JPH09146305A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner having a wide fixing temp. range and excellent high temp. offset resistance which can be used for various copying speed from slow to fast processes. SOLUTION: This electrostatic charge image developing toner has toner particles containing at least a binder resin and a coloring agent. In the binder resin, the resin component in 2000-100000 mol.wt. fraction separated by fractional liquid chromatograph shows that the ratio (M/S) of the wt. average mol.wt. (M) measured by a light-scattering method and the inertia radius (S) measured by a light-scattering method is >200.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in image forming methods such as electrophotography, electrostatic recording and electrostatic printing.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Numerous methods are known as described in Japanese Patent Application Laid-Open Publication No. Hei. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, a toner image is formed on a transfer material such as paper. Is transferred, and then fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a toner image.

Various methods and apparatuses have been developed for fixing the toner image to a sheet such as paper, which is the above-mentioned final step, but the most common method at present is a pressure heating method using a heat roller.

In the pressure contact heating method using a heating roller, the surface of the heat roller having releasability for toner and the toner image surface of the fixing sheet are brought into contact with each other under pressure to pass the fixing sheet to form a toner image. It is for fixing. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so that the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and quick fixing is required. You can

However, at present, different toners are used depending on the model of copying machine or printer. This is mainly due to the difference in fixing speed and fixing temperature. Since the surface of the heating roller and the toner image are in a molten state and contact with each other under pressure, part of the toner image adheres to the surface of the fixing roller and is transferred, and this is retransferred to the next sheet to be fixed and stains the sheet to be fixed. This is because the offset phenomenon is greatly affected by the fixing speed and the fixing temperature. Generally, when the fixing speed is low, the heating roller surface temperature is low, and when the fixing speed is high, the heating roller surface temperature is high. This is because the amount of heat given to the toner by the heating roller for fixing the toner is made substantially constant regardless of the fixing speed.

However, since the toner on the sheet to be fixed forms several toner layers, the fixing speed is particularly high, and in a system where the heating roller temperature is high, the toner layer contacting the heating roller and the fixing layer are fixed. The temperature difference of the lowermost toner layer in contact with the sheet becomes very large. Therefore, when the temperature of the heating roller is high, the toner of the uppermost layer causes an offset phenomenon, while when the temperature of the heating roller is low, the toner of the lowermost layer is not sufficiently melted, so The toner is not fixed and a phenomenon called low temperature offset occurs.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing to anchor the toner to the fixing target sheet is usually used. With this method, the temperature of the heating roller can be lowered to some extent, and the high temperature offset phenomenon of the uppermost layer toner can be prevented. However, since the shearing force applied to the toner becomes extremely large, the sheet to be fixed is wound around the fixing roller, and there is a wrapping offset, or after separation of a member (for example, a separating claw) for separating the sheet to be fixed from the fixing roller. Appears in the image, and because the pressure is high, the line image is crushed at the time of fixing and the toner flies off, so that the image quality of the fixed image easily deteriorates.

Therefore, in general, in high-speed fixing, toner having a lower melt viscosity than that in low-speed fixing is used, and the heating roller temperature and fixing pressure are lowered to fix the toner while preventing high temperature offset and winding offset. However, when such a toner having a low melt viscosity is used for low-speed fixing, an offset phenomenon easily occurs at a high temperature because of the low viscosity.

Generally, as a method for lowering the viscosity of toner,
A method of lowering the glass transition point of the polymer or lowering the molecular weight of the polymer can be mentioned. However, the former method lowers the storage stability, and the latter method lowers the high temperature offset resistance and the triboelectrification property, and moreover the toner is apt to be fused to the photoreceptor. In a vinyl resin, as a method for increasing the degree of branching of the polymer, JP-A-3-87753
Japanese Patent Application Laid-Open No. 3-203746 and Japanese Patent Application Laid-Open No. 3-203746 propose a method using a macromonomer, and Japanese Patent Application Laid-Open No. 4-24648 proposes a method using an ε'-caprolactone-modified hydroxyvinyl monomer. However, when many macromonomers are used to increase the degree of branching by these methods, the glass transition temperature of the resin is lowered and the storage stability is lowered. In order to maintain good storage stability of the toner, the molecular weight of the polymer main chain is increased to raise the glass transition temperature of the polymer main chain, or the monomer composition of the polymer main chain is changed to increase the molecular weight. There is a method of increasing only the glass transition temperature without changing it. However, in either of these methods, the fixing temperature rises and the effect of lowering the toner temperature by fixing the branching degree is small. this is,
This is because the composition distribution of the macromonomer in the polymer is greatly affected, and thus when many macromonomers are polymerized in the polymer chain, this polymer deteriorates the storage stability. Therefore, in order to improve the storage stability of this polymer, the glass transition temperature of the main chain must be increased excessively due to some polymers in which many macromonomers are unevenly distributed. Sex decreases. Since the glass transition temperature in the main chain and the glass transition temperature in the side chain are so different from each other, the effect of lowering the viscosity due to branching is offset by the increase in viscosity due to the increase in the glass transition temperature of the main chain.

In the polyester resin, as a method for increasing the branching degree, a method of using a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol, or a method of using a side chain-containing dicarboxylic acid or a side chain diol, JP 59
No. 228658 and Japanese Patent Laid-Open No. 62-195678. Since the side chains of dicarboxylic acids and diols having a side chain are aliphatic group side chains, this side chain lowers the glass transition temperature of the polymer and increases the degree of branching as in the case of the vinyl resin. Therefore, the effect of lowering the viscosity is lost by increasing the glass transition temperature of the main chain. In the method using a trivalent or higher polycarboxylic acid or polyhydric alcohol, the degree of branching is high,
The gel content (THF insoluble content) increases, and the high temperature offset resistance is improved, but the fixing temperature rises.

JP-A-63-225244 to 225246
Japanese Patent Laid-Open No. 5-2497 proposes a method of blending two kinds of non-linear polyesters having different softening points.
Japanese Patent Laid-Open No. 36-36 proposes a method of using a resin composed of high-density crosslinked microgel particles containing a linear portion and a crosslinked portion.

In the former case, since the divalent carboxylic acid and the divalent alcohol and the trivalent or higher polyvalent carboxylic acid or the polyhydric alcohol are simultaneously charged in the vessel for synthesis, it is very difficult to adjust the branching degree.

There is a demand for a toner having a wide fixing temperature range and excellent offset resistance, which can be applied satisfactorily from low speed to high speed in heat and pressure fixing.

Furthermore, in recent years, it has been desired to improve the quality of copied images by digitizing copying machines and making toner particles finer. In a photographic image containing characters, the characters of the copied image are clear, and the photographic image is required to have density gradation that is faithful to the original. Generally, in copying a photographic image containing characters, if the line density is increased to make the characters clear, not only the density gradation of the photographic image is impaired, but also the image becomes very rough in the halftone portion.

Further, when the line density is increased, the amount of toner adhered in the toner transfer step is large, so that the toner is pressed against the photoconductor during the transfer and adheres to the photoconductor, and the toner in the line is removed. A dropout phenomenon occurs, and a low-quality copy image is likely to occur. On the contrary, if the density gradation of the photographic image is improved, the density of the character line is lowered and the sharpness is lowered.

By reducing the particle size of the toner, the resolution and sharpness of the image can be increased, but various problems are likely to occur.

First, the fixing property of the halftone portion is lowered due to the reduction of the particle size of the toner. This phenomenon is particularly remarkable in high-speed fixing. This is because the toner amount in the halftone portion is small, the toner transferred to the concave portion of the fixing sheet has a small amount of heat applied from the heating roller, and the fixing pressure is also suppressed by the convex portion of the fixing sheet. Because of that. Since the toner transferred to the convex portion of the fixing sheet in the halftone portion has a small toner layer thickness, the shearing force applied to each toner particle is much larger than that of the solid black portion having a large toner layer thickness. , An offset phenomenon is likely to occur, and a low-quality copy image is likely to be obtained.

Further, by reducing the diameter of the toner particles, the surface area of the toner per unit weight increases, the width of the distribution of the toner charge amount increases, and fogging is likely to occur. By increasing the surface area of the toner per unit weight, the triboelectrification characteristics of the toner are more susceptible to the environment.

When the diameter of the toner particles is reduced, the dispersion state of the magnetic substance and the colorant is more likely to affect the charging property of the toner.

When such a small-diameter toner is applied to a high-speed copying machine, it tends to become overcharged under low humidity, resulting in fog and reduced density.

In a multifunctional copying machine, a part of an image is erased by exposure and then another image is inserted into the part to perform multicolor copying, or the periphery of the copy paper is framed. With such a function, fogging is likely to occur in a portion of the image to be whitened.

When an image having a polarity opposite to the latent image potential with respect to the development reference potential is erased with strong light by means such as an LED or a fuse lamp, the fog tends to occur at that portion.

[0023]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image, which solves the above problems.

An object of the present invention is to provide a toner excellent in offset resistance without impairing the fixing property from low speed to high speed copying machines.

The object of the present invention is to provide excellent fixability in the halftone portion, and to obtain a copy image of good quality, even when the particle size is reduced and the particle size is reduced from low speed to high speed copying machines. To provide toner.

An object of the present invention is to provide a toner capable of obtaining a high-density copy image without fog from low speed to high speed copying machines.

An object of the present invention is to provide a toner which gives good images even under low humidity and high humidity without being affected by environmental changes.

An object of the present invention is to provide a toner which gives a stable and good image even in a high-speed machine and has a wide range of applicable models.

An object of the present invention is to provide a toner which is excellent in durability, has a high image density even when continuously used for a long time, and can obtain a copy image without white background fog.

An object of the present invention is to provide a toner in which, in a photographic image containing characters, the characters of the copied image are clear and the photographic image has density gradation that is faithful to the original.

[0031]

The present invention relates to an electrostatic charge image developing toner having toner particles containing at least a binder resin and a colorant, which is fractionated by preparative liquid chromatography on the binder resin. Molecular weight 2,000-10
The resin component in the range of 20,000 has a ratio (M / S) of the weight average molecular weight (M) measured by a light scattering method and the radius of gyration (S) measured by a light scattering method of 200 or more. And a toner for developing an electrostatic charge image.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a molecular weight of 2,000 to 100, which is fractionated by a preparative liquid chromatograph,
The reason for focusing on the resin component (polymer) in the area of 000 will be described below.

In the case of a resin component (especially polyester resin) having a molecular weight of less than 2,000, it is feared that a dimer and a trimer of a monomer are formed, and the branched chain aimed at by the present invention is This is because it may not be the polymer that it has.

Further, in the case of a resin component (polymer) having a molecular weight of 100,000 or more, when it was examined by fractionation, the elasticity became stronger than the viscosity, and it is difficult to consider that it is a component that improves the fixing property. Is.

In the region of molecular weight of 2,000 to 100,000, which was fractionated by preparative liquid chromatography, M
The meaning of / S of 200 or more means that the polymer has a large molecular weight per unit length, and therefore there are many branched polymers.

A polymer having a large number of branches has a smaller radius of gyration as compared with a polymer having a smaller number of branches, and the interaction between the polymers is reduced to lower the viscosity.

Here, in the resin component having a molecular weight of 2,000 to 100,000, which is fractionated by preparative liquid chromatography, if the M / S is less than 200, the polymer may be a branched polymer. However, the effect of lowering the viscosity due to branching is low, and the fixability is not the same as that of an unbranched polymer.

The M / S of the resin component in the molecular weight range of 2,000 to 100,000 separated by preparative liquid chromatography is preferably 300 or more, more preferably 400 or more, and most preferably 420 to 2,000. Is.

When the value of M / S is larger than 200 (that is, the more branched polymers are present), the magnetic substance with respect to the binder resin during the production of the toner particles,
Dispersibility of the charge control agent or other additives is good, developability as a toner is good, selective developability is suppressed as image characteristics, and environmental stability is good.

An example of a method for controlling the branching degree of the binder resin and the glass transition temperature will be described below.

In the polyester resin, for example, a low molecular weight polyester and a high molecular weight polyester are separately synthesized in advance, and when these are blended, a trivalent or higher carboxylic acid and / or a trivalent or higher alcohol is added to carry out condensation polymerization. To do. By this method, a polyester resin having a large number of branched chains can be synthesized, and further, the branched chain length can be controlled by the molecular weight of the polyester to be synthesized first separately, so that the binder resin in the most preferable form for the present invention can be obtained. You can

In the case of vinyl resin, for example, there may be mentioned a method in which a trifunctional or higher functional radical polymerization initiator is added to the reaction system in plural times during the polymerization to form a polymer having a branched chain.

When it is desired to add the radical polymerization initiator in plural times, the number of branched chains in one polymer chain is
Most of the number is 2 less than the number of functional groups of the radical polymerization initiator, and the effect of decreasing the viscosity by increasing the branching degree in the present invention is hardly obtained.

In the present invention, in the measurement of the molecular weight distribution of the THF-soluble component of the toner or the binder resin by gel permeation chromatography (GPC method), the abundance of the resin component in the molecular weight range of 2,000 to 100,000. Is preferably 50 to 90%. This resin component is important for imparting viscosity to the toner and improving fixability. Molecular weight 2,000-100,000
If the content of the component in the region of 0 is less than 50%, the viscosity of the toner decreases, and especially in a high speed copying machine, the fixability decreases.
90 in the molecular weight range of 2,000-100,000
When it exceeds%, the viscosity of the toner becomes strong, and the high temperature offset resistance and scatter resistance offset level decrease.

Examples of the binder resin used in the present invention include polyester resin, vinyl resin and epoxy resin. Among them, polyester resins and vinyl resins are more preferable because of their fixability and chargeability, and polyester resins are particularly preferable.

The following may be mentioned as monomers for forming the polyester resin.

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 bisphenol derivative represented by the formula (A)

[0048]

[Outside 1]

Further, diols represented by the formula (B)

[0050]

[Outside 2] And other diols.

Examples of the divalent carboxylic acid include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride, or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or the like. An anhydride, and further, succinic acid substituted with an alkyl group having 6 to 18 carbon atoms or its anhydride; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or its anhydride, and the like. .

Polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxylalkylene ethers of novolac type phenolic resins; trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their anhydrides. Examples thereof include carboxylic acids.

The glass transition temperature of the polyester resin is preferably 45 to 80 ° C., more preferably 50 to 70 ° C., and the number average molecular weight (Mn) by the GPC method is preferably 1,000 to 80,000, more preferably Is 1,
500 to 50,000, and the weight average molecular weight (Mw) by the GPC method is preferably 5,000 to 1 × 10 ⁷ ,
It is more preferably 1 × 10 ^{4 to} 5 × 10 ⁶ .

The polyester resin having an acid value of 2 to 70 and an OH value of 50 or less (preferably 2 to 45) is less likely to be affected by the environment (temperature and humidity), and the toner is more easily charged. Stabilize.

Examples of the monomer for forming the vinyl resin include the following.

For example, styrene; o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylene, propylene, Ethylenically unsaturated monoolefins such as butylene and isobutylene; unsaturated diolefins such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate, benzoic acid Vinyl ester acids such as vinyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacrylic acid. Α-methylene aliphatic monocarboxylic acid esters such as phenyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; 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; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; esters of the above-mentioned α, β-unsaturated acids and diesters of dibasic acids.

Maleic acid, citraconic acid, itaconic acid,
Unsaturated dibasic acids such as alkenyl succinic acid, fumaric acid and mesaconic acid; maleic acid, citraconic anhydride, itaconic anhydride, unsaturated dibasic anhydrides such as alkenyl succinic anhydride; maleic acid methyl half ester , Maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, Unsaturated dibasic acid half esters such as mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid;
Α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, and the α, β-unsaturated acids And lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof and vinyl monomers having a carboxyl group such as monoesters thereof.

Examples of radically polymerizable trifunctional or higher functional polymerization initiators include tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane, and
2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t)
-Amylperoxycyclohexyl) propane, 2,2
Radical-polymerizable polyfunctional initiators such as -bis (4,4-di-t-octylperoxycyclohexyl) propane and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) butane. To be A binder resin having an M / S of 200 or more can be synthesized by the above-mentioned method using these polyfunctional polymerization initiators.

The vinyl resin preferably has a molecular weight of 2,000 to 100,000 in the molecular weight distribution by GPC.
A compound having at least one peak in the range of 0 and having at least one peak in a region having a molecular weight of 100,000 or more is preferable.

The glass transition temperature of the vinyl resin is preferably 45 to 80 ° C, more preferably 50 to 70 ° C.

In the toner of the present invention, a charge control agent can be used, if necessary, in order to further stabilize its chargeability. The charge control agent is 0.1% by weight per 100 parts by weight of the binder resin.
It is preferable to use 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

Charge control agents known in the art today include the following:

To control the toner to be negatively charged,
For example, organic metal complexes and chelate compounds are effective. Examples thereof include monoazo metal complexes, aromatic hydroxycarboxylic acids, metal complexes, and metal complexes of aromatic dicarboxylic acids. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives of bisphenol.

In the case of a positively chargeable toner, examples of the charge control agent having a positive chargeability include nigrosine, triphenylmethane type compounds, rhodamine type dyes, polyvinyl pyridine and the like. In the case of producing a color toner, an aminocarboxylic acid-containing ester such as dimethylaminomethyl methacrylate having a positive charge property is used as a monomer in an amount of 0.1 to 0.1%.
It is preferable to use a binder resin contained in an amount of 40 mol%, preferably 1 to 30 mol%, or to use a colorless or pale color positive charge control agent that does not affect the color tone of the toner. Examples of the positive charge control agent include structural formula (C),
Examples include the quaternary ammonium salt represented by (D).

[0065]

[Outside 3]

Among the quaternary ammonium salts represented by the structural formulas (C) and (D), the positive charge control agents represented by the structural formulas (C) -1 and -2 and the structural formula (D) -1 are used. But,
It is preferable because it exhibits good chargeability with little environmental dependence.

[0067]

[Outside 4]

In the case of using an aminocarboxylic acid-containing ester such as dimethylaminomethyl methacrylate, which exhibits positive charging characteristics, as the resin component of the binder resin in the positively chargeable toner, a positive charge control agent or a negative charge control agent is required. Good to use according to.

When an aminocarboxylic acid-containing ester such as dimethylaminomethyl methacrylate showing a positive charging characteristic is not used as a resin component in the positively chargeable toner, the positive charge control agent is preferably added to 100 parts by weight of the binder resin. It is preferable to use 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight. When the aminocarboxylic acid-containing ester is used, a positive charge control agent and / or a negative charge control agent may be added to the binder resin in an amount of 0 relative to 100 parts by weight for the purpose of providing good chargeability with little environmental dependence. -10 parts by weight, preferably 0-8 parts by weight.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co and Ni. Or a metal such as Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

As the magnetic material, iron trioxide (Fe)
₃ O ₄ ), ferric sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (Z
nFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ),
Iron oxide cadmium (CdFe ₂ O ₄ ), iron cadmium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ),
Lead iron oxide (PbFe ₁₂ —O ₁₉ ), iron nickel oxide (Ni
Fe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (M
gFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni), and the like. The above-mentioned magnetic materials may be used alone or in combination of two or more. Particularly preferred magnetic materials for the purposes of the present invention are fine powders of iron tetroxide or γ-iron sesquioxide.

These magnetic materials have an average particle size of 0.1 to 2 μm.
m (preferably 0.1 to 0.5 μm), the magnetic properties under application of 10 K oersted are 20 to 150 oersted for coercive force and 50 to 200 emu / g for saturation magnetization (preferably 5).
0-100 emu / g), remanent magnetization 2-20 emu / g
Are preferred.

The magnetic material 1 is added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

As the colorant, carbon black, titanium white, or any other pigment and / or dye can be used. When used as a magnetic color toner, the dye may be C.I. I. Direct Red, C.I.
I. Direct Red 4, C.I. I. Acid Red 1,
C. 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. 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 and the like. Pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow N.
CG, tartrazine lake, red lead yellow lead, 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, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final Yellow Green G, etc.

Examples of the colorant for the full-color image forming color toner include the following. Examples of magenta color pigments include C.I. I. Pigment Red 1, 2,
3,4,5,6,7,8,9,10,11,12,1
3,14,15,16,17,18,19,21,2
2,23,30,31,32,37,38,39,4
0, 41, 48, 49, 50, 51, 52, 53, 5
4,55,57,58,60,63,64,68,8
1, 83, 87, 88, 89, 90, 112, 114,
122, 123, 163, 202, 206, 207, 2
09, C.I. I. Pigment Violet 19, C.I. I.
Bat red, 1, 2, 10, 13, 15, 23, 2
9, 35 and the like.

The pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment in combination. Magenta dyes include C.I. I. Solvent Red 1, 3, 8, 23,
24, 25, 27, 30, 49, 81, 82, 83, 8
4,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,13,1
4, 21, 27, C.I. I. Disperse Violet 1
Oil-soluble dyes such as C.I. I. Basic Red 1,2,9,
12, 13, 14, 15, 17, 18, 22, 23, 2
4,27,29,32,34,35,36,37,3
8, 39, 40, C.I. I. Basic Violet 1,
3,7,10,14,15,21,25,26,27,
28 and the like basic dyes.

As the color pigment for cyan, 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 in the phthalocyanine skeleton having the structure represented by the chemical formula 3 is exemplified.

[0078]

[Outside 5]

As the coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the colorant used is 0.1 to 60 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the binder resin.

In the present invention, one kind or two or more kinds of releasing agents may be contained in the toner, if necessary.

Examples of the release agent used in the present invention include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax can be mentioned.

As the aliphatic hydrocarbon wax, for example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or by a Ziegler catalyst under low pressure, an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer, A wax such as a synthetic hydrocarbon obtained by a hydrogenation of a hydrocarbon distillation residue obtained from a synthesis gas composed of carbon monoxide and hydrogen by the Arge process can be used. Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a fractional crystallization method can be used. As an example of the aliphatic hydrocarbon wax, in the DSC curve measured by a differential scanning calorimeter, regarding the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature decrease, the endothermic onset temperature is in the range of 50 to 110 ° C. And an aliphatic hydrocarbon wax having at least one endothermic peak in the temperature range of 70 to 130 ° C., and having a maximum exothermic peak during cooling within the peak temperature of the endothermic peak ± 9 ° C. it can. The hydrocarbon as a matrix is one synthesized by a reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component system), for example, gintol method, hydrocoal method (fluidized catalyst bed). use),
Alternatively, it is possible to use a hydrocarbon having a large number of wax-like hydrocarbons, which is obtained by the Luage method (using a fixed catalyst bed) and has up to several hundred carbon atoms, or a hydrocarbon obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst. . A wax synthesized by a method not depending on the polymerization of alkylene can be used.

As the release agent, an oxide of an aliphatic hydrocarbon wax such as oxidized polyethylene wax, or
Block copolymers thereof; waxes having a fatty acid ester as a main component such as carnauba wax and montanic acid ester wax, and those obtained by partially or completely deoxidizing a fatty acid ester such as deoxidized carnauba wax can be used. it can. Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as blancinic acid, eleostearic acid, and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol , Saturated alcohols such as melisyl alcohol; polyhydric alcohols such as sorbitol, linoleic acid amides, fatty acid amides such as oleic acid amides and lauric acid amides, methylenebisstearearic acid amides, ethylenebiscapric acid amides, ethylenebislauric acid amides Saturated fatty acid bisamides such as hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'-dioleyl adipamide, N, N'-diole Such unsaturated fatty acid amides of Rusebashin acid amide; m-xylene bis-stearic acid amide, N, N'-distearyl such aromatic bisamides of isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate,
Fatty acid metal salt such as magnesium stearate (generally called metal soap); Graft wax obtained by grafting aliphatic hydrocarbon wax with vinyl monomer such as styrene and acrylic acid; Behenic acid monoglyceride Partial esterified products of fatty acids and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats, and the like.

The releasing agent particularly preferably used in the present invention includes an aliphatic alcohol wax and an alkyl monocarboxylic acid wax.

The aliphatic alcohol wax is represented by the following formula (1).

CH ₃ (CH ₂ ) _x CH ₂ OH (1) (x represents an average value and is 20 to 250)

The alkyl monocarboxylic acid wax is represented by the following formula (2).

CH ₃ (CH ₂ ) _Y CH ₂ COOH (2) (Y represents an average value and is 20 to 250)

The amount of the releasing agent used in the present invention is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

The mold releasing agent is usually prepared by dissolving a resin in a solvent, raising the temperature of the resin solution, and adding and mixing with stirring.
It is contained in the binder resin by a method of mixing at the time of kneading.

A fluidity improver may be used in the toner of the present invention. As the fluidity improver, one that can increase the fluidity of the toner particles before and after the addition can be used. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder, fine silica powder such as wet process silica and dry process silica, and silane coupling agent, titanium coupling agent, silicone oil, etc. There is a treated silica which has been subjected to a surface treatment by.

A preferable fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is called dry process silica or fumed silica, and is produced by a conventionally known technique. 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 manufacturing process, it is also possible to obtain a fine composite powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound. Included as silica. The average particle size of the particles is preferably in the range of 0.001 to 2 μm, and particularly preferably 0.002 to 2 μm.
It is good to use a silica fine powder in the range of (1).

Examples of commercially available silica fine powders produced by vapor phase oxidation of a silicon halogen compound include those commercially available under the following trade names.

AEROSIL (Japan Aerosil Co.) 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 N 20 V15 (WACK) -CHEMIE GMBH) N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Francol (Fransil)

Further, it is more preferable to use a treated silica fine powder obtained by subjecting the silica fine powder produced by the vapor phase oxidation of the silicon halogen compound to a hydrophobic treatment. 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.

As a method of hydrophobizing, it is imparted by chemically treating with an organosilicon compound which reacts with or physically adsorbs on silica fine powder. The preferred method is
Silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated as an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl. Dimethylchlorosilane, brommethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, 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.

As the positively chargeable fluidity improver, one obtained by treating the aforementioned dry process silica with a coupling agent having an amino group as described below or a silicone oil is used.

[0102]

[Outside 6]

[0103]

[Outside 7]

As the silicone oil, an amino-modified silicone having a partial structure having an amino group in the side chain of the following formula is generally used.

[0105]

[Outside 8] (In the 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 hydrogen, an alkyl group or an aryl group. The above-mentioned alkyl group, aryl group, alkylene group, and phenylene group may contain an amine, and may have a substituent such as halogen within a range not impairing the charging property, and m and n are positive. Indicates an integer.)

Examples of such silicone oil having an amino group are as follows.

[0107]

[Outside 9]

The amine equivalent is the equivalent per amine (g / eqiv) and is the value obtained by dividing the molecular weight by the number of amines per molecule.

The fluidity improver has a specific surface area of 30 m ² / g or more, preferably 5 or more, by nitrogen adsorption measured by the BET method.
Those with 0 m ² / g or more give good results. The fluidity improver may be used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner particles.

In order to prepare the toner of the present invention, a binder resin, a colorant and / or a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then a kneader or an extruder is used. It may be possible to obtain toner particles by melting, kneading and kneading a resin using a heat kneader such as a ruder to make the resins compatible with each other, cooling and solidifying the melt kneaded product, crushing the solidified product, and classifying the crushed product. it can.

Further, the fluidity improver charged to the same polarity as the toner particles and the toner particles are sufficiently mixed by a mixing machine such as a Henschel mixer to obtain a toner having the fluidity improver on the surface of the toner particles.

The measuring method of each characteristic of the binder resin was carried out as follows.

(1) Fractionation of Binder Resin and Toner by Fractionation Liquid Chromatograph for Fraction of Molecular Weight 2000 to 100000: Fractionation of Binder Resin and Toner by Fractionation Liquid Chromatograph for Fraction of Molecular Weight 2000 to 100000 ,
Nippon Analytical Industry Co., Ltd. recycle preparative HPLC LC
It was carried out using a -908 model.

The sample of the preparative liquid chromatograph is prepared, for example, as follows.

After mixing the sample and chloroform and leaving them at room temperature for several hours (for example, 5 to 6 hours), shake them well and mix the chloroform and sample well (until the coalescence of the samples disappears), and further to room temperature. Let stand for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and chloroform to the end of the standing should be 24 hours or more. After that, a sample processing filter (bore size 0.45 to 0.5 μm, for example, Mysholydisc H-25-2 manufactured by Toso Corporation, Ekikurodisc 25C)
R Gelman Science Japan Co., Ltd. and the like are preferably used) as a sample for the preparative liquid chromatograph.

As a preparative column in the preparative liquid chromatograph, a preparative column JA manufactured by Nippon Analytical Industry Co., Ltd. is used.
IGEL-1H, JAIGEL-2H, JAIGEL-
3H, JAIGEL-4H, JAIGEL-LS25
5, a preparative column selected from JAIGEL-5H and JAIGEL-6H is used.

(2) Measurement of weight average molecular weight (M) and radius of gyration (S) by light scattering method The weight average molecular weight (M) and radius of gyration (S) were measured by the static light scattering method. The measuring device is Otsuka Electronics Co., Ltd.
A light scattering photometer DLS-700 was used. In the molecular weight measurement by the static light scattering method, it is necessary to measure the rate of change (dn / dc) of the sample's differential refractive index with respect to the sample concentration.
High sensitivity differential refractometer manufactured by Otsuka Electronics Co., Ltd.
DRM-1020 was used. The measurement was performed by the following procedure.

The resin and toner to be measured are dissolved in tetrahydrofuran (THF) or chloroform, left to stand overnight, and the concentration of the sample filtered with a 0.2 μm filter is adjusted. The scattered light intensity and the measurement angle of the sample of which the concentration was adjusted were changed, and the weight average molecular weight (M) and the radius of gyration (S) were obtained from the formula (I) shown below.

[0119]

[Outside 10]

Here, M represents a weight average molecular weight, and A ₂
Is the second virial coefficient, S is the radius of gyration, C is the concentration of the solution, λ is the wavelength in the solution,

[0121]

[Outside 11]

The weight average molecular weight (M) and the radius of gyration (S) were calculated from the formula (I).

(3) Measurement of molecular weight by GPC method The molecular weight distribution in the chromatogram of the binder resin and the toner by GPC method (gel permeation chromatography) is measured under the following conditions.

The measurement sample is prepared as follows.

The sample and tetrahydrofuran (THF) were mixed at a concentration of about 0.5 to 5 mg / ml (for example, about 5 mg / ml), and the mixture was allowed to stand at room temperature for several hours (for example, 5 to 6 hours). Shake well mix the THF with the sample (until the samples are no longer coalesced) and let stand at room temperature for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the time after the end of standing was 24
Try to be over time. After that, the one that passed through a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysholydisk H-25-2 manufactured by Tosoh Corporation, Excicrodisk 25CR Gelman Science Japan Co., Ltd. can be preferably used) was passed through GPC. Of the sample. Sample concentration of resin component is 0.5-5 μm / m
Adjust to be l.

In the GPC measuring apparatus, the column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was flown through the column at this concentration at a flow rate of 1 ml / min to obtain T
Approximately 100 μl of the HF sample solution is injected for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample
It is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. A standard polystyrene sample for preparing a calibration curve has a molecular weight of 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, for example.
It is suitable to use a standard polystyrene sample having at least about 10 points. RI for the detector
A (refractive index) detector is used. As the column, a plurality of commercially available polystyrene gel columns are preferably combined. For example, a Shodex GPC K manufactured by Showa Denko KK
F-801, 802, 803, 804, 805, 80
6,807,800P combination and Tosoh T
SKgel G1000H (H _XL ), G2000H
(H _XL ), G3000H (H _XL ), G4000H
(H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), TSK guard
A combination of columns can be mentioned.

Generally, in the measurement of a GPC chromatogram, the measurement is started from the baseline on the high molecular weight side from the starting point of the chromatogram, and on the low molecular weight side up to about 400.

Molecular weight 2 in GPC chromatogram
The abundance ratio of the region of 000 to 100,000 can be calculated by obtaining the ratio of the integrated value of the region of molecular weight 2000 to 100000 to the integrated value of the chromatogram. Alternatively, a GPC chromatogram is cut out, and the weight of the cut out GPC chromatogram is measured to obtain a molecular weight of 2
The abundance ratio of the region having a molecular weight of 2000 to 100,000 can be obtained by cutting out the region of 000 to 100,000 and measuring the weight, and obtaining the ratio to the weight of the entire chromatogram of GPC.

(4) Glass transition temperature Tg Differential thermal analysis analyzer (DSC analyzer), DSC-7
(Perkin Elmer).

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min at a normal temperature and normal humidity in a measurement temperature range of 30 to 200 ° C. During this temperature raising process, the temperature of 40 to 10
The endothermic peak of the main peak in the range of 0 ° C is obtained. At this time, the intersection of the line at the midpoint of the baseline before and after the appearance of the endothermic peak and the differential heat curve is taken as the glass transition temperature Tg in the present invention.

(5) Method of measuring acid value / OH value 1) Acid value A sample is precisely weighed, dissolved in a mixed solvent and water is added. This solution is subjected to potentiometric titration with 0.1N-NaOH using a glass electrode to determine the acid value (according to JIS K1557-1970).

In the molecular weight distribution measurement, the acid value of the developer is measured in the same manner as above as a sample by attaching a fractionation device, drying the fractionated sample.

2) OH number The sample is precisely weighed in a 100 ml round-bottomed flask, and 5 ml of the acetylating reagent is correctly added to this. Then 100 ° C ± 5
Dip in a bath at ℃ and heat. After 1-2 hours, the flask is taken out of the bath and allowed to cool, then water is added and shaken to decompose acetic anhydride. To further complete the decomposition, the flask is again heated in the bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using a glass electrode to determine a hydroxyl value. (According to JIS K0070-1966).

[0134]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples.

Resin Production Example 1 Fumaric acid 51 mol% Bisphenol derivative represented by the formula (A) 49 mol% (R: propylene group x + y = 2.2)

Polyester resin (α) having a number average molecular weight (Mn) of 2,600, a weight average molecular weight (Mw) of 8,000 and a Tg of 50 ° C., obtained by subjecting these to condensation polymerization. Got Polyester resin (α)
The number average molecular weight (Mn) according to the GPC method is 15,000, the weight average molecular weight (Mw) is 89,000, and the Tg is 60 with the same composition as the above but with a longer reaction time.
A polyester resin (β) having a temperature of ° C was obtained.

Polyester resin (α) and (β) 3: 1
In a weight ratio of, and trimellitic anhydride was added so that the amount of addition was 10 mol%, and condensation polymerization was performed.
No F insoluble component, number average molecular weight (M
n) is 9,000 and the weight average molecular weight (Mw) is 5
Resin No. 0 having a Tg of 60.degree. 1
I got

Resin No. Using a preparative liquid chromatograph, the resin component in the molecular weight range of 2000 to 100000 was fractionated, and the weight average molecular weight (M) and the radius of gyration (S) were measured by a light scattering method. M)
Was 850,000, the radius of gyration (S) was 700Å, and the M / S was 1,214.

Resin Production Examples 2 to 4 Resin Nos. Shown in Table 1 were prepared in the same manner as in Resin Production Example 1 except that the composition, reaction conditions and blend ratio were changed. 2-4
I got

Resin Production Example 5 Polyester resin (α) in Resin Production Example 1 and Resin No. 1 in Resin Production Example 4 4 was mixed at a weight ratio of 2: 1 and the amount of trimellitic anhydride added was 20 mol%.
And the number average molecular weight (Mn) by the GPC method is 16,000, the weight average molecular weight (Mw) is 842,000, and the Tg is 61 ° C. 5 was obtained.

Resin No. When the weight average molecular weight (M) and the radius of gyration (S) were measured by fractionating the resin component in the molecular weight range of 2000 to 100000 using a preparative liquid chromatograph and measuring the weight average molecular weight (S) by the light scattering method, M)
Is 1,176,000 and the radius of gyration (S) is 367
It was 5Å and M / S was 320.

Resin Production Example 6 Polyester resin (α) in Resin Production Example 1 and Resin No. 1 in Resin Production Example 4 4 was mixed at a weight ratio of 1: 1 and further added so that the amount of trimellitic anhydride was 30 mol%, and condensation polymerization was performed. The number average molecular weight (Mn) by GPC method was 18,200. Resin No. 1 having an average molecular weight (Mw) of 887,000 and a Tg of 60 ° C. 6 was obtained.

Resin No. The resin component in the molecular weight range of 2000 to 100,000 was fractionated using a preparative liquid chromatograph and the weight average molecular weight (M) and the radius of gyration (S) were measured by a light scattering method. M)
Is 1,278,000 and the radius of gyration (S) is 5,7
It was 82Å and M / S was 221.

Resin Production Example 7 (Comparative Example) Terephthalic acid 24 mol% Dodecenylsuccinic acid 18 mol% Trimellitic anhydride 8 mol% Bisphenol derivative 17 mol% represented by the formula (A) (R: propylene group x + y = 2.2) Formula 33 mol% of the bisphenol derivative represented by (A) (R: ethylene group x + y = 2.2)

These were subjected to condensation polymerization to give a THF insoluble content of 0%.
And the number average molecular weight (Mn) by the GPC method is 3,1.
Resin No. 80 having a weight average molecular weight (Mw) of 48,100 and a Tg of 58 ° C. 7 was obtained.

Resin No. Using a preparative liquid chromatograph, the resin component in the molecular weight range of 2000 to 10000 was fractionated, and the weight average molecular weight (M) and
When the radius of gyration (S) was measured, the weight average molecular weight (M) was 54,600, and the radius of gyration (S) was 28.
It was 7Å and M / S was 190.

Resin Production Example 8 (Comparative Example) Fumaric acid 5 mol% Trimellitic anhydride 46 mol% Bisphenol derivative represented by the formula (A) 49 mol% (R: propylene group x + y = 2.2)

Resin No. 1 having a number average molecular weight (Mn) of 17,000, a weight average molecular weight (Mw) of 850,000, and a Tg of 62 ° C., obtained by condensation polymerization of these, is used. 8 was obtained.

Resin No. 8, the resin component in the molecular weight range of 2000 to 100000 was fractionated using a preparative liquid chromatograph, and the weight average molecular weight (M) and the radius of gyration (S) were measured by a light scattering method. (M) is 576,000 and the radius of gyration (S) is 3
It was 600Å and M / S was 160.

Resin Production Example 9 (Comparative Example) Fumaric acid 49.5 mol% Trimellitic anhydride 0.5 mol% Bisphenol derivative represented by the formula (A) 25 mol% (R: propylene group x + y = 2.2) Formula 25 mol% of the bisphenol derivative represented by (A) (R: ethylene group x + y = 2.2)

Resin No. 1 having a number average molecular weight (Mn) of 6,000, a weight average molecular weight (Mw) of 40,000, and a Tg of 60 ° C. obtained by condensation polymerization of these by GPC method. 9 was obtained.

Resin No. 9 was used to fractionate a resin component in the molecular weight range of 2000 to 100000 and the weight average molecular weight (M) and the radius of gyration (S) were measured by a light scattering method. (M) is 87,360 and the radius of gyration (S) is 54
It was 6Å and the M / S was 160.

The characteristic values of Resin Nos. 1 to 9 are shown in Table 1.

[0154]

[Table 1]

Resin Preparation Example 10 Styrene 83 parts by weight n-Butyl acrylate 12 parts by weight Maleic acid monobutyl ester 5 parts by weight Ditertiary butyl peroxide 1 part by weight Xylene 200 parts by weight was put in a reactor and the inside of the container was thoroughly filled. After replacing with nitrogen,
Polymerization was initiated at 144 ° C. After the initiation of the polymerization, 0.3 parts by weight of a polyfunctional radical polymerization initiator (tristarial butylperoxytriazine) represented by the following structural formula was added 5 times at intervals of 30 minutes, and the pressure was reduced at 4 hours after the initiation of the polymerization reaction. The xylene was removed while the temperature was raised to 200 ° C. below. This resin was designated as resin No. It is assumed to be 10.

[0156]

[Outside 12]

The resulting resin No. No. 10 has a (Mn) of 5,300, a weight average molecular weight (Mw) of 11,300 and a Tg of 60 in the molecular weight measurement by the GPC method.
° C.

Resin Production Example 11 Resin No. 11 was prepared in the same manner as in Resin Production Example 10 except that 0.3 parts by weight of tristar butylperoxytriazine was added twice at 1-hour intervals after the initiation of polymerization.
11 was obtained.

The resulting resin No. 11 has a number average molecular weight (Mn) of 5,750 as measured by GPC method.
The weight average molecular weight (Mw) was 11,700, and the Tg was 59.5 ° C.

Resin Production Example 12 Resin No. 12 was prepared in the same manner as in Resin Production Example 10 except that tristarial butylperoxytriazine was not added after the initiation of polymerization. I got 12.

The obtained No. No. 12 had a number average molecular weight (Mn) of 5470, a weight average molecular weight (Mw) of 11,450, and a T
The g was 60.7 ° C.

Resin Preparation Example 13 Styrene 83 parts by weight n-butyl acrylate 12 parts by weight Maleic acid monobutyl ester 5 parts by weight Diter-butyl butyl peroxide 1 part by weight Tristar butyl peroxytriazine 0.3 parts by weight xylene 200 parts by weight Part was put in the reactor and the inside of the reactor was sufficiently replaced with nitrogen.
Polymerization was initiated at 44 ° C. 4 hours after the start of the polymerization reaction,
Xylene was removed while raising the temperature to 200 ° C. under reduced pressure. 13 was obtained.

The resulting resin No. No. 13 has a number average molecular weight (Mn) of 5,4 in the molecular weight measurement by GPC method.
70, the weight average molecular weight (Mw) was 11,550, and Tg was 59.8 ° C.

Resin Production Example 14 Styrene 70 parts by weight n-butyl acrylate 24.7 parts by weight Maleic acid monobutyl ester 5 parts by weight Divinylbenzene 0.03 parts by weight Benzoyl peroxide 0.1 parts by weight

170 parts by weight of water in which 0.12 parts by weight of a partially saponified polyvinyl alcohol was dissolved was added to the above mixture, and the mixture was vigorously stirred to give a suspension dispersion. The above suspension dispersion was added to a reactor in which 500 parts by weight of water was charged and the atmosphere was replaced with nitrogen.
A suspension polymerization reaction was carried out at a reaction temperature of 80 ° C. for 8 hours. After the reaction, the resin No. 14 was obtained.

The resulting resin No. No. 14 has a number average molecular weight (Mn) of 236,000, a weight average molecular weight (Mw) of 14,277,000 and a Tg of 6 when measured by GPC method.
It was 0.5 ° C.

Resin Production Example 15 Resin No. 10 and resin No. Resin No. 14 was mixed with a resin xylene solution in a weight ratio of 4: 1, and then xylene was removed and dried to obtain Resin No. 15 was obtained.

Resin Production Example 16 Resin No. 11 and resin No. Resin No. 14 was prepared in the same manner as in Resin Production Example 15 except that the weight ratio of 4 was 14: 1. I got 16.

Resin Production Example 17 Resin No. 12 and resin No. Resin No. 14 was prepared in the same manner as in Resin Production Example 15 except that the weight ratio of 4 was 14: 1. 17 was obtained.

Resin Production Example 18 Resin No. 13 and resin No. Resin No. 14 was prepared in the same manner as in Resin Production Example 15 except that the weight ratio of 4 was 14: 1. I got 18.

Characteristic values of the resins 15 to 18 are shown in Table 2.

[0172]

[Table 2]

Example 1 Resin No. 1 100 parts by weight Magnetic iron oxide 90 parts by weight (average particle size 0.15 μm, Hc115 oersted, σs80 emu / g, σr11 emu / g) Release agent (a) 5 parts by weight [Aliphatic alcohol wax CH ₃ (CH ₂ )] _X CH ₂ OH (x = 48, OH value = 70)] Monoazo metal complex (negative charge control agent) 2 parts by weight

The above materials were premixed with a Henschel mixer, and then melt-kneaded at 130 ° C. with a twin-screw kneading extruder. After allowing the kneaded product to cool, after roughly crushing with a cutter mill,
The particles were pulverized with a fine pulverizer using a jet stream and further classified with an air classifier to obtain magnetic toner particles having a weight average particle diameter of 6.5 μm. Hydrophobic dry silica (BET 300 m ² / g) 1.0 is added to 100 parts of the magnetic toner particles.
Part of the toner was externally added with a Henschel mixer to obtain a toner.

Using a preparative liquid chromatograph of this toner, the resin component in the molecular weight range of 2000 to 100000 was fractionated, and the weight average molecular weight (M) and the radius of gyration (S) were measured by the light scattering method. The weight average molecular weight (M) was 840,950, the radius of gyration (S) was 695Å, and the M / S was 1,210.

When this toner was used to evaluate the image characteristics with a Canon digital copying machine (GP-55), good results were obtained as shown in Table 3-2. Remove the fixing device of Digital Copier GP-55, add external drive and temperature control function, change the fixing speed,
When a fixing test was conducted, good results as shown in Table 3-2 were obtained.

In the image characteristic evaluation, the density gradation was good. Furthermore, even after copying 20,000 sheets, the phenomenon of selective development in which only the toner with a small particle size is developed and consumed does not occur, the halftone image quality is almost the same as the initial stage, and a smooth image without density unevenness is obtained. It was

The evaluation method will be described below.

Halftone image quality The halftone image quality is the maximum image density obtained by arbitrarily measuring the image density at 10 points using a Macbeth reflection densitometer on an image obtained by copying an A4 0.3 halftone full-face solid original. The evaluation criterion was the difference between the value and the minimum value.

The halftone image quality here means the halftone density uniformity of the halftone image obtained by copying.

Poor halftone density uniformity (poor halftone image quality) means that the halftone image obtained by copying has uneven density and there are many variations in halftone image density. Is.

The evaluation criteria for halftone image quality are shown below.

[0183]

[Table 3]

Image Density The image density evaluation standard was the image density at the end of multiple durability tests.

The image density evaluation criteria are shown below.

[0186]

[Table 4]

Density Gradient A 17-gradation image chart containing halftone images with different shades was prepared, and the image obtained by copying the chart was visually evaluated in comparison with the original chart and evaluated in 5 levels. .

A ... Excellent B ... Good C ... Normal D ... Slightly bad E ... Poor

[0189] Toner was evaluated selective development of a number on the developing sleeve after the durability test toner and evaluated toner having a volume average particle diameter of each was measured by a Coulter counter method, the volume average particle diameter of the toner on the developing sleeve after the durability The difference in volume average particle size was determined.

[0190]

[Table 5]

Line Tobichiri (line image blurring tool
The following procedure was used for the evaluation of Rheinbychili.

A pattern consisting of five thin lines having the same line width and spacing, and 2.8, 3.2, 3.6, and 6 mm intervals within 1 mm.
4.0, 4.5, 5.0, 5.6, 6.3, 7.1,
Create an original image that looks like 8.0, 9.0, 10.0 lines. An image obtained by copying an original document having these 12 types of line images under appropriate copying conditions is observed with a magnifying glass, and the number of images (lines / mm) in which fine lines are clearly separated is used as an evaluation means. Using.

Here, the larger the value of the number of images (lines / mm) in which fine lines are clearly separated is, the better the level of line blurring of the copied image is.

The evaluation criteria of Rheinbitilli are shown below.

[0195]

[Table 6]

[0196] For environmental stability environmental stability, N / N environment (temperature 23.5 ℃,
Humidity 60% RH, H / H environment (temperature 30 ° C, humidity 80
% RH) and N / L environment (temperature 23.5 ° C, humidity 5% R
The image output durability in H) was performed up to 20,000 sheets, and the image density after 20,000 sheets was used as an evaluation standard.

Of the image densities in the three environments when the image output durability is 20,000, the difference between the value of the image density having the highest image density and the value of the image density having the lowest image density is determined as the environmental stability. Was used as the evaluation standard. The smaller the difference between the image density values, the better the environmental stability.

[0198]

[Table 7]

[0199] For fixing property fusing characteristics, Canon copier NP-9800
The fixing unit used in the above was modified to create an external fixing experiment device in which the process speed (fixing speed) and the fixing roller temperature were variable, and the fixing characteristics were evaluated.

An unfixed image of a solid black image and a halftone image before being passed through the fixing device, which were produced by Canon Copier GP-55, were used for the experiment of fixing characteristics.

An unfixed image of solid black and halftone is passed through an external fixing experiment device in which the fixing roller temperature is changed from 100 ° C. to 240 ° C. at 5 ° C. intervals, and the fixed image after passing is evaluated for fixing property. Using.

The fixing property was evaluated by rubbing the image with sillbon paper 10 times in a reciprocating manner under a load of about 100 g, and peeling of the image was evaluated by the reduction rate (%) of reflection density. The larger the reduction rate of the reflection density after rubbing (the reduction rate of image density), the greater the rate of peeling of the image due to rubbing, and the poorer the fixability of the toner.

While the fixing roller temperature was increased from 100 ° C. at intervals of 5 ° C., the unfixed image was passed through an external fixing experimenter, and the value of the reduction rate of the reflection density after rubbing of the fixed image after passing was 10%. The fixing roller temperature when the temperature became less than was set as the fixing start temperature.

Regarding high-temperature offset resistance, high-temperature offset occurs up to the fixing roller temperature of 240 ° C. (The toner on the unfixed image that has passed through the fixing roller is melted and softened by the heat of the fixing roller, and is transferred to the upper fixing roller. However, the case where there is no phenomenon in which the upper fixing roller is contaminated by the toner) was evaluated as Good.

Regarding the anti-winding offset, when a curled image such that the fixed image passing through the external fixing device is wound around the upper fixing roller during the experiment of the fixing characteristic, it is evaluated as Bad and the curl is generated. The case where there was no was evaluated as Good.

Examples 2 to 10 The same procedure as in Example 1 was carried out except that the binder resin and the release agent were changed as shown in Table 3-1. 2-10 were obtained. The grain size after copying 20,000 sheets was almost unchanged from the initial stage, and good image characteristics were obtained. The results are shown in Table 3-2.

In Examples 8 to 10, the following wax (b) was used as a release agent. Wax (b)
From the hydrocarbon wax synthesized by the Arge method,
It was obtained by fractional crystallization. Wax (b)
The DSC characteristics of were measured according to the following procedure.

In DSC measurement of wax, heat exchange is measured and its behavior is observed. Therefore, from the principle of measurement, it is necessary to measure with a highly accurate internal heat input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used.

The measurement method is ASTM D3418-82.
Perform according to. The DSC curve used in the present invention has a temperature rate of 10 ° C./min after the temperature is raised once and a previous history is taken.
A DSC curve measured when the temperature is lowered and raised in a temperature range of 0 to 200 ° C. is used. The definition of each temperature is defined as follows.

Endothermic peak of wax (endothermic in the positive direction) Onset temperature (OP) of endothermic wax: The tangent line of the curve at the lowest temperature among the temperatures at which the derivative of the peak curve is maximum. Temperature at the intersection of the tangent line and the base line Wax endothermic peak temperature (PP): Peak top temperature

Wax exothermic peak (minus direction is assumed to be exothermic) Wax exothermic peak temperature: peak top temperature of maximum peak

When DSC measurement of wax b was performed,
The onset temperature during heating was 67 ° C, the endothermic peak temperature during heating was 105 ° C, and the maximum exothermic peak temperature during cooling was 103 ° C. DSC of wax (b)
The characteristics are shown in FIGS. 1 and 2.

Comparative Examples 1 to 5 Toners were prepared in the same manner as in Example 1 except that the binder resin was changed as shown in Table 3-1 and evaluated in the same manner as in Example 1.

The results are shown in Table 3-2.

[0215]

[Table 8]

[0216]

[Table 9]

[0219]

The toner for developing an electrostatic charge image of the present invention has the following effects.

(1) Good fixing property and anti-offset property from low speed to high speed copying machine.

(2) From low speeds to high speed copying machines, good fixing properties can be obtained and good image quality can be obtained in the halftone portion.

(3) It is excellent in environmental stability without being affected by environmental changes.

(4) Good image density is obtained, and good density gradation is obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing a DSC curve of a wax (b) used in an example of the present invention when the temperature is raised.

FIG. 2 is a diagram showing a DSC curve when the temperature of a wax (b) used in an example of the present invention is lowered.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadashi Michigami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (24)

[Claims] 1. A toner for developing an electrostatic charge image having toner particles containing at least a binder resin and a colorant,
The resin component in the range of molecular weights of 2,000 to 100,000 separated by preparative liquid chromatography in the binder resin is measured by a light scattering method and a weight average molecular weight (M) measured by a light scattering method. Ratio of inertia radius (S) (M /
S) is 200 or more, an electrostatic charge image developing toner characterized by the above-mentioned. 2. The toner for developing an electrostatic charge image according to claim 1, which has an M / S of 300 or more. 3. The toner for developing an electrostatic charge image according to claim 1, wherein M / S is 400 or more. 4. The toner for developing an electrostatic charge image according to claim 1, wherein M / S is 420 to 2,000. 5. The binder resin has a molecular weight of 2,000 to 100,0 in a molecular weight distribution measurement of a THF-soluble component by gel permeation chromatography (GPC method).
The toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the amount of the resin component present in the area 00 is 50 to 90%. 6. The binder resin is a polyester resin, and the polyester resin has a number-average molecular weight (Mn) of THF-soluble components of 1,000 to 80,000 according to GPC method, and a weight-average molecular weight according to GPC method. (Mw) is 5,000
The toner for developing an electrostatic image according to any one of claims 1 to 5, wherein the toner has an amount of 0 to 10,000,000. 7. The binder resin is a polyester resin, and M
/ S is 300 or more, the abundance in the region of the molecular weight of 2,000 to 100,000 is 50 to 90% in the measurement of the molecular weight distribution by the GPC method, and the Mn by the GPC method is 1,000 to 80,000. , Mw by GPC method
Is 5,000 to 10,000,000, and the electrostatic image developing toner according to any one of claims 1 to 6. 8. The polyester resin has a number average molecular weight (Mn) of 1,500 to 50,000 and a GP according to the GPC method.
Weight average molecular weight (Mw) by method C is 10,000 to
The toner for developing an electrostatic charge image according to claim 6, which has an amount of 5,000,000. 9. The toner for developing an electrostatic charge image according to claim 6, wherein the polyester resin has an acid value of 2 to 70. 10. The toner for developing an electrostatic charge image according to claim 6, wherein the polyester resin has an OH value of 50 or less. 11. The toner for developing an electrostatic charge image according to claim 6, wherein the polyester resin has a glass transition temperature of 45 to 80 ° C. 12. The toner for developing an electrostatic charge image according to claim 6, wherein the polyester resin has a glass transition temperature of 50 to 70 ° C. 13. The polyester resin is prepared by mixing separately prepared low molecular weight polyester resin component and high molecular weight polyester resin component, and adding trivalent or higher polyvalent carboxylic acid or polyhydric alcohol to the obtained mixture. 7. It is produced by carrying out a polycondensation reaction.
13. The toner for developing an electrostatic charge image according to any one of 1 to 12. 14. The binder resin is a vinyl resin, and the vinyl resin has at least one peak in a molecular weight range of 2,000 to 100,000 in a molecular weight distribution measurement of a THF-soluble component by a GPC method. And molecular weight 100,
The electrostatic image developing toner according to claim 1, which has at least one peak in a region exceeding 000. 15. The toner for developing an electrostatic charge image according to claim 14, wherein the vinyl resin has an M / S of 300 or more. 16. The toner for developing an electrostatic charge image according to claim 14, wherein the vinyl resin has an M / S of 400 or more. 17. The vinyl resin has an M / S of 420 to 2,
15. The toner for developing an electrostatic charge image according to claim 14, which is 000. 18. The glass transition temperature of the vinyl resin is 45.
The toner for developing an electrostatic charge image according to any one of claims 14 to 17, which has a temperature of -80 ° C. 19. The vinyl resin has a glass transition temperature of 50.
The toner for developing an electrostatic charge image according to any one of claims 14 to 18, which has a temperature of about 70 ° C. 20. The vinyl resin is produced by adding a trifunctional or higher functional polyfunctional radical polymerization initiator to the reaction system a plurality of times during the polymerization reaction.
The toner for developing electrostatic images according to any one of the above. 21. The toner for developing an electrostatic charge image according to claim 14, wherein the vinyl resin is a styrene-acrylic acid ester copolymer. 22. The toner particles have an endothermic onset temperature of 5 with respect to an endothermic peak during temperature rise and an exothermic peak during temperature fall in a DSC curve measured by a differential scanning calorimeter.
An aliphatic hydrocarbon which is in the range of 0 to 110 ° C., has at least one endothermic peak in the temperature range of 70 to 130 ° C., and has the maximum exothermic peak at the time of cooling within the peak temperature of the endothermic peak ± 9 ° C. 22. The toner for developing an electrostatic charge image according to claim 1, which contains a wax. 23. The toner particles are represented by the following formula (1) CH ₃ (CH ₂ ) _X CH ₂ OH (1) [wherein, X represents an average value and represents a positive number from 20 to 250]. 23. The toner for developing an electrostatic charge image according to claim 1, which contains an aliphatic alcohol wax. 24. The toner particles are represented by the following formula (2) CH ₃ (CH ₂ ) _Y CH ₂ COOH (2) [wherein Y represents an average value and a positive number from 20 to 250]. The toner for developing an electrostatic charge image according to any one of claims 1 to 22, which contains an alkylmonocarboxylic acid wax.