JPH02212855A - Color toner composition - Google Patents

Abstract

PURPOSE:To obtain a toner compsn. having a fine black color in spite of a single coloring component by using a specified phthalocyanine compd. having arylthio groups. CONSTITUTION:A compsn. obtd. by introducing a phthalocyanine dyestuff represented by formula I into resin by covalent bond is used. In the formula I, R<1> is amino or hydroxyl, when R<1> is amino, R<2> is H, halogen, alkyl or alkoxy and all of R<2>'s in the formula are the same group, when R<1> is hydroxyl, R<2> is H, halogen, alkyl, alkoxy, alkoxyalkyl, alkylcarboxy, etc., and all of R<2>'s are the same group, and n is an integer of 2-4. The compsn. is a black toner compsn. having a fine neutral black color in spite of a single coloring component and giving a clear image free from fog.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a colored toner used in electrophotography,
More specifically, it is a composition used as a black component for full color copying.

(Prior Art and Problems to be Solved by the Invention) Various toner compositions including color developer compositions used in electrostatic photography have been proposed, and some have already been put into practical use. These compositions generally include a resin, a colored colorant, and carrier particles.

Cyan, magenta, yellow, and black dyes or pigments are selected as the coloring materials.

Compared to R materials, dyes have the advantage of greater color value because they can be molecularly dispersed in the toner resin, but they tend to aggregate when exposed to heat, pressure, or moisture, resulting in lower color variation. . Furthermore, when these are used for printing, a so-called fogging phenomenon occurs due to the bleeding of the dye, resulting in a blurred image, which sometimes poses a problem.

As a means to overcome these drawbacks, several methods have been reported in which dye molecules are covalently immobilized in toner resins. These methods can be roughly divided into the following two types.

1) A method of introducing a dye into the main chain by covalently bonding a dye molecule with a reactive functional group to an ordinary polymeric monomer (
For example, Japanese Patent Publication No. 47-6587, Japanese Patent Publication No. 47-3378
(Special Publication No. 48-25667, No. 62-245268)
, representative examples of which are schematically shown below.

2) A method in which a dye is introduced pendantly into the main chain of the polymer (for example, Japanese Patent Publication No. 47-1.1399;
86058), representative examples of which are schematically shown below.

-G-eNH-11-Nlle-L turtle! ”−〇÷“Anthraquinone or an azo compound is usually used as the pigment component in these resins, but there was no pigment that showed a good black color with a single component, so there was a desire to develop one.

If you try to mix the three primary colors of cyan, magenta, and yellow and use the above reaction to make black, the reactivity of each color's pigment is different, so the desired hue may deviate.
Moreover, there is no reproducibility and it is difficult to put it into practical use.

[Means to solve the problem]

As a result of intensive studies on black dyes having a single component and a reactive functional group, the present inventors have found that phthalocyanine compounds having an arylthio group exhibit good properties and have completed the present invention.

That is, the present invention relates to the general formula (I) [where ill is an amino group or a water group, and R'6
(In the case of an amino group, R: is a hydrogen atom, a halogen atom,
An alkyl group, an alkoxy group, and all R2 in the formula
represent the same group. If 1171 is a hydroxyl group, R2
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 R1's represent the same group. Further, the present invention is a colored toner composition in which a phthalocyanine dye represented by ], where n represents an integer of 2 to 4, is introduced into a resin through a covalent bond.

-m The compound of 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. Can be synthesized.

Specific examples of R1 and R8 in general formula (I) include formula (I
), when II' in ) is an amino group, specific examples of R1 include halogen atoms such as hydrogen atom, chlorine atom, and bromine atom;
Methyl group, ethyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group,
Examples include alkyl groups such as heptyl group, octyl group, nonyl group, and decyl group, and alkoxy groups such as methoxy group, ethoxy group, and butoxy group. In this case, -1 4n in formula (I)
All R1's represent the same group.

Further, when R1 is a hydroxyl group, specific examples of R1 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, and a 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, T-phenylpropyl groups, methoxycarbonyl groups,
Examples include alkoxycarbonyl groups such as ethoxycarbonyl group and i-propoxycarbonyl group, and alkylcarboxy groups such as acetyloxy group, ethylcarboxy group, and lowpropylcarboxy group. In this case, all 4n Rz's in general formula (I) represent the same group.

There are two methods for introducing the dye represented by the general formula (I) into the main chain of a resin polymer through a covalent bond: a method of polycondensing the dye with the polymer on the polymer, and a method of reacting with the dye. Examples of seven polymers that react with dyes include phthalic acid chloride, inophthalic acid chloride, terephthalic acid chloride, glutaryl chloride, Sierra acid chloride, Examples include diacyl halides such as adipoyl chloride, bishaloformates such as ethylene glycol bischloroformate, diethylene glycol bischloroformate, propylene glycol chloroformate, tetramethylene diisocyanate, hexamethylene diisocyanate, etc. Examples include alkylene diisocyanates such as diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate; Examples include aromatic diisocyanates such as isocyanates, and examples of the case where dyes are bonded to polymers include acid halides.

The above-mentioned reactive hexamer or polymer and -M
If necessary, the dye of formula (I) is heated together with a copolymerizable compound such as bisphenol A in an organic solvent such as dioxane or dimethylimidazolidinone (D?11) in the presence of a base such as pyridine. By stirring, a dye-containing polymer can be obtained.

One of the important properties of toner is its charging property.
Charge control agents are added for this purpose. Specific examples of charge control agents include ■-alkylpyridinium compounds such as N-cetylpyridinium chloride, quaternary ammonium such as octadecyl ammonium chloride, and metals such as bis(4-t-butylsalicylic acid) chromium (Il). Complexes can be mentioned.

Additionally, specific examples of carrier materials that can be used in combination with the pigmented color toners of the present invention include granular zircon, granular silicon, polymethyl methacrylate, glass, steel,
Examples include nickel, iron ferrite, silicon dioxide, etc.
Particle sizes typically about 50 to 1000 microns in diameter are used. The carrier particles can be mixed with the toner particles in various suitable proportions, but typically 10 to 200 parts by weight of carrier material are used for about 1 part by weight of toner.

(Functions and Effects) The phthalocyanine compound of the present invention exhibits a good natural black color as a single component, and when introduced into a resin through a covalent bond, a black toner with high transparency and a clear image without fog can be obtained. It is a composition. Moreover, it was also found that the light resistance was extremely high.

As described above, the black color toner composition of the present invention is extremely valuable in practice.

〔Example〕

The colored toner composition of the present invention will be explained in detail by way of Examples below, but these Examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Part ``r'' in the figure indicates 1 part by weight.

Example 1 3.3 parts of a phthalocyanine compound represented by the following formula (I) and 32 parts of 2,2-bis(p-human mixyphenyl)propane (bisphenol A) were mixed with 400 parts of 1,4-dioxane and 40 parts of pyridine. diethylene glycol bischloroforme) 411Mi was dissolved at 5-10°C under Iff for 10
The addition took 30 minutes at ~15°C. After reacting for 2R at the same temperature, 5 (I) was added to 100 parts of hexane under vigorous stirring.
Added gradually. The generated precipitate is filtered, washed with water, and dried.
74 parts of black polycarbonate were obtained.

40 parts of this resin finely pulverized by a jet mill and 1 part of tetraoctylammonium chloride with an average diameter of 100
It was mixed with 100 parts of iron particles of ~150 mesh to form the development side. Using this developing side, a clear black image was obtained when copying was carried out with a dry Sotsugi electrophotographic copying machine (trade name Np-5000, manufactured by Canon Co., Ltd.). Moreover, the light resistance of the copy was good at grade 7.

Example 2 Part of salt MlO was added to a mixture of 100 parts of 40% formalin and 90 parts of phenoxyacetic acid, heated and stirred at 103 to 108°C for 4 hours, and immediately after adding 500 parts of warm water at 50°C, water was diluted with decanethisilane. After removing 500 parts of water at room temperature, the mixture was filtered and washed with water.

The temperature of the obtained product was gradually raised while stirring under a reduced pressure of 30+u+Hg, and the reaction was carried out at 110 to 115'C for 5 hours to form a polyphenethylene compound 10 represented by the following formula.
I got 1 copy.

101 parts of this resin were dispersed in 500 parts of toluene, 180 parts of thionyl chloride was added at room temperature, and the mixture was reacted at 40°C for 74 parts. Thereafter, excess thionyl chloride was distilled off under reduced pressure, and 1 phthalocyanine compound of formula (I) was added to 100 parts of dioxane.
A solution containing 50 parts of pyridine was added dropwise at the same time as 50 parts of pyridine.
The mixture was heated and stirred at 00°C for 2 hours.

After the reaction, the mixture was filtered, washed with water, and dried to obtain 98 parts of black powder.

This resin powder was mixed with a charge control agent (tetraoctylammonium chloride) and a carrier (iron powder) in the same manner as in Example 1 to obtain a black toner composition. The durability was grade 7, indicating good properties.

Example 3 1.6 parts of 111ff of the phthalocyanine compound of the above formula (+) and 80 parts of bisphenol A were dissolved in 250 parts of 0.
After 60 parts of hexamethylene diisocyanate was added dropwise at 50° C. for 1 hour under a nitrogen atmosphere, the mixture was stirred at 100° C. for 4 hours. After cooling, 500 parts of ethanol was added under stirring, followed by filtration, washing with ethanol twice, washing with water, and drying. The yield is 14
There were 6 parts.

Charge adjustment i! of this resin powder was carried out in the same manner as in Example 1.
The 0 toner, which was mixed with pI (N-cetylpyridinium chloride) and a carrier (iron powder) to obtain a black toner composition, also gave a clear image and exhibited good light resistance of grade 7.

Examples 4 to 25 Black toner compositions were obtained in exactly the same manner as in Example 3 using the phthalocyanine compounds shown in Tables 1 and 2, and then copied.

This toner also gives clear images, It was in good condition.

Its durability is 7 Table-1 (Margin below) a-C1 -cl n-Br P-e! □! 'l5 P-C+aH! □１ p-cd)1 0 Fear-CilisO -Ce O-C)Is o-C,! ! ,drop o-C2H@O Layer-C) 1ffO -CJs o-CsH+F o-Ci! .

Stomach - Br Table - 2 Procedural Chief Ho Ho's official seal) April 1990, Director General of the Japan Patent Office Yoshi 1) Moon Takeshi 1, Indication of the case 1999 Patent Application No. 32644 2, Name of the invention colored Toner composition 3, relationship with the case of the person making the amendment Patent originator's address 3-2-5-4 Kasumigaseki, Chiyoda-ku, Tokyo Number of inventions increased by the amendment 6 Contents of the amendment (3) Specification No. On page 10, line 10, "polymethyl methacrylate" is corrected to "polymethyl methacrylate J.

(4) Description on page 12, line 20 of the specification: ``Add the following words after 500 copies of hot water.''

Add r (5) MeimlF, page 13, line 117

Claims (1)

[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(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 represents the same group. If R^1 is a hydroxyl group, R
^2 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 R^2's represent the same group. Moreover, n represents an integer of 2 to 4. ] A colored toner composition characterized in that a phthalocyanine dye represented by the following is introduced into a resin through a covalent bond.