4-ethyl-6-tert-butylphenol), 2 ' -thiobis- (6-tert-butyl-4-methylphenol), 2 ' -thiodiethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-methyl-4, 6-bis (octylmercaptomethyl) phenol, 2 ' -isobutylidenebis (4, 6-dimethylphenol), isooctyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 ' -butylidenebis (4, 6-dimethylphenol), isooctyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like, N, N '-hexane-1, 6-diylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide, 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' -ethylenebis (4, 6-di-tert-butylphenol), 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid and C13-15 alkyl ester, 2, 5-di-tert-amylhydroquinone, hindered phenol polymer (product name "AO.OH.98" manufactured by ADEKA PALMALOLE Co., Ltd.) ], 2, 2' -methylenebis [6- (1-methylcyclohexyl) -p-cresol ], 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 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 (dioxaphosphohepin), hexamethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, Bis [ monoethyl (3, 5-di-tert-butyl-4-hydroxybenzyl) phosphonate ] calcium salt, the reaction product of 5, 7-bis (1, 1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone with o-xylene, 2, 6-di-tert-butyl-4- (4, 6-bis (octylthio) -1,3, 5-triazin-2-ylamino) phenol, DL-a-tocopherol (vitamin E), 2, 6-bis (alpha-methylbenzyl) -4-methylphenol, bis [3, 3-bis- (4 '-hydroxy-3' -tert-butyl-phenyl) butanoic acid ] diol ester, 2, 6-di-tert-butyl-p-cresol, o-xylene, 2, 6-diphenyl-4-octadecyloxyphenol, stearyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3, 5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3, 5-tert-butyl-4-hydroxybenzylthio acetate, thiodiethylene bis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 4 '-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2' -methylenebis (4-methyl-6-tert-butylphenol), Bis [3, 3-bis (4-hydroxy-3-tert-butylphenyl) butanoate ] diol ester, 4 ' -butylidenebis (2, 6-di-tert-butylphenol), 4 ' -butylidenebis (6-tert-butyl-3-methylphenol), 2 ' -ethylenebis (4, 6-di-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [ 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] terephthalate, 1,3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethylbenzene, 1,3, 5-tris [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, tetrakis [ methylene-3- (3 ', 5 ' -tert-tributyl-4 ' -hydroxyphenyl) propionate ] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3, 9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) cinnamyl ] isocyanurate ) -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], stearyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid amide, and 3- (3, 5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as palmityl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, myristyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, and lauryl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide. The amount of the phenolic antioxidant to be blended is 0.001 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, per 100 parts by mass of the curable components of the curable composition of the present invention.
Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, hepta (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis (nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenylpropylene glycol diphosphite, trisnonylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris [ 2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylsulfanyl) -5-methylphenyl ] phosphite, tris (decyl) phosphite, octyldiphenyl phosphite, bis (decyl) monophenyl phosphite, a mixture of distearylpentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, tetraphenyl-tetratridecyl pentaerythritol tetraphosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4, 4' -n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2, 4-di-tert-butylphenyl) biphenylene diphosphonite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (1, 1-dimethylethyl) -5-methyl-4, 1-phenylene) hexa-tridecyl phosphite (1-methyl-1-propenyl-3-ylidene), 2 '-methylenebis (4, 6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2' -methylenebis (4, 6-di-tert-butylphenyl) -octadecyl phosphite, octadecyl ester, 2,2 ' -ethylenebis (4, 6-di-tert-butylphenyl) fluorophosphite, 4 ' -butylidenebis (3-methyl-6-tert-butylphenyl ditridecyl) phosphite, tris (2- [ (2,4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1,3,2] dioxaphosphepin-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, poly-4, 4 ' -isopropylidenediphenol C12-15 alcohol phosphite, Bis (diisodecyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, 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-diisopropylphenylphenyl) pentaerythritol diphosphite, and the like. The amount of the phosphorus antioxidant to be blended is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the curable components of the curable composition of the present invention.
Examples of the thioether-based antioxidant include tetrakis [ methylene-3- (dodecylthio) propionate ] methane, bis (methyl-4- [ 3-n-alkyl (C12/C14) thiopropionyloxy ] 5-t-butylphenyl) sulfide, ditridecyl-3, 3 ' -thiodipropionate, dilauryl-3, 3 ' -thiodipropionate, dimyristyl-3, 3 ' -thiodipropionate, distearyl-3, 3 ' -thiodipropionate, lauryl/stearyl thiodipropionate, 4 ' -thiobis (6-tert-butyl-m-cresol), 2 ' -thiobis (6-tert-butyl-p-cresol), distearyl disulfide. The amount of the thioether antioxidant to be blended is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the curable component of the curable composition of the present invention.
Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2, 4-dihydroxybenzophenone and 5, 5' -methylenebis (2-hydroxy-4-methoxybenzophenone); 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, 2- (2-hydroxy-3, 5-diisopropylphenylphenyl) benzotriazole, 2' -methylenebis (4-tert-octyl-6-benzotriazolyl phenol), polyethylene glycol esters of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, polyethylene glycol esters of N-methyl-2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, and mixtures thereof, 2- [ 2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl ] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl ] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl ] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl ] -5-chlorobenzotriazole, 2- [ 2-hydroxy-5- (2-methacryloyloxyethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl ] benzotriazole Phenylethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl ] -5-chlorobenzotriazole, 2- (2-hydroxyphenyl) benzotriazoles such as 2- [ 2-hydroxy-4- (2-methacryloyloxymethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl ] benzotriazole, and 2- [ 2-hydroxy-4- (3-methacryloyloxypropyl) 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, dodecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, benzoates such as tetradecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, and behenyl (3, 5-di-tert-butyl-4-hydroxy) benzoate; substituted oxalanilides such as 2-ethyl-2 '-ethoxyoxalanilide and 2-ethoxy-4' -dodecyloxalanilide; cyanoacrylates such as ethyl- α -cyano- β, β -diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts, or metal chelates, in particular salts of nickel, chromium, or chelates, etc. The amount of the ultraviolet absorber to be added is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the curable components of the curable composition of the present invention.
Examples of the hindered amine compound include 2,2,6, 6-tetramethyl-4-piperidine stearate, 1,2,2,6, 6-pentamethyl-4-piperidine stearate, 2,2,6, 6-tetramethyl-4-piperidine benzoate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butane tetracarboxylic acid ester, tetrakis (1,2,2,6, 6-pentamethyl-4-piperidyl) -1,2,3, 4-butane tetracarboxylic acid ester, bis (2,2,6, 6-tetramethyl-4-piperidyl) -bis (tridecyl) -1,2,3, 4-butanetetracarboxylate, bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -ditridecyl-1, 2,3, 4-butanetetracarboxylate, 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, and mixtures thereof, 1, 6-bis (2,2,6, 6-tetramethyl-4-piperidylamino) hexane/2, 4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8, 12-tetrakis [2, 4-bis (N-butyl-N- (2,2,6, 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5,8, 12-tetraazadodecane, 1,5,8, 12-tetrakis [2, 4-bis (N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5, 8-12-tetraazadodecane, 1,6, 11-tris [2, 4-bis (N-butyl-N- (2,2,6, 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl ] aminoundecane, 1,6, 11-tris [2, 4-bis (N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] aminoundecane, bis {4- (1-octyloxy-2, 2,6, 6-tetramethyl) piperidyl } sebacate, bis {4- (2,2,6, 6-tetramethyl-1-undecyloxy) piperidyl) carbonate, and the like. The amount of the hindered amine compound to be blended is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the curable components of the curable composition of the present invention.
Examples of the nucleating agent include metal carboxylates such as sodium 2,2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, lithium 2,2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, aluminum hydroxybis [2,2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate ], sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, and sodium bicyclo [2.2.1] heptane-2, 3-dicarboxylate; polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3, 4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol; amide compounds such as N, N ' -tris [ 2-methylcyclohexyl ] -1,2, 3-propanetricarboxylic acid amide, N ' -tricyclohexyl-1, 3, 5-benzenetricarboxylic acid amide, N ' -dicyclohexylnaphthalene dicarboxamide, and 1,3, 5-tris (dimethylisopropionylamino) benzene. The amount of the nucleating agent to be added is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 part by mass, based on 100 parts by mass of the curable components of the curable composition of the present invention.
Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, cresyldiphenyl-2, 6-dimethylphenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylene) -4, 1-phenylenetetraphenyl diphosphate, 1, 3-phenylenetetra (2, 6-dimethylphenyl) phosphate, aromatic phosphates of "Adekastab FP-500", "Adekastab FP-600" and "Adekastab FP-800", manufactured by ADEKA; phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate, and 1-butenyl phenylphosphonate; phenylphosphinate esters such as diphenylphosphinic acid ester, methyl diphenylphosphinate ester, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, and the like; phosphazene compounds such as bis (2-allylphenoxy) phosphazene and xylenolphosphazene; phosphorus flame retardants such as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds, and red phosphorus; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; brominated bisphenol a-type epoxy resins, brominated phenol novolac-type epoxy resins, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1, 2-dibromo-4- (1, 2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene oxide, brominated polystyrene, and 2,4, 6-tris (tribromophenoxy) -1,3, 5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol a-type dimethacrylate, pentabromobenzyl acrylate, and brominated styrene. These flame retardants are preferably used in combination with an anti-dripping agent such as a fluororesin or a flame retardant aid such as a polyol or hydrotalcite. The amount of the flame retardant to be added is 1 to 100 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the curable components of the curable composition of the present invention.
The lubricant is added for the purpose of imparting lubricity to the surface of the molded article and improving the scratch preventing effect. Examples of the lubricant include unsaturated fatty acid amides such as oleamide and erucamide; saturated fatty acid amides such as behenamide and stearamide; butyl stearate, stearyl alcohol, glyceryl monostearate, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hardened castor oil, stearamide, oleamide, ethylene bis stearamide, and the like. These can be used alone in 1 kind, also can be combined with more than 2 kinds. The amount of the lubricant to be blended is 0.01 to 2 parts by mass, and more preferably 0.03 to 0.5 part by mass, based on 100 parts by mass of the curable component of the curable composition of the present invention.
Hydrotalcite-like compound is a complex salt compound composed of magnesium, aluminum, hydroxyl groups, carbonate groups and optionally crystal water, which is known as natural or synthetic, and includes those in which a part of magnesium or aluminum is substituted with an alkali metal or another metal such as zinc, or in which hydroxyl groups and carbonate groups are substituted with another anionic group, and specifically includes those in which the metal of hydrotalcite represented by the following general formula (5) is substituted with an alkali metal. Further, as Al-Li hydrotalcite, a compound represented by the following general formula (6) can be used.
Mgx1Znx2Al2(OH)2(x1+x2)+4(CO3)pH2O (5)
In the general formula (5), x1 and x2 each represent a number satisfying the condition represented by the following formula, and p represents 0 or a positive number.
0≤x2/x1＜10，2≤x1+x2≤20
[Li1/3Al2/3(OH)2]·[Aq- 1/3q·pH2O](6)
Here, in the general formula (6), Aq-Represents a q-valent anion, and p represents 0 or a positive number.
In addition, carbonate anions in hydrotalcite-like compounds may be partially substituted with other anions.
The hydrotalcite may be one obtained by dehydrating crystal water, or one obtained by coating with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, a higher fatty acid ester, a wax or the like.
The hydrotalcite may be natural or synthetic. As the method for synthesizing the compound, known methods described in Japanese patent publication No. 46-2280, Japanese patent publication No. 50-30039, Japanese patent publication No. 51-29129, Japanese patent publication No. 3-36839, Japanese patent application No. 61-174270, Japanese patent application No. 5-179052 and the like can be cited. The hydrotalcite-like compound may be used without limitation to its crystal structure, crystal grains, and the like. The amount of hydrotalcite to be blended is 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable components of the curable composition of the present invention.
Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium salt and polyamine quaternary salt; anionic antistatic agents such as higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfate ester salts, higher alcohol ethylene oxide adduct sulfate ester salts, and higher alcohol ethylene oxide adduct phosphate ester salts; nonionic antistatic agents such as polyol fatty acid esters, polyalkylene glycol phosphate esters and polyoxyethylene alkyl allyl ethers; amphoteric alkyl betaines such as alkyldimethylaminoacetic acid betaine; amphoteric antistatic agents such as imidazoline type amphoteric active agents. The antistatic agent can be used alone, in addition, can also be combined with more than 2 kinds of antistatic agent use. The amount of the antistatic agent to be added is 0.03 to 2 parts by mass, and more preferably 0.1 to 0.8 part by mass, based on 100 parts by mass of the curable components of the curable composition of the present invention.
Commercially available pigments can also be used as the pigment, and examples thereof include 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.
The fluorescent whitening agent is a compound that promotes the whiteness or blue color of the molded article by the action of fluorescence emitted by absorbing ultraviolet rays of sunlight or artificial light and converting the ultraviolet rays into violet to blue visible rays. As the fluorescent whitening agent, benzoxazole-based compound C.I. fluorescent brightener Brightner 184; a coumarine-based compound c.i. fluorenscent brightner 52; diaminostilbene disulfonic acid-based compounds c.i. fluorescent bright 24, 85, 71, and the like. The amount of the fluorescent whitening agent to be used is 0.00001 to 0.1 part by mass, more preferably 0.00005 to 0.05 part by mass, based on 100 parts by mass of the curable components of the curable composition of the present invention.
Examples of the dye 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, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and a plurality of these dyes may be used in combination.
The curable composition of the present invention can be molded by a known molding method. For example, a molded article can be obtained by injection molding, extrusion molding, blow (blow) molding, vacuum molding, inflation molding, calender molding, slush (slide) molding, dip molding, foam molding, or the like.
The curable composition of the present invention can be preferably used in the fields of electric and electronic materials such as semiconductor integrated circuits, optical members, liquid crystal panels, adhesive sheets for bonding various light sources, diffusion plates, and the like, film-forming materials for organic films, coating materials such as inks, paints, various coating agents, and the like, vehicles, building materials, sealing materials, and the like.
Examples
The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples and the like.
Production example 1
Compound No.1 was synthesized according to the following reaction scheme. The manufacturing example is described in order.
(1) Production of intermediate 1
100g (0.22mol) of 4, 4' - (1,3, 5-triazine-2, 4, 6-triyl) tris (2-methylbenzene-1, 3-diol), 72.3g (0.44mol) of n-hexyl bromide, 30.3g (0.22mol) of potassium hydroxide, 270g of dimethylformamide and 270g of n-decane were added to a 2L 5-neck eggplant type flask, and the mixture was stirred at 100 ℃ for 6 hours to effect a reaction. After the reaction, the reaction mixture was cooled to 80 ℃ and neutralized by adding formic acid, and the temperature was raised to 130 ℃. Drying under reduced pressure to remove solvent, and cooling to room temperature. The obtained product was washed with methanol and toluene, purified by silica gel chromatography, and further dried at 75 ℃ using a vacuum drier, to obtain 21.8g of a yellow powder. The resulting yellow powder was confirmed to be intermediate 1 using 1H-NMR. The analysis results are shown in Table 1.
[ Table 1]
1H-NMR(DMSO-d6)
(2) Production of intermediate 2
86.2g of intermediate 1, 0.25g (6.2mmol) of sodium hydroxide and 185g of cyclohexanone were added to a 2L 5-neck eggplant type flask, respectively. After the temperature was raised to 140 ℃, the pressure was reduced to 30kPa with stirring, and reflux dehydration was performed until water was not distilled off. Then, 13.9g (0.16mol) of ethylene carbonate was added to the reaction system, and the mixture was stirred for 17 hours to effect a reaction. After the reaction was completed, the reaction mixture was cooled to 70 ℃ and neutralized by adding formic acid. A solvent of 5/1 (methanol/distilled water) was added to the system, and the mixture was stirred for a while to precipitate a solid. The mixture was filtered and washed with methanol. Drying was carried out in a vacuum drier at 75 ℃ under reduced pressure to obtain 100.5g of an orange powder. The obtained product was confirmed to be intermediate 2 using 1H-NMR. The analysis results are shown in Table 2.
[ Table 2]
1H-NMR(DMSO-d6)
(3) Production of Compound No.1
To a 2L 5-neck eggplant type flask, intermediate 2(90.0g), 4-methoxyphenol 0.8g (0.80mmol), p-toluenesulfonic acid 1 hydrate 2.3g (12.0mmol), methacrylic acid 19.3g (0.22mol), and o-xylene 200g were added, and the mixture was stirred for 10 hours while being dehydrated by normal pressure reflux using a Dean-Stark apparatus at 145 ℃ to carry out a reaction. After completion of the reaction, the reaction mixture was cooled to 80 ℃ and 100g of distilled water was added thereto, and the mixture was cooled to room temperature while stirring to precipitate a reaction product. The precipitate was filtered and washed with methanol. The obtained crude crystal was crystallized from a methyl ethyl ketone/ethanol-2/1 solvent, and then dried in a vacuum drier at 130 ℃ under full reduced pressure to obtain 58.3g of a yellow powder. The obtained product was confirmed to be Compound No.1 by 1H-NMR. The analysis results are shown in Table 3.
[ Table 3]
1H-NMR(CDCl3)
Examples 1 to 3 and comparative examples 1 to 4
A composition prepared by adding 5.0g (49.9mmol) of Methyl Methacrylate (MMA), 0.33g (30 mol%/MMA ratio) of azobisisobutyronitrile, and the ultraviolet absorber (UVA) and the solvent described in Table 4 to a 100mL four-necked eggplant type flask was stirred at room temperature. After stirring, bubbling with nitrogen gas was performed for 20 minutes, followed by degassing. The numerical values in parentheses in the columns for the ultraviolet absorber and the solvent in table 4 are the parts of each component relative to 100 parts by mass of MMA.
Next, the 4-neck eggplant type flask was heated in an oil bath at 86 ℃ to perform the reaction for the time shown in Table 4. After completion of the reaction, the 4-neck flask was taken out of the oil bath and cooled to room temperature. Subsequently, the reacted composition was dropped into 200mL of methanol while stirring, to precipitate a polymer. The polymer was filtered, washed with methanol, and dried to obtain a polymer.
In a glass vial, 3mL of tetrahydrofuran and 2 to 3 spoon portions of the obtained polymer were added, and the polymer was dissolved by stirring with ultrasonic waves. The molecular weight of the polymer was measured using a High Performance Liquid Chromatograph (HPLC) under the following conditions.
(measurement conditions)
The device comprises the following steps: high performance liquid chromatograph (manufactured by Japan Spectroscopy Co., Ltd.)
Column: GPC KF-805L (manufactured by SHOWA AND ELECTRIC JUSY)
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.50 mL/min
Column temperature: 40 deg.C
A detector: RI (Ri)
Injection amount: 100 μ L
[ Table 4]
From comparative example 3, it was confirmed that when the comparative compound was used, both the molecular weights Mn and Mw were larger than those of comparative examples 1 and 2 in which no ultraviolet absorber was added, and a high molecular weight product was formed. The formation of a high molecular weight material makes it difficult to adjust the film thickness of a coating film or a thin film, and hence the moldability is greatly impaired.
In comparative example 4, the reaction was terminated at this point in time because the composition gelled and could not be stirred for 15 minutes after the reaction started. The polymer was obtained as a yellow powder when washed with methanol, but it was not dissolved in DMF and was not measured by Gel Permeation Chromatography (GPC).
On the other hand, from examples 1 to 3, it can be confirmed that when the triazine compound of the present invention is used, there is no problem in solubility in a solvent, and the influence on polymerization of PMMA is small.
Further, 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 the compound No.1 is shown in FIG. 1, and the UV absorbance spectrum of the comparative compound No.2 is shown in FIG. 2. From FIG. 1, the compound No.1 also has an absorption ability in the UV-B region (wavelength 280-315nm), and can shield ultraviolet light with a low addition amount. On the other hand, as is clear from FIG. 2, comparative compound No.2, which has only 1 aromatic group having a hydroxyl group at the 2-position, has insufficient ultraviolet absorption performance in the wavelength region of more than 300 nm.
Thus, by using the compound of the present invention, a curable composition having excellent ultraviolet absorbability and good moldability can be provided.
Claims (10)
1. A triazine compound comprising a triazine ring and 3 aromatic groups substituted with a hydroxyl group at the 2-position, wherein 1 or 2 of the 3 aromatic groups are aromatic groups having at least 1 group selected from the group consisting of an acrylic group, a methacrylic group, an epoxy group and an allyl group.
2. The triazine compound according to claim 1, which is represented by the following general formula (1),
in the general formula (1), X represents a C1-20 linear or branched alkyl group, an acrylic group, a methacrylic group, or a group in which a hydrogen atom of a part of the alkyl group is substituted with an acrylic group, a methacrylic group, an epoxy group or an allyl group, and R1X, or a linear or branched alkyl group having 1 to 10 carbon atoms, R2Represents a straight-chain or branched alkyl group having 1 to 10 carbon atoms, R3～R11Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, all of the alkyl groups, alkenyl groups, and alkoxy groups are optionally straight-chain or branched, a part of the carbon chain is optionally substituted with a carbonyl group, an imide group, an amide bond, or an oxygen atom, and a hydrogen atom of the carbon chain is optionally substituted with a hydroxyl group.
3. The triazine compound according to claim 1, which is represented by the following general formula (2),
in the general formula (2), R12Represents an alkyl group having 1 to 8 carbon atoms or a group represented by the following formula (3), R13And R14Represents a hydrogen atom or a methyl group,
in the formula (3), R1’Represents an alkyl group having 1 to 8 carbon atoms.
4. A curable composition comprising 0.001 to 20 parts by mass of the triazine compound according to any one of claims 1 to 3, based on 100 parts by mass of the total of the curable monomer, the curable oligomer, and the curable polymer.
5. The curable composition according to claim 4, further comprising 0.1 to 10 parts by mass of a polymerization initiator.
6. The curable composition according to claim 5, wherein the polymerization initiator is a photopolymerization initiator.
7. The curable composition according to claim 5, wherein the polymerization initiator is a thermal polymerization initiator.
8. A method for producing a cured product, which comprises irradiating the curable composition according to claim 6 with light to form a cured product.
9. A method for producing a cured product, which is characterized in that a cured product is formed by heating the curable composition according to claim 7 at 50 to 200 ℃.
10. A cured product obtained by using the curable composition according to any one of claims 4 to 7.
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| JP2017103497 | 2017-05-25 | ||
| JP2017-103497 | 2017-05-25 | ||
| PCT/JP2018/019906 WO2018216750A1 (en) | 2017-05-25 | 2018-05-23 | Triazine compound, curable composition, method for producing cured product, and cured product |
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| JP (2) | JP7229915B2 (en) |
| KR (1) | KR20200010304A (en) |
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| CN114133409A (en) * | 2021-11-17 | 2022-03-04 | 万华化学集团股份有限公司 | IVB group metal ligand containing triazine structure, catalyst system thereof and production method of polyolefin elastomer |
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| EP0526399B1 (en) * | 1991-07-29 | 1995-09-27 | Ciba SC Holding AG | Light-stabilized copolymer compositions as a binder in coating films |
| JPH0928785A (en) * | 1995-07-18 | 1997-02-04 | Asahi Denka Kogyo Kk | Ophthalmological lens |
| US5976512A (en) * | 1997-03-03 | 1999-11-02 | Roche Vitamins Inc. | Symetrical hydroxyphenyl-s-triazine compositions |
| JP4070156B2 (en) * | 1997-08-29 | 2008-04-02 | 株式会社Ａｄｅｋａ | Triazine compounds and ultraviolet absorbers |
| JP2007230093A (en) | 2006-03-01 | 2007-09-13 | Bridgestone Corp | Weatherproof hard coat film and film-reinforced glass |
| JP6156214B2 (en) * | 2013-04-01 | 2017-07-05 | 信越化学工業株式会社 | Reactive ultraviolet absorber, method for producing the same, and coating composition and coated article containing the same |
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2018
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- 2018-05-23 WO PCT/JP2018/019906 patent/WO2018216750A1/en active Application Filing
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| CN1130625A (en) * | 1994-10-04 | 1996-09-11 | 希巴-盖吉股份公司 | 2-hydroxyphenyltriazines |
| DE19500441A1 (en) * | 1995-01-10 | 1996-07-11 | Agfa Gevaert Ag | Colour photographic material contains immobile photostable UV absorber |
| DE19536376A1 (en) * | 1995-09-29 | 1996-05-15 | Agfa Gevaert Ag | Photographic material having photostable layer with optimum UV absorption |
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Cited By (2)
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| CN114133409A (en) * | 2021-11-17 | 2022-03-04 | 万华化学集团股份有限公司 | IVB group metal ligand containing triazine structure, catalyst system thereof and production method of polyolefin elastomer |
| CN114133409B (en) * | 2021-11-17 | 2023-09-19 | 万华化学集团股份有限公司 | Triazine structure-containing IVB metal ligand, catalyst system thereof and production method of polyolefin elastomer |
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| JP7229915B2 (en) | 2023-02-28 |
| JP2023065460A (en) | 2023-05-12 |
| TWI743364B (en) | 2021-10-21 |
| WO2018216750A1 (en) | 2018-11-29 |
| JPWO2018216750A1 (en) | 2020-03-26 |
| KR20200010304A (en) | 2020-01-30 |
| TW201906823A (en) | 2019-02-16 |
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