JPH01164957A - Light transmission type blue toner - Google Patents

Abstract

PURPOSE:To obtain a blue toner which has sufficient light transparency and distinct colors even when transferred to a light transparent sheet by incorporating a polymer produced by bringing the chain micromolecule having a reactive substituent in the side chain and a specific rhodanine deriv. into reaction as a coloring component into the toner. CONSTITUTION:The polymer produced by bringing the macromolecule having the reactive substituent in the side chain and the rhodanine deriv. expressed by formula I into reaction is incorporated as the coloring component into the light transmission type blue toner. In formula I, B denotes the substituent having reactivity; C denotes a divalent org. group; R1 denotes hydrogen, lower alkyl group, substd. or unsubstd. aryl group, hydroxyl group; P denotes 0 or 1. If the polymer having such rhodanine deriv. in the side chain is used, the polymer itself is the blue polymer having excellent light transparency and, therefore, the toner of the light transmission type is obtained by merely granulating the polymer. The blue toner of the distinct color having the excellent light transparency is thereby obtd. by transferring the developed image onto the light transparent sheet.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a color toner used for developing color electrophotography, and particularly to a light-transmitting color toner that constitutes a developed image transferred to a light-transmitting sheet. Regarding.

[Prior art]

At conferences and research presentations, an overhead projector (Of-I
P) is frequently used. In this OHP, an original image is formed on a transparent sheet, and the original image is projected onto the screen by applying light that has passed through the transparent sheet to a screen.

When using such an OHP, attempts have been made to emphasize and identify specific characters, etc. in an image using a color other than black. For this purpose, it is necessary to form a developed image using a color toner other than black on the transparent sheet.

[Problem that the invention seeks to solve]

However, the light-transmitting color toner used in -g is obtained by dispersing colored pigments in resin, so the light that enters the toner is scattered by the pigments, resulting in a loss of translucency. . Therefore, a coloring agent with excellent translucency is required.

The present invention is intended to solve the above problems,
The purpose of this is to have sufficient translucency even when transferred to a translucent sheet, so that the developed image can be transferred to a translucent sheet using a normal method and then projected onto a screen using an OHP. The purpose of the present invention is to provide a color toner that can provide vivid colors.

[Means for solving problems]

In order to solve the above problems, the toner of the present invention comprises a chain polymer having a reactive substituent in its side chain and a rhodanine derivative having the following structural formula (where B is a reactive substituent and C is 2 valent organic group,
R represents hydrogen, a lower alkyl group, a substituted or unsubstituted aryl group, a hydroxyl group, and P represents 0 or 1. It accomplishes its purpose.

[Effect]

The polymer used in the light-transmissive blue toner of the present invention is distinctive in that a rhodanine derivative is introduced into the side chain of the chain polymer. The rhodanine derivative located in this side chain has a rhodanine ring and a quinoline group introduced into the 5-position of the rhodanine ring via an ethanediilidene group. The absorption of visible light is due to the formation of an intramolecular charge transfer complex in which the rhodanine ring serves as an electron acceptor and the quinoline group serves as an electron donor. In other words, the π electrons delocalized in the electron donor in the ground state become the group r=C=CH-CH=
When it transfers to the empty orbit of an electron acceptor through J, it absorbs light energy and produces color.

When a polymer having this rhodanine derivative in its side chain is used as a toner coloring agent, it is itself a blue polymer with excellent translucency, so simply granulating it can produce a light-transmitting toner. is obtained.

Furthermore, unlike conventional dyes, it has excellent moisture resistance, making it possible to obtain a toner that is not dependent on humidity.

The present invention will be explained in detail below.

The polymer used in the light-transmissive blue toner of the present invention can be obtained by reacting and bonding a rhodanine derivative having a reactive substituent with a polymer compound having a reactive substituent.

The rhodanine derivative, which is a component of such a polymer, has the following structure:
R-hydrogen, lower alkyl group, monosubstituted or unsubstituted aryl group, hydroxyl group, P represents 0 or 1).

Examples of the alkyl group for R1 include lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butylisobutyl, tart-butyl, pentyl, and hexyl groups.

Further, examples of the aryl group which may have a substituent include phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, etc., and examples of the substituent include lower alkyl groups having 1 to 4 carbon atoms, methoxy, ethoxy, propoxy, etc. Examples include an alkoxy group, an amino group, an alkylamino group such as a dimethylamino, diethylamino, and dipropylamino group, and a halogen atom.

in particular, can be mentioned.

As shown in the above specific example, the reactive substituent B is -C
OOII, -CHgC1, -0il, -COCI, -N
An example is tl□.

These rhodanine derivatives can be synthesized by various methods, such as the following reaction formula.

(In the formula, B and R are the same as above.) That is, the rhodanine derivatives are 3-1 rhodanine and 4-β
-Acetanilidevinylquinolinealkyl iodide can be obtained by reacting in alcohol.

Examples of the polymer having a reactive substituent to which the rhodanine derivative described above is bound include the following repeating unit 1+CHz-CH)-(CHz)-NH.

(In the formula, m represents an integer of θ to 3), the following repeating unit 1←CH! -CH)- (wherein R2 is -ClbC1, -NHt, -5OzC1,
-COOII), the following repeating unit C0OHC6O Ht R3Rz C=OCOC1 (CHz)-NH1 (in the formula, R5 is hydrogen or a methyl group, m is an integer from θ to 3) Examples include acrylic or methacrylic polymers and copolymers thereof, and polycarbonate resins represented by the following repeating units.

Furthermore, a polymer having a phenyl ring in the main chain or side chain, such as the styrene polymer or polycarbonate resin, is reacted with CHz COCHz CI, and a polymer having -CI2CI as a reactive substituent is exemplified. be done.

The reaction between these polymers and rhodanine derivatives is achieved, for example, by the following reaction.

c In the above specific examples, n represents an integer of 20,000 to 200,000.

In the light-transmissive blue toner of the present invention, the above polymer alone can be granulated to form toner powder, but various binder resins can be used in combination for the purpose of improving the properties of the toner. .

The binder resin is preferably a translucent styrene polymer, acrylic polymer, methacrylic polymer, or styrene-acrylic copolymer.

Examples of unsaturated monomers used in the above-mentioned polymers include styrene, α-methylstyrene, 0-methylstyrene, p-
Styrenic monomers such as methylstyrene, p-methylstyrene, p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, acrylic 2-ethylhexyl acrylate, dodecyl acrylate, stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate,
Acrylic-2-hydroxypropyl, glycidyl acrylate, diethylaminoethyl acrylate, acrylamide, acrylonitrile, methacrylic acid, methyl methacrylate, ethyl methacrylate, -butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylate Acrylics such as 2-ethylhexyl acid, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, diethylaminoethyl methacrylate, etc. Alternatively, methacrylic monomers and the like can be exemplified. The above monomers may be used singly or in a mixture of two or more.

These polymers have a weight average molecular weight of 130.000 to 20
0,000, particularly preferably 50,000 to 15o, oooO, and one type or a mixture of two or more types may be used.

Further, as other toner additives, colorless toner additives that do not adversely affect the color of the toner, such as charge control agents, offset inhibitors, etc., can be added according to well-known formulations.

Examples of the charge control agent include naphthenic acid, salicylic acid, octylic acid, metal soaps that are metal salts of manganese, iron, cobalt, lead, zinc, cerium, calcium, nickel, etc. of fatty acids and resin acids, and metal-containing azosols. Examples include dyes, pyrimidine compounds, alkylsalicylic acid metal chelates, and the content thereof is preferably 0.1 to 10% by weight per toner.

The offset preventing agent is a polyamide resin that has good compatibility with the binder resin and has transparency, such as 11-nylon, which is a polymer of ω-aminoundecanoic acid, and 12-nylon, which is a ring-opening polymer of laurolactam. - Nylon, 6,1O-nylon, 6,12- which is a polymer of hexamethylene diamine, sebacic acid, and dodecasine dicarboxylic acid
It is preferable that 1 to 20 parts by weight, particularly 5 to 10 parts by weight, of nylon, a polyamide resin which is a polymer of the alkyl diamine and dimer acid, etc., is added to 100 parts by weight of the binder resin.

Next, the method for manufacturing the toner of the present invention will be briefly described.

First, a polymer having a rhodanine derivative, other additives, reinforcing resin, etc. are mixed, mixed and dispersed using a heated kneader such as a heated roll or extruder, and then pulverized using a pulverizer such as a hammer mill or jet mill. At the same time, the particles are classified using a classifier in order to have a predetermined particle size.

It can also be produced by a spray drying method in which a polymer having the rhodanine derivative is dissolved in a suitable solvent and the solution is spray dried to form granules to a predetermined particle size.

[Experiment example]

Hereinafter, the present invention will be explained in more detail based on Examples.

(Example 1) [Synthesis of rhodanine derivative] Synthesis of 3-carboxymethyl-5-(4-(1-ethylquinoline)dimetine) rhodanine 19.1 g of 3-carboxymethyl rhodanine and 4-β-acetanilide vinylquinoline After refluxing 46.6 g of ethiodide and 12.1 g of triethylamine in ethanol for 930 minutes, the product was recrystallized from pyridine to obtain the above compound (yield: 53%).

[Synthesis of polymer with rhodanine derivative supported on side chain]

15.2 g of polychloromethylstyrene and 3-carboxymethyl-5-(4-(1-ethylquinoline)dimethine)
37.2 g of rhodanine and 12 ml of triethylamine in 1
The solution was dissolved in 00ml of dimethylforma and amide and reacted at 100°C for 3 hours. After the reaction, the solution was poured into methanol and the resulting precipitate was washed with water and methanol, then T H,F /
By reprecipitating with methanol and drying under reduced pressure, a polymer having N-substituted-5-(4-(1-ethylquinoline)dimethine)rhodanine supported on the side chain of polystyrene was obtained.

[Preparation of toner]

・100 parts by weight of polystyrene carrying the above 3-carboxymethyl-5-(4-(1-ethylquinoline)dimethine) rhodanine ・Bontron E-8
4 (manufactured by Orient Chemical Co., Ltd.) and mixed uniformly using a Henschel mixer FM20B (manufactured by Mitsui Miike Kakoki Co., Ltd.).
-30 (manufactured by Ikegai Tekko Co., Ltd.) and solidified with cold air.Then, the coarsely pulverized product was crushed in a feather mill (manufactured by Micron Co., Ltd. for wires), and the coarsely pulverized product was A blue toner having an average particle size of 11 μm was obtained by pulverizing the toner using an Alpine classifier 132MPL (manufactured by Yasuyo Denki Co., Ltd.) to remove fine powder with a particle size of 5 μm or less.

To 100 parts by weight of the above blue toner, 0.5 parts by weight of Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.), which is a hydrophobic silica as a fluidity imparting agent, was added, and after surface treatment using a Henschel mixer, the aggregates were formed using a vibrating sieve. was removed. Then, the above toner and ferrite carrier (average particle size 70 μm, manufactured by Nippon Tetsuko Co., Ltd.) were mixed using a Nauta mixer.
A developer having a toner concentration of 4.5% by weight was prepared.

(Example 2) - 100 weight 1 part polystyrene carrying the rhodanine derivative used in Example 1 on the side chain - Styrene-acrylic copolymer (XPA 525 manufactured by Mitsui Toatsu Kogyo Co., Ltd.)
) 50 parts by weight, Bontron E-84 (manufactured by Orient Chemical Co., Ltd.), 3 parts by weight, and 5 parts by weight of polyamide resin having a structural unit of 12 nylon (X4434, manufactured by Daicel-Hüls). A blue toner and developer were prepared.

(Comparative example) ・Eisenspiron Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.) 1
．． 5 parts by weight styrene-acrylic copolymer (manufactured by Mitsui Toatsu Kogyo Co., Ltd.
A blue toner and developer were prepared in the same manner as in Example 1 using 100 parts by weight of PA 525) and 3 parts by weight of Bontron E-84 (manufactured by Orient Chemical Co., Ltd.).

(Evaluation) Using the toners of Example 1.2 and Comparative Example produced as described above, a document image was developed using a normal color electrophotographic copying machine (DC-2055 manufactured by Sanda Kogyo Co., Ltd.), and the developed image was was transferred and fixed onto a translucent sheet (polyethylene terephthalate).

When the image was projected onto a white projection surface using an OHP, the image according to Example 1.2 had clearer colors than the image according to the comparative example.

〔Effect of the invention〕

According to the present invention, as described above, by using a polymer produced by reacting a chain polymer having a reactive substituent in the side chain with a rhodanine derivative as a coloring agent, translucency can be achieved. Excellent blue toner can be obtained, and clear color images can be projected on the OHP screen.

Patent applicant: Mita Kogyo Co., Ltd.

Claims (1)

[Claims] A chain polymer having a reactive substituent in its side chain and a rhodanine derivative having the following structural formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, B is a reactive substituent, C is a divalent organic group,
R_1 is hydrogen, a lower alkyl group, a substituted or unsubstituted aryl group, a hydroxyl group, and P is 0 or 1.