JPH04347863A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To provide the high-quality electrostatic charge image developing toner with which a stable electrical conductivity is obtainable at the time of continuous copying and continuous printing and which substantially prohibits the generation of in-machine staining, etc., by incorporating compds. having specific structures into the toner. CONSTITUTION:One or more kind of the compds. expressed by formula I or II and one or more kinds of the metal-contg. azo dyes or oxycarboxylic acid metal compds. which may have a substituent are provided into the electrostatic charge image developing toner contg. at least a resin and coloring agents. In the formula I, A<1> and A<2> have a naphthyl group or anthranyl group which has a hydroxyl group and carboxyl group in the adjacent substitution positions on one piece of carbon 6-membered ring at the respective ends and is coupled to an alkylene group connecting A<1> and A<2> in another substitution position on the carbon 6-membered ring; (n) denotes integer 1 to 3. In the formula II, A denotes formulas III, IV, etc.; X denotes a hydrogen atom, alkyl group, amino group or alkoxy group. The stable electrostatic chargeability is obtd. in this way and the high-quality toner is obtd.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to an electrostatic charge developing toner, and more particularly to an electrostatic charge developing toner that contains a specific electrostatic charge imparting agent and has excellent charging stability and can produce good images. It is related.

0002

[Prior Art] Electrophotography is disclosed in U.S. Pat.
As disclosed in Japanese Patent Application No. 748, etc., in general, an electrical latent image of electrostatic charge is formed on a photoreceptor containing a photoconductive material by various means, and then the latent image is transferred in advance to a carrier or a developing tank. It is developed as a powder image using toner that is electrically charged upon contact with the container wall, and if necessary, the powder image is transferred onto paper or the like and then fixed by heating, pressurization, solvent vapor, or the like. The toner is a powder obtained by dispersing various dyes, pigments, etc. in a resin such as styrene acrylic and pulverizing it to a particle size of about 1 to 30 μm.The toner is supported by electrostatic force on the surface and is itself magnetically supported. Iron powder with a diameter of about 30 to 200 μm, called a carrier, is transported to the vicinity of the photoreceptor.
It is used as a two-component developer by mixing it with ferrite and magnetite, or it is used as a one-component developer that does not use a carrier and is replaced by magnetic powder in which the carrier function is contained in the toner particles.

[0003] To impart chargeability to the toner, the binder resin or the colorant itself may be used, but if necessary, for example, a metal-containing azo dye or a metal complex salt of an aromatic oxycarboxylic acid which may have a substituent may be used. A common method is to add a charge imparting agent.

0004

[Problems to be Solved by the Invention] However, these conventional charge-imparting agents cause changes over time during continuous copying and printing, and when the charge increases, the image density decreases, and conversely, when it decreases, toner scattering occurs. This will cause dirt inside the machine. Stabilizing the charging properties during continuous copying and continuous printing is an essential condition for extending the service life.

[0005]

[Means for Solving the Problems] Therefore, the present inventors have developed a high-quality electrostatic charge developing toner that can obtain stable chargeability during continuous copying and printing, has a constant image density, and is less likely to cause internal stains. As a result of intensive studies to provide a toner, it was discovered that these problems could be solved by incorporating a compound having a specific structure into the toner, and the present invention was achieved.

That is, the gist of the present invention is that an electrostatic image toner containing at least a resin and a colorant contains one or more compounds represented by the following general formula [I] or [II]. The present invention relates to a toner for electrostatic charge development characterized by containing one or more metal-containing azo dyes or oxycarboxylic acid metal compounds which may have substituents.

[0007]

[Chemical formula 3]

[In the formula, A1 and A2 each have a hydrogen group and a carboxyl group at adjacent substitution positions on one 6-membered carbon ring at the end thereof, and have a hydrogen group and a carboxyl group at adjacent substitution positions on one 6-membered carbon ring at the end thereof, and It represents a naphthyl group or anthranyl group bonded to an alkylene group connecting A1 and A2 at a substitution position, and these may have an alkyl group, an amino group, or an alkoxy group at any one substitution position. Also, n represents a positive number from 1 to 3]

[0009]

[C4]

The present invention will now be described in detail. The electrostatic charge developing toner of the present invention has the general formula [I] according to claim 1 above.
or [II] and one or more metal-containing azo dyes or aromatic oxycarboxylic acid metal compounds which may have substituents.

In formula [I], it is usually preferable that A1 = A2. Further, specific examples of substituents that A1 to A3 may have include a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples include alkyl groups such as a tert-butyl group; amino groups; and alkoxy groups such as methoxy and ethoxy groups. formula[
II], specific examples of the substituent X include a hydrogen atom; an alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, or tert-butyl group; an amino group ; Examples include alkoxy groups such as methoxy group and ethoxy group.

Among the compounds represented by the general formula [I] or [II], specific examples of compounds suitable for inclusion in the electrostatic charge developing toner of the present invention include compounds represented by the following structural formula. Examples include, but are not limited to.

[0013]

[C5]

[0014]

[C6]

As the metal-containing azo dye, Orient Kagaku Kogyo Co., Ltd., which is usually used as a negative charge imparting agent, is used.
Bontron S-32, S-34, S-37 manufactured by Hodogaya Chemical Co., Ltd. Spiron black TRH or ICI
Protoner CCA7 manufactured by Co., Ltd., and Bontron E-81 and E-84 manufactured by Orient Chemical Industry Co., Ltd. as aromatic oxocarboxylic acid compounds that may have substituents.
, carboxylic acid salts such as E-88, or complexes, but are not limited thereto.

The resin to be contained in the toner for electrostatic images of the present invention can be selected from a wide range of known resins, such as polystyrene, crotopoistyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, and styrene-chlorostyrene. Propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic ester copolymer (styrene-methyl acrylate) copolymers, styrene-ethyl acrylate copolymers, styrene-butyl acrylate copolymers, styrene-octyl acrylate copolymers, styrene-phenyl acrylate copolymers, etc.), styrene-methacrylate ester copolymers (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, and styrene-phenyl methacrylate copolymer), styrene-α-methyl chloroacrylate copolymer, and Styrene-acrylonitrile-
Acrylic acid, styrene resins such as ester copolymers (styrene or styrene-substituted monopolymers or copolymers), vinyl chloride resins, rosin-modified maleic acid resins,
There are phenolic resins, epoxy resins, polyester resins, low molecular weight polyethylene, low molecular weight polypropylene, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins, and polyvinyl butyral resins.
Particularly preferred resins for use in the present invention include styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, saturated or unsaturated polyester resins, and epoxy resins.

Further, the above resins are not limited to being used alone, but can also be used in combination of two or more. Furthermore, the electrical properties of the toner can be controlled by adding solid electrolytes, polymer electrolytes, charge transfer complexes, metal oxide conductors such as tin oxide, semiconductors, ferroelectric materials, magnetic materials, and the like. In addition, auxiliary agents such as various plasticizers and mold release agents may be added to the toner for the purpose of adjusting thermal properties, physical properties, etc. Furthermore, toner particles contain TiO2, Al2O3, SiO2.
The fluidity and agglomeration resistance of the toner can be improved by adding fine powders such as these and coating the surfaces of the toner particles. Furthermore, the toner of the present invention can be applied to encapsulated toners, polymerized toners, and one-component developers in addition to two-component developers.

Various conventional toner manufacturing methods can be applied to the toner manufacturing method of the present invention, and examples of general manufacturing methods include the following. First, resin,
Uniformly disperse the coloring agent, etc. using a ball mill, V-type mixer, S-type mixer, Henschel mixer, etc. Next, the dispersion is melt-kneaded using a double-arm kneader, pressure kneader, extruder, roll mill, or the like. The kneaded material is pulverized using a pulverizer such as a hammer mill, cutter mill, jet mill, or ball mill, and the resulting powder is further classified using an air classifier or the like.

The obtained toner can be mixed with a carrier and used as a two-component developer, and can also be used as an encapsulated toner, a polymerized toner, and a non-magnetic or magnetic one-component developer. As the carrier, a magnetic material such as a known iron powder-based, ferrite-based, or magnetite-based carrier, or a material obtained by coating the surface with a resin, or a magnetic resin carrier can be used.

The toner of the present invention contains two or more of the compounds represented by the general formula (I) or (II) and a metal-containing azo dye or an aromatic oxycarboxylic acid complex salt which may have a substituent as a charge imparting agent. It is blended. The content of the compound represented by the general formula (I) or (II) is the content of the compound represented by the general formula (I) or (II).
────A Metal-containing azo dye
────B Aromatic oxycarboxylic acid complex salt which may have a substituent──
──C means that A+B or A+C in the binder resin is 0.
1 to 10% by weight (hereinafter abbreviated as %) is preferable, and 0.5% by weight
If A+B or A+C, which is more preferably 5%, is too small, it will be difficult to control the amount of charge, and if it is too large, the stability of charging will be poor.

[0021] The ratio of B or C to A is 1:0.1
The ratio is preferably 1:0.1 to 10%, and more preferably 1:0.1 to 10%.

[0022]

EXAMPLES The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples unless the gist thereof is exceeded. In addition, "parts" in each example and comparative example shall represent "parts by weight." (Example-1) Styrene acrylic resin
100 parts (styrene butyl acrylate) carbon black
8 parts (MA-8 manufactured by Mitsubishi Kasei Corporation) Exemplary compound (1)
1 part metal-containing azo dye
Part 1 (S
-34 manufactured by Orient Kagaku Kogyo Co., Ltd.) The above materials were blended, kneaded, pulverized and classified to obtain a black toner having an average particle size of 11 μm.

To 100 parts of this black toner, 0.2 parts of fine silica powder (R972 manufactured by Nippon Aerosil Co., Ltd.) was externally added using a Henschel mixer. A developer was prepared by mixing 4 parts of this toner and 100 parts of a magnetite carrier coated with an acrylic resin with an average particle size of 100 μm, and a modified copying machine with an organic photoconductor as a photoreceptor at 40 sheets per minute was used to produce a developer. A 10,000-shot live-action test was conducted.

The replenishment toner used in the actual photography test had the same composition as the toner used in the developer described above. As a result of the photocopying test, the image density of the copies was high and the amount of charge of the developer was stable even after 10,000 copies were photocopied. (Examples 2, 3, 4/Comparative Examples 1, 2, 3) Exemplary compounds (
1), the metal-containing azo dye, and the aromatic oxycarboxylic acid compound which may have a substituent (E-84, manufactured by Orient Kagaku Kogyo Co., Ltd.) were changed in the same manner as in Example 1 above. The test results, including Example 1, are shown in Table 1. The image density was measured using a Macbeth densitometer RD917, and the image density was 1.35 or higher.
◎1.35-1.25 ○ 1.25-1.00 △ 1.00 or less ×.

[0025] Also, the charge amount was measured using a blow-off powder charge measuring device manufactured by Toshiba Chemical, and the charge amount stability was within ±5 μC/g from the initial value.◎±10 μC/g
Within ±15 μC/g: ○ Within ±15 μC/g: △ Within ±10 μC/g: ×.

[0026]

[Table 1]

(Example-5) Example-1 except that 1 part of Exemplified Compound (13) is used instead of Exemplified Compound (1)
When the same procedure was carried out as above, the result of the actual copying test was that the image density of the copies was high and the amount of charge of the developer was stable even after 10,000 copies were actually copied. (Examples 6, 7, 8) The amounts used of Exemplary Compound (13), metal-containing dye, and aromatic oxycarboxylic acid compound that may have a substituent (E-84 manufactured by Orient Kagaku Kogyo Co., Ltd.) were changed. Other than that, the test results were conducted in exactly the same manner as in Example 5, and the results, including Example 5, are shown in Table 2.

[0028]

[Table 2]

[0029]

Effects of the Invention The toner for developing electrostatic images of the present invention is a high quality toner for developing electrostatic images that does not cause stains on copies due to continuous copying.

Claims (1)

[Claims] Claim 1: An electrostatic image toner comprising at least a resin and a colorant, comprising at least one compound represented by the following general formula (I) or (II) and a metal-containing azo dye or a substituent. A toner for developing an electrostatic image, characterized in that it contains one or more types of aromatic oxycarboxylic acid metal compounds which may have the following. [Formula 1] [In the formula, A1 and A2 each have a hydrogen group and a carboxyl group at adjacent substitution positions on one carbon 6-membered ring at the end thereof, and A1 at the substitution position
represents a naphthyl group or anthranyl group bonded to an alkylene group connecting and A2, and these may have an alkyl group, an amino group, or an alkoxy group at any one substitution position. Also, n represents a positive number from 1 to 3] [Chemical formula 2]