JP3148959B2 - Toner for developing electrostatic images and color toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
The present invention relates to a toner for developing an electrostatic image from a mono-color copying machine to a full-color copying machine for developing an electrostatic image in electrostatic printing or the like.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Unexamined Patent Publication (KOKAI) No. Sho-43-24748, and the like. Generally, a photoconductive substance is used, and an electric latent image is formed on a photoreceptor by various means. And then developing the latent image with toner,
After transferring the toner image to a transfer material such as paper as necessary,
The image is fixed by heating, pressure, or solvent vapor to obtain a copy.

Various methods and techniques have been developed for the final step of fixing the toner image on a sheet such as paper. Currently, the most common method is a pressure heating method using a heating roller. The pressure heating method using a heating roller performs fixing by allowing the toner image surface of the sheet to be fixed to pass through the surface of the heating roller having a surface formed of a material having releasability with respect to the toner while pressing the surface under pressure. It is. According to this method, since the surface of the heating roller and the toner image of the sheet to be fixed come into contact with each other under pressure,
The thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly, which is very effective in a high-speed electrophotographic copying machine. However, since the surface of the heating roller and the toner image come into contact with each other under pressure in a molten state, a part of the toner image adheres and transfers to the surface of the fixing roller, and re-transfers to the next sheet to be fixed, thereby causing a so-called offset phenomenon. This may cause the sheet to be fixed to be soiled. That is, at present, the development of a binder resin for toner having a wide fixing temperature range and high offset resistance is desired.

[0004] There have been many studies and commercialization of two-color copying machines and full-color copying machines. For example, “Journal of the Society of Electrophotography,” Vol 22, No. 1 (1983) and "Journal of the Institute of Electrophotography", Vol. 1, P. 52
(1986), there are reports of color reproducibility and gradation reproducibility. However, full color electrophotographic images that are currently in practical use are not immediately compared with the real ones such as televisions, photographs, and color prints, and for those who see color images that are more beautifully processed than the real ones, It is not always satisfactory.

In a full-color electrophotographic method in which development is performed a plurality of times and several types of toner layers having different colors are superposed on the same support, the conditions that the binder resin for color toner should have are as follows. Matters. (1) It is necessary that the fixed toner is in a state close to almost complete melting such that the shape of the toner particles cannot be discriminated so as not to irregularly reflect light and hinder color reproduction. (2) It must have transparency that does not interfere with the toner layers of different tones under the toner layer.

As described above, it is desired to develop a binder resin for toner having a wide fixing temperature range and high anti-offset property for a monocolor copying machine. It is required that the transparency of the resin and the fixing surface be flat when fixed.
The transparency and the smoothness of the fixing surface of these resins greatly affect not only the case where the reflection image is fixed on paper or the like and the reflection image is viewed, but also the quality of the transmitted light image which is fixed and fixed on an OHP sheet or the like.

Further, in recent years, from a mono-color to a full-color copying machine, there have been demands for many things such as high image quality, high speed, reduction of heat-up time of a heating roller and reduction of power consumption.

[0008] In order to satisfy the above-mentioned requirements, by reducing the particle size of the toner, a more faithful image can be formed on the original document.
It can be fixed at low temperature, has a wide fixing area and excellent transparency,
It is necessary to use a toner such that the fixing surface becomes flat when fixed.

However, if the particle size of the toner is simply reduced in order to form a more faithful image on the document, the charge amount of the toner rapidly increases. Therefore, the image is easily affected by the environment, and the image quality is deteriorated due to the deterioration of the developability, particularly, fog, dust and scattering, and the transfer efficiency is lowered. Further, the image is not developed due to a large charge amount, or even if developed, the transfer efficiency is lowered, so that the obtained image has a low density and is poor. Further, since the particle diameter is small and the charge amount is large, cleaning failure is likely to occur. Also,
A phenomenon called so-called electrostatic offset, which adheres to the fixing roller during fixing, also occurs.

Further, as the particle diameter becomes smaller, the surface energy increases and the fluidity deteriorates. When the fluidity deteriorates, the image becomes rough, especially in a halftone image.
Further, if a large amount of a fluidizing agent such as silica is added to improve the fluidity, the fixability deteriorates.

Therefore, it is extremely difficult to simultaneously satisfy these required performances.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner for developing an electrostatic image in which these problems are improved. In other words, by reducing the particle size of the toner, an image faithful to the original can be formed, the charging characteristics are good, and the chargeability is always stable during use, and the flowability and cleaning properties are excellent and clear.
Able to obtain images without fog, dust, and scattering, A wide fixing temperature range where low-temperature fixing is possible and there is no electrostatic offset, An image that is always stable and has no roughness even in halftone images, For full color When used as a toner, a smooth fixing surface can be formed so that the toner fixed does not diffusely reflect light and hinder color reproduction. An object of the present invention is to provide a toner for developing an electrostatic image, which has color mixing properties that do not hinder a toner layer having a different color tone.

[0013]

According to the present invention, there is provided an electrostatic image developing toner comprising a vinyl resin or a polyester resin as a main binder resin component, wherein the weight average particle diameter of the toner is 3 to 8 μm. And a modified silicone compound having a melting point of 15 to 200 ° C. selected from the group consisting of a polyether-modified silicone compound, a higher fatty acid ester-modified silicone compound and a higher alkoxy-modified silicone compound. About. Further, the present invention provides an alcohol component having a bisphenol derivative represented by the following formula (A):
Phthalic acid, terephthalic acid, isophthalic acid, succinic acid, n
An acid component having a dicarboxylic acid selected from the group consisting of dodecenyl succinic acid, fumaric acid, maleic acid, maleic anhydride, and anhydrides thereof, and a tricarboxylic acid selected from the group consisting of trimellitic acid and anhydrides thereof; A polyester resin obtained by condensation polymerization of the above as a main binder resin component, and a color toner for developing an electrostatic image containing a dye and / or a pigment, having a weight average particle diameter of 3 to 8 μm And a modified toner having a melting point of 15 to 200 ° C. and containing a modified silicone compound.

Here, the grounds for the above configuration will be described below.

The weight average diameter of the toner is usually about 10 μm. However, the toner particle size has a particle size distribution having a width of about 4 to 25 μm, and when a toner having a large particle size is developed, a rough image is formed particularly in a halftone portion. Although it varies depending on the toner charge amount and developing conditions,
In particular, when the toner particle size that is easily developed is smaller than the toner weight average particle size, the image quality gradually decreases because the toner having a large particle size remains as the number of durable images produced by the copying machine increases. You can see the phenomenon that goes on. Conversely, when the toner particle size that is easily developed is large, the toner having a small particle size appears as fog in the initial image. In recent years, toners having a weight average diameter of about 9 μm have been proposed and put to practical use. Surely, the above-described fixing property and developing property have been improved and the image quality has been improved in terms of reproducibility of fine lines. Is not yet enough.

Therefore, in the present invention, the melting point is 15 to
A modified silicone compound at 200 ° C. is used. This compound not only functions as an anti-offset agent but also has excellent transparency when used as a color toner. Further, unlike wax conventionally used for toners, it has no plasticizing effect on the binder resin, and therefore has excellent storage stability. Further, since the toner is given an appropriate and uniform lubrication, it exhibits good charging characteristics particularly when the toner particle size is smaller than that of the conventional toner, and also has excellent cleaning properties from the developing drum.

A method of adding silicone oil to a toner for the purpose of improving the fluidity and developability of the toner and the dispersibility of the photoconductive substance in the photoconductive toner is disclosed in, for example, JP-A-54-54039. Gazette, JP-A-62-62
No. 66 and the like. With these methods,
Certainly, it has the effect of improving fluidity, developability, and dispersibility,
The image quality of the halftone image is still not sufficient because the toner particle size is large. Furthermore, in order to solve the above-mentioned problems using a modified silicone compound, a certain amount (2 to 3) is required.
However, these methods tend to cause poor triboelectric charging, resulting in a decrease in concentration, or excessively slipping, resulting in poor cleaning.

The monomers constituting the vinyl binder resin used in the present invention include the following. For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-
Ethylstyrene, 2,4-dimethylstyrene, pn-
Butylstyrene, p-tert-butylstyrene, p-
n-hexylstyrene, pn-octylstyrene, p
-N-nonylstyrene, pn-decylstyrene, p-
n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene,
Styrene derivatives such as ethylene, propylene, butylene, isobutylene and the like, and unsaturated monoolefins such as butadiene, isoprene and the like, and vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc. And vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate, and methacrylic acid and methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-methacrylic acid.
-Butyl, isobutyl methacrylate, n-methacrylate
Octyl, dodecyl methacrylate, methacrylic acid-2-
Α-methylene aliphatic monocarboxylic esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, acrylic acid and methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic acid Acrylic esters such as n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate, and vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether And vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, and N-vinyl pyrrole, N-
N-vinyl compounds such as vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; acroleins; and acrylic acid and methacrylic Polymerization using one or more acid monomers such as acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid, maleic acid and their monoesters such as methyl, ethyl, butyl and 2-ethylhexyl Those that have been used are used.

The glass transition temperature of the vinyl binder resin used in the present invention is 45 to 90 ° C., preferably 50 to 65 ° C.
And a number average molecular weight Mn of 1,000 to 30,000, preferably 2,000 to 25,000, and a weight average molecular weight Mw of 6,000.
８００800,000, preferably 8,000 to 600,000.

As a more preferred vinyl binder resin,
GPC molecular weight distribution of 5000 to 30
It is desirable to have at least one maximum in each of 000 and 50,000 to 600,000.

The acid value is preferably 90 or less, more preferably 50 or less. This means that when the acid number increases,
This is because the charging characteristics of the toner are greatly dependent on the environment.

The composition of the polyester resin used in the present invention is as follows.

The polyester resin used in the present invention comprises:
45 to 55 mol% of all components are alcohol components,
55 to 45 mol% is an acid component.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and (A)
Bisphenol derivative represented by the formula

[0025]

Embedded image Also, diols represented by the formula (B)

[0026]

Embedded image And polyhydric alcohols such as glycerin, sorbit and sorbitan.

Carboxylic acids are used as the acid component, and phthalic acid, terephthalic acid, isophthalic acid,
Benzenedicarboxylic acids such as phthalic anhydride or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or anhydrides thereof, and succinic acid further substituted with an alkyl group having 6 to 18 carbon atoms Or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, and anhydrides thereof; and the trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid. Examples include carboxylic acids and anhydrides thereof.

The alcohol component of the polyester resin particularly preferred in the practice of the present invention is a bisphenol derivative represented by the above formula (A), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, Examples thereof include n-dodecenyl succinic acid or an anhydride thereof, fumaric acid, maleic acid, dicarboxylic acids such as maleic anhydride, and trimellitic acid or a tricarboxylic acid anhydride thereof.

This is because the polyester resins obtained with these acids and alcohols show sharp melting characteristics, have good color mixing properties as toners for full color and heat roller fixing, and have excellent offset resistance. .

The polyester resin obtained here has a glass transition temperature of 50 to 75 ° C., preferably 55 to 65 ° C.
° C, number average molecular weight Mn 1500-50,000, preferably 2000-20,000, weight average molecular weight Mw 60
00 to 100,000, preferably 10,000 to 90,0
00 is preferred.

The acid value is desirably 90 or less, preferably 50 or less, and the OH value is desirably 50 or less, preferably 30 or less. This is because when the number of terminal groups in the molecular chain increases, the toner has a large environmental dependency in the charging characteristics of the toner.

The melting point used in the present invention is 15 to 200 ° C.
Examples of the modified silicone compound include polyether-modified silicone compounds, higher fatty acid ester-modified silicone compounds, and higher alkoxy-modified silicone compounds.

The amount of the modified silicone compound to be added is preferably 2 to 30 parts by weight based on 100 parts by weight of the binder resin for toner. If the amount is less than 2 parts by weight, the effect of the addition is negligible. If the amount is too large, on the other hand, the charge amount of the toner is reduced and the toner is not developed.

In order to use the toner of the present invention as a one-component toner, a magnetic powder may be contained. As such a magnetic powder, a substance which is magnetized when placed in a magnetic field is used, and there is a powder of a ferromagnetic metal such as iron, cobalt, and nickel, or an alloy or a compound such as magnetite, hematite, or ferrite. The content of the magnetic powder is 15 to 70% by weight based on the weight of the toner.

As the colorant irrespective of the one-component or two-component toner, carbon black, titanium white, and any other pigments and / or dyes can be used. For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I.
I. Direct Blue 2, C.I. I. Acid blue 9,
C. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I.
Basic Green 4, C.I. I. Basic Green 6
Etc. As pigments, graphite, cadmium yellow,
Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Red Lead Yellow, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red,
Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indanthrene Blue BC,
Chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the following may be mentioned. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable to use the dye and the pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,
22, 23, 24, 27, 29, 32, 34, 35, 3
6, 37, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
And basic dyes such as 26, 27 and 28.

Other color pigments include cyan color pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by Chemical Formula 4.

[0039]

Embedded image Coloring pigments for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12,
13, 14, 15, 16, 17, 23, 65, 73, 8
3, C.I. I. Bat Yellow 1, 3, 20 and the like.

The amount of the colorant is 0.1 to 60 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the binder resin.
0 parts by weight.

The toner according to the present invention has a negative charge property,
The positive chargeability is not limited, but when a negatively chargeable toner is prepared, a charge control agent may be added for the purpose of stabilizing the negative charge characteristics. Examples of the negative charge control agent include resins containing carboxyl groups such as phenolic resins, polymethacrylic acid, copolymers of styrene and acrylic acid, methacrylic acid, and maleic acid-added styrene butadiene copolymers, and polyesters. Or a resin having a carboxyl group or -OH group at the polymer chain end by condensation polymerization, such as an azo-based metal complex or a metal complex of an alkyl-substituted salicylic acid (for example, a chromium complex of di-tert-butylsalicylic acid, an aluminum complex, a zinc complex, etc.) ).

When a positively chargeable toner is prepared, nigrosine, a triphenylmethane compound, a rhodamine dye, polyvinyl pyridine, or the like may be used as a charge control agent having a positive charge. When a color toner is produced, a toner containing 0.1 to 40 mol%, preferably 1 to 30 mol% of an aminocarboxylic acid ester having a positive charge property such as dimethylaminomethyl methacrylate as a monomer is contained. A coloring resin may be used, or a colorless or light-colored positive charge control agent that does not affect the color tone of the toner may be used. Examples of the positive charge control agent include quaternary ammonium salts represented by structural formulas 5 and 6.

[0043]

Embedded image

[0044]

Embedded image Among the quaternary ammonium salts represented by the above structural formulas (5) and (6), the use of a positive charge control agent represented by the following structural formulas (7) and (8) can provide good chargeability with little environmental dependence. It is preferable because it is shown.

[0045]

Embedded image

[0046]

Embedded image In addition, as the resin component of the binder resin in the positively chargeable toner, when an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate showing positive charge characteristics is used, a positive charge control agent or a negative charge control agent is optionally used. use.
In the case of a negatively chargeable toner, the amount of the negative charge control agent used is
0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, is desirable based on 100 parts by weight of the binder resin.

When a positively chargeable toner does not use an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate having a positive charge characteristic as a resin component, a positive charge control agent is added to 100 parts by weight of the binder resin. 0.1-1
It is desirable to use 5 parts by weight, preferably 0.5 to 10 parts by weight. When aminocarboxylates are used, a positive charge control agent and / or a negative charge control agent may be added to 100 parts by weight of the binder resin, if necessary, for the purpose of providing good chargeability with little environmental dependency. It is desirable to use 0 to 10 parts by weight, preferably 0 to 8 parts by weight.

Further, in the toner according to the present invention, a fluidity improver may be added for the purpose of improving the fluidity of the toner.

The flow improver used in the present invention includes
Any material can be used as long as the fluidity can be increased before and after the addition by adding to the colorant-containing resin particles. For example, <fluorinated resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fatty acid metal salts such as zinc stearate, calcium stearate, and lead stearate <metal oxides such as zinc oxide powder, wet-process silica, There are finely divided silicas such as dry-processed silicas, and silicas which have been surface-treated with a silane coupling agent, a titanium coupling agent, silicone oil or the like.

Preferred flow improvers are fine powders produced by the vapor phase oxidation of silicon halides, so-called dry silica or fumed silica, which are produced by conventionally known techniques. It is. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl In this production process, another metal halide such as aluminum chloride or titanium chloride is used together with a silicon halide to produce a composite fine powder of silica and another metal oxide. It is also possible to obtain bodies, including them. The particle size is 0.0 as an average primary particle size.
It is desirable to be within the range of 01 to 2 μm, and it is particularly preferable to use silica fine powder within the range of 0.002 to 0.2 μm.

Commercially available silica fine powder produced by vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Japan) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 (WACKER) -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil) Further, treated silica obtained by hydrophobizing silica fine powder generated by gas phase oxidation of the silicon halide. It is more preferable to use fine powder. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating an organic silicon compound or the like which reacts with or physically adsorbs silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, dimethylpolysiloxane having a hydroxyl group bonded to Si and having one siloxane unit as a terminal unit may be used. These are used alone or as a mixture of two or more.

The particle size of the treated silica fine powder is as follows:
It is preferable to use one having a range of 0.003 to 0.1 μm. Commercial products include Taranox-500 (Talco) and AEROSIL R-972 (Nippon Aerosil).

For the positively chargeable toner, positively chargeable silica fine particles may be used in order not only to improve the fluidity but also to obtain good chargeability that is less dependent on the environment. In order to obtain such positively charged silica fine particles, it is preferable to treat them with a coupling agent containing an amino group or silicone oil. Examples of such a treating agent include an aminosilane coupling agent represented by the following formulas 9 to 10.

[0058]

Embedded image

[0059]

Embedded image As the silicone oil, an amino-modified silicone oil having a partial structure having an amino group in a side chain represented by the following formula (11) is generally used.

[0060]

Embedded image In the above formula, R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent a hydrogen, an alkyl group or an aryl group. Express. However, the above alkyl group,
The aryl group, alkylene group and phenylene group may contain an amine, or may have a substituent such as halogen as long as the chargeability is not impaired. m and n are positive integers.

Examples of the silicone oil having an amino group include the following.

Viscosity at 25 ° C. Amine Equivalent Trade name (cps) SF8417 (manufactured by Toray Silicone Co.) 1200 3500 KF393 (manufactured by Shin-Etsu Chemical Co.) 60 360 KF857 (manufactured by Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (manufactured by Shin-Etsu Chemical Co., Ltd.) 7600 KF861 (Shin-Etsu Chemical Co., Ltd.) 3500 2000 KF862 (Shin-Etsu Chemical Co., Ltd.) 750 1900 KF864 (Shin-Etsu Chemical Co., Ltd.) 1700 3800 KF865 (Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-3680 (Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-3810B (Shin-Etsu Chemical Co., Ltd.) Shinetsu Gakusha Ltd.) 1300 1700 It is noted that the amine equivalent, equivalent weight per amine (g / e
qiv) is the value obtained by dividing the molecular weight by the number of amines per molecule.

It is preferable to use these silica fine particles treated with a coupling agent or a silicone oil containing an amino group, after further hydrophobizing them with the aforementioned organosilicon compound.

When the toner according to the present invention is used for a two-component toner, the carrier used to sufficiently exhibit the effect plays an important role. As the carrier used in the present invention, for example, surface oxidized or unoxidized iron,
Metals such as nickel, copper, zinc, cobalt, manganese, chromium, rare earths, and alloys or oxides thereof, and ferrites can be used. In addition, there is no particular limitation on the manufacturing method.

A system in which the surface of the carrier is coated with a resin or the like is particularly preferable in the J / B developing method. As the method, any conventionally known method such as a method of dissolving or suspending a coating material such as a resin in a solvent, coating and adhering to a carrier, and a method of simply mixing with a powder can be applied.

The substance fixed to the carrier surface varies depending on the toner material. Examples thereof include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, and the like.
Use metal complex of ditertiary butyl salicylic acid, styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, silica fine powder, alumina fine powder, etc. singly or in combination. Is suitable, but is not necessarily limited to this.

The amount of the compound to be treated may be appropriately determined so that the carrier satisfies the above conditions, but is generally 0.1 to 30% by weight (preferably 0.5 to 20% by weight) based on the carrier of the present invention. % By weight) is desirable. The average particle size of these carriers is 10 to 100 μm, preferably 2 to 100 μm.
It preferably has a thickness of 0 to 70 μm.

In a particularly preferred embodiment, Cu—Zn—
Fe ternary ferrite whose surface is a combination of a resin such as a fluorine resin and a styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin, polytetrafluoroethylene and styrene-methyl methacrylate resin, A fluorine-based copolymer and a styrene-based copolymer are used in an amount of 90:10 to 20:80, preferably 7
A mixture having a ratio of 0:30 to 30:70,
0.01 to 5% by weight, preferably 0.1 to 1% by weight, and a coated ferrite carrier having the above average particle diameter, in which 250 mesh pass, 400 mesh on carrier particles are coated in an amount of 70% by weight or more. Can be As the fluorine-based copolymer, vinylidene fluoride-
Tetrafluoroethylene copolymer (10:90 to 90:
10), and styrene-based copolymers such as styrene-2-ethylhexyl acrylate (20:80 to 8
0:20), styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-30: 10)
50) is exemplified. The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectric charging properties to the toner of the present invention, and has the effect of improving electrophotographic properties.

When a two-component developer is prepared by mixing with the toner according to the present invention, the mixing ratio is 2 to 15% by weight, preferably 4 to 13% by weight as the toner concentration in the developer.
In general, good results are obtained. 2% toner concentration
If it is smaller, the image density is low and it becomes impractical. If it exceeds 15%, fog and scattering in the machine are increased, and the useful life of the developer is shortened.

The measuring method used in the present invention will be described below. (1) Measurement of glass transition temperature Tg In the present invention, measurement is performed using a differential thermal analysis measurement device (DSC measurement device), DSC-7 (manufactured by PerkinElmer). The measurement sample is precisely weighed in an amount of 5 to 20 mg, preferably 10 mg.

The sample was placed in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 200 ° C. and 200 ° C. During this heating process, the temperature is 40 to 100 ° C.
The endothermic peak of the main peak in the range is obtained.
The intersection of the line at the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg according to the present invention. (2) Measurement of melting point A measurement sample was prepared in the same manner as in the measurement of the glass transition temperature, and the same apparatus was used to increase the temperature at a measurement temperature of 30 to 150 ° C. and a heating rate of 10 ° C.
The temperature is kept at 150 ° C. for 10 minutes after the temperature is raised at / min. Thereafter, it is rapidly cooled at a rate of 30 to 50 ° C./min to −50 ° C.
Hold at -50 C for minutes. Then, at 10 ° C / min, 15
Heat to 0 ° C. At this time, an endothermic peak of the main peak is obtained. The endothermic peak at this time is defined as the melting point in the present invention. (3) Measurement of molecular weight In the present invention, the molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and the sample concentration was 0.05 to 0.6% by weight. % Of the THF sample solution of the resin adjusted to 50% to 200 μl is measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical
Co. Or Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6
× 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and it is appropriate to use at least about 10 standard polystyrene samples. Also, the detector uses RI
A (refractive index) detector is used.

The column used is 10 ³ to 2 × 10
^In order to accurately measure the molecular weight region of ^6, a plurality of commercially available polystyrene gel columns are preferably combined.
μ-styragel 500, 10 manufactured by Aters
Combination of ³ , 10 ⁴ and 10 ⁵ and Showa Denko sho
dex KF-80M, KF-801, 803, 80
4, 805, KA-802, 803, 804,
805 combination or TSKgel manufactured by Toyo Soda
G1000H, G2000H, G2500H, G300
0H, G4000H, G5000H, G6000H, G
A combination of 7000H and GMH is preferred. (4) Acid value The acid value is important as an indicator of the progress of esterification in a short time and with high accuracy. In general, the esterification check starts at the 80th acid value and ends as needed between 20 and 50 positions. Here, the acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the carboxyl group contained in 1 g of the resin. Therefore, the acid value indicates the number of terminal groups. The measuring method is as follows.

[0074] 200 to 300 ml of sample 2 to 10 g
Weighed in an Erlenmeyer flask, and methanol: toluene = 3
About 50 ml of a 0:70 mixed solvent is added to dissolve the resin.
If the solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, a standardized N / 10
Titrate with potassium hydroxide to alcohol solution, and determine the acid value from the consumption of potassium hydroxide solution by the following calculation.

Acid value = KOH (ml number) × N × 56.1 / sample weight (where N is a factor of N / 10 KOH) (5) Weight average particle size The particle size distribution can be measured by various methods. In the present invention, the measurement was performed using a Coulter counter.

That is, a Coulter counter TA-II type (manufactured by Coulter) was used as a measuring device, and an interface (manufactured by Nikkaki) for outputting the number average distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) were connected. Then, a 1% aqueous NaCl solution is prepared using primary sodium chloride as an electrolyte. As a measuring method, a surfactant, preferably an alkylbenzene sulfonate, is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution.
Add 5 ml, and further add 2-20 mg of the measurement sample.
The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of the toner were measured using the Coulter Counter TA-II, using a 100 μm aperture as the aperture. The volume distribution and number distribution of particles of 40 μm were calculated. Then, according to the present invention, the weight-average weight-average diameter determined from the volume distribution (the median value of each channel is a representative value for each channel) was determined from the volume distribution.

[0077]

The present invention will be described in detail below with reference to examples.

(Resin Production Example 1) 340 g of styrene 240 g of n-butyl methacrylate 6 g of benzoyl peroxide 1000 g of toluene These were placed in a reaction vessel and reacted at 90 ° C. for 16 hours.
A polymer having Mn = 4000, Mw = 20,000 and Tg = 58 ° C. was obtained. The polymer obtained here is referred to as resin A.

(Resin Production Example 2) • 310 g of styrene • 270 g of n-butyl methacrylate • 1 g of benzoyl peroxide • 3 g of poval These were put into a reaction vessel, subjected to suspension polymerization, and thereafter, Bhopal was removed by alkali washing to remove Mn. = 80000, Mw
= 500000, Tg = 55 ° C. The polymer obtained here and the resin A are dissolved and mixed at a weight ratio of 3: 7 in a solution, and the polymer obtained by drying is referred to as a resin B.

Mn = 8000, Mw = 3800 of resin B
0, Tg = 57 ° C., GPC molecular weight distribution
000 and 500,000 each had one maximum value.

(Resin Production Example 3) Propoxylated bisphenol A 64 g Ethoxylated bisphenol A 68 g Terephthalic acid 20 g Dodecenyl succinic acid 18 g Trimellitic acid 30 g Mn = 4000, Mw = 2000
A polyester having 0, Tg = 60 ° C. and acid value = 10 was obtained.
The polyester obtained here is referred to as resin C.

Example 1 100 parts by weight of resin A. 5.0 parts by weight of a copper phthalocyanine pigment having a structure represented by Formula 3. 4.0 parts by weight of a zinc complex of ditertiary butyl salicylic acid. 4.0 parts by weight of a polyether-modified silicone compound. (Melting point: 25 ° C.) 5.0 parts by weight were melt-kneaded by a roll mill, cooled, pulverized and classified, and further treated with hexamethyldisilazane as a flow improver. Eight parts by weight were externally added to obtain a toner.

At this time, the weight average particle diameter of the toner is 3.
It was 8 μm.

As the carrier, styrene-acryl 2
C coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30)
u-Zn-Fe ferrite carrier (average particle size 30μ)
Using m), a developer was prepared such that the toner concentration was 3.0% by weight.

Using these developers and toners, an image output test was performed using a full color copying machine CLC-500 manufactured by Canon.

Even after 20,000 sheets of images were formed, clear images were obtained without fog and without halftone roughness. In addition, the image fixed on the OHP also had good translucency.

Example 2 100 parts by weight of resin B ・ 90 parts by weight of magnetic iron oxide ・ 3 parts by weight of nigrosine ・ 5 parts by weight of a higher fatty acid ester-modified silicone compound (melting point: 64 ° C.) Classify,
Further, 0.8 part by weight of a positively charged hydrophobized dry silica was externally added as a flow improver to 100 parts by weight of the classified product to obtain a one-component magnetic toner.

The weight average particle size of this toner was 4.0 μm.

This toner is used in a Canon copier NP-48.
An image-drawing test was performed using No. 35. As a result, even after printing for 100,000 sheets, a clear image having no offset to the fixing roll, no fogging or unevenness, and no halftone roughness was obtained.

Example 3 100 parts by weight of resin C as a binder resin and a higher alkoxy-modified silicone compound (melting point 5
(0 ° C.) A toner having a weight average particle size of 3.5 μm was prepared in the same manner as in Example 1 except that 5 parts by weight was used.

Using this toner, a developer was prepared in the same manner as in Example 1, and an image formation test was performed using CLC-500.
As a result, even after printing for 20,000 sheets, there was no offset to the fixing roll, and a clear image free of fog and unevenness and free of halftone roughness was obtained. Also OH
The image fixed on P also had good translucency.

Comparative Example 1 A toner having a weight average particle size of 3.7 μm was obtained in the same manner as in Example 1 except that the polyether-modified silicone compound was not used. A developer was prepared in the same manner as in Example 1, and CL was prepared.
When the image was evaluated by C-500, a decrease in density due to charge-up was observed. In addition, fog and scumming were poor, and the offset to the fixing roll was rather poor.

[0093]

According to the present invention, by reducing the particle size of the toner, an image faithful to the original can be formed, the chargeability is good, and the chargeability is always stable during use. An image without fog, flying dust and scattering can be obtained. Further, the fixing temperature range in which low-temperature fixing is possible and there is no electrostatic offset is wide, so that a stable and non-cracked image can be obtained even in a halftone image.
The transmissivity of the image fixed to is also good.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-184356 (JP, A) JP-A-3-257463 (JP, A) JP-A-4-119361 (JP, A) JP-A-59-1984 37555 (JP, A) JP-A-59-200264 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (7)

(57) [Claims] 1. An electrostatic image developing toner comprising a vinyl resin or a polyester resin as a main binder resin component,
The weight average particle diameter of the toner is 3 to 8 [mu] m, polyether
Modified silicone compound, higher fatty acid ester modified silicone
Corn compounds and higher alkoxy-modified silicone compounds
Melting point selected from the group consisting of
A toner for developing electrostatic images, characterized by containing a modified silicone compound of the formula: 2. The toner according to claim 1, wherein the modified silicone compound is
2 to 30 parts by weight based on 100 parts by weight of the binder resin
The electrostatic image developing device according to claim 1, wherein
Ner. 3. The main binder resin component is a vinyl resin.
The vinyl resin has a glass transition temperature of 45 to 90 ° C.
Having a number average molecular weight (Mn) of 1,000 to 30,0.
00 and a weight average molecular weight (Mw) of 6,000 to 8
3. The method according to claim 1, wherein
The toner for developing an electrostatic image according to the above. 4. The main binder resin component is a polyester resin.
Yes, the polyester resin has a glass transition temperature of 50 to
75 ° C. and a number average molecular weight (Mn) of 1,500 to 5
000 and a weight average molecular weight (Mw) of 6,000
10. The method according to claim 1, wherein the number is from 0 to 100,000.
3. The electrostatic image developing toner according to item 2. 5. The following formula (A) : An alcohol component having a bisphenol derivative represented by
And phthalic acid, terephthalic acid, isophthalic acid,
Succinic acid, n-dodecenylsuccinic acid, fumaric acid, maleic
Glue composed of acid, maleic anhydride and their anhydrides
Dicarboxylic acids selected from the group
Bird is selected from the group consisting of acids and anhydrides
Obtained by condensation polymerization of an acid component having a carboxylic acid
A polyester resin as a main binder resin component; and
Color for developing electrostatic images containing dye and / or pigment
In the toner, the weight average particle diameter of the toner is 3 to 8 μm
And a modified silicone compound having a melting point of 15 to 200 ° C.
Color toner for developing electrostatic images, characterized by containing
- 6. The toner according to claim 1, wherein the modified silicone compound is
2 to 30 parts by weight based on 100 parts by weight of the binder resin
6. The electrostatic image developing device according to claim 5, wherein
Lartner. 7. The polyester resin has a glass transition temperature.
Is 50 to 75 ° C., and the number average molecular weight (Mn) is 1,5.
00 to 50,000, and the weight average molecular weight (Mw) is
6,000 to 100,000
7. The color toner for developing an electrostatic image according to claim 5 or 6.