JPH06329880A - Epoxy resin fluorescent colorant - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of an epoxy resin containing a fluorescent dye, capable of remarkably improving the light resistance and withstanding the outdoor use for a long period and useful as a light scattering filler, etc., for lighting or agriculture. CONSTITUTION:The objective composition is composed of an epoxy resin containing a fluorescent dye. Furthermore, e.g. a cyanopyrazine-based or a benzopteridine-based dye is used as the dye.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent colorant used as a light scattering filler for lighting or agriculture, a filler used for decoration or various marking materials, and the like.

[0002]

Fluorescent dyes are generally highly reactive and inferior in fastness to light. As a countermeasure, there is a method in which a fluorescent dye is dissolved in a synthetic resin as a colorant powder for improving the robustness, and the colorant powder is kneaded into a molded body or formed into a paint and applied. Conventional carriers for fluorescent dyes include acrylic resins, styrene resins, vinyl chloride resins, aromatic sulfonamide resins,
Alkyd resin, urea resin, melamine resin, benzoguanamine resin, acrylic urethane resin and their copolymerization and cocondensation resins have been used. These colorants that do not use an epoxy resin have improved light resistance as compared with the case where a fluorescent dye is directly kneaded into a molded body, and have come to withstand outdoor use, but they are not yet satisfactory.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fluorescent colorant having a high light resistance and a molded product having the fluorescent colorant dispersed therein.

[0004]

The present invention is a molded product comprising (1) a fluorescent colorant comprising an epoxy resin containing a fluorescent dye, and (2) the fluorescent colorant according to item (1) above. . The molded body referred to here also includes a film.

The fluorescent dye is not particularly limited, and polyphenyl type, stilbene type, styrylbenzene type, oxazole type, oxadiazole type, coumarin type, naphthalic acid type,
Quinolone-based, xanthene-based, oxazine-based, thiazine-based, polymethine-based, perylene-based, anthraquinone-based, pyrazoline-based, thioindigo-based, naphtholine-based, formula [I] described in JP-A-5-32640 and Japanese Patent Application No. 4-354165.

[0006]

[Chemical 1]

[Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents hydrogen, a hydrocarbon group which may have a substituent, a trialkylsilyl group, COR ⁵ , COOR ⁶ , C
ONR ⁷ R ⁸ , COCONR ⁹ R ¹⁰ (R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represent hydrogen, a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent. ), R ¹ and R ² , or / and R ³ and R ⁴ may be taken together to form a ring, and further, R ¹ and R ² or / and R ³ and R ⁴ together, = C (R ¹¹ ) OR
¹² , = CHNR ¹³ R ¹⁴ , = SR ¹⁵ R ¹⁶ , = C (SR ¹⁷ )
₂ (R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different and each represents an alkyl group or an aryl group). ] A cyanopyrazine-based compound represented by the formula [II] described in JP-A-5-105683.

[0008]

[Chemical 2]

[Wherein R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ each represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, or an aryl group, and R ²² ,
R ²³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a mono- or dialkylamino group, or an alkylthio group, and R ²⁴ represents an optionally substituted alkyl group. ] The benzopteridine compounds and the like represented by the above formula] can be used alone or in combination.

The epoxy resin and the curing agent are not particularly limited, but the following are preferable examples.

As the epoxy resin, a bifunctional or higher polyfunctional epoxy resin is preferably used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin, polyglycol type epoxy resin, glycidyl amine type epoxy resin. Resin, isocyanuric acid type epoxy resin, halogenated bisphenol A type epoxy resin, halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin, epoxidized polybutadiene, polybutadiene modified epoxy resin (Japanese Patent Publication No. 62-
27093), an alicyclic epoxy resin represented by the following formula,

[0012]

[Chemical 3]

Examples thereof include urethane-modified epoxy resin and acryl-modified epoxy resin, which are modified products thereof. These may be used alone or in combination of two or more. Further, a known monofunctional epoxy compound such as butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether may be used in combination with the polyfunctional epoxy resin for the purpose of adjusting viscosity.

The epoxy curing agent is a generally used curing agent for epoxy resin, and includes, for example, trimethylamine, triethylamine, triethanolamine, N.
-Tertiary amines such as dimethylaniline and N-dimethylbenzylamine; 2-ethylimidazole, 2-heptadecylimidazole, imidazole 16, 4-methyl-
Imidazoles such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1- (2-hydroxy-3-phenoxypropyl) imidazole; DBU,
Salts thereof; quaternary ammonium salts such as choline chloride; aliphatic polyamines such as diethylenetriamine, triethylenediamine, triethylenetetramine; aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone; N-aminoethylpiperazine alicyclic polyamines such as menthane _{diamine; H 2 N-CH 2 CH} 2 NHCO-R-CONH
-NH ₂ polyamides; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Acid anhydrides such as hexachloroendomethylenetetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, dodecylsuccinic anhydride, benzophenonetetracarboxylic acid anhydride; dicyandiamide; phenol novolac resin Cresol novolac resin; aniline / formaldehyde resin; poly-p-vinylphenol and its bromide; polyamide resin; polysulfide resin; mercapto compounds; phosphines such as triphenylphosphine;
Urea derivatives; quaternary phosphonium salts such as phenylphosphonium tetraphenylborate, butyltriphenylphosphonium salt of 2,2 ', 6,6'-tetrabromobisphenol A; zinc naphthenate, lead stearate, Lead naphthenate, zinc octylate, tin oleate, tin octylate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, bis (acetylacetonato) dipyridine cobalt, acetylacetone iron, tetrakis (acetylacetonato) zirconium, acetylacetone Examples thereof include organic metal salts such as manganese and tetrabutyl titanate; and the like. These are used alone or in combination of two or more.

The fluorescent colorant comprising the epoxy resin of the present invention is an epoxy resin, a curing agent, a fluorescent dye, and a UV absorber, an antioxidant, a singlet oxygen quencher, and a hindered amine type which do not impair the purpose of the present invention. Light stabilizers, other stabilizers, and additives are mixed and cured by a known method, then crushed, or emulsified with an emulsifier or stabilizer in an aqueous or non-aqueous system and then cured to obtain spherical fine particles. It can be manufactured.

Further, particularly in the case of an alicyclic epoxy resin,
2,2-diethoxyacetophenone, 2-hydroxy-
2-methyl-1-phenyl-propan-1-one, 1-
(4'-Isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one, benzophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, benzyl dimethyl ketal, 1-
It is also possible to perform UV curing with a cationic photopolymerization initiator such as (4'-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one.

The concentration of the fluorescent dye dissolved in the cured epoxy resin is 0.01 to 2.0%, preferably 0.05 to 0.5.
%. When the concentration is lower than 0.01%, the fluorescence intensity is weak, and when the concentration is 2.0% or higher, the dye molecules interact with each other to weaken the fluorescence intensity, which is not preferable.

If desired, the fluorescent colorant may be rosin acid soap, stearic acid soap, oleic acid soap, Na-di-β-naphthylmethane disulfate, Na-lauryl sulfate, Na-lauryl phosphate, Na-diethylhexyl sulfate. With surfactants such as phosuccinate, Na-dioctylsulphosuccinate, 3-octadecylaminopropylamine, etc., it is compounded into paint to form a fluorescent coating film, or it is compounded with a thermoplastic resin for extrusion molding and inflation. A molded body is formed by molding, calendering, or the like.

Examples of paints include acrylic, polyurethane, acrylic urethane, polyvinyl formal, amino resin, alkyd, epoxy resin, phenol resin, polyester, polyester imide, polyamide imide, and polyimide. Solvent type or emulsion type such as silicone resin type, polyvinylidene chloride type and polyethylene vinyl alcohol type can be used.

Examples of the thermoplastic resin include polyethylene; polypropylene; (soft, semi-rigid, hard) PVC;
Polyvinyl acrylate; Polymethyl acrylate; Polyethyl acrylate; Polymethyl methacrylate; Polyvinyl alcohol; Polyacrylonitrile; Polybutadiene; Polystyrene; Ethylene-vinyl acetate copolymers; Vinyl chloride-vinyl acetate copolymers; Polyvinyl butyral; Polyvinyl formal; PET Polyester such as PBT; Polyarylate; Polycarbonate; Polyester carbonate; Phenoxy resin; Nylon 6, Nylon 6/6, Nylon 11, Nylon 12, MXD6
Polyamides such as nylon; polydimethylcycloxane; polytrimethylsilylpropyne; polyurethane; ionomers; cellophane; polyethylene cellophane;
Soft and hard resins such as cellulose acetate; cellulose propionate; ethyl cellulose; nitrocellulose; etc. can be used.

[0021]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, "part" represents part by weight. The fluorescence spectrum was measured using "Fluorescence Spectrophotometer Model 850" manufactured by Hitachi, Ltd.

Example 1 (Production of block resin) 1000 parts of bisphenol A type epoxy resin (YD-8125, Toto Kasei Co., Ltd.), alicyclic acid anhydride curing agent (H
N-5500, Hitachi Chemical Co., Ltd. 900 parts, benzylamine-based curing accelerator 10 parts, N, N, N ', N'-tetramethyl-3,6-diamino-2,5-pyrazinedicarbonitrile ( Hereinafter, abbreviated as AP-501) 4 parts, N-
Benzoyl-3,6-diamino-2,5-pyrazinedicarbonitrile (hereinafter abbreviated as AP-401) 4
Parts and 40 parts of UV absorber (Biosorb 910, Kyodo Yakuhin Co., Ltd.) were mixed and dissolved at 80 ° C. and gelled in a polypropylene cup at 100 ° C. × 5 hours, and the obtained gel was 150 ° C. × 3 Heat curing was performed for a period of time to obtain a cured epoxy resin (a).

Example 2 (Production of block resin) An alicyclic epoxy resin (ERL-42) was used as the epoxy resin.
21, Union Carbide Co., Ltd.), and heat-cured in the same manner as in Example 1 to obtain a cured epoxy resin (b).

Example 3 (Production of block resin) 1000 parts of bisphenol A type epoxy resin (YD-128, Tohto Kasei Co., Ltd.), triethylenetetramine 80
Part, AP-501 2 parts, and Biosorb 91020 parts were mixed at room temperature and kept at room temperature for 4 days to obtain a cured epoxy resin (c).

Example 4 (Production of Fluorescent Film) A part of the cured epoxy resins (a) and (b) was crushed in a magnetic mortar to obtain fine particles having a particle size of 50 to 100 μm. 10 parts of the obtained fine particles were used as an aqueous urethane emulsion (HW-3
33, Dainippon Ink & Co., Inc. 100 parts and coated on a soft vinyl chloride film to prepare fluorescent films (A) and (B).

Comparative Example 1 Vinyl chloride resin (GEON-103EP, Zeon Corporation) 100 parts Dioctyl phthalate 50 parts, epoxidized soybean oil 2 parts, barium stearate 0.5 part, zinc stearate 1.0 part, Biosorb 910 3 parts, A
P-501 0.3 parts, AP-401 0.3 parts 16
After kneading for 4 minutes on a hot roll at 5 ℃, 170 ℃ × 100
Hot pressing was performed at kg / cm ² to prepare a fluorescent film (D) having a thickness of about 100 μm.

Test Example 1 The fastness to sunlight of the fluorescent films (A), (B) and (D) was evaluated by the following two accelerated tests. The powder particles side of (A) and (B) was made into the irradiation surface. (1) Chemical lamp irradiation (FL20S-BL, 20
W, Toshiba Corp., main wavelength 305 nm, irradiation distance 5 cm (2) Reflective sunlight lamp (DR400, 400 W, Toshiba Corp.), irradiation distance 5 cm, 200,000 Lux, irradiation surface temperature 75 ° C. -1.

[0028]

[Table 1]

Note) Regarding the fluorescence intensity retention rate of AP-401, when two fluorescent dyes (α) and (β) are used together and the fluorescence wavelength of the dye (α) and the absorption wavelength of the dye (β) overlap,
Since a part of the fluorescence energy of the dye (α) is used as the excitation energy of the dye (β), the fluorescence intensity of the dye (α) itself is generally smaller than that of the dye (α) alone. The fluorescence intensity of AP-401 in the table increased more than twice
P-501 decreases, A used for excitation of AP-501
This is because the fluorescence energy of P-401 has decreased.

[0030]

【The invention's effect】

(1) The fluorescent colorant of the present invention can remarkably improve the light resistance. (2) The fluorescent color of the molded product formed by dispersing them can withstand long-term outdoor use, and is used as a light scattering filler for lighting and agriculture; decorative or various marking materials; markers for prepaid cards, commuter passes, securities, etc. can do.

Claims (2)

[Claims] 1. A fluorescent colorant comprising an epoxy resin containing a fluorescent dye. 2. A molded article obtained by dispersing the fluorescent colorant according to claim 1 in a resin.