JP2012201768A - Resin composition for coating fluorescent member and fluorescent member coated with the same - Google Patents

Abstract

A resin composition for coating a fluorescent member that can improve the light resistance of the fluorescent member, and a fluorescent member with improved light resistance.
A resin composition for coating a fluorescent member, comprising 0.001 to 20 parts by mass of a specific triazine compound per 100 parts by mass of a synthetic resin.
[Selection figure] None

Description

  The present invention relates to a resin composition for coating a fluorescent member containing a specific triazine-based compound and a fluorescent member formed by applying the resin composition. Specifically, a display object such as a sticker or a label using a fluorescent dye, The present invention relates to a resin composition for coating a fluorescent member capable of improving the light resistance of a fluorescent substance such as clothing, and a fluorescent member having improved light resistance.

  Conventionally, fluorescent members using fluorescent dyes or fluorescent pigments (hereinafter sometimes referred to as fluorescent substances) are stickers, labels and other display items, textiles such as textiles, markers for cards such as commuter passes, and lighting. Widely used in various applications such as light diffusing members such as signboards. However, the fluorescent substance easily deteriorates in color or fades or discolors due to light (ultraviolet rays), and the fluorescent member using the fluorescent substance has a great problem in light resistance.

  As a method for improving the light resistance of a fluorescent member, a technique of adding a light stabilizer (such as an ultraviolet absorber, an antioxidant and a hindered amine light stabilizer) to a coating resin (pigment) (Patent Document 1 below), a resin molded product Technology for adding a light-proofing agent (Patent Document 2 below), Technology for adding a light-proofing agent to the overcoat layer (Patent Document 3 below), Technology for blending microbeads containing a fluorescent substance and a light-proofing agent into a coating resin (Patent Document 4 below) and a fluorescent colorant (Patent Document 5 below) in which a fluorescent material is dispersed in an epoxy resin are disclosed.

JP 2001-106976 A JP 2004-338222 A JP 2003-055610 A Japanese Patent Laid-Open No. 08-208976 Japanese Patent Laid-Open No. 06-329880

  However, none of the techniques described in the above-mentioned patent documents are sufficient in terms of improving light resistance, and there is room for further improvement.

  Accordingly, an object of the present invention is to provide a resin composition for coating a fluorescent member capable of improving the light resistance of the fluorescent member and a fluorescent member having improved light resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a triazine-based compound having a specific structure exerts a remarkable effect on the light resistance of a fluorescent member to complete the present invention. It came.

（式中、Ｒ^１は炭素原子数１〜１２の直鎖又は分岐のアルキル基、炭素原子数３〜８のシクロアルキル基、炭素原子数２〜８のアルケニル基、炭素原子数６〜１８のアリール基、炭素原子数７〜１８のアルキルアリール基又は炭素原子数７〜１８のアリールアルキル基を表す。但し、これらのアルキル基、シクロアルキル基、アルケニル基、アリール基、アルキルアリール基又はアリールアルキル基は、ヒドロキシ基、ハロゲン原子、炭素原子数１〜１２のアルキル基又はアルコキシ基で置換されていてもよく、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基又はイミノ基で中断されていてもよい。また、上記の置換及び中断は組み合わされてもよい。Ｒ^２は炭素原子数１〜８のアルキル基又は炭素原子数２〜８のアルケニル基を表す。） That is, the resin composition for coating a fluorescent member of the present invention is obtained by blending 0.001 to 20 parts by mass of a triazine compound represented by the following general formula (1) with respect to 100 parts by mass of a synthetic resin. It is a feature.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 6 to 18 carbon atoms. An aryl group, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, provided that these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups, or arylalkyls. The group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and is interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. and may be. Moreover, good .R ² be combined is substituted and interruption of the alkenyl alkyl group or C 2 -C 8 1 to 8 carbon atoms A representative.)

  In the resin composition for coating a fluorescent member of the present invention, the amount of the triazine compound represented by the general formula (1) is 0.05 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin. preferable.

（式中、Ｒ^３は炭素原子数１〜１２の直鎖又は分岐のアルキル基を表す。但し、これらのアルキル基はヒドロキシ基、ハロゲン原子又はアルコキシ基で置換されていてもよく、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基又はイミノ基で中断されていてもよい。） Moreover, it is preferable that the resin composition for fluorescent member coating of the present invention is a triazine compound in which the general formula (1) is represented by the following general formula (2).

(In the formula, R ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms. However, these alkyl groups may be substituted with a hydroxy group, a halogen atom or an alkoxy group, an oxygen atom, (It may be interrupted by a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group.)

  The fluorescent member of the present invention is characterized in that the fluorescent member coating resin composition is applied to a material containing a fluorescent pigment and / or a fluorescent dye, or a material in which a fluorescent paint is applied on a substrate. To do.

  The fluorescent pigment of the present invention contains 0.001 to 20 parts by mass of the triazine compound represented by the general formula (1) and 0.01 to 100 parts by mass of the fluorescent dye with respect to 100 parts by mass of the synthetic resin. It is characterized by doing.

  The fluorescent paint of the present invention comprises 0.001 to 20 parts by mass of the triazine-based compound represented by the general formula (1), and a fluorescent pigment and / or fluorescent with respect to 100 parts by mass of a solvent-based or water-based synthetic resin. It contains 0.01 to 100 parts by mass of a dye.

  The fluorescent member coating resin composition containing the triazine compound having a specific structure of the present invention is useful for improving the light resistance of the fluorescent member.

  The resin composition for coating a fluorescent member of the present invention is a resin composition for use in coating a fluorescent member containing a fluorescent pigment and / or a fluorescent dye. Preferably, it is used by applying to the surface of the fluorescent member. The light resistance of the fluorescent member can be improved by coating with the resin composition for covering a fluorescent member of the present invention. The fluorescent member is a member containing a fluorescent pigment and / or a fluorescent dye, which will be described in detail later. Moreover, you may use the resin composition for fluorescent member coating of this invention by apply | coating from after apply | coating the fluorescent paint to a base material.

（式中、Ｒ^１は炭素原子数１〜１２の直鎖又は分岐のアルキル基、炭素原子数３〜８のシクロアルキル基、炭素原子数２〜８のアルケニル基、炭素原子数６〜１８のアリール基、炭素原子数７〜１８のアルキルアリール基又は炭素原子数７〜１８のアリールアルキル基を表す。但し、これらのアルキル基、シクロアルキル基、アルケニル基、アリール基、アルキルアリール基又はアリールアルキル基は、ヒドロキシ基、ハロゲン原子、炭素原子数１〜１２のアルキル基又はアルコキシ基で置換されていてもよく、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基又はイミノ基で中断されていてもよい。また、上記の置換及び中断は組み合わされてもよい。Ｒ^２は炭素原子数１〜８のアルキル基又は炭素原子数２〜８のアルケニル基を表す。） The triazine compound used in the present invention is represented by the following general formula (1).

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 6 to 18 carbon atoms. An aryl group, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, provided that these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups, or arylalkyls. The group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and is interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. and may be. Moreover, good .R ² be combined is substituted and interruption of the alkenyl alkyl group or C 2 -C 8 1 to 8 carbon atoms A representative.)

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ¹ in the general formula (1) include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary Examples include linear or branched alkyl groups such as butyl, amyl, tertiary amyl, hexyl, octyl, secondary octyl, tertiary octyl, 2-ethylhexyl, decyl, undecyl, and dodecyl. Among them, the hexyl group is excellent in light resistance. Therefore, it is preferable. Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, hexyl, octyl, And a tertiary octyl group. Among them, a methyl group is preferable because of excellent light resistance.

Examples of the alkenyl group having 2 to 8 carbon atoms represented by R ¹ and R ² include linear and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups regardless of the position of the unsaturated bond.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ¹ include phenyl, naphthyl, and biphenyl groups. Examples of the alkylaryl group having 7 to 18 carbon atoms include methylphenyl and dimethyl. Examples thereof include phenyl, ethylphenyl, and octylphenyl groups. Examples of the arylalkyl group having 7 to 18 carbon atoms include benzyl, 2-phenylethyl, 1-methyl-1-phenylethyl group, and the like. Examples of the aryl group having a substituent or interruption include 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl, 4-glycidyloxyphenyl, and 4-isocyanuratephenyl group. Etc.

  The ester group is a group formed by dehydration condensation of a carboxylic acid and an alcohol, and the amide group is a group formed by dehydration condensation of a carboxylic acid and an amine.

  Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexaoxy, octoxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy groups.

Examples of the alkyl group or cycloalkyl group of R ¹ which may have a substituent or interruption include 2-hydroxypropyl, 2-methoxyethyl, 3-sulfonyl-2-hydroxypropyl, 4-methylcyclohexyl group and the like. It is done.

（式中、Ｒ^３は炭素原子数１〜１２の直鎖又は分岐のアルキル基を表す。但し、これらのアルキル基はヒドロキシ基、ハロゲン原子又はアルコキシ基で置換されていてもよく、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基又はイミノ基で中断されていてもよい。） The triazine compound represented by the general formula (1) of the present invention is preferably represented by the following general formula (2).

(In the formula, R ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms. However, these alkyl groups may be substituted with a hydroxy group, a halogen atom or an alkoxy group, an oxygen atom, (It may be interrupted by a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group.)

The linear or branched alkyl group having 1 to 12 carbon atoms in R ³ represented by the general formula (2) is the same as the linear or branched alkyl group represented by R ¹ in the general formula (1). Groups. The alkoxy group is the same as the above alkoxy group.

  Examples of the compound represented by the general formula (1) or (2) of the present invention include the following compound No. 1-No. 4 etc. are mentioned.

  The synthetic resin in the resin composition for coating a fluorescent member of the present invention is not particularly limited, but is preferably a solvent-based or water-based resin because it can be easily applied to a fluorescent member or a substrate. From the viewpoint of durability and durability, an acrylic resin, a polyester resin, a urethane resin, an acrylic urethane resin, or the like can be preferably used. As a specific conventional solvent-based or water-based conventional product, for example, a product such as “One Coat Leuhi Overlay Clear” (acrylic resin) manufactured by Sinloihi Co., Ltd. may be used.

  The compounding amount of the triazine compound represented by the general formula (1) or (2) of the present invention is 0.001 to 20 parts by mass, preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the synthetic resin. 10 parts by mass, particularly preferably 0.1 to 6 parts by mass. If the blending amount is less than 0.001 part by mass, the effect of light resistance is small, and even if the amount exceeds 20 parts by mass, the effect of improving light resistance cannot be expected.

  The fluorescent pigment is not particularly limited, and a known fluorescent pigment can be used. In general, a fluorescent pigment is a powder of a fluorescent dye in a solid solution in a synthetic resin.

  Synthetic resins that solidify the fluorescent dye used in the fluorescent pigment include acrylic resin, polyester resin, styrene resin, vinyl chloride resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin, epoxy resin , Urethane resins, acrylic urethane resins, and the like. Known fluorescent pigments are obtained by dyeing or dissolving fluorescent dyes in these resins, and pulverizing the obtained colored bulk resin. Specific examples of commercially available fluorescent pigments include FZ-2000, FZ-5000, FZ-6000, FZ-3040, FA-40, FA-200, FR-50, and SB-10 (all of which are Sinloi Corporation). Manufactured) and the like.

  The fluorescent dye is not particularly limited. For example, polyphenyl, stilbene, styrylbenzene, oxazole, oxadiazole, coumarin, naphthalic acid, quinolone, xanthene, oxazine, thiazine , Polymethine-based, perylene-based, anthraquinone-based, pyrazoline-based, thioindigo-based, naphthilene-based, and methine-based fluorescent dyes. Specifically, CI Solvent Yellow 98, CI Solvent Yellow 160, CI Vat Red 15, CI Vat Orange 7, CI Solvent Yellow 5, Lumogen F Yellow 083, Lumogen F Red I 305, CIVat Red Red 305, CIVat Red Red 305, CIVat Red Red 305 Red 150, CI Solvent Red 197, CI Solvent Red 150, CI Disperse Yellow 82 (manufactured by BASF), Macrolex Fluorescent Red G (manufactured by Bayer), SF-4G, SF-B, SF-G, and Blue-FR Japan HF-G, HF-4G, FL-7G, and BlueS (manufactured by Sumitomo Chemical Co., Ltd.) Can be mentioned.

  The fluorescent paint is a solvent-based or water-based synthetic resin paint in which a fluorescent substance is dissolved or dispersed in a solvent-based or water-based synthetic resin such as acrylic resin, polyester resin, alkyd resin, and acrylic urethane resin. Specific examples of commercially available products include solvent-based fluorescent paints such as those manufactured by Sinloihi Co., Ltd., product names One Coat Roihi Red, Orange, Lemon and Yellow.

  Examples of the member containing the fluorescent pigment and / or fluorescent dye or the substrate coated with the fluorescent paint include, for example, synthetic resin, metal, cloth, glass, glass fiber, earthenware, wood, paper, natural rubber, concrete, and the like. Asphalt etc. can be mentioned, and the resin composition for coating a fluorescent member of the present invention can be applied to all these members or substrates.

  The synthetic resin in the substrate is not particularly limited, and examples thereof include high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, polybutene-1, poly-3-methyl-1-butene, Polyolefin resins such as poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or random copolymer, ethylene-vinyl acetate copolymer, olefin-maleimide copolymer, and the like Copolymers of monomers giving polymers; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-chloride Vinylidene-vinyl acetate terpolymer, salt Halogen-containing resins such as vinyl-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexylmaleimide copolymer; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate ( PEN), polyester resins such as poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polyhexamethylene terephthalate; polystyrene, high impact polystyrene (HIPS) ), Acrylonitrile butadiene styrene (ABS), chlorinated polyethylene acrylonitrile styrene (ACS), styrene acrylonitrile (SAN), acrylonitrile butyl acrylate styrene Styrene resins such as (AAS), butadiene styrene, styrene maleic acid, styrene maleimide, ethylene propylene acrylonitrile styrene (AES), butadiene methyl styrene methacrylate (MBS); polycarbonate resins such as polycarbonate and branched polycarbonate; polyhexamethylene azide Polyamide resins such as polyamides using aromatic dicarboxylic acids and alicyclic dicarboxylic acids such as pamide (nylon 66), polycaprolactam (nylon 6), nylon 6T; polyphenylene oxide (PPO) resins; modified polyphenylene oxide resins; Polyphenylene sulfide (PPS) resin; polyacetal (POM); modified polyacetal; polysulfone; polyethersulfone; polyetherketone; Polyoxyethylene, petroleum resin, coumarone resin, cycloolefin resin such as norbornene resin, cycloolefin-olefin copolymer resin, polyvinyl acetate resin, polyvinyl alcohol resin, acrylic resin such as polymethyl methacrylate, polycarbonate and styrene resin Polyvinyl alcohol resin; Cellulose resins such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; liquid crystal polymer (LCP); silicone resin; urethane resin; fat Aliphatic polyesters from aliphatic dicarboxylic acids, aliphatic diols, aliphatic hydroxycarboxylic acids or cyclic compounds thereof, and these may be diisocyanates. Biodegradable resins such as aliphatic polyester having a molecular weight is increased; and these recycled resins. Furthermore, thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin and unsaturated polyester resin can be mentioned. Furthermore, natural rubber (NR), polyisoprene rubber (IR), styrene butadiene rubber (SBR), polybutadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber, acrylonitrile butadiene rubber (NBR) And rubber polymer compounds such as silicone rubber. These synthetic resins may be used alone or in a combination of two or more.

  The resin composition for coating a fluorescent member of the present invention includes an antioxidant (phenolic, phosphorous, thioether, etc.) that is usually used depending on the application, and a triazine represented by the general formula (1) or (2). In addition to the compound, additives such as an ultraviolet absorber, a hindered amine light stabilizer, a plasticizer, and an antistatic agent can be used in combination.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) Nol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary) Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4- Hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethy Bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2- Tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4- Hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) Propionate], tocopherol and the like.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol 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) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-ditert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Ditertiarybutylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis 4,6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine) -6-yl) oxy] ethyl) amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-trakis (1,1-dimethylethyl) Dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] propyl] phenol, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol A phosphite etc. are mentioned.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include β-alkyl mercaptopropionic esters of polyols.

  Examples of the other UV absorbers include benzotriazole UV absorbers, other triazine UV absorbers, benzophenone UV absorbers, and benzoate UV absorbers.

  Examples of the benzotriazole-based ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole, 2,2 ′ 2- (2′-hydroxyphenyl) benzotriazoles such as methylenebis (4-tert-octyl-6-benzotriazolyl) phenol It is below.

  Examples of the other triazine ultraviolet absorbers include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy- 4-hexyloxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-dimethylphenyl) -s- Triazine, 2- [2-hydroxy-4- (3-dodecyloxy-2-hydroxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy -4- (3-tridecyloxy-2-hydroxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydride Xy-4- [3- (2-ethylhexyloxy) -2-hydroxypropyloxy] phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- Hexyloxyphenyl) -4,6-dibiphenyl-s-triazine, 2- [2-hydroxy-4- [1- (i-octyloxycarbonyl) ethyloxy] phenyl] -4,6-dibiphenyl-s-triazine 2,4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine, 2,4-bis (4-butoxy-2-hydroxyphenyl) -6 Triary such as-(2,4-dibutoxyphenyl) -s-triazine, 2,4,6-tris (2-hydroxy-4-octoxyphenyl) -s-triazine Le triazines, and the like.

  Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). And 2-hydroxybenzophenones.

  Examples of the benzoate ultraviolet absorber include phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl- 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and the like can be mentioned.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate , Tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2, , 6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2 -Butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate Condensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2 4- Chloro-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-ylaminoundecane, 1,6,11-tris [2, 4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl And hindered amine compounds such as -4-piperidyl) amino) -s-triazin-6-ylaminoundecane.

  The amount of these antioxidants, other ultraviolet absorbers and hindered amine light stabilizers to be used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 100 parts by mass of the synthetic resin to be blended. -5 parts by mass.

  Although it does not specifically limit as said plasticizer, For example, a phosphate ester type plasticizer and a polyester type plasticizer are mentioned, These may be used individually by 1 type, or may mix and use 2 or more types. Good.

  Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.

  Examples of the polyester plasticizer include linear polyesters composed of aliphatic dibasic acids, aromatic dibasic acids and diol compounds, and linear polyesters of hydroxycarboxylic acids.

  Examples of the aliphatic dibasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3 -Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, 2,5-norbornene dicarboxylic acid, etc. Phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, anthracene dicarboxylic acid, terphenyl dicarboxylic acid and the like.

  Examples of the diol compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methylpropanediol, 1,3- Dimethylpropanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2 2,4-trimethyl-1,6-hexanediol, 2-ethyl-2-butylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, thiodiethylene glycol, 1 , 3-siku Hexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2, 4,8,10-tetraoxaspiro [5,5] undecane and the like.

  Examples of the hydroxycarboxylic acid include 4-hydroxymethylcyclohexanecarboxylic acid, hydroxytrimethylacetic acid, 6-hydroxycaproic acid, glycolic acid, and lactic acid.

  Other polyester plasticizers include trivalent or higher polyols and monocarboxylic acid polyesters. Examples of the trivalent or higher polyols include glycerin, trimethylolpropane, pentaerythritol, sorbitol, and their condensates such as dipentaerythritol and tripentaerythritol. Further, polyether polyols obtained by adding alkylene oxides such as ethylene oxide to these polyols may be used.

  Examples of the monocarboxylic acid include benzoic acid, p-methylbenzoic acid, m-methylbenzoic acid, dimethylbenzoic acid, p-tert-butylbenzoic acid, p-methoxybenzoic acid, p-chlorobenzoic acid, naphthylic acid, and biphenyl. Examples thereof include aromatic carboxylic acids such as carboxylic acids; alicyclic carboxylic acids such as cyclohexanecarboxylic acid; and aliphatic acids such as acetic acid, propionic acid, and 2-ethylhexanoic acid. Monocarboxylic acid may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate esters, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic type Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agents such as oxyethylene alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric activators. Such an antistatic agent may be used alone, or two or more kinds of antistatic agents may be used in combination.

  In addition, the triazine compound represented by the general formula (1) or (2) of the present invention can be blended with a fluorescent dye in a fluorescent pigment or in a fluorescent paint, or the base material of the fluorescent member is When it is a synthetic resin, it can also be blended in the synthetic resin by melt kneading. These are preferable because the light resistance tends to be further improved by the resin composition for coating a fluorescent member of the present invention.

  The fluorescent pigment of the present invention contains 0.001 to 20 parts by mass of the triazine compound represented by the general formula (1) and 0.01 to 100 parts by mass of the fluorescent dye with respect to 100 parts by mass of the synthetic resin. It is characterized by doing. Except for containing the triazine compound represented by the general formula (1), it is the same as the fluorescent pigment described above.

  The fluorescent paint of the present invention comprises 0.001 to 20 parts by mass of the triazine-based compound represented by the general formula (1), and a fluorescent pigment and / or fluorescent with respect to 100 parts by mass of a solvent-based or aqueous synthetic resin. It contains 0.01 to 100 parts by mass of a dye. Except for containing the triazine compound represented by the general formula (1), it is the same as the fluorescent paint described above.

  The use of the fluorescent member according to the present invention is not particularly limited, and can be used in products containing a fluorescent substance. For example, display materials such as stickers and labels, marking materials such as striped tape, commuter pass cards, etc. Markers, lighting signboards, light diffusing members such as light diffusing sheets of liquid crystal display devices, textiles for clothing, fireproof signs such as fire extinguishers and fire alarms, leisure equipment such as skis and surfboards, fluorescent pens, etc. It can be used for applications such as writing instruments and paints.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Examples 1 to 3 and Comparative Examples 1 to 9]
<Test piece preparation>
On the metal plate, the fluorescent paint described in the following Table 1 or 2 is applied so that the dry film thickness becomes 80 μm, and after drying and curing at room temperature overnight, an acrylic resin paint (Shinloihi Co., Ltd.) is further applied. (Product name, One Coat Leuhi Overlay Clear, solid content 35%) 100 parts by mass of a resin composition for coating a fluorescent member containing 2 parts by mass of the ultraviolet absorber shown in Table 1 or 2 below is used as a dry film thickness. Was applied to a thickness of 60 μm, dried and cured at room temperature overnight, and allowed to stand at room temperature for 1 week to obtain a test piece for light resistance evaluation.

<Light resistance test>
The test piece prepared above was tested with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd .; 83 ° C., no rain, light source carbon arc), and color difference was measured using a multi-light source spectrocolorimeter (manufactured by Suga Test Instruments Co., Ltd.). (ΔE ^* ab) was measured to evaluate light resistance. The results are also shown in Table 1 or 2.

＊１：シンロイヒ（株）製、製品名ワンコートロイヒ イエロー
＊２：シンロイヒ（株）製、製品名ワンコートロイヒ レモン
＊３：シンロイヒ（株）製、製品名ワンコートロイヒ オレンジ
＊４：化合物Ｎｏ．１

* 1: Sinloihi Co., Ltd., product name One Coat Leuhi Yellow * 2: Sinroihi Co., Ltd., product name One Coat Leuhi Lemon * 3: Sinroihi Co., Ltd., product name One Coat Leuhi Orange * 4: Compound No. . 1

* 1: Compound No. 5

* 2: Compound No. 6

* 3: Compound No. 7

* 4: Compound No. 8

* 5: Compound No. 9

  In Table 2 (Comparative Example), in all of the benzophenone (Comparative Example 1), benzoate (Comparative Example 4), and benzotriazole ultraviolet absorbers (Comparative Examples 5 and 7), the results showed that the light resistance was inferior. In addition, in Comparative Examples 2 and 8 which are monohydroxyphenyltriazine compounds having a structure similar to that of the present triazine compound, the effect of improving light resistance was insufficient. On the other hand, as is clear from the examples, the resin composition for coating a fluorescent member according to the present invention containing the specific triazine compound showed a good light resistance improvement effect.

  As described above, the specific triazine-based compound according to the present invention has a remarkable effect that cannot be obtained with other ultraviolet absorbers in improving light resistance, and can provide a fluorescent member excellent in light-coloring resistance. Is possible. In particular, it is very useful for improving the light-coloring resistance of fluorescent materials such as stickers and labels, such as display items and painted items, and clothing items, and can provide fluorescent members with excellent light resistance.

Claims (6)

A resin composition for coating a fluorescent member, characterized in that 0.001 to 20 parts by mass of a triazine compound represented by the following general formula (1) is blended with 100 parts by mass of a synthetic resin.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 6 to 18 carbon atoms. An aryl group, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, provided that these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups, or arylalkyls. The group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and is interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. and may be. Moreover, good .R ² be combined is substituted and interruption of the alkenyl alkyl group or C 2 -C 8 1 to 8 carbon atoms A representative.)   The resin composition for coating a fluorescent member according to claim 1, wherein the amount of the triazine compound represented by the general formula (1) is 0.05 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin. The resin composition for coating a fluorescent member according to claim 1 or 2, wherein the general formula (1) is a triazine-based compound represented by the following general formula (2).

(In the formula, R ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms. However, these alkyl groups may be substituted with a hydroxy group, a halogen atom or an alkoxy group, an oxygen atom, (It may be interrupted by a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group.)   The resin composition for coating a fluorescent member according to any one of claims 1 to 3 is applied to a material containing a fluorescent pigment and / or a fluorescent dye, or a material in which a fluorescent paint is applied on a substrate. The fluorescent member characterized by the above-mentioned. Fluorescence characterized by containing 0.001 to 20 parts by mass of a triazine compound represented by the following general formula (1) and 0.01 to 100 parts by mass of a fluorescent dye with respect to 100 parts by mass of a synthetic resin. Pigments.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 6 to 18 carbon atoms. An aryl group, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, provided that these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups, or arylalkyls. The group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and is interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. and may be. Moreover, good .R ² be combined is substituted and interruption of the alkenyl alkyl group or C 2 -C 8 1 to 8 carbon atoms A representative.) 0.001 to 20 parts by mass of a triazine compound represented by the following general formula (1) and 0.01 to 100 parts by mass of a fluorescent pigment and / or a fluorescent dye with respect to 100 parts by mass of a solvent-based or aqueous synthetic resin. A fluorescent paint characterized by containing a part.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 6 to 18 carbon atoms. An aryl group, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, provided that these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups, or arylalkyls. The group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, and is interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. and may be. Moreover, good .R ² be combined is substituted and interruption of the alkenyl alkyl group or C 2 -C 8 1 to 8 carbon atoms A representative.)