JPH02195361A - Black color toner composition - Google Patents

Abstract

PURPOSE:To obtain a transparent black dyestuff good in lightfastness and the like by incorporating a specified phthalocyanine derived dyestuff. CONSTITUTION:The phthalocyanine derived dyestuff to be used is represented by formula I in which R<1> is amino or hydroxy, when R<1> is amino, R<2> is H, halogen, alkyl, or alkoxy, and all of R<2> in formula I are same, and when R<1> is hydroxy, all of R<2> are H, halogen, or the like, and each is same as each other, and n is 2, 3, or 4, thus permitting the obtained dystuff to be superior in melt miscibility, transparent and black, stable in the image density obtained by repeated successive copying, and good in lightfastness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to color toners, particularly color toner compositions for electrostatic charge development.

Conventionally, electrostatic printing, electrophotography, and the like are well-known methods for forming visible images by developing electrical latent images with color toners. Generally, a photoconductive material is used to form an electrical latent image on a photoconductive photoreceptor by various means, and the latent image is then developed with toner to obtain a visible image; After transferring the powder image to paper or the like as necessary, it is fixed by heating, pressure, solvent vapor, etc. to obtain a visible image.

To obtain a multicolor image, a document is exposed to light using a color separation filter, and the above steps are repeated multiple times using color toners such as yellow, magenta, cyan, and black to create a color image.

As a toner for developing an electrical latent image, conventionally used particles are particles obtained by dispersing a coloring agent in a binder resin such as polystyrene and pulverizing the particles to about 0.1 to 50 microns. This color toner is usually mixed with a carrier material such as glass beads or iron powder and used to develop an electrical latent image.

(Prior Art and Problems to be Solved by the Invention) These color toners are required to have various physical and chemical properties as shown below.

(I) A one degree change does not affect the triboelectric properties of the color toner.

(2) The density obtained changes due to collision between color toner particles and carrier particles due to repeated development for continuous use, and mutual deterioration of those particles and the photosensitive plate, or
The background density must not increase and reduce the quality of the copy.

(3) If an attempt is made to increase the density of a copied image by increasing the amount of color toner adhering to the surface of the photosensitive plate having the Wl image, the background density will normally increase, so the so-called fog phenomenon must not occur.

(4) Do not lose transparency when layering multiple colors.

(5) Each color toner needs to have excellent melt miscibility.

(6) In order to accurately reproduce the original, it is necessary to have good spectral reflection characteristics.

In particular, with regard to black, carbon black has been widely used because no single pigment has a good color tone, but it has the disadvantage of lack of transparency, so its development has been strongly desired.

(Means for Solving the Problem!) The present invention has been made through intensive studies to solve the problems of the above-mentioned color toners, and has been developed to satisfy the above-mentioned required properties and to have transparency. The present invention was completed by discovering a black pigment with good light fastness.

That is, the present invention provides a binder resin containing the following soft formula (I) (% formula%) [wherein R1 is an amino group or a hydroxyl group, and when R1 is an amino group, 1rt is a hydrogen atom, a halogen atom, an alkyl atom, group, alkoxy group, and all R2 in the formula are substituted with the same group.If 171 is a hydroxyl group, R1
represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an aralkyl group, an alkoxycarbonyl group, or an alkylcarboxy group, and all 1tt's are substituted with the same group. In addition, n represents an integer of 2 to 4.] This is a black color toner composition for electrostatic charge development, characterized by containing a phthalocyanine dye represented by the following.

When ill in formula (I) is an amino group, specific examples of Bx include halogen atoms such as hydrogen atom, chlorine atom, and bromine atom, methyl group, ethyl group, isopropyl group, butyl group, isobutyl group, and pentyl group. , an alkyl group such as an isopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group. In this case, all 16 C's in -a formula (I) are substituted with the same group.

Further, when R- is a hydroxyl group, specific examples of the R term include a hydrogen atom, a halogen atom such as a fluorine atom, a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isobutyl group, an n-octyl group, Methoxy group, ethoxy group, n-
Alkoxy groups such as propoxy group and n-hexyloxy group, alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, n-butoxyethyl group, methoxymethoxy group, ethoxymethoxy group, Alkoxyalkoxy groups such as ethoxyethoxy groups, aralkyl groups such as benzyl groups, phenethyl groups, γ-phynylpropyl groups, methoxycarbonyl groups,
Examples include alkoxycarbonyl groups such as ethoxycarbonyl group and n-propoxycarbonyl group, and alkylcarboxy groups such as acetyloxy group, ethylcarboxy group, and n-propylcarboxy group. In this case - all 16 R1 in soft formula (I) are substituted with the same group.

The compound of general formula (I) can be easily obtained by reacting phthalocyanine green with hydroxythiophenols or aminothiophenols in a polar solvent under a nitrogen atmosphere in the presence of a base such as potassium carbonate by a known method. .

A method for producing a color toner using the black pigment of the present invention is to obtain a color toner by incorporating preferably 0.1 to 10 parts by weight of a compound of the formula (R) into a binder resin. Can be done.

Hereinafter, the constituent components of the color toner of the present invention will be explained in detail.

Particularly important components of the color toner are the phthalocyanine compounds represented by the general formula (I) described above.

The amount of these black color toner pigments to be added depends on the chargeability of the binder resin, the chargeability of the auxiliary colorant or additive, the compatibility with the binder resin, or the dispersion method. etc., so it is not uniformly limited, but generally speaking, it is approximately 0 for the binder resin.
．． It is desirable to use it in the range of 1 to 10 (wt%).

All known binder resins can be used as the binder resin for the color toner of the present invention, such as polystyrene,
Monopolymers of styrene and its substituted products such as polyP-chlorostyrene and polyvinyltoluene, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-
Butyl acrylate copolymer, styrene-octyl 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 ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Polymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-
Styrenic copolymers such as acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene , polyester, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. They can be used alone or in combination.

One of the important properties of toner is its electrostatic property, and for that purpose it needs to be charged! J regulator is added.

As the charge control agent, a colorless compound is preferable so as not to change the color tone, and examples thereof include bis(4-(-butylsalicylic acid) chromium(n)ti form, N-octadecylpyridinium chloride, tetraoctylammonium chloride, etc.). Can be mentioned.

Further, as a carrier agent for a developer, for example, iron,
Magnetic substances such as cobalt and nickel, alloys and mixtures thereof, or coatings on the surfaces thereof.

(Function) Conventional toners have had problems such as fogging of copies and poor transparency, but the toner composition of the present invention has excellent melt miscibility, is transparent and It is a dye with stable black image density and good light fastness, which can be obtained by continuous copying by repeated development, and is extremely valuable in practice.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. The compounds used were produced by conventional methods.

The light resistance of Examples 1 to 48 was determined after 60 hours of irradiation using a fetometer (carbon arc lamp) at 63°C.

Example 1 5 parts of the black copper phthalocyanine derivative shown in Example 1, 95 parts of toner resin [styrene-acrylic acid ester copolymer; trade name Hymer TB-1000F (manufactured by Sanyo Chemical Co., Ltd.]) and 2 parts of tetraoctylammonium chloride were mixed in a ball mill. After mixing and pulverizing, the mixture is heated to 150° C., melt-mixed, cooled, and then coarsely pulverized using a hammer mill, and then finely pulverized using an air jet type pulverizer. Further classify 1
~20II is selected and used as toner.

For 10 parts of this toner, carrier iron powder (trade name, E
F V250/400. (manufactured by Nippon Iron Powder) were uniformly mixed to prepare a developer. Using this developer, a dry plain paper electrophotographic copying machine (product name, NP-5000; Canon, K
When copying was carried out using a printer (manufactured by Fujitsu Co., Ltd.), a clear black image with no fog was obtained. Moreover, the light resistance of the copy was also good and was grade 7.

Examples 2 to 48 High-performance color toner compositions were obtained in exactly the same manner as in Example 1 using the dyes shown in Tables 1 and 2.

(Margin below) Table-1 Table-2 -C1 p-Cffi Shaved-Br 1)-C2H4 1)-CIOH2, ρ-OC,I(9 11+-0C2H5 -C1 o-CH.

o-C,)I,.

0-C! ISO m-0Cf13 -C2H5 o-CaL? -C1 -Br Procedural amendment (method) May 17, 1999 Commissioner of the Japan Patent Office Yoshi 1) Takeshi Moon 1, Indication of the case 1999 Patent Application No. 13982 2, Name of the invention Black color toner composition 3. Relationship with the case of the person making the amendment Patent applicant address: 3-2-5-4 Kasumigaseki, Chiyoda-ku, Tokyo Date of amendment order: April 25, 1999 (shipped) 5. Invention of the specification subject to the amendment Detailed explanation column 6, page 2, line 4 of the statement of contents of the amendment, next to “3゜Details of the invention”

Claims (1)

[Claims] 1) General formula (I) ▲Mathematical formula, chemical formula, table, etc. are present in the binder resin▼(I) [In the formula, R^1 is an amino group or a hydroxyl group, and R^1
is an amino group, R^2 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and all R in the formula
^2 is substituted with the same group. When R^1 is a hydroxyl group, R^2 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an aralkyl group, an alkoxycarbonyl group. or represents an alkylcarboxy group, and all R^2 are substituted with the same group. Moreover, n represents an integer of 2 to 4. ] A black color toner composition for electrostatic charge development, characterized by containing a phthalocyanine dye represented by the following.