JPS63141073A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain an electrostatic charge developing toner high in quality and not causing staining of a copy due to successive copying by incorporating a specified charge enhancing agent in the toner. CONSTITUTION:The toner contains at least one of the charge enhancing agent represented by the formula shown on the right in which each of R1 and R2 is H, alkyl, phenyl or alkylphenyl; and R3 is H, OH, alkenyl, or -N=(R1, R2). It contains also a binder resin, such as styrene resins, addition polymerization type resins like syyrene-acrylic resins, polycondensation type resins like polyester resins, and epoxy resins. As the monomers to be used for the addition polymerization type resins, ethylenically unsaturated monoolefins can be used, and as the monomers to be used for the polycondensation type resins, polyols, such as ethlene glycol, are enumerated, and as the charge enhancing in agent, for example, 1,4-bis(p-toluidino)anthraquinone and the like are used in amount of 0.01-10wt% preferably, 0.1-5wt% of the toner.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a toner for developing electrostatic images used in electronic copying machines and the like.

<Prior Art> In the development process, the developer used in electronic copying machines and the like is once attached to an image carrier such as a photoconductor on which an electrostatic image is formed, and then in the transfer process, the developer is applied to the photoconductor. After being transferred from the image to a transfer paper, it is fixed to the copy paper surface in a fixing step. At that time, the developer for developing the electrostatic charge image formed on the latent image holding surface is a two-component developer consisting of a carrier and toner, and a one-component developer (magnetic toner) that does not require a carrier. It has been known.

Conventionally, charge control agents such as nigrosine dyes and primary ammonium salts, carrier coating agents, and the like have been known as agents for imparting charge to the developer.

<Problems to be Solved by the Invention> However, these conventional charge-imparting agents have a problem in that the charging effect is not sufficient and copy stains occur due to continuous copying, resulting in a reduction in copy quality.

Means for Solving the Problems> Therefore, the inventors of the present invention conducted intensive studies to provide a toner for developing electrostatic images with a high quality that does not cause copying stains, etc. As a result, the present inventors developed a toner having a specific structure. The inventors have discovered that these problems can be solved by incorporating a charge improver into the toner, and have arrived at the present invention.

That is, the gist of the present invention is to provide an electrostatic image developing toner comprising at least a colorant and a resin, characterized in that the toner contains at least one charge improver represented by the following general formula (I). Exists in toner for developing charged images.

(In the above formula, "I'm R1 and R1 represent a hydrogen atom, an alkyl group, a phenyl group, or an alkylphenyl group, and R
, represents a hydrogen atom, a hydroxyl group, or a hydrogen atom. ) Hereinafter, the present invention will be explained in detail.

Various known resin components can be used as the resin component of the toner of the present invention.

That is, examples include condensed heavy mold resins such as styrene resins and styrene-acrylic polyamide resins, as well as epoxy resins.

Among these resins, monomers for forming addition polymerization type resins include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2. Hiro-dimethylstyrene,
p -n-7'tylstyrene, p -t+9rt-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-"-nonylstyrene, p-n-dicilstyrene, p-"- Dogsylstyrene, p-methoxystyrene, p-7enylstyrene, p-chlorostyrene, 3. Styrenes such as u-dichlorostyrene: Ethylenically unsaturated vinyls such as ethylene, chlorostyrene, butylene, isobutylene: Vinyl acetate, vinyl propionate, vinyl benzoate, vinyl esters of polyvinylnato; methyl acrylate, acrylic acid Ethyl, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate,
lauryl acrylate, coethylhexyl acrylate,
stearyl acrylate, λ-chloroethyl acrylate,
Phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodefflu methacrylate, Lauryl methacrylate, methacrylic eJRJ-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid derivatives; vinyl methyl ether, vinyl ethyl ether, vinyl ethers of vinyl indolnato. ; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinylpyrrole, N
- N-vinyl compounds such as vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; monoolefin monomers such as vinylnaphthalene; propadiene,
Examples include diolefin monomers such as butadiene, inoprene, chloroprene, pentadiene, and hexadiene. These monomers can be used alone or in combination of two or more.

In addition, the monomers forming the condensation polymerization type resin include ethylene glycol, triethylene glycol,
Co-propylene glycol, /, J-70 pyrene glycol, /, ≠l butanediol, neopentyl glycol % 'l≠l boondiol, /, 4C-bis(hydroxymethyl)cyclohexane, bisphenol A,
Polyhydric alcohols such as hydrogenated bisphenol A1 polyoxyethylenated bisphenol A1 polyoxypropylenated bisphenol A, polyhydric amines such as ethylene diamine, tetramethylene diamine, pentamethylene diamine, piperazine, hexamethylene diamine, and
Maleic acid.

Fumaric acid, mesaconic acid, citraconic acid, itanconic acid, geltaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, cepatic acid, malonic acid, or acid anhydrides or lower alcohols thereof Examples include polycarboxylic acids such as esters with and dimers of liluic acid.

Further, the colorant used in the present invention is not particularly limited as long as it is a conventionally used colorant, but carbon black is preferably used.

Note that the toner of the present invention may contain a charge control agent as in conventional products. Known charge control agents can be used, such as nigrosine dyes, high grade ammonium salts, polyamine resins, amino group-containing styrene resins, and chromium-containing metal dyes.

In the present invention, it is necessary to further contain a charging improver represented by the following general formula (1) in the toner containing the above-mentioned components.

(In the above formula, R1 and R1 represent a hydrogen atom, an alkyl group, a phenyl group, or an alkylphenyl group, and R8 represents a hydrogen atom, a hydroxyl group, or an alkyl group.) Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. The alkylphenyl group is preferably a substituted phenyl group substituted with at least 7 of the above alkyl groups.

Specific examples of the above-mentioned charging improver are /, 4t-bis(p-)
The charge improver of the present invention may be one or more of these compounds, preferably a mixture of the three compounds mentioned above. It is preferable to use

The amount of charge improver used is 0,000 for 100 parts by weight of toner.
The amount is preferably 0.01 to 10 parts by weight, preferably 0.7 to 5 parts by weight. If the amount of the charge improver used is less than the above range, the effect of improving chargeability will not be improved, and if it is more than the above range, the quality of the toner will deteriorate, which is not preferable. Further, it is preferable to treat the coloring agent used in the present invention with a metal salt of carboxylic acid because copy quality can be further improved.

Examples of metal salts of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, cabroic acid, dinandoic acid,
Caprylic acid, pelargonic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecylic acid, stearic acid group nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacanoic acid, montanic acid, melisin tR , "+ Mg+ zn+aa, Ba" of fatty acids with a linear structure such as rough cellic acid
, metal salts such as Pb; acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, centomeleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, arachidonic acid, propiolic acid, stearolic acid, etc. of unsaturated fatty acids, At, Mg,
Zn, C! a.

Metal salts such as Ba and Pb; abietic acid and malic acid,
Kl, M of resin acids, which is a general term for organic acids that exist free or as esters in natural resins such as benzoic acid and cinnamic acid.
Examples include metal salts such as Zn, Ca, Ba, and Pb. An example of a method for treating the surface of a colorant with a metal salt of a carboxylic acid is to add and mix an aqueous alkaline solution of the base acid to an aqueous suspension of the colorant, and then add a metal salt solution containing the necessary metal. By adding , the desired metal salt of carboxylic acid can be precipitated on the surface of the colorant particles. Then, the particle size may be adjusted by purifying, drying, and crushing.

In the present invention, the metal salt of carboxylic acid is applied to the surface of the colorant in an amount of about 0.1-2% per colorant. Weight %, preferably /~/! weight%
It is better to include it.

Also, the softening point of metal salts of carboxylic acids is 70~! ! Q″
C1 is preferably in the range of ioo to λ00°C. If the softening point is below 70° C., the toner tends to aggregate and fuse during continuous use, and the phenomenon of filming on the surface of the photoreceptor is likely to occur, which is not preferable.

In addition, additives such as a low molecular weight olefin polymer and finely powdered silica may be included as the toner components of the present invention in order to improve fixing properties and fluidity.

The toner can be produced by kneading the above-mentioned components in a kneader or the like, cooling them, and then crushing and classifying them. Furthermore, the toner of the present invention can be applied not only to two-component developers but also to so-called one-component developers (magnetic toners) such as encapsulated toners, polymerized toners, and magnetite-containing toners.

The average particle size of the toner is preferably 5 to 20 μm.

The carrier to be mixed with the toner of the present invention to form a developer is not particularly limited, but iron powder having an average particle size of 10 to 200 μm is preferable.

Note that there is no particular restriction on the particle size of the iron powder. In this case, a so-called coated carrier coated with a fluororesin or the like can also be used for the purpose of improving durability during continuous use. Further, ferrite-based and magnetite-based iron powders can also be used.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited in any way by the following Examples unless the gist thereof is exceeded.

In addition, "parts" in the examples indicate "parts by weight."

Examples/〉 Styrenic resin (SBM-600 manufactured by Sanyo Chemical Co., Ltd.) 100
70 parts and 1 part of carbon black (MA-100 manufactured by Mitsubishi Kasei Co., Ltd.) were blended and kneaded, and the mixture was pulverized and classified to obtain an average particle diameter/l/j (Q
A black toner was obtained.

This toner! A developed material was prepared by mixing and stirring a portion of a fluorine foil resin coated carrier having an average particle diameter of 100 μm. Next, a copying machine using an organic photoconductor as a photoconductor (Example λ) was prepared using this current extender, except that the amount of 1,4-bis(p-toluidino) anthraquinone used was 3 parts.
When a toner was prepared in the same manner as in Example 1 and an actual copy was taken, a clear copy with little capri was obtained as in Example 1.

<Example 3> A toner was prepared in the same manner as in Example 1, except that 1,4-bis(p-)luidino)anthraquinone was used as the charging improver, and a toner was photographed. A very clear copy was obtained.

<Example Hiro> A toner was prepared in the same manner as in Example except that 1 part of 4L-bis(p-toluidino)anthraquinone/-(p-toluidino)-Hiro-hydroxyanthraquinone was used as the charge improver. When the image was converted into a live photo, a clear copy with little capri was obtained.

<Example! 〉 Example except that 1 part of l,cubis(p-toluidino)anthraquinone, 1 part of l-methylaminoanthraquinone and /-(p-)luidino)-p-hydroxyanthraquinone/fHJf were used as charge improvers. When the image was converted into toner and photographed in the same manner as /, a clear copy with little fogging was obtained.

Comparative Example/〉 When the toner was made in the same manner and the copy was actually copied, a copy with many capri and poor copy quality was obtained.

<Effects of the Invention> The toner for developing an electrostatic image of the present invention is a high quality toner for developing an electrostatic image that does not cause copy stains or the like due to continuous copying.

Claims (7)

[Claims] (1) A toner for developing electrostatic images comprising at least a colorant and a resin, characterized in that the toner contains at least one charge improver represented by the following general formula (I): Toner▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above formula, R_1 and R_2 represent a hydrogen atom, an alkyl group, a phenyl group, or an alkylphenyl group, and R_
3 is a hydrogen atom, a hydroxyl group, or a mathematical formula, a chemical formula,
There is a table etc. ▼ (R_1 and R_2 are as described above). ) (2) Charge improver is 0.0 parts by weight per 100 parts by weight of toner.
The toner for developing an electrostatic image according to claim 1, wherein the toner contains 1 to 10 parts by weight. (3) The toner for developing an electrostatic image according to claim 1, wherein the charge improver is 1,4-bis(p-toluidino)anthraquinone. (4) The toner for developing an electrostatic image according to claim 1, wherein the charge improver is 1-methylamino-anthraquinone. (5) The toner for developing electrostatic images according to claim 1, wherein the charge improver is 1-(p-toluidino)-4-hydroxyanthraquinone. (6) The charge improver is 1,4-bis(p-toluidino)
The toner for developing electrostatic images according to claim 1, which is a mixture of anthraquinone, 1-methylamino-anthraquinone, and 1-(p-toluidino)-4-hydroxyanthraquinone. (7) The toner for developing an electrostatic image according to claim 1, wherein the colorant is carbon black.