JPH04338976A - Electrostatic photographic toner - Google Patents

Abstract

PURPOSE:To inexpensively provide the color toner having light resistance, non- migratability, bright color tone property, and transparency by incorporating the coloring agents obtd. by bringing a polymer having a carboxyl group, sulfonyl group, etc., in the side chain group and basic dyes into reaction into the toner. CONSTITUTION:The so-called high-polymer dyes obtd. by bringing the polymer having at least one kind of the carboxyl group, sulfonyl group or the salts thereof the in the side chain group and the acidic dyes into reaction are used as the coloring agents. Particularly this polymer is preferably the polymer contg. the styrene driv., acryl(methacryl) deriv. and ester acryl(methacryl) driv. expressed by formulas I to III as a unit. In the formulas I to III, (n) is 2, 3; (m) is 0 to 2; X is -COOM, -SO2M, -O-(C2H4O)lSO2M, -O-(C2H4O)lCOOM; M is H, Na, K, NH4; l is 1 to 8; R1 is H, CH3; R2 is CH3, C2H5.

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 provide clear color tones, lack transparency, and have problems such as poor OHP transparency and poor color reproducibility when overlapping colors. Although dyes have excellent color tone and transparency, they have problems such as poor light resistance, migration of dyes during storage, blurring of images, and staining of films when left in contact with them. Polymer dyes are a solution to these problems. Tokukai Showa 6
2-245268 is a polymer dye in which a bisphenol type dye is introduced into a polyester skeleton, which is disclosed in Japanese Patent Application Laid-Open No. 63-856.
44, polymer dyes obtained by polymerizing azo dyes having vinyl groups are disclosed in JP-A-1-147472, 147476, 16.
1362-161365, 164956-164959
, 173056-173060, 173064-173
There are polymer dyes in which rhodanine dyes are added to 068 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 provides a so-called polymer in which a polymer having at least one of a carboxyl group, a sulfonyl group, or a salt thereof in a side chain group is reacted with a basic dye. By using polymeric dyes as colorants, we aim to provide color electrophotographic toners at low cost that have both the light fastness and non-migration properties of pigments and the vivid color tone and transparency of dyes. purpose. In particular, the polymer has the following general formulas (I), (II) and (I).
It is more effective when it is a polymer containing units shown in II). Further, the polymer may be a copolymer containing units represented by (I), (II) and (III).

[0007]

[C4]

[0008]

[C5]

[0009]

embedded image However, in the above formulas (I), (II) and (III), n=2,3; m=0-2 )lCOOM M=H, Na, K, NH4 l=1~8 R1=H, CH3 R2=CH3, C2H5

Polymers having carboxyl groups and sulfonyl groups used in the present invention include vinylbenzenesulfonic acid, vinyltoluenesulfonic acid, sodium vinylbenzenesulfonate, vinyltoluerylic acid,
There are polymers or copolymers made of monomers having acidic groups such as -sulfoethyl acrylate, 2-sulfoethyl methacrylate, sodium salt of 2-sulfoethyl methacrylate, and 2-carboxyethyl methacrylate. 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,
As a copolymer with an alkyl ester monomer of acrylate or methacrylate such as n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, etc. Also good. If the amount of monomers having acidic groups is small, there are problems such as low coloring power, poor solubility in water, and difficulty in reaction with basic dyes.
The amount of the monomer having an acidic group is suitably 3 parts by weight or more, preferably 5 parts by weight or more, based on 100 parts by weight of the entire monomer. These polymers can be made by solution polymerization. Tables 1 to 3 show basic dyes that are specifically used. The basic dye and the resin are allowed to react at room temperature, optionally by heating or the like. reaction

0011
]

[Table 1]

0012

[Table 2]

[0013]

[Table 3] *U. K. Pat. App. 87-121571,
Cpd. 5, Formula 2

[0014]

Table 4 Time: 20 minutes to 2 hours at 40-60°C. Further, the solvent does not have to be water, but may be an organic solvent such as N-vinylpyrrolidone or 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 a dye or pigment, a charge control agent, 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. As a polarity control agent,
For example, 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, nitro groups, and halogen-introduced styrene. Examples include oligomers, chlorinated paraffins, and melamine resins. Also, if necessary, colloidal silica,
A fluidizing agent such as a metal oxide fine powder such as titanium oxide or aluminum oxide, an abrasive such as silicon carbide, a lubricant such as a fatty acid metal salt, etc. may be included. 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, the particle diameter is 20-2
00 μm iron powder, nickel powder, ferrite powder, magnetite powder, glass beads, or these as the core material,
A material whose surface is coated with a resin such as a fluororesin, a silicone resin, a styrene resin, or an acrylic resin can be used.

[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. Styrene 100g, n-butyl methacrylate 2
0 g of dimethylaminoethyl acrylate, and 1.5 g of benzoyl peroxide were added dropwise over 1 hour using a dropping funnel. 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 acid rhodamine B were dissolved in 500 g of water, 5 g of 50% acetic acid aqueous solution was added, and the mixture was stirred at 60° C. for 1 hour. This was reprecipitated with ether, purified, and dried to obtain a polymer dye.

[Production Example 2] 500 g of toluene was placed in a polymerization flask purged with nitrogen, and heated to 80° C. on an oil bath. 80 g of styrene, 20 g of n-ethylhexyl methacrylate, 20 g of vinylbenzenesulfonic acid, 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 18 g of Cachilon Yellow GLH were dissolved in 500 g of water, and 50% of the 5 g
Aqueous acetic acid solution was added and stirred at 60°C for 1 hour. The precipitate was purified and dried to obtain a polymer dye.

[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. The mixture was further mixed with a silicone resin coated carrier to prepare a two-component developer, and a copied image was obtained using a PPC copying machine 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
24 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.

[0017]

[Effect of the invention] By using the toner of the present invention,
Cheap color electrophotographic toner with excellent light resistance, colorant does not migrate during layering, clear color tone, good transparency, color reproducibility on OHP, and color reproducibility when layering colors. can be provided to

Claims (4)

[Claims] 1. An electrostatic photographic toner containing a colorant obtained by reacting a polymer having at least one of a carboxyl group, a sulfonyl group, or a salt thereof in a side chain group with a basic dye. . 2. The electrostatic photographic toner according to claim 1, wherein the polymer is a polymer containing a unit represented by the following general formula (I). 3. The electrostatic photographic toner according to claim 1, wherein the polymer is a polymer containing a unit represented by the following general formula (II). 4. The polymer has the following general formula (III):
The electrostatic photographic toner according to claim 1, which is a polymer containing a unit represented by: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] However, in the above formulas (I), (II) and (III), n=2,3; m=0-2 X= -COOM, -SO2M -O-(C2H4O)1SO2M -O-(C2H4O)lCOOM M=H, Na, K, NH4 l=1~8 R1=H, CH3 R2=CH3, C2H5