JPH04330462A - Toner for color electrostatic photography - Google Patents

Abstract

PURPOSE:To make compatible light resistance, non-transforming property, transparency by containing a coloring agent obtained by making a polymer having amino group or hydroxyl group on a side chain group to react with a reactive dyestuff. CONSTITUTION:The so called polymer dyestuff obtained by making the polymer having amino group or hydroxyl group on the side chain group of the polymer main chain to react with the reactive dyestuff is used. And the polymer has an unit of styrene derivative or acryl(methacryl)derivative expressed by the formula I or II. In the formula I, II, (n) is 2-3, (m) is 0-2, X is -NH2, -OH and Y is C2nH4nOH, R1 is H, CH3 and R2 is CH3, C2H5. Thus the toner for color electrostatic photography having both light resistance, non-transforming property of pigment and clear color, transparency of dyestuff is obtained low in cost.

Description

[Detailed description of the invention]

0003

[Industrial Application Field]] Regarding toner for color electrostatic photography.

0004

BACKGROUND OF THE INVENTION Various pigments and dyes have been used as toners for color electrostatic photography. However, although pigments have good light resistance, they do not produce clear color tones.
Due to lack of transparency, there are problems such as poor transparency of OHP and poor color reproducibility when superimposing colors.On the other hand, dyes have excellent color tone and transparency, but have poor light fastness, and dyes may bleed during storage. This causes problems such as the image smearing and the film becoming smudged if left in contact with the film. Polymer dyes are a solution to these problems. Japanese Patent Application Laid-Open No. 62-245268 discloses a polymer dye in which a bisphenol type dye is introduced into a polyester skeleton.
644, polymer dyes obtained by polymerizing azo dyes having vinyl groups are disclosed in JP-A-1-147472, 147476, and 1-1.
61362-161365, 164956-16495
9, 173056-173060, 173064-17
There are polymer dyes in which rhodanine dyes are added to 3068 and 2-2576, but both have problems in that the dyes are special and the resulting polymer dyes are also expensive.

[0005]

[Problems to be Solved by the Invention] The present invention provides a color electrophotographic toner at a low cost that has both the light fastness and non-migration properties of pigments and the vivid color tone and transparency of dyes. It's about doing.

[0006]

[Means for Solving the Problems] The present invention is directed to coloring a so-called polymer dye obtained by reacting a polymer having an amino group or a hydroxyl group in the side chain group with a reactive dye. The purpose of the present invention is to provide, at a low cost, a toner for color electrophotography that has both the light fastness and non-migration properties of pigments and the clear color tone and transparency of dyes, by using the toner as an agent. In particular, if the polymer has the following general formula (
It is even more effective when the polymer contains units represented by I) and (II).

[0007]

[C3]

[0008]

[C4] However, in the above formulas (I) and (II)

0009
] The polymer having an amino group used in the present invention includes a polymer or copolymer consisting of a monomer having an amino group such as aminostyrene, t-butylaminoethyl acrylate, and t-butylaminoethyl methacrylate. Alternatively, a styrene polymer or styrene copolymer may be chloromethylated and further reacted with an amine to form a vinylbenzylalkylammonium copolymer, or a polymer such as polyethyleneimine or polyvinylamine may be used. Also good. Examples of the polymer having a hydroxyl group used in the present invention include a polymer or copolymer consisting of hydroxystyrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. be. In addition, in order to increase compatibility with the binder resin, styrene monomers such as styrene, α-methylstyrene, and divinylbenzene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl methacrylate, i- Butyl methacrylate, t-butyl methacrylate,
hexyl acrylate, cyclohexyl acrylate,
It may also be a copolymer with an alkyl ester monomer of acrylate such as octyl acrylate or 2-ethylhexyl acrylate, or methacrylate. If the amount of monomers with basic groups is small, there are problems such as low coloring power, poor solubility in water, and difficulty in reaction with acidic dyes. The amount of
When the total amount of monomers is 100 parts by weight, the amount is suitably 3 parts by weight or more, preferably 5 parts by weight or more. These polymers can be made by solution polymerization.

The reactive dyes of the present invention are suitably water-soluble and react rapidly and in high yields with hydroxyl groups or amino groups, and are of the type commonly used extensively in the textile industry. be. These dyes include anthraquinone, monoazo dye, diazo dye, phthalocyanine,
Contains water-soluble chromophores such as azo(18)annulene, formazan copper complex, triphenodioxazine, etc., and these chromophores include dichlorotriazine, monochlorotriazine, dichloroquinoxaline, aminoepoxide, mono(m'-carboxypyridinium )-triazine, 2,4,5-trihalogenopyrimidine, 2,4
-dichloropyrimidine, 2,3-dichloroquinoxaline, monofluorotriazine, 4,5-dichloro-6-methyl-2-methylsulfonylpyrimidine, 1,4-dichlorophthalazine, chlorobenzothiazole, sulfatoethylsulfone, β- Chloroethyl sulfone, 4,5-
Reactive groups such as dichloro-6-pyridazone, α-promoacryloylamide, α,β-dibromoprobylamide, etc. are covalently attached. Examples of suitable dyes include Repafix Brilliant Yellow E-GA, Repafix Yellow E2RA, Repafix Brilliant Red E6B.
A, and Repafix Brilliant Blue EFFA (B
ayer); Procion Turcuoise PA, Procion Turcuoise HA, Procion Turcuoise H-5G, Procion Turcuoise H-7G, Procion Red MX-5B, Procion Red MX8BGN
S, Procion Red G, Procion Yellow MX-8
G, Procion Black H-EXL, Procion Black PN, Procion Blue MX-R, Procion Blue MX-4GD, Procion Blue MX-G and Procion Blue MX-2GN (manufactured by ICI); Cibacron Red F-B, Cibacron Black BG, Lanazol Black B, Lanazol Red 5B, Lanazol Red B,
and Lanazol Yellow 4G (manufactured by Ciba-Geigy); Basilen Black P-BR, Basilen Yellow E
G, Basilene Brilliant Yellow P-3GN, Basilene Yellow M-6GD, Basilene Brilliant Red P
-3B, Basilens Scar Red E-2G, Basilens Red E-B, Basilens Red E-7B, Basilens Red M
-5B, Basilene Blue E-R, Basilene Brilliant Blue P-3R, Basilene Black P-BR, Basilene Turquoise Blue P-GR, Basilene Turquoise M-2G, Basilene Turquoise E-G and Basilene Green E-6B (manufactured by BASF); Sumifix Starcue Ise Blue G, Sumifix Starcquoise Blue H-GF, Sumifix Black B, Sumifix Black H-BG, Sumifix Yellow 2
Examples include GC, Sumifix Splash Scarlet 2GF, and Sumifix Red 5F (manufactured by Sumitomo Chemical Co., Ltd.). The reaction between the reactive dye and the resin is carried out in water for 4 to 24 hours, and heating may be carried out as needed. N-vinylpyrrolidone,
The reaction may be carried out in an organic solvent such as acrylonitrile.

As the binder resin used in the present invention, known resins for toners can be used. For example, monopolymers of styrene and its substituted products such as polystyrene, polyp-chlorostyrene, and polyvinyltoluene,
Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer Coalescence, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Styrenic compounds such as vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Copolymer, polyethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene,
Polyurethane, polyamide, polyester resin, epoxy resin, polyvinyl petitral, polyacrylic acid resin,
Rosin, modified rosin, derpene resin, phenolic resin,
Aliphatic or aliphatic hydrocarbon resins, aromatic petroleum resins,
Chlorinated paraffin, paraffin wax, etc. can be used alone or in combination.

Furthermore, the toner of the present invention may contain a small amount of a polarity control agent, such as dyes and pigments, charge control agents, etc., in order to provide more efficient charging, but this may inhibit the effects of the present invention. It is preferable to use a colorless or light-colored polarity control agent to prevent this from occurring. Examples of polarity control agents include metal complexes of monoazo dyes, nitrohumic acid and its salts, metal complexes of salicylic acid, naphthoic acid, dicarboxylic acids, and their derivatives such as Co, Cr, and Fe, sulfonated copper phthalocyanine pigments, and nitro groups. , halogen-introduced styrene oligomers, chlorinated paraffins, melamine resins, etc. Further, if necessary, a fluidizing agent such as a metal oxide fine powder such as colloidal silica, titanium oxide, or aluminum oxide, an abrasive such as silicon carbide, a lubricant such as a fatty acid metal salt, etc. may be contained.

The toner of the present invention can be used either as a one-component developer or as a two-component developer by mixing it with a carrier. When used as a two-component developer, conventionally known carriers can be used. For example, iron powder, nickel powder, ferrite powder, magnetite powder, glass beads with a particle diameter of about 20 to 200 μm, or these are used as a core material, and the surface is coated with fluorine resin, silicone resin, styrene resin, acrylic resin, etc. A material coated with resin such as resin can be used.

[0014]

【Example】

[Production Example 1] 500 g of toluene was placed in a polymerization flask purged with nitrogen, and heated to 80° C. on an oil bath. 100g styrene, 20g n-butyl methacrylate
, 20 g of aminostyrene, and 1.5 g of benzoyl peroxide were added dropwise using a dropping funnel over 1 hour. After dropping, polymerization was carried out for 6 hours, and the polymer was precipitated and purified in methanol. 50 g of the obtained resin and 15 g of Revafix Brilliant Red E6BA were dissolved in 500 g of water and stirred at room temperature for 18 hours. This was reprecipitated with ether, purified, and dried to obtain a polymer dye.

[Production Example 2] Polyamine resin 50g and 20g
g of Sumifix Yellow 2GC was dissolved in 500 g of water and stirred at room temperature for 18 hours. This is reprecipitated into ether,
After purification and drying, a polymer dye was obtained.

[Example 1] Polyester resin
100 parts by weight (softening point 90°C) Polymer dye of Production Example 1
30 parts by weight
Bontron E-84 (charge control agent; Orient Chemical Co., Ltd.) 3 parts by weight The above raw materials were mixed in a Henschel mixer, kneaded in a three-roll mill, and cooled. The kneaded material was coarsely pulverized, further pulverized using a jet pulverizer, and then pulverized using an air classifier to obtain a toner having an average particle size of 10.8 μm. 1 part by weight of hydrophobic silica fine powder (R972; Nippon Aerosil) was added to 100 parts by weight of the above toner and mixed with a Henschel mixer. Furthermore, it was mixed with a silicone resin coated carrier to prepare a two-component developer, and a copied image was obtained using FT6550 (manufactured by Ricoh). It exhibited a bright red color, and no fading or discoloration was observed when the image was exposed to direct sunlight for two weeks. When an image was formed on an OHP film and projected, it showed a bright red color.

[Example 2] Styrene/n-butyl methacrylate copolymer 100 parts by weight (softening point 9
5℃) Polymer dye of Production Example 2
12 parts by weight
Bontron E-84 (charge control agent; Orient Chemical Co., Ltd.) 4 parts by weight The above raw materials were kneaded to prepare a toner in the same manner as in the examples, and image evaluation was performed. It exhibited a bright yellow color, and no fading or discoloration was observed when the image was exposed to direct sunlight for two weeks. When an image was formed on an OHP film and projected, it showed a bright yellow color.

[Comparative Example 1] Polyester resin
100 parts by weight (softening point 90°C) Rhodamine 6G
3
Parts by weight Bontron E-84 (charge control agent; Orient Chemical Co., Ltd.) 2 parts by weight The above raw materials were kneaded to prepare a toner in the same manner as in the example, and a bright red image was obtained.
When an image was formed on an OHP film and projected, it showed a bright red color. However, when the image was exposed to direct sunlight for two weeks, the color fading and discoloration was significant.

[Comparative Example 2] Polyester resin
100 parts by weight (softening point 90°C) Rhodamine 6G lake
3 parts by weight Bontron E-84 (charge control agent; Orient Chemical Co., Ltd.) 2 parts by weight The above raw materials were kneaded to prepare a toner in the same manner as in the examples, and image evaluation was performed. It showed a bright red color, and after exposing the image to direct sunlight for two weeks, it did not fade or fade.
No discoloration was observed. However, when an image was formed on an OHP film and projected, only a dark red color was obtained.

[0021]

[Effect of the invention] By using the toner of the present invention,
A toner for color electrostatic photography that has excellent light resistance, colorant does not migrate during overlaying, clear color tones, good transparency, and good color reproducibility on OHP and when overlapping colors. Can be provided at low cost.

Claims (3)

[Claims] 1. An electrophotographic toner comprising a colorant obtained by reacting a polymer having an amino group or a hydroxyl group in a side chain group with a reactive dye. 2. Claim 1, wherein the polymer is a polymer containing a unit represented by the following general formula (I).
The electrophotographic toner described. 3. The electrophotographic toner according to claim 1, wherein the polymer is a polymer containing a unit represented by the following general formula (II). [Chemical Formula 1] [Chemical Formula 2] However, in the above formulas (I) and (II),