JPH0367268A - Dry toner, dry developer and image forming method - Google Patents

Abstract

PURPOSE:To maintain such characteristics as high printing or image quality and nonscatterability of a toner by adding specified amts. of silica powder and magnetic powder of <=0.8 mum average particle size to the base of the toner and mixing them. CONSTITUTION:The base of a toner is composed essentially of a binding resin, a colorant and 0.5-5 wt.%, in total, of a metallic complex (C-1) of oxycarboxylic acid and a metallic complex (C-2) of an azo compd. as electrostatic charge controlling agents. The weight ratio of (C-1)/(C-2) is 1/9-9/1. Silica powder and magnetic powder of <=0.8 mum average particle size are added to the base by-.1-1 wt.% and 0.05-2wt.%, respectively, a metallic salt of fatty acid is further added by 0.01-0.5 wt.% as required and they are mixed. The resulting toner causes no printing trouble, ensures required printing density and fog resistance and can be used over a long period of time.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a dry toner, a dry developer, and an image forming method used in fields such as electrophotography and electrostatic recording. More specifically, high-speed continuous paper printers with a photoconductor circumferential speed of 50 cm/sec or more, high-speed cut paper printers with a photoconductor circumferential speed of 25 cm/sec or more and a printing speed of 60 sheets per minute or more, and organic photoconductive materials. The present invention relates to a dry toner, a dry developer, and an image forming method using the same, which are effectively used in a printer equipped with a photoreceptor comprising:

(Prior Art) The electrophotographic method is described in U.S. Patent No. 2,297,691, British Patent No. 1,165,406, and British Patent No.
, 165,405, a charging process using a photoconductive substance to apply an electrostatic charge to the photoreceptor, and an exposure process of irradiating light to form an electrostatic latent image. , a developing process in which toner is attached to the latent image area, a transfer process in which the toner image is transferred to a support, a fixing process in which the toner image is fixed to the image support by heat, pressure, flash light, etc., and toner remaining on the photoreceptor. It consists of a cleaning process to remove the static charge on the photoreceptor and an antistatic process to return it to its initial state.

These steps are repeated to obtain a number of printed materials.

Dry toners for developing electrostatic images used in the field of electrophotography include toners using polystyrene resin
4-16118), toner using styrene-butyl methacrylate copolymer resin (Japanese Patent Publication No. 56-11143)
toner using styrene-acrylic resin such as
A toner using a bisphenol-type epoxy resin obtained by reacting bisphenol and epichlorohydrin (Japanese Patent Application Laid-Open No. 57-96354), a toner using a polyester resin obtained by reacting a glycol having a bisphenol skeleton with a polybasic acid. (Tokuko Showa 52-2542
However, compared to other resins, styrene-acrylic resins can control the physical properties of the tree layer such as molecular weight, glass transition point, and melt viscosity over a wide range, and are extremely advantageous in designing toners. For some reason, most toner is made of styrene.
The market is dominated by toners that use acrylic resin.

In addition, in order to impart preferable negative chargeability to these toners, a substance that imparts negative chargeability to the binder resin 1, such as a metal complex of an azo compound (Japanese Unexamined Patent Publication No. 57-141452,
JP-A-58-111049, JP-A-58-208
Publication No. 750, etc.).

Metal complex of oxycarboxylic acid (JP-A-53-12772
6, JP-A-57-104940, etc.),...
Logenated paraffin (JP-A No. 48-97542,
JP-A-50-68140, etc.) is added.

Sweet. - There is also a method of mixing silica powder with the toner particles and adhering the silica powder to the surface of the toner particles after producing the toner particles.

Examples of devices to which the electrophotographic method using toner as described above is applied include printers, copying machines, and facsimile machines. In particular, printers are rapidly gaining popularity as terminal devices that can quickly handle a large amount of information from computers.

The types of printers are broadly classified into A4.
B4. Types such as letter and legal that use paper cut to a predetermined size (hereinafter referred to as "letter" and "legal").

There are two types: the cut paper printer (hereinafter abbreviated as "cut paper printer") and the type that uses seven sheets of continuous paper (hereinafter abbreviated as "continuous paper printer").The former type can print on both sides of the paper and is capable of high-density printing. It has many advantages, such as being able to carry out various tasks and being easy to handle, so it has been put into practical use.

By the way, in recent years, photoconductive materials used in electrophotographic photoreceptors installed in the above-mentioned equipment have been used.

Amorphous selenium, zinc oxide, and titanium oxide in this 1.

There has been a remarkable shift from inorganic materials such as cadmium sulfide to organic photoconductive materials that have no toxicity problems, have excellent transparency, flexibility, and lightness, and can be manufactured at low cost. A photoconductor made of a photoconductive material is one in which a photosensitive layer is formed on a conductive layer.

Organic photoconductors have recently shown excellent sensitivity.

A functionally separated type, in which the charge generation layer and the charge transport layer are different, has been widely used.

In general, the charge generating organic compounds contained in the charge generation layer include azoxybenzene-based, disazo-based, trisazo-based, benzimidacyl-based, polycyclic quinoline-based, indigoid-based, quinacridone-based, phthalocyanine-based, perylene-based, Pigments such as methine are known &ll JP-A-47
-3754 Bone No. 18543, JP-A-47-18544, JP-A-48
-43942, JP-A-48-70538, JP-A-4
9-1231, JP-A-49-105536, JP-A-50-75214, and JP-A-50-92738) as organic compounds that transport charges contained in the charge transport layer.

Pyrazoline derivatives ( Journal of Photo
graphicScience and Engineering
eering Volume 21, No. 2.

73 pages, 1977), oxazole derivatives (JP-A-55-35319, JP-A-58-87557, and JP-A-58-182640), hydrazone derivatives (JP-A-54-59143, JP-A-58-182640), Showa 54-1501
28 and JP-A-55-46760), enamine derivatives (Journalof Imaging Sci.
ence, Vol. 29, No. 1, p. 7, 1985).

(Problem to be Solved by the Invention) However, although the toner used in this electrophotographic photoreceptor having an organic photoconductive layer causes no problems during initial printing, after printing several dozen sheets, Decrease in print density,
Printing problems such as uneven print density and inability to obtain a visible image were likely to occur.

In general, the above-mentioned conventional toner has no problems with its initial charging properties, but when used repeatedly, the charging properties deteriorate and the toner scatters, resulting in contamination inside and outside the device and dirt on the printed background (hereinafter referred to as "contamination"). .

In many cases, the print density was lower than that of a practical level and became difficult to read due to increased electrostatic charge. This tendency is not a big problem in copying machines due to the nature of the documents handled, but photoconductors used as computer terminals have a much higher load on the paper, toner, and developer per unit time. Circumferential speed is 25
This problem is particularly noticeable in high-speed continuous paper printers and high-speed cut paper printers that operate at speeds of cm/sec or higher.9 This is a serious problem.

Additionally, cut paper printers have several problems compared to continuous paper printers. For example, when transferring a toner image from a photoreceptor to an image support such as paper, a charge of opposite polarity to the toner is applied from the back side of the image support by a transfer device, but if the load is increased.

Although toner transfer efficiency is high and high-quality images can be obtained, the probability of occurrence of so-called jam, in which the image support sticks to the transfer device, increases. On the other hand, if the charge from the transfer device is reduced, jams will not occur.

The amount of toner transferred is small, resulting in a poor image. Sweet.

After printing on the front surface, passing through a fixing process, and then printing on the back surface, the image is likely to be disturbed due to changes in the water content of the image support and the occurrence of fine wrinkles.

The present invention solves each of the above problems.

Even when used in an electrophotographic photoreceptor having an organic photoconductive layer, the toner does not cause any printing failure, has the printing density and capri resistance required as a toner, and can withstand long-term use. It is an object of the present invention to provide a long-life dry toner, a dry developer, and an image forming method.

Another object of the present invention is to provide a dry toner, a dry developer, and an image forming method that are effective for use in high-speed printers, do not cause jams, and do not disrupt images even in cut paper printers.

(Means for Solving the Problems) The present invention uses a metal complex of oxycarboxylic acid (C-1) as a binder resin (A), a colorant (B), and a charge control agent (C).
) and an azo compound metal complex (C-2) as essential components, and the weight ratio of (C-1)/(C-2) is 1.
/9 to 9/1, silica powder was added to the toner base containing 0.5 to 5 weight more of the total amount of (C-1) and (C-2), and fatty acid metal salt was added to the toner base. A dry toner made by adding and mixing 0.01 to 0.5% by weight to the toner base,
The present invention relates to a dry developer containing the same and an image forming method using the same.

As the binder resin fA) of the dry toner of the present invention, styrene-acrylic resin or polyester resin is preferable.

Examples of monomers that form the base of the styrene-acrylic resin include the following.

Styrene, α-methylstyrene, p-methylstyrene,
Styrene derivatives such as pt-butylstyrene, p-chlorostyrene, and hydroxystyrene.

Methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, hebutyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate 1 methacrylate Dodecyl, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate.

Butoxyethyl methacrylate, methacrylate diethylene glycol, ethoxydiethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxytriethylene glycol methacrylate, methoxydipropylene glycol methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetra methacrylate Ethylene glycol, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, N-vinyl-2 methacrylate
-pyrrolidone, methacrylonitrile, methacrylamide, N-methylolmethacrylamide, methacrylic acid 2-
hydroxyethyl, hydroxypropyl methacrylate,
Hydroxybutyl methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, phthalimidoethyl methacrylate, phthalimidopropyl methacrylate, morpholinoethyl methacrylate.

Methac: Morpholinopropyl norate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diacetone methacrylamide, acrylic acid, methyl acrylate, ethyl acrylate.

Propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, butyl acrylate, octyl acrylate, nonyl acrylate.

Decyl acrylate, undecyl acrylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxy acrylate Triethylene glycol, methoxydibrobylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, benzyl acrylate,
Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, N-vinyl-2-pyrrolidone acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, acrylic acid 2-hydroxy-3-phenyloxypropyl, glycidyl acrylate, acrylonitrile,
Acrylamide, N-methylolacrylamide, diacetone acrylamide, vinylpyridine, phthalimidoethyl acrylate.

Phthalimidopropyl acrylate, morpholinoethyl acrylate, morpholinopropyl acrylate.

Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid 1 For example, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate , 1゜5-bentanediol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, hydroxypivalic acid neo Pentyl glycol ester dimethacrylate, trimethylol ethane trimethacrylate, trimethylol propane trimethacrylate, pentaeryth J soto trimethacrylate, pentaerythritol tetraacrylate, tris methacryloyl ethyl phosphate, bis(methacryloyloxyethyl) hydroxyethyl isocyanurate, tris(methacryloyl) (oxyethyl)in cyanurate, ethylene glycol diacrylate, 1゜3-butylene glycol diacrylate, 1,4-butanediol diacrylate,
1.5-pentanediol diacrylate), 1.6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene diacrylate, hydroxypiparic acid Neopentyl glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trisacryloxyethyl phosphate, bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, tris(methacryloyl) (oxyethyl)in cyanurate, half esters of glycidyl methacrylate and methacrylic acid or acrylic acid, half esters of bisphenol-type epoxy resin and methacrylic acid or acrylic acid, norphesters of glycidyl acrylate and methacrylic acid or acrylic acid. monster.

Among these monomers, those having one vinyl group in one molecule are preferred.

Examples include styrene, styrene derivatives, methacrylic esters, acrylic esters, and alkyl esters of methacrylic acid or acrylic acid having 1 to 5 carbon atoms in the alkyl group are particularly preferred.

Preferred examples of monomers having two or more vinyl groups in one molecule include divinylbenzene, dimethacrylates and diacrylates of alkylene glycols having 2 to 6 carbon atoms. 20% by weight is used.

Mixtures of the various monomers mentioned above can be used in solution polymerization, bulk polymerization, emulsion polymerization,! ! The binder resin for the toner of the present invention can be obtained by polymerizing by any method such as cloud polymerization. In this polymerization, the polymerization initiators used include acetyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl percarbonate, Di-2-ethylhexyl perdicarbonate, acetylcyclohexane sulfonyl peroxide, tert-butyl peracetate, perisobutyl (jll tert-butyl, azobisisobutyronitrile, 2,2'-azohis-2,4-dimethylvalero) Nitrile, 2,2'-azobis-4-methoxy-24
-dimethylvaleronitrile, per2-ethylhexanoic acid t
Known polymerization initiators such as ert-butyl and tert-butyl perbenzoate are used. It is preferable that these are used in an amount of 0.1 to 15% by weight based on the total amount of monomers. Puta. It is preferable to use it dissolved in a monomer.

The following raw materials can be mentioned as the base material of the polyester resin used in the present invention.

The alcohol component is polyoxypropylene (Z2)
-2,2-bis(4-hydroxyphenyl)propane,
Polyoxypropylene (3,3)-2,2-bis(4-
Hydroxyphenyl) propane, polyoxyethylene (
General formula of 2-0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(10)-polyoxyethylene(2,0)-2゜2-bis(4-hydroxyphenyl)propane, etc. Diol, ethylene glycol, diethylene glycol, represented by (in the formula, +R1 and H are an ethylene group or a propylene group, X and y are each an integer of 1 or more, and the average value of the sum is 2 to 7); Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, isopentyl glycol, hydrogenated bisphenol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol,
Xylylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylalpropane, pentaerythritol, bis-(β-
hydroxyethyl) terephthalate.

Tris-(β-hydroxyethyl)in cyanurate,
2,2.4-)riftylpentane-1,3-diol, etc., and an oxycarboxylic acid component can be further added. For example, p-oxyamne, e, aromatic acid.

These include vanillic acid, dimethylolpropionic acid, malic acid, tartaric acid, and 5-hydroxyisophthalic acid.

On the other hand, specific examples of acid components include malonic acid, succinic acid, glutaric acid, timer acid, phthalic acid, isophthalic acid, dimethyl isophthalate, dibutyl terephthalate, dimethyl terephthalate, and monomethyl terephthalate.

Tetrahydrophthalic acid, methyltetrahydrophthalic acid,
Hexahydrophthalic acid, dimethyltetrahydrophthalic acid, endomethylene hexahydrophthalic acid, naphthalenetetracarboxylic acid, diphenolic acid, trimellitic acid, pyromellitic acid, trimesic acid, cyclopentanedicarboxylic acid, 3.3. '4.4'-benzophenonetetracarboxylic acid, 1,2,3.4-phthanetetracarboxylic acid, 2.2'-bis-(4-carboxyphenyl)propane, trimellitic anhydride and 4.4' -diimidocarboxylic acid obtained from diaminophenylmethane, tris-(
β-carpoxyethyl)in cyanurate, isocyanurate m-containing polyimide polycarboxylic acid obtained from isocyanurate ring-containing polyisocyanurate and trimellitic anhydride 9, 3-conversion reactant of for example tolylene diisocyanate, xylylene diisocyanate or isophorone diisocyanate and isocyanurate m-containing polyimide polycarboxylic acid obtained from trimellitic anhydride. One or more of these may be used.

Furthermore, the polyester resin used in the present invention is as follows.

Performances such as pigment dispersibility and fixing properties can be improved by adding monohydric carboxylic acid or monohydric alcohol to some of the constituent components. Such compounds include phenylacetic acid,
o-Toluic acid, cyclohexanecarboxylic acid, caprylic acid, lauric acid, myristic acid, valmitic acid, stearic acid, benzoic acid.

Monovalent carboxylic acids such as p-tert-butylbenzoic acid, stearyl alcohol, lauryl alcohol, ethyl cellosolve, butyl cellosolve, methylcarpitol,
There are monohydric alcohols such as butyl carpitol and benzyl alcohol. When used, the amount of these added is 0.1 to 10.0% by weight, preferably 1 to 0.0% by weight, based on the total amount charged.
It is desirable to increase the weight by 5 to 5.0. If it is less than 0.1% by weight, no modification effect can be expected, and if it exceeds 10.0% by weight, blocking resistance tends to decrease.

Polyester resins obtained from these raw materials are produced by conventional methods. For example, an acid component and an alcohol component are charged into a reaction vessel at a predetermined ratio, and an inert gas, such as N!
The reaction is started at a temperature of 150-190°C while blowing gas. Low molecular weight compounds produced as by-products are continuously removed from the reaction system. After that, the reaction temperature was further increased to 210-250℃.
to accelerate the reaction and obtain the desired polyester resin. When manufacturing polyester resin, 1'1! When the carboxylic acid component used is a free carboxylic acid compound that does not contain an ester group, the esterification catalyst 1 may be an organic metal such as dibutyltin dilaurate or dibutyltin oxide, or a metal alkoxide such as tetrabutyl titanate. If the carboxylic acid component is a lower alkyl ester, use a transesterification catalyst (9) such as a metal acetate such as zinc acetate, lead acetate, or magnesium acetate, or zinc oxide. , metal oxides such as antimony oxide, metal alkoxides such as tetrabutyl titanate, etc., at a rate of 0.0% relative to the total amount of raw materials charged.
0.005 to 0.05 weight may be used.

The binder resin for toner of the present invention has a glass transition temperature of 50 to 9.
It is particularly advantageous if the temperature is adjusted to 0°C.

If the glass transition temperature is less than 50° C., the toner is likely to cause caking (a phenomenon in which toner particles aggregate to form lumps) during storage or in a developing machine. Further, when the glass transition temperature exceeds 90° C., when the toner is manufactured by a process of melting, mixing, and pulverizing into nine classifications.

The grinding process takes time and tends to reduce productivity.

Furthermore, if the method of fixing the toner to the transfer material is a heat roll method or an oven method, the fixing temperature must be increased, which goes against energy savings.

In addition to the above-mentioned binder resin, in the dry toner of the present invention,
Other resins may be used, or two or more types may be used in combination.

Other resins include KR-216, KR-220,
KR, -152, KR-271, KR-255 (manufactured by Shin-Etsu Chemical), 5R-2400゜5R-2406,
8H-840 (all silicone u), etc. (D silicone resin, norbornene polymer of l-Solex (manufactured by CdF Cheminck).

C-20OA, C-25OA (manufactured by Mitsubishi Kasei ■).

Polyester carbonate such as Kneepilon P-1000 (manufactured by Mitsubishi Gas Chemical ■), Lignol R-70°R-12
Xylene resin such as 0, R-140, P-2 (all made by Lignite), Ebiko) 1004゜1007.1009
, 1010. YL-903゜906, Epicote 604
(Manufactured by Shell).

Epoxy resins such as Ebomisoku R304, R307, R309 (manufactured by Mitsui Petrochemical Industries ■), Nitzball BR-
1220, 1032, 1441, Nippor lR220
0, Nimball NBR.

Diene resins such as 20578.2007J (manufactured by Nippon Zeon ■), PC4BSIN 2F (, 3H).

8H, 11 people (manufactured by Hitachi Chemical), ATR200
5, 2009, 2010, HTFL-1゜HTR-2 (
(manufactured by Kao ■), FCO17,034゜035.036
Commercially available polyester resins such as (manufactured by Mitsubishi Rayon), phenolic resins, terpene resins, coumaron resins, amide resins, amide imide resins, butyral resins, amino resins, urethane resins, ethylene/vinyl acetate copolymers, ethylene/acrylic esters There are copolymers, etc. In the present invention, it is particularly preferable that the styrene-acrylic resin is used as the main component, and other resins are used in the toner in an amount of 0 to 30% by weight.

The binder resin (A) in the present invention includes residual monomers and/or
Or, it is preferable that the content of the solvent is 0.15 weight or less! Yes. Residual monomer and/or solvent content is 0.1
If the weight exceeds 5, there is a tendency for the probability that printing problems such as a decrease in print density or uneven print density will occur during mounting to occur.

Among these, the amount of residual monomer and/or solvent can be measured by gas chromatography or the like. For example, create a gas chromatograph calibration curve for each monomer or solvent, dissolve the copolymer in a certain amount of solvent, apply it to the gas chromatograph, and use the calibration curve to quantify each residual monomer or residual solvent. can do. A lawsuit.

In the Examples described later, quantification was performed using this method.

It is preferable that the binder resin (Al) is incorporated in the toner matrix in a mass amount of 60 to 94.5%. If this amount is less than 60% by weight, the toner binding force to the toner image support is weak, and the toner When the image support is bent and rubbed, toner images are likely to be missing and printing problems may occur.On the other hand, if the binder resin exceeds 94.5% by weight, the toner image may be missing. Print quality tends to be poor due to insufficient hiding power of the image.

Colorants CB) include carbon blank, nigrosine dye, acetylene blank, aniline black, cyanine blank, graphite, black colorants such as iron black, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chrome yellow, naphthol yellow, Hansa yellow. , yellow coloring agents such as Hygment Yellow, Benzidine Yellow Permanent Yellow, Quinoline Yellow Lake, Anthrapili ε Gin Yellow, a-covering coloring agents such as Permanent Orange, Molybdenum Orange, Palcan Fast Orange, Benzidine Orange, and Indanthrene Brilliant Orange.

Iron oxide, amber, brown colorants such as permanent brown, red bengal, rose bengal, antimony powder, permanent red, fire red.

Brilliant Carmine, Light Fast Red Toner, Permanent Carmine, Pyrazolonelet, Bordeaux, Heliobordeaux, Rhodamine Lake, Dupont Oil Red, Thioindigo Red.

Red colorants such as thioindigo maroon, watching red strontium, cobalt violet, first violet, dioxazine violet.

Purple colorant such as methyl violet lake, Methi L/
7 Flu+ Aniline blue, cobalt-flucerulean blue, calco oil blue, metal-free phthalocyanine blue, phthalocyanine blue, ultramarine blue, indanthremble-blue colorants such as indigo, chrome green, cobalt green, pigment green B
Pigments or dyes such as green colorants such as green gold, phthalocyanine green, malachite green oxalate, polychrome bromo copper phthalocyanine, etc.

There are metal oxide powders such as titanium oxide and zinc oxide.

Among these, it is preferable to use carbon black.

As a carbon blank, carbon black◆30.
32. 33. 40. φ44. 45° 50. 52. 55. φ600. MCF-88゜MA-10
0, MA-600, MA-11 and MA-8 (all manufactured by Mitsubishi Kasei (?11), Zuben 11,15°30.35
．． 40, 50, 150, 410, 420°430.45
0,500,825,850,890H,890,10
00,1020,1030,1035°1040.10
85,1170.1200,1250°1255.15
00,1800,2000,2100°3500.52
50, 5750, 7000, 8000 and 8800 pen series, Neo Spectra Mark I, Mark ■,
Mark ill, AG and TA's Neo Spectra series, Statex F-12 and Statenx B-12.
Moraco H and Moraco LS, Conductex SC,
950,975 beads (manufactured by Columbia Carbon), Monarch 700,800,880,900,100
0゜1100 and 1300 Monarch series, Mocal L, IJ-tj Le 400R, 660J 500
R.

330J 300R, 99R, 660, 500゜400
．． 330, 3001.991 and 99 legal series, blank pearls 700, 800° 880.900
, 1000, 1100, 1300°L and 2000 Blank Pearls series, Palkan XC-72R and Palkan X-72, Elftex 8. Elftex 1
2. Those overwritten as Stellling R (manufactured by Cavont Co., Ltd.) and the like can be used. These colorants (
B) is.

It is preferable that the toner be blended in an amount of 2 to 15% by weight, more preferably 4 to 12% by weight. Particularly preferred is 6 to 12 i'-folds. If the weight is less than 2, variations in printing density are likely to occur due to insufficient coloring power or unstable charging.

On the other hand, if the weight exceeds 15%, the adhesion to the toner image support is insufficient and toner scattering is likely to occur due to an insufficient amount of charge.

Among these carbon blanks, the oil absorption is 150cC/
100g or more, volatile content of 3.0% by weight or less, surface area of 240 m2/9 or more, especially oil absorption of 160cC/
100g or more, a volatile content of 20% by weight or less, and a surface area of 250m''/g or more.Oil absorption is carbon black 1009.
Add dibutyl phthalate dropwise.

Each time, mix thoroughly with a spatula and add 9 drops.

The kneading process is repeated until the entire mixture becomes a hard putty, which is the end point, and the amount of dibutyl phthalate required for this process is measured. The volatile content of carbon blank is about 95
It is measured as the percentage of weight loss after heating to 0°C. Cut 1
Surface area ij Braunauer-Emmett-T
It is measured by the nitrogen adsorption method (BET method) using the Eller method. In the present invention, if a carbon blank that does not meet these conditions is used.

It lacks charging stability and tends to cause toner scattering and changes in print density. Carbon blacks that meet the above conditions include Blank Barhas 2000 and Palcan
Commercially available products such as C-72EL, Palcan X-72 (manufactured by Cabo Soto), Conductex 950 beads, and Conductex 795 beads (manufactured by Columbia Carbon) are applicable.

The dry toner of the present invention has a band in the toner matrix! As a control agent (C), a metal complex of oxycarboxylic acid (C-i)
and a metal complex of an azo compound (C-2> is (C-1)/
(C-2) weight ratio 1/9 to 9/1. Good 1 Shikuba 1/9
~8/2, and the total amount of (C-1) and (C-2) is 0.
．． It is contained in an amount of 5 to 5 weight, preferably 1 to 3 weight.

If the weight ratio of (C-1)/(C-2) is less than 1/9, the amount of charge of the toner will decrease during repeated use over a long period of time, causing toner scattering and contaminating the inside and outside of the printer/copy machine. Also, a so-called capri phenomenon occurs in which toner adheres to the printed background area. on the other hand.

If this weight ratio exceeds 9/1, the amount of charge increases with repeated use, resulting in a decrease in print density. Further, if the amount of a is less than 0.5 weight in the toner matrix, the finishing characteristics of the band's WL amount will be poor.

Capri occurs because the amount of charge of the replenishing toner is small.

If the weight exceeds 5, the amount of charge is high from the beginning,
The print density is low, and the transfer performance from the photoreceptor to the toner support (often paper) is poor.

Problems such as poor cleaning performance of the photoreceptor occur.

In particular, as the metal complex (C-1) of oxycarboxylic acid,
The following - formation (denoted by Il is preferred).

-Formation (I); (In the formula, Arl and Ar2 represent residues of aromatic oxycarboxylic acid or its derivatives, and these may be the same or different. 9M1 represents a chromium or zinc atom; 1 person ヱ0 is , hydrogen ions, sodium ions.

Specific examples of compounds represented by general 2 (1) (representing potassium ions or ammonium ions) include a5-sita.
- zinc complex compound of shabutylsalicylic acid, zinc complex compound of 2-hydroxy-3-naphthoic acid, zinc complex compound of tert-butyl-2-hydroxy-3-naphthoic acid,
Chromium complex compounds of 3.5-ditertibutylsalicylic acid, chromium complex compounds of 2-hydroxy-3-naphthoic acid, chromium complex compounds of tert-butyl-2-hydroxy-3-naphthoic acid, etc. (respectively, hydrogen, sodium,
Contains potassium or ammonium ions. ).

Among them, Arl and Ar2 in -formation (1) may be the same or different.

As the metal complex (C-2) of the azo compound, in particular, the following -
Preferably, those shown by the formation (■) and/or the general 2G11).

General formula (■); (wherein, X! and X2 are hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or)
・Represents a rogen atom, ml and m2 are integers from 1 to 3,
nl and n represent 1 or 2 integers.

These may be the same or different (1M2 represents a chromium or zinc atom, and A2 represents a hydrogen ion, sodium ion, potassium ion, or ammonium ion). + nl and n2 are 1 or 2, and Sj) + Mz is chromium or zinc (containing hydrogen, sodium, potassium, or ammonium ions, respectively).

Among them, − formation (X of Ill, and X2+”l and m2 and n
l and n may be the same or different.

-Formation ([[I): % formula %() (wherein X3 and X4 are -NO,, -CH3, -8o3
H.

-CI! or -80,NH, represents kl and ni2ba1
or an integer of 2, which may be the same or different; 9M3 represents Cr or Zn; + A3 is a hydrogen ion.

Represents sodium ion, potassium ion or ammonium ion) Specific examples of compounds represented by the general formula ([[) are:

-NO2, -C
H5.

-803H, -CI! or −SO2NH2 + k
I and 2 are 1 or 2 (i.e. the substituent h
9. Compounds in which M3 is Cr or Zn (respectively hydrogen ions).

(containing sodium ions, potassium ions, or ammonium ions).

In addition, - X3 and Nagi (forming plate), two X3s together, two Nagis together, k1. ! :kg may be the same or different. Ota. X3 and Nagi may be bonded to any of the 2nd to 4th positions of the benzene ring.

When the photoreceptor is made of an organic photoconductive substance, a combination in which the metal complex of the oxycarboxylic acid is a zinc complex compound and the metal complex of the azo compound is a chromium complex compound is particularly favorable in terms of printing quality. .

Further, other known charge control agents may be further added to the toner matrix of the present invention. If kept, nigrosine dyes, fatty acid-modified nigrosine dyes, carboxyl group-containing fatty acid-modified nigrosine dyes, quaternary ammonium salts, amine compounds, organometallic compounds.

Examples include chlorinated paraffin and silica powder.

In addition, the toner of the present invention may contain additives CD as necessary.
) is included.

Such additives include ethylene, propylene, butene, pentene, hexene, heptene.

octene, nonene, decene, 3-methyl-aftene,
Polymers of olefin monomers such as 3-methyl-2-pentene and 3-propyl-5-methyl-2-hexene, or copolymers of the above-mentioned olefin monomers with acrylic acid, methacrylic acid, vinyl acetate, etc., stearic acid Lower alcohol esters of fatty acids such as butyl and propyl stearate, polyhydric alcohol esters of fatty acids such as casta wax (manufactured by Ito Oil Co., Ltd.), diamond wax (manufactured by Shin Nippon Chemical Co., Ltd.), palm acetate (manufactured by Nippon Oil & Fats Co., Ltd.),
Hoechstwax E, Hoechstwax-〇P (manufactured by Hoechst Akchengesellschaft), higher alcohol esters of fatty acids such as carnauba wax, Bisamide Blast Flow (manufactured by Nitto Kagaku Kogyo ■), Amide 6L,
Alkylene bis fatty acid amide compounds such as 78 and 6H (manufactured by Yoken Fine Chemical ■) and Hoechst Wax C (manufactured by Hoechst Akchengesellschaft).

Nimball NBJ 20578, 2007J.

Diene resins and hydroxyl group-containing vinyl resins with a weight average molecular weight of 50,000 or more, such as BR1220.

Examples include carboxyl group-containing vinyl resins.

These additives (D) reduce the adhesion of the toner image to the heat roll when the toner image fixing method is the heat roll fixing method, and reduce the adhesive force of the toner image to the heat roll when the toner image fixing method is the blade method. It serves to prevent damage to the photoreceptor by the blade, and is preferably added to the toner matrix in an amount of 0.1 to 20 weight, particularly 1 to 10 weight.

The above binder resin (A), colorant (B), charge control agent (
C) and other additives (D) added as necessary
H.

A toner matrix is manufactured through a homogenization process. For example, the above components are dry mixed using a Henschel mixer, and then micromixed in a molten state using a kneader.

Next, the cooled kneaded product is finely pulverized using a bottle mill or a jet mill to obtain a toner matrix having an average particle size of preferably 5 to 30 μm, particularly preferably 8 to 15 μm.

In the dry toner of the present invention, 0.1 to 1 weight of silica powder is added to the toner base.

Preferably, the weight is 0.2 to 0.8, and the average particle size is 0.8μ.
m or less magnetic powder by 0.05 to 2 weight, preferably tL<0.
5 to 1.5 weight, preferably in order to improve characteristics such as the life of the photoreceptor and developer.

Fatty acid metal salt is added in an amount of 0.01-0.5 weight, particularly preferably 0.02-0.2 weight, and if necessary, a modifier is preferably added and mixed in an amount of 1 weight or less. can get. Here, if the silica powder is less than 0.1 weight.

Fluidity and chargeability decrease. On the other hand, if it exceeds 1 weight, the fixing strength will decrease. Dimensions. If the amount of magnetic powder is less than 0.05% by weight, the charging property will decrease and toner scattering will increase.

On the other hand, if the weight exceeds 2, the amount of capri increases. ! Ta.

When the fatty acid metal salt is less than 0.01% by weight, printing problems tend to occur.

The lifespan of the photoreceptor and developer tends to be shortened.

If the weight exceeds 0.5, the fluidity of the toner will be extremely reduced, making it impractical, and it will tend to adhere to the photoreceptor and the inside of the developing machine. Furthermore, if the amount of the modifier exceeds 1 weight, fog will increase and fixing strength will also decrease.

Hydrophobic silica powder is most suitable as the silica powder used in the present invention. Such hydrophobic silica powder is a fine powder of silicon dioxide in which one surface silicon atom is a silanol group, such as octyltrichlorosilane or decyltricrylsilane.

Nonyltrichlorosilane, 4-isopropylphenyltrichlorosilane, 4-tert-butylphenyltrichlorosilane, dimethyldichlorosilane.

Dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dinonyldichlorosilane, didecyldichlorosilane, cytotesyldichlorosilane, 4-tert-butylphenyloctyldichlorosilane, dioctyldichlorosilane, didecenyldichlorosilane Chlorsilane, dinonenyldichlorosilane, di-2-ethylhexyldichlorosilane, 3.3-dimethylpentyldichlorosilane, trimethylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tritesilane, Hydrophobic groups are bonded to the surface silicon atoms of silicon dioxide particles via oxygen atoms by reacting with compounds such as dioctylchlorosilane, octyldimethylchlorosilane, and 4-isopropylphenyldiethylchlorosilane. be.

These silica powders have an average particle size of primary particles of 〃n mel. A value of 30-30 or less is preferable in terms of protecting the photoreceptor.

As such hydrophobic silica powder, Aerosil R9
72, Silica D-17. T-805. R812, RA2
00) I, RX-C (manufactured by Nippon Aerosil ■) and Taranox 500 (manufactured by Talco), Cab-0
-8il, M-5, MS-7゜MS-75, H8-5
, EH-5, 5-17, TS-720 (all manufactured by Cavonto), etc. are commercially available.

The magnetic powder used in the present invention is iron, manganese, nickel,
Metal powder such as cobalt, magnetite.

Copper-zinc ferrite, barium-nickel ferrite,
Preferred are various ferrites, such as dinokeru-zinc ferrite, manganese-zinc ferrite, lithium-zinc ferrite, magnesium-manganese ferrite, magnesium-copper-zinc ferrite, barium-nickel-zinc ferrite, and barium-copper-zinc ferrite. In particular, magnetite is favorable in terms of effectiveness and price. Regarding the present invention,
These magnetic powders used have an average particle size of 0.8 μm or less. If the average particle diameter exceeds 0.8 μm, the photoreceptor is likely to be damaged, resulting in poor printing properties in terms of image density and toner scattering. In addition, in terms of the dullness of the two images, particles with an average particle size of 0.1 μm or less are particularly favorable.

It was a cabinet. Magnetic powder has a long-chain aliphatic compound on its surface.

For example, stearic acid, oleic acid, valmitic acid, caproic acid, linoleic acid, ricinoleic acid, ricyllic acid,
Aliphatic dicarboxylic acids having 10 to 22 carbon atoms, their hydroxy-containing compounds, and their combination with zinc, magnesium, and calcium.

Cadmium, lead, iron, nickel, cobalt, copper.

Particularly preferred is one coated with aluminum salt, etc., in terms of bidispersity, adhesion to the toner base material, and print quality.

In addition, magnetic powder has a magnetization strength of 64±4 emu/g when the external magnetic field strength is 1K oersted, because it has a toner scattering prevention effect and magnetic powder is difficult to stay in the developing device. Especially nice.

Fatty acid metal salts used as necessary in the present invention include:
Metal salts of saturated or unsaturated fatty acids 1 such as maleic acid, stearic acid, oleic acid, valmitic acid, caproic acid,
Examples include salts of linoleic acid, ricinoleic acid or wasillic acid with zinc, magnesium, calcium, cadmium, lead, iron, nickel, cobalt, copper or aluminum.

Zinc stearate, calcium stearate or magnesium stearate, aluminum stearate are preferred. Among these, zinc stearate is particularly preferred since it exhibits good properties.

Other modifiers can be further added to the toner of the present invention, if necessary. Such modifiers include aluminum oxide, zinc oxide, and titanium oxide.

Examples include magnesium oxide, calcium carbonate, and polymethyl methacrylate. These can be used alone or in combination of two or more. These modifiers speed up toner charging. Improve print 1 image quality (density, fog, resolution 1 gradation, etc.).

Adjust resistance. Lowers the coefficient of friction with the photoreceptor.

This is preferable because it plays the role of removing toner components adhering to the photoreceptor and additive components of the image support.

The silica powder, magnetic powder, fatty acid metal salts and other modifiers used as necessary to be added to the toner base must be added in the above-mentioned specified amounts, and if all of these conditions are met, For the first time, this method effectively works to prevent toner scattering and fogging, and to achieve a high density of two printed images.

The toner base, silica powder, magnetic powder, fatty acid metal salt, and other modifiers can be mixed with a V-type mixer, a Henschel mixer, a Tarpura mixer hybridizer, etc., for example.

The dry toner obtained as described above and a carrier can be combined to form a dry developer of the present invention.

As a carrier, flat shape, cavernous shape, coin shape, 9 spherical shape,
Iron oxide powder in 9 different shapes including spherical, ferrite such as manganese, cobalt, nickel, zinc, tin, magnesium, lead, strontium, barium, lithium, etc., Teflon resin, acrylic resin, polyester resin, silicone resin, melamine Examples include iron oxide powder and ferrite whose surfaces are coated with resin, butadiene resin, butyral resin, etc., and particles made of kneaded materials of various resins and magnetic powder.

Among these, one in the present invention is copper-zinc ferrite, barium-zinc ferrite, barium nickel ferrite, nickel-zinc ferrite, manganese-zinc ferrite, lithium-zinc ferrite, and magnesium-manganese ferrite.

Various metal ferrites such as magnesium-copper-zinc ferrite, barium-nickel-zinc ferrite, and barium-copper-zinc ferrite can be used.

Copper-zinc ferrites are particularly well suited for the purposes of the present invention. Furthermore, carriers made of ferrite coated with acrylic resin are particularly preferred because they can be used repeatedly, have a long life, and have excellent environmental resistance! Yes.

The developer of the present invention is produced by mixing the above-described toner and carrier. The mixing ratio of toner is usually 1 to 10% more by weight than the total amount of toner and carrier.

Preferably, the weight is increased by 1 to 6. 1 layer! If it is less than -1, the density of the printed image will be low or the carrier will adhere to the photoconductor. So-called carrier stick is likely to occur.

On the other hand, when the toner mixing ratio exceeds 10% by weight, contamination inside and outside the printer due to toner scattering and fine staining of the printed background become noticeable.

The dry toner and dry developer of the present invention can be applied to various known development methods. The dry toner and dry developer of the present invention can be used in various fixing methods, such as oil-less and oil-coated heat roll methods.

It can be used for flash method, open method, etc.

Further, the dry toner and dry developer of the present invention can be used in various cleaning methods such as fur brush method and blade method.

The dry toner and dry developer of the present invention can be effectively applied to an image forming method in particular in combination with a photoreceptor made of an organic photoconductive substance.

As such a photoreceptor, a functionally separated type photoreceptor in which a highly sensitive charge generation layer and a charge transport layer are different is preferable.

The organic photoconductive substances that generate charges and are contained in the charge generation layer include azoxypencene, suazo, trisazo, benzimidacyl, polycyclic quinoline, indigoid, and quinacridone.

Phthalocyanine-based, perylene-based, methine-based pigments, and other pigments are known, and any of them can be used, but phthalocyanine-based pigments are particularly preferred. It was a residue. ! Pyrazoline derivatives, oxazole derivatives, hydrazone derivatives, enamine derivatives, and the like are known and used as organic photoconductive substances that transport charges contained in the charge transport layer.

Sweet. Polycarbonate resin is used as the binder resin for fixing these organic photoconductive substances to the support material.

Resins such as esterified polycarbonate resin, silicone resin, styrene resin, styrene-acrylic resin, polyamide resin, polyester resin, and polyvinyl alcohol are used.

Among these, a charge generation layer containing titanyl 7-thalocyanine as a gold component; A photoreceptor having a charge transport layer containing a gold component ('-methoxyphenyl)]vinylhydrazone has particularly excellent characteristics such as sensitivity, photoresponsivity, and dark decay. Ideal for image forming methods.

In the image forming method of the present invention, the electrostatic latent image formed on the photoreceptor is first visualized using the developer of the present invention, and then transferred to a support such as paper and then fixed to form a target image. You can get the image.

As mentioned above, the dry toner and dry developer of the present invention are suitable for use in high-speed continuous paper printers where the circumferential speed of the photoreceptor is 50 cm/sec or more, and where the circumferential speed of the photoreceptor is 25 cm/sec or more and the printing speed is 2, for example. Especially when used in image forming methods such as those for high-speed cut paper printers that print 60 sheets per minute or more on A-4 size paper.
This is the obtained image.

(Examples) The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 7 and Comparative Examples 1 to 7 (1) Production of copolymer R-1 Partially saponified polyvinyl alcohol (Denka Poval W-
24. Into a reaction vessel containing 2,000 parts by weight of an aqueous dispersion medium containing 3 parts by weight (manufactured by Denki Kagaku Kogyo ■), i, o o o parts by weight of the monomers shown in Table 1 and a polymerization initiator were added, and the mixture was heated with a nitrogen stream. The reaction was then carried out at 80 to 90°C for 10 hours.

A copolymer was obtained by filtering and drying with hot air.

(2) Production of copolymer R-2,3 1.000 parts by weight of xylene 1 1.0 parts of the monomer shown in Table 2
00 parts by weight and monomers, 3 parts by weight of azobisisobutyronitrile and 1 part by weight of 2-ethylhexyl peroxybenzony were added, and after reacting at 135°C for 8 hours, the mixture was dried in a vacuum dryer at 160°C. The xylene was distilled off and the resin L-
1 and L-2 were obtained. Next, a mixture of monomers, resins, and polymerization initiators having the compositions shown in Table 1 was prepared in the same manner as in section (1) above to obtain each copolymer.

Note 1) Thermomechanical analysis method, penetration mode, load 709. The same applies to the following examples.

1) Kölpermeation chromatography method, create a standard polystyrene calibration curve and convert, the same applies to the following examples.

Table 2 (3) Manufacture of toner base After premixing the ingredients shown in Table 3 in a batch using a Henschel mixer.

Molten metal in a twin-screw kneader I practiced.

Next, the cooled mixture was passed through a pin mill and a jet mill to obtain a toner matrix having an average particle size of 10 to 13 μm.

(4) Production of toner The formulations shown in Table 4 were mixed in a turbulence mixer to obtain a final toner.

Note 1) General formula + Ii CCA-1 General formula (If) - OCA-4 General formula (1) - CCA-2 Note 2) Characteristics of carbon black General formula (n) - OCA-3 Note 3) Viscol 660P; Sanyo Bonopropylene (5) manufactured by Kasei Kogyo ■ Evaluated toner: 3.5% by weight and 2.5% in apparent density. ．． 5-3.09/d
A developer was prepared by mixing an acrylic resin coated Cu-Zn ferrite carrier with an electrical resistance of 1013 Ω or more and a particle size content of 44 to 105 μm of 95 g/w. After using a corona voltage to negatively charge an organic photoconductive photoreceptor using phthalocyanine in the charge generation layer.

Information was written using a semiconductor laser, and printing was repeated using a high-speed continuous paper printer with a circumferential speed of about 30 cm/sec using a magnetic brush method. The results are summarized in Table 5.

(2) Print density and Capri density The printed matter was measured using a microphotometer MPM type (manufactured by Union Optical Co., Ltd.).

■ Toner scattering 6. The presence or absence of toner scattering was determined by visual inspection.

■ Resolution The printed matter was visually inspected at 10 times magnification and rated as good or poor.

Examples 8 to 14 and Comparative Examples 8 to 12 (1) Evaluation-■ The formulations shown in Table 6 were mixed in a tarp mixer to obtain final toners. Next, a developer was produced in the same manner as in Example 1,
They were evaluated in the same way. However, for printing, (2) Evaluation-■ Using the same developer as in (1) above and the developer in Comparative Examples 1 and 2 above, an organic photoconductive photoreceptor having a charge generation layer containing phthalocyanine was corona-coated. A cut paper printer with a circumferential speed of approximately 70 cm/sec (9/min) and a print speed of 135 sheets (A-4), which writes information using a semiconductor laser after being negatively charged with a voltage, and then develops it in reverse using a magnetic brush method. Repeated printing. The results are summarized in Table 8.

■Print density and fog density Same as above.

■ Toner scattering Same as above.

■ Resolution Same as above.

■ Image disturbance It was determined visually.

■ Frequency of jam occurrence The number of jams in the transfer section was counted and expressed as the number of occurrences per 10,000 sheets.

(3) FF value - ■ ■ The same procedure was carried out except that the developer of Example 8 was used and the printer was changed to a cut paper printer with a circumferential speed of the photoreceptor of about 50 an/sec and a printing speed of 120 sheets/min. As a result of the evaluation,
After printing 500,000 sheets, the print density was 1.3. Fog density 0
．． 09. There was no toner scattering, no image disturbance, and a jam occurrence frequency of O times/10,000 sheets.

■ Evaluation result 1 in the same manner as in Example 9 except that the developer was used and the printer was changed to a cut paper printer with a photoreceptor circumferential speed of approximately 25 an/sec and a printing speed of 60 sheets/min.
The same results as in Example 2 in Table 8 were obtained.

Examples 15-23. Comparative Examples 13 to 22 (1) Production of copolymers CP-1 to CP-4
Copolymers CP-i and CP-2 were produced in the same manner as in Copolymer R-2, except that the monomers, resins, and polymerization initiators shown in Table 2 were used. Combined CP
-3 and CP-4 were manufactured.

(2) Production of toner matrix The materials shown in Table 10 were premixed in a Henschel mixer, and then melted and kneaded in a twin-screw niegu. The cooled mixture was then pulverized using a hammer mill and a jet mill to obtain an average particle size of 10-13 μm<,4S,';::7. - (3) Manufacture of toner The composition shown in Table 11 was dispersed using a ■ type mixer (Note 1) MG-1: Mitsui Mining & Co., Ltd. (Magnetite) MGWL,
Average particle size approximately Q, 5. c+m, 64 emu/g.

MG-2: Magnetite made by Mitsui Mining & Smelting Co., Ltd.) MG-WL
Magnetite with an average particle size of about 0.8 μm, sieved with an Albine zigzag classifier, 65
emu/g.

MG-3: M()-199 weight and zinc stearate 1
Surface-treated magnetite mixed with heavy weight in a V-type blender, 63 emu/g.

MO-4: Magnetite MG-WLL manufactured by Mitsui Mining & Co., Ltd.
Magnetite with an average particle size of 1.5 μm, 61
emu/9° Note 2) C-1: Approximately 50 overlapping parts of 74 to 105 μm, 63 to 74
A copper-zinc ferrite carrier having a particle size distribution of approximately 20 overlapping parts in μm and approximately 30 overlapping parts in 44 to 63 μm, 64 emu/g.

C-2: Carrier whose surface is coated with C-1 carrier with hydroxyl group-containing acrylic resin-melamine resin, 64 emu/9°.However, the value expressed in emu/g is the magnetization under an external magnetic field of 1K Oersted. Shows the strength of

(4) Evaluation After negatively charging an organic photoconductor using 7 talocyanine in the charge generation layer to approximately -700V with a corona voltage, information is written using a semiconductor laser and reverse development is performed using a magnetic brush method.The circumferential speed of the photoreceptor is approximately 70cm/sec.

Printing was carried out using a cut paper printer with a development gap of 1.7 mm and a bias voltage of -400 V, and the results shown in Table 12 were obtained.

The method for measuring each characteristic is as follows.

■ Image density and fog density The density of the printed image was measured using a microphotometer MPM type (manufactured by Union Optical ■).

For the capri density of the background part of the image, use the reflectance meter Mod.
The difference from the unprinted paper was measured using el TC-6D S (manufactured by Tokyo Electric Power Co., Ltd.).

■ Resolution The printed image was enlarged 10 times and evaluated to see how many lines per inch could be resolved.

(4) Toner scattering The toner scattering from the developing device was visually observed and judged into four levels: a lot of scattering, medium, little, and no scattering.

(2) Photoreceptor Characteristics Appearance was determined by visual inspection, and photoresponsivity and sensitivity were measured using Cynthia-30HC (manufactured by Gix7 Tech Co., Ltd.).

■ Conditions for measuring photoresponsiveness After printing 700,000 sheets, the organic photoconductor was set in Cynthia 30HC, and after charging the surface potential Vo to -700V with a corona voltage, a halogen lamp with an exposure intensity of 20 mJ/m2 was used for 50 ns. The surface potential VR was examined 0.2 seconds after the start of irradiation. Among them, the characteristic of the unused product was VRlooV.

■ Similar to the sensitivity measurement conditions, 50 halogen lamps with different exposure intensities were applied to the organic photoconductor after printing 700,000 sheets with Vo charged to -700V.
The exposure intensity of a halogen lamp was investigated in which the surface potential decreased to 1350 V after 0.2 seconds of irradiation for m seconds. Among them, the characteristics of the unused product are 3.6 mJ/m'', :f;-・;7 Examples 24 to 32 The compositions shown in Table 13 were dispersed using a ■ type mixer to obtain the final toner and developer. Ta.

Next, using the developer, Example 3 was carried out in the same manner as in Example 15.
3 to 41 and Comparative Examples 23 to 25 (1) Production of toner The composition shown in Table 15 was dispersed using a V-type mixer to obtain a final toner. This was mixed with the carrier shown in Table 15 so that the toner concentration shown in Table 15 was obtained.

-・-2 Note) MG-4 Niokamura Oil Co., Ltd. magnetite, a product with an average particle size of approximately 0.01 μm classified by FB.

54emu/g.

MG-5: A product with an average particle size of approximately 0.05 μm obtained by classifying magnetite and FB manufactured by Okamura Oil ■.

55emu/g.

MG-6: A product with an average particle size of about 0.08 μm obtained by classifying magnetite and FB manufactured by Okamura Oil ■.

55emu/g.

MG-7: MG-190% by weight and 10% zinc stearate
% by weight of surface-treated magnetite mixed in a turbo sneaker mixer, 53 emu/g.

MG-8: Magnetite MG-WLL manufactured by Mitsui Mining & Co., Ltd.
Magnetite with an average particle size of 1.5 μm, 51 emu/g, was sieved using an Alvin zigzag classifier.

(2) Evaluation ! The material that generates the damage is titanyl phthalocyanine.

The charge transport material is 1,1-diphenylhydradi/-3-methylidene N-methylcarbazole, 1,1-diphenyl-3
(2,'2'(di-41-methoxyphenyl)]vinylhydrazone and 2,4bis(n-octylthio)6-(hydroxy-&5ditertiarybutylanilino)1,3,
5. ) After negatively charging an organic photoconductor consisting of a mixture of riazine to about -700 V with a corona voltage.

Information was written using a semiconductor laser, and printing was performed using a high-speed cut paper printer with a circumferential speed of the photoreceptor that performs reverse development using a magnetic brush method, approximately 70 cm/sec, a development gap of 1.7 mm, and a bias voltage of -400 V, and the results shown in Table 9 and 16 were obtained. Ta.

The method for measuring each characteristic is the same as in Example 15.

Among them, the degree of abrasion of the organic photoconductor is determined by measuring the film thickness of the organic photoconductor after printing using a surface profile measuring device Dektak 3030. The materials were premixed all at once using a Henschel mixer, and then melt-kneaded using a twin-screw Neegoo mixer. The cooled mixture is then pulverized with a hammer mill and a jet mill to give an average particle size of 10 to 13 μm (2) Production of toner and developer The compositions shown in Table 18 are mixed in a V-type mixer to produce the final toner and developer. I got it.

Note 1) Magnetite MG-8: Magnetite with an average particle size of 0.4 to 0.5 μm
(64 emu/g) MG-9: Magnetite with an average particle size of 0.5 to 0.6 μm
(6 s emu/g) MG-10: Magnetite with an average particle size of 0.7 to 0.8 μm (66 emu/g) MG-11: Mix MG-990 lit% and 10 wt% zinc stearate in a shaker mixer. Surface-treated magnetite (63 emu/g) MG-12: Surface-treated magnetite prepared by mixing MG-995% by weight and 5% by weight of hydroxystearic acid in a shaker mixer (63 emu/g) MG-13: Average particle size Approximately 0.01 μm magnet tie)
(66 emu/g) MG-14: Magnetite (6 emu/g) with an average particle size of approximately 1.5 μm
4emu/g) *The value in parentheses indicates the strength of magnetization greater than an external magnetic field of 1K Oerstend.

Note 2) Carrier C-3 = apparent density Z 7 g/cm's saturation magnetization 5
4 efflu/g, particle size distribution 74-1105
Copper zinc ferrite carrier surface-coated with hydroxyl group-containing acrylic resin/melamine resin with about 90% by weight of P and about 10% by weight of 63-74 μm.

C-4 apparent density i12.6 g/cm" + saturation magnetization 65 emu/g, particle size distribution 74-1105p approx. 60% by weight, 53-74 pm approx. 10% by weight, 44~
Copper-zinc ferrite carrier having a diameter of 63 μm and approximately 30% by weight and whose surface is coated with hydroxyl group-containing acrylic resin/melamine resin.

(3) On the surface of the aluminum support on the evaluation cylinder, a charge generation layer containing polycarbonate resin as a binder resin and titanyl phthalocyanine as a charge generation material, and a charge generation layer thereon.

1,1-diphenylhydrazino-3 as charge transport material
- methylidene-N-methylcarbazole about 70i% by weight,
1.1-diphenyl-3-[τ2'(di-4'-methoxyphenyl)]vinylhydrazone about 25% by weight, 2.4
-bis(n-octylthio)-6-hydroxy-3,5
- ditertiarybutylanilino) 1.3.5-An organic photoconductor drum (photoreceptor drum) formed with a charge transport layer containing about 5% by weight of triazine is subjected to reversal development using a magnetic brush method. The circumferential speed of the photoreceptor drum is approximately 70
0mm/sec, development gap 1.7mm, bias voltage -
Installed in a 400V ultra-high speed cut paper printer. This printer and the developer were evaluated as follows.

After the organic photoconductor drum was negatively charged with a corona voltage to about -700 cm, information was written using a semiconductor laser.

After visualization using each of the above-mentioned developers, the images were transferred to two sheets of paper, fixed, and printed repeatedly to obtain the results shown in Table 1.

The environmental conditions are temperature 15-30℃ and humidity 30-70%.
It is RH. The measurement method for each characteristic was almost the same as in Example 15, but the cuff density of the background part of 9 images was measured using a color difference meter (Co1 or Diff).
ence meter) D 25-2 C Hunter Associates Laboratory, Inc.
Made by Iates Laboratory, INC)]
The difference in reflectance from that of unprinted paper was measured using the same method as in Example 8, and the frequency of jam occurrence was evaluated in the same manner as in Example 8.

′:,<,f? ” Examples 49 to 57 and Comparative Examples 39 to 51 (1) Production of toner base The materials shown in Table 20 were premixed all at once in a Henschel mixer, and then melt-kneaded in a twin-screw kneader.Then, the cooled mixture was pulverized using a hammer mill and a jet mill to obtain a toner matrix having an average particle size of 10 to 13 μm.

Note 1) General formula (m) -c c person-5 General formula (I[[)-CCA-6 (2) Production of toner and developer The compositions shown in Table 21 were mixed in a V-type mixer to produce midwinter toner. and a developer was obtained.

) Characteristics were evaluated in the same manner as in Evaluation Example 42, and the results were shown in Table 2.
It was shown to.

(Effects of the Invention) As is clear from the above results, the dry toner of the present invention,
The dry developer and image forming method provide high print and image quality over a long period of time even under high speed printing.

This maintains properties such as non-toner scattering.

Dimensions. Even when combined with a photoreceptor made of an organic photoconductive substance, prevention of deterioration of the photoreceptor characteristics can be maintained.

Furthermore, it exhibits good characteristics even in high-speed printers, and in particular, when installed in ultra-high-speed cut paper printers, it exhibits high reliability without causing poor paper running even under high speeds.

Claims (1)

[Scope of Claims] 1. A metal complex of oxycarboxylic acid (C-1) and a metal complex of an azo compound (C-2) as a binder resin (A), a colorant (B), and a charge control agent (C). ) as an essential component, and the weight ratio of (C-1)/(C-2) is 1/9
~9/1, and the total amount of (C-1) and (C-2) is 0.
．． A toner base containing 5 to 5% by weight of silica powder, 0.1 to 1% by weight of silica powder to the toner base, and an average particle size of 0.5% by weight.
Magnetic powder of 8 μm or less is added to the toner base by 0.05 to 2
Dry toner made by adding and mixing weight percent. 2. The dry toner according to claim 1, wherein the toner base further contains another additive (D). 3. The dry toner according to claim 1 or 2, wherein the binder resin (A) contains a styrene-acrylic resin having a residual monomer and/or solvent content of 0.15% by weight or less. 4.Claim 1, wherein the colorant (B) is carbon black.
, 2 or 3. 5. Carbon black has an oil absorption of 150cc/100g
Above, volatile content 3.0% by weight or less, surface area 240m^2
5. The dry toner according to claim 4, wherein the dry toner contains at least /g. 6. The metal complex (C-1) of oxycarboxylic acid has the general formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, Ar_1 and Ar_2 are aromatic oxycarboxylic acids or a residue of a derivative thereof, which may be the same or different, M_1 represents a chromium or zinc atom,
6. The dry toner according to claim 1, wherein A_1^■ represents a hydrogen ion, a sodium ion, a potassium ion, or an ammonium ion. 7. The azo compound metal complex (C-2) has the general formula (II)
▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...(II) (In the formula, X_1 and X_2 are hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or Represents a halogen atom, m_1 and m_2 represent integers of 1 to 3, n_1 and n_2 represent integers of 1 or 2, which may be the same or different, M_2 represents a chromium or zinc atom, A_2^■ represents a hydrogen ion, sodium ion, potassium ion, or ammonium ion) and/or general formula (III); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・・・・(III) X_3 and X_4 are -NO_2, -CH_3,
-SO_3H, -Cl or -SO_2NH_2,
k_1 and k_2 represent an integer of 1 or 2, these may be the same or different, M_3 represents a chromium or zinc atom, A_3^■ represents a hydrogen ion, sodium ion, potassium ion or ammonium ion) The dry toner according to any one of claims 1 to 6. 8. The dry toner according to claim 6, wherein the metal complex of the oxycarboxylic acid represented by the general formula (I) is a zinc complex salt compound. 9. The dry toner according to claim 7 or 8, wherein the metal complex of the azo compound represented by the general formula (II) and/or the general formula (III) is a chromium complex salt compound. 10. The dry toner according to any one of claims 1 to 9, which is formed by adding and mixing other modifiers in an amount of 1% by weight or less (excluding 0) with respect to the toner base, together with silica powder and magnetic powder. . 11. The dry toner according to claim 1, wherein 0.01 to 0.5% by weight of a fatty acid metal salt is added and mixed with the silica powder and magnetic powder based on the toner base. 12. Together with silica powder, magnetic powder and fatty acid metal salt,
Furthermore, 1% by weight of other modifiers based on the toner base.
The dry toner according to claim 11, wherein the following (excluding 0) are added and mixed. 113, silica powder has an average primary particle diameter of 30 mμ
The dry toner according to any one of claims 1 to 12, which is as follows. 14. The dry toner according to claim 1, wherein the magnetic powder is magnetite. 15. The dry toner according to claim 14, wherein the magnetite has a magnetization strength of 64±4 emu/g under an external magnetic field of 1 K Oersted. 16. 0.5 to 2% by weight of magnetic powder based on the toner base
The dry toner according to any one of claims 1 to 15, which is obtained by adding and mixing. 17. The dry toner according to claim 11 or 12, wherein the fatty acid metal salt is zinc stearate. 18. The dry toner according to claim 10 or 12, wherein the other modifier is at least one fine powder selected from aluminum oxide, zinc oxide, titanium oxide, magnesium oxide, calcium carbonate, and polymethyl methacrylate. 19. The binder resin (A) is 60 to 9 with respect to the toner matrix.
The dry toner according to any one of claims 1 to 18, wherein the dry toner contains 4.5% by weight. 20. The dry toner according to claim 1, wherein the colorant (B) is contained in an amount of 2 to 15% by weight based on the toner matrix. 21. A dry developer comprising the dry toner according to any one of claims 1 to 20 and a carrier. 22. Claim 21, wherein the carrier is a ferrite carrier.
Dry developer as described. 23. The dry developer according to claim 22, wherein the carrier is a copper-zinc ferrite carrier. 24. The dry developer according to claim 21, 22 or 23, wherein the carrier is coated with an acrylic resin. 25. Claims 21 to 21, wherein the toner concentration is 1 to 10% by weight.
25. The dry developer according to any one of 24. 26. The dry developer according to any one of claims 21 to 25, which is used for high-speed printers. 27. The dry developer according to any one of claims 21 to 26, which is used for cut paper printers. 28. The dry developer according to claim 27, which is used in a cut paper printer having a printing speed of 60 sheets per minute or more. 29. The dry developer according to any one of claims 21 to 28, which is used in combination with a photoreceptor made of an organic photoconductive substance. 30. The dry developer according to claim 29, which is used in combination with a photoreceptor using a phthalocyanine pigment as the organic photoconductive substance. 31. An image forming method comprising using the dry toner according to any one of claims 1 to 20 or the dry developer according to any one of claims 21 to 30. 32. The image forming method according to claim 31, which is carried out in a high-speed printer. 33. The image forming method according to claim 32, wherein the peripheral speed of the photoreceptor of the high-speed printer is 25 cm/sec or more. 34. Claim 3 carried out in a cut paper printer
1. The image forming method according to 1. 35. The image forming method according to claim 34, wherein the print speed of the cut paper printer is 60 sheets per minute or more. 36. The image forming method according to claim 31, wherein the image forming method is used in combination with a photoreceptor made of an organic photoconductive substance. 37. The image forming method according to claim 36, wherein a phthalocyanine pigment is used as the organic photoconductive substance. 38. A photoreceptor made of an organic photoconductive substance has a charge generating layer containing titanyl phthalocyanine as a component, 1,1-diphenylhydrazino-3-methylidene-N-methylcarbazole and 1,1-diphenyl-3- 37. The image forming method according to claim 36, further comprising a charge transport layer containing [2', 2'(di-4''-methoxyphenyl)] vinyl hydrazone.