JPS59197053A - Developer - Google Patents

Abstract

PURPOSE:To obtain a developer stabilizing the extent of triboelectric charge between toner and carrier, making the distribution of the extent of triboelectric charge sharp and uniform, and capable of controlling the extent of electrostatic charge to that suitable for a developing system used by adding thiazine or a thiazine deriv. CONSTITUTION:Thiazine represented by formula I , II, III or IV or a thiazine deriv. represented by formula V or VI (where each of R1-R3 is H, halogen, alkyl, phenyl, OH, NO2 or the like) is added. The resulting developer stabilizes the extent of triboelectric charge among toner particles or between toner and carrier, makes the distribution of the extent of triboelectric charge sharp and uniform, and can control the extent of electrostatic charge to that suitable for a developing system used. When development is carried out with the developer, a fogging phenomenon and the scattering of the toner at the peripheral part of a latent image are not caused, high image density is attained, and the halftone part is well reproduced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer used in electrophotography, electrostatic printing, etc., and particularly to a positively charging developer.

Conventionally, as an electrophotographic method, U.S. Patent No. 2.297,69
A number of methods are known, such as in the specification of No. 1.

Further, a developing method for visualizing an electrical latent image using a developer (generally toner) is described, for example, in U.S. Patent No. 2.874,0.
No. 63, No. 2,618,552, No. 2,221,77
Various methods are known, as described in the specifications of No. 6 and No. 3,909,258.

As toners applied to these developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 μm are used as toner. As the magnetic toner, one containing magnetic particles such as magnetite is used. In the case of a system using a so-called two-component developer, the toner is usually mixed with carrier particles such as glass beads and iron powder.

Positive charge control agents used in such dry developing toners include, for example, generally amino compounds, quaternary ammonium compounds, and organic dyes, particularly basic dyes and their salts. Common positive charge control agents include benzyldimethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, nigrosine base, nigrosine hydrochloride, 7-lanine gamma, and crystal violet. In particular, nigrosine base and nigrosine hydrochloride are used as positive charge control agents. These are usually added to a thermoplastic resin, heated and melted and dispersed, and then finely ground to adjust the particle size to an appropriate particle size as necessary before use.

However, these dyes used as charge control agents have complex structures, inconsistent properties, and poor stability. In addition, decomposition or deterioration occurs due to decomposition during thermal kneading, mechanical impact, friction, changes in temperature and humidity conditions, etc., resulting in a phenomenon in which charge controllability decreases.

Therefore, when a toner containing these dyes as a charge control agent is used for development in a copying machine, as the number of copies increases,
The dye decomposes or changes in quality, causing toner deterioration during durability. Furthermore, many of the substances generally known to be positively chargeable have a dark color, and therefore have the disadvantage that they cannot be incorporated into a bright chromatic developer.

In addition, many of the positive charge controllable dyes are hydrophilic, and due to poor dispersion in these resins, the dyes are exposed on the toner surface when the toner is crushed after melting. When these toners are used under high humidity conditions, they have the disadvantage that good quality images cannot be obtained because these dyes are hydrophilic.

In this way, when a conventional dye having positive charge control properties is used in a toner, the toner particles are formed between the toner particles, between the toner and the carrier, or between the toner and the toner carrier such as a sleeve. Variations 5 occur in the amount of charge generated on the particle surface, causing problems such as development fog, toner scattering, and carrier contamination. Moreover, these phenomena become particularly noticeable when a large number of copies are made, and the result is practically unsuitable for copying machines.

Furthermore, under high humidity conditions, the toner image transfer efficiency is significantly reduced, making it unusable. Furthermore, even at room temperature and humidity, when the toner is stored for a long period of time, the toner often aggregates and becomes unusable due to the instability of the positive charge control dye used.

That is, an object of the present invention is to stabilize the amount of triboelectric charge between toner particles, between a toner and a carrier, or between a toner and a toner carrier such as a sleeve in the case of -component development, and to maintain a stable triboelectricity distribution. To provide a developer that is sharp and uniform, and whose charge amount can be controlled to suit the developing system used.

Still another object is to use a developer for faithfully developing and transferring the latent image, i.e., toner adhesion in the background area during development, without fogging or toner scattering around the etch of the latent image. To provide a developer capable of obtaining high image density and good halftone reproducibility.

Still another object is to provide a developer that maintains its initial characteristics even when the developer is used continuously over a long period of time, and that causes no toner aggregation or change in charging characteristics.

Another purpose is to develop a developer/agent that reproduces stable images unaffected by changes in temperature and humidity, especially a developer with high transfer efficiency that prevents scattering and transfer failure during transfer at high and low humidity. It is provided by.

Another objective is to provide a developer with excellent storage stability that maintains its initial characteristics even during long-term storage.

Still another object is to provide a bright chromatic developer.

The present inventors have solved the various problems associated with conventional positively charged toners as described above, and have developed an electrophotographic method that is uniformly and strongly positively charged, visualizes negative electrostatic charge images, and produces high-quality images. As a result of intensive research aimed at providing a developer for use in electrophotography, it was discovered that if the developer contains thiazine or a thiazine thread derivative as a positive charge control agent, an electrophotographic developer exhibiting various excellent properties can be obtained. I found it.

The developer toner contains binder resin, colorant, and
Use additives, etc. FIG. 1 is an explanatory diagram showing an example of a combination of toner components.

As the positive charge control agent, thiazine itself is of course effective, but its derivatives are preferred in consideration of handling and charging stability.

The following types of thiazine are known: (1), (1), and (Kl), all of which have the same substantial effects.

(1) (1) 4H-1,4-thiazine 2H-1,4-thiazine (
1) These derivatives include, for example, those with a 1,3-thiazine skeleton, and have the general formula (where, 几, , R, l R8e B+, is hydrogen,
halogen, alkyl group, artenyl group, alkynyl group,
alkoxy group, ester group, alkoxycarbonyl group,
Phenyl group, substituted phenyl group, hydroxy group, mercapto group, alkylmercapto group, imino group, phenyl imino group, cyano group, substituted azo group, diazoamide group, ureido group, oxo group, or nitrogen, sulfur or oxygen group. Which of the heterocycles it contains! Represents a substituent. ), 1
, 4-thiazine as a skeleton is represented by the general formula (where R, , , R, , R, , R represent the same meanings as above).

The charge control effect of these substituents on thiazine derivatives basically depends on the thiazine skeleton, and color and melting point vary depending on the selection of various substituents, and these may be selected as necessary.

Methods for incorporating at least one of these thiazine or thiazine thread derivatives into the developer include a method of adding it inside the toner particles (internal addition) and a method of adding it to the outside (external addition). When internally added, the content is preferably 0.5 to 50 parts by weight per 100 parts by weight of the donor binder resin. In addition, when externally added, for 100 parts by weight of resin,
0.01 to 40 parts by weight is desirable.

As the binder resin of the toner, monopolymers of styrene and its substituted products such as polystyrene, polyP-chlorostyrene, and polyvinyltoluene; styrene-P-chlorostyrene copolymers, styrene-propylene copolymers, and styrene-
Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, Styrene-ethyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-alpha chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinylethyl ether copolymer, styrene-vinyl methyl carbon copolymer, styrene-butadiene copolymer,
Styrenic copolymers such as styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, Butyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic resin, tetradine, modified rosin, terpene resin, phenol resin, aliphatic or Alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, etc. can be used alone or in combination.

Any suitable pigment or dye can be used as a colorant in the toner of the present invention. For example, carbon black,
There are known dyes and pigments such as iron black, 7-thalocyanine blue, ultramarine blue, quinacridone, and benzidine yellow. When the toner is a magnetic toner, conventional materials such as ferromagnetic elements and alloys and compounds containing them such as iron, cobalt, nickel, and manganese such as magnetite, hematite, and ferrite, and other ferromagnetic alloys are used. It may also contain magnetic powder known as a magnetic material. Additives may be mixed with the toner as necessary. Such additives include, for example, lubricants such as Teflon and zinc stearate, or fixing aids (such as low molecular weight polyethylene), as well as flow agents, anti-caking agents (such as tetrahydrocylene), or conductive agents. Examples of the imparting agent include metal oxides such as tin oxide.

It is also possible to have the above toner structure supported on the wall material, the core material, or both of them in the microcapsule toner. The toner is mixed with carrier particles such as iron powder, glass beads, nickel powder, and ferrite powder as necessary.
It may also be used as a developer for electrical latent images. When manufacturing toner, after kneading the constituent materials well using a heat kneading machine such as a hot roll, kneader, or extruder,
A method of obtaining by mechanical crushing or classification, or a method of obtaining by spray drying after dispersing the material in a binder resin solution, or a method of obtaining by spray drying after dispersing the material in a binder resin solution, or after mixing the specified material with the monomer that should constitute the binder resin. , a polymerization method to obtain a toner (by polymerizing this emulsified suspension), a toner production method, and other methods can be applied.

The developer of the present invention can be applied to various development methods. For example, a magnetic brush development method, a cascade development method, a method using a conductive magnetic toner described in U.S. Pat. A method using
Examples include methods described in Japanese Patent Nos. 4-42141, 55-18656, and 54-43027, fur brush development methods, powder cloud methods, and impression development methods.

Further, when the developer is held in a developer carrier such as a sleeve, it is possible to use magnetic force, Coulomb force, electrostatic force, image force, mechanical force, etc.

Examples will be described below, but the present invention is not limited thereto. In addition, all parts are parts by weight.

[Synthesis Example 1] While stirring a solution of benzoyl chloride 6,79 (0,048 mol) and dry acetone 20 cc at 30°C, 4.7 f (0,048 mol) of powdered potassium thiocyanate was added.
and 3Qcc of dry acetone.

The reaction mixture is then heated to boiling point for 5 minutes.

3-4-3-phenylpropylamine hydrochloride (produced from 1-phenyl-3-aminopropatol hydrochloride and thionyl chloride. Melting point 114-117
A suspension of 9.7 f (0,048 mol) and 100 cc of dry acetone is added, and then powdered potassium carbonate 6,69 (0,048 mol) is slowly added. 8
After refluxing for an hour, an additional 6.69 g of potassium carbonate was added to the coolant, the reaction mixture was stirred at room temperature for 30 minutes, passed through a suction port while refluxing for 30 minutes, the liquid was evaporated in vacuo, and the residue was removed. Remove from ethanol and neutralize with ethereal hydrochloric acid. After adding excess ether, 2-benzoylamino-6-phenyl-4H-5,6-sihydro-1,3-
Thiazine hydrochloride (compound 1) separates out in the form of a colorless precipitate. The melting point of this material was 196-198'O.

Next, the human tetrachloride 8.3 f (0,025 mo/
I/) is heated under reflux for 3 hours with 5 cc of 2N hydrochloric acid.

The cooled reaction mixture is made alkaline with dilute sodium hydroxide solution and extracted several times with ether. After removing the ether in vacuo, the residue is taken up with ethanol and mixed with ethanolic hydrochloric acid until the reaction is slightly acidic, then with ether.

2-Amino-6-phenyl-4H-5,6-sihydro-1,3-thiazine hydrochloride (compound 2) is thus precipitated. The melting point was 202-204'0.

The following compounds are obtained by a similar method.

2-Amino-4H-4-(3'-chlorophenyl)-5
,6-sihydro1,3-thiazine hydropromide. Melting point 112-115°0 (Compound 3) 2-amino-4H
-6-(4'-methoxyphenyl)-5,6-sihydro-1,3-thiazine.

Melting point: 137°0 (Compound 4) [Synthesis Example 2] 3.6 g of N-methylthiourea and 7.6 g of ethyl 2-methoxymethylene-3-ethoxypropionate were dissolved in 300 ml of ethanol, and 8 ml of concentrated hydrochloric acid was added thereto. Reflux on water bath for 7 hours. The reaction solution was concentrated under reduced pressure, the residue was neutralized with sodium hydrogen carbonate, and then extracted with ethyl acetate. After washing the extract with water and drying, the solvent was distilled off, and the remaining liquid was treated with nityl to give 2-methylamino-5-ethoxycarbonyl-6.
2.2 g of H-1,3-thiazine was obtained. This product was recrystallized from benzene to obtain colorless scale crystals with a mp of 108-109°C. (Compound 5) N,N'-dimethylthiourea 1.09.2-methoxymethylene-3-ethoxypropionic acid ethyl/I/1.
9g and 2.0ml of concentrated hydrochloric acid! 100m
reflux on a water bath for 6 hours. After repulsion, concentrate under reduced pressure, neutralize the residue with hydrogen carbonate solution, and extract with chloroform. After washing the extract with water and drying, the solvent was distilled off, 15% hydrochloric acid was added to the residue, and the mixture was extracted with ethyl acetate.The hydrochloric acid layer was neutralized with sodium hydrogen carbonate, and extracted with ethyl acetate.
After drying the extract, the solvent was distilled off and 2-methylimino-3
-Methyl-5-ethoxycarbonyl-2,3-dihydro-6H-1,3-thiazine 0.711 was obtained.

This product is recrystallized from petroleum benzine, mp 51-53
C. colorless prism crystals were obtained. (Compound 6) [Synthesis Example 3] Assimilated potassium 61 y (o, 094 mol) was dissolved in water 1.5
25.411 (0,094
A solution of mol) dissolved in 380 cc of water was dropped over 10 minutes. The mixture was stirred at room temperature overnight, then acidified with 48% hydrobromic acid and heated to 40° C. with stirring for 3 hours. After adding 10 F of activated carbon, the mixture was stirred for a further 2 hours at 40°C, filtered and the resulting solution was evaporated under vacuum at 70°C.

The pale yellow solid residue was slurried with a small amount of ice-cold water, filtered off with suction, and recrystallized using ethanol. Hydrobromide of 2-amino-4H-5,6-cyhydro-6-phenyl-1,3-thiazine (melting point 196°
0) was obtained.

(Compound 7) The following compounds were synthesized in a similar manner.

2-amino-4H-6(4'-methoxyphenyl)-5
,6-sihydro-1,3-thiazine.

Melting point 137°0 (Compound 8) 2-amino-4H-4-(2'-chlorophenyl)-5
, 6-dihydro-1,3-thiazine.

Melting point 132°C (Compound 9) 2-amino-4H-4-(2'-methylphenyl)-3
, 6-dihydro-I+3-thiazine.

Melting point 124-129°C (compound 10) 2-ami7-4
H-4-(3'-acetylaminopheni#)-5,6-
Sihydro 1,3 thiazine△. Melting point: 179-181'0 (Compound 11) [Synthesis Example 4] 38f of 3-benzyl-4-methyl-4-thiazolium chloride was suspended in 270ml of N,N-dimethylformamide, and while stirring under cooling with ice water, triethylamine 3
4 g, 3 f of water, then 81.4 f of benzoylphos 7-ionic acid diethyl ester were added, and after stirring for 10 minutes, 10~
Stir for 20 minutes at 18°C. The mixture was further heated and stirred at about 110°C for 7 hours, and N,N-dimethylformamide was distilled off under reduced pressure at a temperature below 50°C. Dissolve the residue in benzene to 10%
After washing with sodium hydroxide, 10% hydrochloric acid and then water, drying over magnesium sulfate and distilling off benzene. Add a small amount of ethanol to the residual oil, polish with water cooling, collect the precipitated crystals by filtration, and recrystallize from 99% ethanol to obtain a melting point of 79-8.
2-phenyl-4-benzyl-5-methyl-2°3-dihydro-4H-1,4-thiazin-3-one was obtained as colorless crystals of 1°0. (Compound 12) [Synthesis Example 5] Salicylaldehyde-thiosemicarbazone 9f and β-propiolactone 9f were dissolved in 80 m/g of glacial acetic acid, heated to reflux for about 3 hours, and then cooled to precipitate crystals. After washing and recrystallizing from glacial acetic acid, white needle-like crystals with a melting point of 248°C were obtained.
5.81 of 3-thiazin-4-one were obtained. (Compound 13) [Example 1] 100 parts of the above toner having an average particle size of 8 μm was mixed with 1000 parts of iron powder carrier to prepare a developer.

When this developer was used to print an image on a Canon NP-8500 copying machine, a good image with a bright blue color and no fog was obtained, and the image did not change even after printing 100,000 copies. There wasn't.

Also, under a high humidity environment of 35°C and 90% RH, and at 15°C.
Even under low humidity conditions of 10% RH, images with almost no difference from normal humidity were obtained.

[Example 2] When images were produced using a Canon NP-200 copying machine modified to form a negative charge latent image, good images with no fogging were obtained, and 10,000 copies were obtained. Even after image printing, the condition continued to be good. Also, 35℃, 90
Even under high humidity conditions of % RH and low humidity conditions of 15° C. and 10% RH, images with almost no difference from normal humidity were obtained.

[Examples 3 to 7] Instead of using compound 1 of synthesis example 1 in example 1, compounds 3 and 4 of synthesis example 1, compound 5 of synthesis example 2,
and 6, and Compound 7 of Synthesis Example 3 were used, respectively.
When the same experiment as in Example 1 was conducted, similarly good results were obtained.

[Examples 8 to 13] In Example 2, instead of using Compound 2 of Synthesis Example 1, Compounds 8, 9, 10, and 11 of Synthesis Example 3, Compound 12 of Synthesis Example 4, and Compound 13 of Synthesis Example 5 were used, respectively. When the same experiment as in Example 2 was carried out except for the use of this material, similarly good results were obtained.

[Comparative Example 1] When an experiment was conducted in the same manner as in Example 1 except that Compound 1 of Synthesis Example 1 was not used in Example 1, only images with low density and a lot of scattering and fog were obtained.

[Comparative Example 2] An experiment was conducted in the same manner as in Example 2 except that Compound 2 of Synthesis Example 1 was not used in Example 2. Images with a lot of fog were obtained. When 500 images were continuously obtained, I could only get a very faint image.

[Brief explanation of drawings]

Figure 1 is an explanatory diagram showing an example of a combination of toner components.
tP) Ro. Applicant Canon Co., Ltd.

Claims (1)

[Claims] A developer containing thiazine or a thiazine derivative.