JP3043818B2 - Electrostatic toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a toner for color electrostatography.

[0002]

2. Description of the Related Art Conventionally, various pigments and dyes have been used as color electrostatographic toners. However, although pigments have good light fastness, etc., they do not have a clear color tone and lack transparency, and have problems such as OHP transparency and color reproducibility when colors are superimposed. -It has problems such as excellent transparency but poor light fastness, dye migration during storage, image bleeding, and soiling of the film if kept in contact with a film or the like.

[0003] As a solution to these problems, there is a polymer dye. Polymeric dye introduced bisphenol type dye polyester skeleton in JP 62-245268 Patent Publication, Japanese Patent Publication No. Sho 63-85644 is polymeric dye obtained by polymerizing an azo dye having a vinyl group, Special Kaihei 1-14
7472, JP-A No. 1 147 476, JP
Flat 1-one hundred sixty-one thousand three hundred and sixty-two, JP-A No. 1-161363
Gazette, JP-A-1-161364, JP-A-1-16
1365, JP-A No. 1 164 956, JP
JP-A-1-164957, JP-A-1-164958
Publication Hei 1 one hundred and sixty-four thousand nine hundred fifty-nine JP, Hei 1- 17
No. 3056 , Japanese Patent Application Laid-Open No. 1-173057,
Japanese Unexamined Patent Publication No. Hei 1-173058, Japanese Patent Laid-Open No. Hei 1-173059
Publication Hei 1 one hundred and seventy-three thousand and sixty JP, Hei 1- 17
No. 3064 , Japanese Patent Application Laid-Open No. 1-173065,
JP-A-1-173066, JP-A-1-173667
Publication Hei 1-one hundred seventy-three thousand and sixty-eight JP, Hei 2-25
Polymeric dye such as rhodanine dye was added to 76 Patent Publication No.
Have been described, both dyes special, resulting polymeric dye was also a problem that a fairly expensive.

[0004]

SUMMARY OF THE INVENTION The present invention provides an inexpensive color electrostatographic toner having both the light fastness and non-migration property of a pigment and the vivid color tone and transparency of a dye. It is in.

[0005]

SUMMARY OF THE INVENTION The present invention is an amino group or the alkyl substituents, or at least one of their salts possess a side group, and 100 parts by weight of the total polymer units
At least represented by the following general formula (I) or (II)
Toner containing a colorant obtained by reacting a polymer containing at least 3 parts by weight of polymerized units with an acid dye.
-

[0006]

Embedded image

[0007]

Embedded image [However, A is _{-NR 3 R 4, -NR 3 R} 4 R 5 X, -CH 2 N
R ₃ R ₄ , —CH ₂ NR ₃ R ₄ R ₅ X, where X = C
l, Br, I, R ₁ = H, CH ₃ , R ₂ = C
H ₃ , C ₂ H ₅ , R ₃ , R ₄ , R ₅ = H, CmH ₂ m +
1, n = 0 to 2, and m = 1 to 18]

[0008] As the polymer having an amino group or a salt thereof used in the present invention, aminostyrene, dimethylamino styrene, dimethylamino ethyl Le acrylate,
There is a polymer or copolymer composed of a basic monomer such as dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl methyl methacrylate. Further, a styrene polymer or a styrene copolymer may be chloromethylated and further reacted with a tertiary amine to obtain a vinylbenzyltrialkylammonium copolymer. In order to increase the compatibility with the binder resin, styrene-based monomers such as styrene, α-methylstyrene, divinylbenzene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate It may be a copolymer with an acrylate such as acrylate, t-butyl methacrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, or 2-ethylhexyl acrylate, or an alkyl ester monomer of methacrylate. When the amount of the monomer having a basic group is small, there is a problem that the coloring power is low, the water is hardly soluble and the reaction with the acid dye does not easily proceed, and therefore, the monomer having a basic group The amount of is suitably at least 3 parts by weight, preferably at least 5 parts by weight, based on 100 parts by weight of the whole monomer. These polymers Ru can be made by solution polymerization.

[0009] In those specifically used as acid dyes, acid yellow, acid yellow 2S, Acid Orange II, Acid Orange R, acid green, acid green GG, acid chromium Red B,
Acid cyanine GR, acid cyanine 5R, patent blue AE, naphthalene scarlet 2R, acid violet 5B, chiton blue A, benzyl blue F
R, brilliant milling blue B, benzyl fast yellow RS, benzyl fast red 2G, acid fast red 3G, acid brilliant scarlet 3R, acid fuchsin O, acid red PG, acid rhodamine B, brilliant acid cyanine 6
B, brilliant scarlet 3R, brilliant milling blue B, brilliant milling green B, and the like. Reaction with an acid dye and a resin at ordinary temperature in water, optionally performing as appropriate heating. N- vinylpyrrolidone, and the reaction in an organic solvent may be it line Do of acrylonitrile.

As the binder resin used in the present invention, known resins for toner can be used. For example, polystyrene, poly p-chlorostyrene, a homopolymer of styrene such as polyvinyltoluene and a substituted product thereof,
Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-
Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-methyl methacrylate copolymer,
Styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer,
Styrene - vinyl methyl ketone copolymer, styrene - butadiene copolymer, styrene - iso pin Ren copolymer, styrene - maleic acid copolymer, styrene - styrene copolymer and maleic acid ester copolymers, poly ethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyurethane, polyamide, polyester resins, epoxy resins, polyvinyl Bed butyral, polyacrylic acid resin, rosin, modified rosin, Derupen resins, phenol resins, fats Aromatic or aliphatic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used alone or in combination.

Further, the toner of the present invention may contain a small amount of a polarity controlling agent, for example, a dye or pigment, or a charge controlling agent, in order to give more efficient charging. To avoid this, it is preferable to use a colorless or light-colored polarity control agent. Examples of the polarity controlling agent include metal complex salts of monoazo dyes, nitrohumic acid, and the like.
And their salts, salicylic acid, naphthoic acid, dicarboxylic acids and their derivatives, metal complexes such as Co, Cr and Fe, sulfonated copper phthalocyanine pigments, nitro groups, halogen-introduced styrene oligomers, chlorinated paraffins, melamine resins, etc. There is. If necessary, a fluidizing agent for fine powder of metal oxide such as colloidal silica, titanium oxide, and aluminum oxide, an abrasive such as silicon carbide, and a lubricant such as a fatty acid metal salt may be contained.

[0012] The toner of the present invention, a one-component developer, also as a two-component developer mixed with a carrier, it is possible to use either. 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 having a particle diameter of about 20 to 200 μm , or a core material made of these, and a fluororesin, silicone resin, styrene resin, acrylic Those coated with a resin such as a resin can be used.

[0013]

Take Toluene 500g EXAMPLES] Preparation Example 1] a nitrogen-substituted polymerization flask,
Heated to 80 ° C. on an oil bath. 100 g of styrene,
20 g of n-butyl methacrylate, 20 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 to precipitate and purify a polymer in methanol. 50 g of the obtained resin and 15 g of acid rhodamine B were dissolved in 500 g of water, and 5 g of a 50% aqueous acetic acid solution was added.
For 1 hour. This was reprecipitated with ether, purified and dried to obtain a polymer dye.

[0014] Production Example 2 nitrogen-substituted chloromethyl ether which had been purified in a polymerization flask 800g up, polystyrene 12g, put zinc chloride 2.4 g, was heated at 50 ° C. in a water.
Thereafter, the polymer was precipitated and purified, dissolved in 1500 g of dimethylformamide, and trimethylamine was blown therein, and the mixture was allowed to stand at room temperature for 1 day. This was purified with ether. 10 g of the obtained resin and 2 g of Acid Yellow 2S were dissolved in 500 g of water and stirred at 60 ° C. for 1 hour. This was reprecipitated with ether, purified and dried to obtain a polymer dye.

[0015] In Example 1 100 parts by weight of the polyester resin (softening point 90 ° C.) of polymeric dye 30 parts by weight Bontron E-84 (charge controlling agent = Orient Chemical) Preparation Example 1 3 parts by Henschel mixer the raw materials After mixing, the mixture was kneaded with a three-roll mill and then cooled. The kneaded material is roughly crushed, further crushed by a jet crusher, and crushed by an air classifier to an average particle size of 1
0.8 μ toner was obtained. 1 part by weight of hydrophobic silica fine powder (R972 = Nippon Aerosil) was added to 100 parts by weight of the 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 with a PPC copying machine FT6550 (manufactured by Ricoh Company). The image was bright red, and the image was exposed to direct sunlight for 2 weeks, but no fading or discoloration was observed. Also OH
When an image was formed on the P film and projected, it showed a bright red color.

[0016] Example 2 Styrene / n-butyl methacrylate copolymer 100 parts (softening point 95 ° C.) of polymeric dye 24 parts by weight Bontron E-84 Preparation Example 2 (charge control agent = Orient Chemical) 4 Weight A kneaded toner was prepared from the above raw materials in the same manner as in the example, and the image was evaluated. The image was bright yellow and the image was exposed to direct sunlight for 2 weeks, but no fading or discoloration was observed.
When an image was formed on an OHP film and projected, a bright yellow color was shown.

[0017] The Comparative Example 1 100 parts by weight of the polyester resin (softening point 90 ° C.) Likewise kneading toner and Rhodamine 6G 3 parts by weight Bontron E-84 (the charge controlling agent = Orient Chemical) 2 parts by weight The above raw materials Example A bright red image was obtained, and a bright red image was obtained when an image was formed and projected on an OHP film. However, when the images were exposed to direct sunlight for two weeks, discoloration and discoloration were significant.

[0018] Comparative Example 2 Polyester resin 100 parts by weight (softening point 90 ° C.) Rhodamine 6G Lake 3 parts by weight Bontron E-84 (charge controlling agent = Orient Chemical) Similarly kneading toner and the 2 parts by weight of the raw materials Example Was prepared, and the image was evaluated. The image was bright red, and the image was exposed to direct sunlight for 2 weeks, but no fading or discoloration was observed.
However, when an image was formed on the OHP film and projected, only a dark red color was obtained.

[0019]

By using the toner of the present invention, the light resistance is good, the colorant does not migrate during superposition, the color tone is clear, the transparency is good, the color reproducibility with OHP and the color are superimposed. A toner for color electrostatic photography having excellent color reproducibility can be provided at low cost.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-164956 (JP, A) JP-A-1-164958 (JP, A) JP-A-50-137544 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03G 9/09

Claims (1)

(57) [Claims] 1. A amino group or the alkyl substituents in the side groups, or have at least one of their salts, or
At least the following general formula per 100 parts by weight of
Formula (I) or (II) Embedded image [However, A is _{-NR 3 R 4, -NR 3 R} 4 R 5 X, -CH 2 N
R ₃ R ₄ , —CH ₂ NR ₃ R ₄ R ₅ X, where X = C
l, Br, I, R ₁ = H, CH ₃ , R ₂ = C
H ₃ , C ₂ H ₅ , R ₃ , R ₄ , R ₅ = H, CmH ₂ m +
1, n = 0 to 2, and m = 1 to 18].
An electrophotographic toner containing a colorant obtained by reacting a polymer containing at least 3 parts by weight of a polymerized unit with an acid dye.