JPH11344832A - Toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner contg. an ester wax uniformly dispersed in a bonding resin, having god fixability and superior in anti-offsetting property, blocking resistance, durability in repeated use at many times and property of inhibiting the occurrence of a negative sleeve ghost. SOLUTION: This toner contains a bonding resin, contg. the reaction product of a vinyl copolymer and a polyester resin. The bonding resin contains 2-60 pts.wt. component insoluble in ethyl acetate and 40-98 pts.wt. component soluble in ethyl acetate. The content of the polyester resin component (Gp) in the component insoluble in ethyl acetate is 40-98 wt.%, the content of the polyester resin component (Sp) in the component soluble in ethyl acetate is 20-90 wt.%, and the ratio of Sp to Gp is 0.5-1.

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 a recording method utilizing an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet recording method, and the like, and an image forming method using the toner. About.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
Numerous methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Then, the electrostatic image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a toner image. is there.

Various methods and apparatuses have been developed for fixing the toner image onto a sheet such as paper, which is the above-mentioned final step. The most common method at present is a fixed heat generation through a heat roller or a heat-resistant film. This is a compression heating method using a heater.

In the pressure heating method using a heating roller, the toner image is fixed by passing the surface of the heat roller having a releasing property to the toner and the toner image surface of the sheet to be fixed while pressing the sheet under pressure. Is performed. In this method, since the surface of the heat roller and the toner image on 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. Can be.

[0005] Since the surface of the heating roller and the toner image come into contact with each other in a molten state and under pressure, a part of the toner image adheres to the surface of the fixing roller and is transferred. The offset phenomenon, which stains the sheet, is greatly affected by the fixing speed and the fixing temperature. Generally, when the fixing speed is low, the surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat applied from the heating roller to the toner to fix the toner is made substantially constant regardless of the fixing speed.

Since the toner on the sheet to be fixed forms several toner layers, particularly in a system in which the fixing speed is high and the surface temperature of the heating roller is high, the toner layer in contact with the heating roller includes: When the surface temperature of the heating roller is high because the temperature difference between the lowermost toner layer in contact with the fixing sheet and the lowermost toner layer is large, the toner in the uppermost layer is likely to cause an offset phenomenon, and When the surface temperature is low, the toner in the lowermost layer is not sufficiently melted, so that the toner is not fixed on the sheet to be fixed and a phenomenon of low-temperature offset is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing and anchoring the toner to the sheet to be fixed is usually used. According to this method, the temperature of the heating roller can be reduced to some extent, and the high-temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes very large, the sheet to be fixed winds around the fixing roller, and a winding offset occurs, or after the separation claw for separating the sheet to be fixed from the fixing roller is separated. Easily appear in the fixed image. Furthermore, because of the high pressure, the line image is crushed or the toner is scattered at the time of fixing, and the image quality of the fixed image is likely to deteriorate.

Conventionally, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resin has excellent low-temperature fixability, but it is said that it has the disadvantage that offset phenomenon easily occurs at high temperature.To compensate for this defect, the molecular weight of the polyester resin is increased to increase the viscosity. Attempts have been made to improve the elastic properties, but in this case, there is a problem that the low-temperature fixability is impaired, and the pulverizability during the production of the toner is also deteriorated, which is not suitable for making the toner into fine particles. It becomes a binder resin.

Further, vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production and high in high molecular weight, so they are excellent in high-temperature offset resistance, but in order to improve low-temperature fixability. However, when the molecular weight is lowered or the glass transition temperature is lowered, there is a problem that the blocking resistance and the developability deteriorate.

[0010] In order to make effective use of the advantages of these two types of resins and to compensate for the drawbacks, some methods of mixing and using these resins have been studied.

For example, Japanese Patent Application Laid-Open No. Sho 54-114245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, the compatibility between polyester resin and vinyl copolymer is poor due to the large difference in chemical structure, low-temperature fixability,
It is difficult to satisfy both high-temperature offset resistance and blocking resistance.

Further, it is difficult to uniformly disperse various additives, particularly wax, added during the production of the toner, so that not only the fixing performance of the toner, but also the developability tends to be problematic. This problem is significant for certain toners.

Further, Japanese Patent Application Laid-Open No. 56-116043,
JP-A-58-159546 discloses a toner containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin.

JP-A-58-102246 and JP-A-1-156759 disclose a toner characterized by containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester. It has been disclosed.

Japanese Patent Application Laid-Open No. 2-881 is characterized in that a styrene-based resin obtained by copolymerizing a monomer having an acid group and a polyester resin include a polymer in which an ester bond is formed via an acid group of the styrene-based resin. Is disclosed.

In the above-mentioned binder resin, the compatibility between the polyester resin and the vinyl copolymer is improved, but the fixability at low temperature is almost the same as that of the polyester resin. Difficult to disperse,
When the toner is used, there remains a problem to be improved not only in the fixing property but also in the developing property.

For both copiers and printers, it is required to improve the resolution and sharpness of images. For this purpose, it is effective to reduce the particle size of the toner, but the fixability of the halftone portion tends to deteriorate. According to the study of the present inventor, this is due to the small amount of the toner applied in the halftone portion, and the compression heating method using a high-speed machine using a heat roll fixing device and a fixed heating heater via a heat-resistant film. This is remarkable in medium to low speed machines that use.

Further, printers, copiers, facsimile machines and the like utilizing electrophotographic technology are increasingly required to be smaller, faster, and more durable. In the process, the offset toner accumulates and accumulates on the pressure roller facing the hot roll in the hot roll fixing method and on the pressure roller facing the heat-resistant film in the pressure heating method. Dirt "
There is a phenomenon. When this phenomenon progresses and the accumulated amount increases, the paper wraps around the pressure roller, causing a jam. In order to reduce the size, the simplification of the fixing device such as removing the cleaning member for removing the offset toner, and
In order to realize the requirement of high durability, improvement of the dirt on the pressure roller is required.

On the other hand, there is an increasing demand for higher quality graphic images. One aspect of the quality of graphic images is the uniformity of image density in solid images.

Regarding the uniformity of the density of the solid image, in the one-component developing system, when a solid image such as a halftone is printed, the inversion of the image just printed on the solid image is the cycle of the toner carrier. There is a phenomenon called “negative sleeve ghost” that appears in the above, and there are cases where the quality of graphic images is reduced.

Therefore, from the viewpoint of improving the quality of graphic images, there is a demand for an improvement in "negative sleeve ghost".

[0022]

SUMMARY OF THE INVENTION The present invention provides a toner which has solved the above-mentioned problems.

That is, an object of the present invention is to provide a toner in which wax is uniformly dispersed in a binder resin.

Another object of the present invention is to provide good fixability of a halftone portion even when used in a binder resin of a toner having a small particle diameter in which the content of a coloring agent (particularly a magnetic substance) is increased. This is to provide a toner.

Another object of the present invention is to provide good low-temperature fixability even in a high-speed machine using a hot roll fixing device and a medium to low-speed machine using a press-fit heating method using a fixed heating heater via a heat-resistant film. The present invention is to provide a toner which exhibits a wide fixing temperature range in which offset does not occur even at high temperatures.

Another object of the present invention is to provide a toner capable of obtaining a high-quality graphic image without a negative sleeve ghost.

Another object of the present invention is to provide a toner which does not cause contamination of the pressure roller such that toner adheres / accumulates on the pressure roller.

It is a further object of the present invention to provide an image forming method using these toners.

[0029]

According to the present invention, there is provided a toner containing at least a colorant, a binder resin and an ester wax, wherein the binder resin comprises at least a reaction product of a vinyl copolymer and a polyester resin. (A) the binder resin contains 2 to 6 components (G) insoluble in ethyl acetate based on 100 parts by weight of the binder resin;
0 parts by weight and 40 to 98 parts by weight of the component (S) soluble in ethyl acetate, and (b) the content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate is 4%.
0 to 98% by weight, and (c) the content of the polyester resin component (Sp) in the component (S) soluble in the ethyl acetate is 20 to 90% by weight, and (d) insoluble in the ethyl acetate. Polyester resin component (G) in component (G)
p) and the content of the polyester resin component (Sp) in the component (S) soluble in ethyl acetate (Sp /
Gp) is from 0.5 to 1.

The present invention also provides a charging step of charging by a charging device to which an external voltage is applied; a step of forming an electrostatic charge image on a charged latent image holding member; and a step of forming an electrostatic charge image on the latent image holding member. The charge latent image is developed by the toner layer on the toner carrier whose layer thickness is regulated by a toner layer thickness regulating member for regulating the layer thickness of the toner layer formed on the toner carrier, and an image is formed. In an image forming method having at least a developing step of forming, the toner layer thickness regulating member is pressed against a surface of the toner carrier via a toner layer to form a layer thickness of the toner layer formed on the toner carrier. The present invention relates to an image forming method using the toner having the above-described configuration as the toner.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the study of the present inventor, a toner having a small particle size and an increased content of a coloring agent (particularly a magnetic substance) is suitable for a halftone image irrespective of the fixing system heating method. In order to obtain a toner that exhibits excellent low-temperature fixability, has a high offset generation temperature, and does not offset, it must contain a fixed amount of a component having a composition and a molecular weight in which the binder resin of the toner is selectively dissolved only in a specific solvent. is important.

The same applies to conventionally known tetrahydrofuran, chloroform or ethyl acetate, but the definition of the insoluble content contained in the binder resin of the toner with respect to these solvents is a simple quantitative determination of the crosslinked resin component. It is possible to cope with the occurrence of toner offset to some extent, but it is necessary to evaluate the dispersion state of the wax contained in the toner, which may have a great effect not only on the toner fixing property but also on the developing property. It is not an evaluation from a viewpoint.

According to the study of the present inventors, ethyl acetate is a good solvent for the binder resin, especially the polyester resin component, contained in the toner of the present invention, but it is difficult for the vinyl copolymer and the ester wax to be used. However, it is not always a good solvent. Therefore, the polyester resin component insoluble in ethyl acetate referred to in the present invention has characteristics different from those of a general polyester resin, which simply means that when the molecular weight is extremely large or when it is crosslinked. is not.

The polyester resin component insoluble in ethyl acetate means that the polyester resin component has properties similar to those of a vinyl copolymer or an ester wax. It is necessary to keep the polymer in a state suitable for exhibiting the fixing property and the developing property of the toner.

The polyester resin component insoluble in ethyl acetate is also important for maintaining the dispersion of the ester wax in a state suitable for the toner of the present invention.

Generally, the fixability of a toner at a low temperature is related to a resin composition having a low molecular weight soluble in a solvent, and the occurrence of offset at a high temperature is related to a resin composition insoluble in a solvent. By complementing the above, both fixing property and hot offset resistance are achieved.

In other words, the fixability of the toner at a low temperature is
It may be inhibited by the presence of the resin composition that is insoluble in the solvent. The polyester resin component that is insoluble in ethyl acetate contained in the binder resin of the toner of the present invention is selectively used mutually by stabilizing the dispersion state by showing good compatibility with the ester wax. At the same time, when the toner is heated and fixed, the toner is efficiently softened by the melted ester wax, does not hinder the fixing property, and can achieve good fixing property and hot offset resistance.

In the toner of the present invention, the component (G) insoluble in ethyl acetate contains the binder resin 100 contained in the toner.
It may be contained in an amount of 2 to 60 parts by weight, preferably 5 to 50 parts by weight,
The content is more preferably 10 to 40 parts by weight, and even more preferably 15 to 35 parts by weight. If the amount is less than 2 parts by weight, not only the hot offset resistance of the toner deteriorates, but also it becomes difficult to uniformly disperse the ester wax, which is not preferable. Furthermore, the effect of improving the negative sleeve ghost cannot be obtained. On the other hand, when the amount exceeds 60 parts by weight, the fixing property of the toner deteriorates, which is not preferable.

The component (G) insoluble in ethyl acetate may contain the polyester resin component (Gp) in an amount of 40 to 98% by weight, preferably 50 to 95% by weight, and more preferably 60 to 95% by weight. To 90% by weight. If the amount is less than 40% by weight, the fixability of the toner may deteriorate, which is not preferable. On the other hand, if it exceeds 98% by weight, the compatibility with the ester wax tends to deteriorate, which is not preferable. Further, in both cases of less than 40% by weight and more than 98% by weight, the effect of improving the negative sleeve ghost cannot be obtained.

The component (S) dissolved in ethyl acetate may contain the polyester resin component (Sp) in an amount of 20 to 90% by weight, preferably 25 to 85% by weight, and more preferably 30 to 85% by weight. To 80% by weight. If it is less than 20% by weight,
Since the ester wax is uniformly dispersed throughout the binder resin contained in the toner, the fixability is not improved, and further, the effect of improving the negative sleeve ghost cannot be obtained. 90
If the content is more than 10% by weight, the compatibility with the ester wax tends to deteriorate, and localization occurs, and hot offset does not easily occur.

The ratio (Sp / Gp) may be from 0.5 to 1, preferably from 0.6 to 0.95, and more preferably from 0.65 to 0.9. is there. Even if the ratio (Sp / Gp) is less than 0.5 or the ratio (Sp / Gp) is more than 1, the component insoluble in ethyl acetate and the component soluble in ethyl acetate are not uniformly mixed, This is not preferable because the developability of the toner may deteriorate.

The component (S) soluble in ethyl acetate may have a weight average molecular weight (Mw) of 200,000 or more and Mw / Mn of 30 or more, and preferably has a Mw of 300,000 to 200.
And Mw / Mn is 50 to 300, and more preferably Mw is 400,000 to 1.5 million, and Mw / Mn is more preferable.
This is the case where Mn is 80 to 250. If Mw is less than 200,000 and Mw / Mn is less than 30, undesirably, the toner developability may deteriorate.

In the toner of the present invention, the polyester resin component is preferably a divalent carboxylic acid represented by formulas (1) to (4), a monovalent carboxylic acid represented by formula (5) or a formula (6). At least one of the monohydric alcohols represented by

[0044]

Embedded image [In the formula, R ₁ represents a linear, branched or cyclic alkyl group or alkenyl group having 14 or more carbon atoms. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group or alkenyl group having 3 or more carbon atoms, and may be the same substituent, but are not hydrogen atoms at the same time. R ₅ and R ₆ represent a hydrogen atom, a linear, branched or cyclic alkyl group or alkenyl group having 3 or more carbon atoms, and may be the same substituent, but are not hydrogen atoms at the same time. R ₇ and R _{8 each} represent a linear, branched or cyclic alkyl group having 12 or more carbon atoms;
Represents an alkenyl group. n represents an integer of 12 to 40. As the compound represented by the formula (1), for example,

[0045]

Embedded image And the like.

As the compound represented by the formula (2), for example,

[0047]

Embedded image And the like.

As the compound represented by the formula (3), for example,

[0049]

Embedded image

As the compound represented by the formula (4), for example,

[0051]

Embedded image

As the compound represented by the formula (5), for example,

[0053]

Embedded image And the like.

As the compound represented by the formula (6), for example,

[0055]

Embedded image And the like.

The following are mentioned as monomers of the polyester resin used in the present invention.

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 (7-
1) a bisphenol derivative represented by the formula:

[0058]

Embedded image

Diols represented by the formula (7-2);

[0060]

Embedded image And the like.

Examples of the acidic component include benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid and anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid and anhydrides thereof; Succinic acid or its anhydride substituted with an alkyl group of Formulas 6 to 12; fumaric acid, maleic acid, citraconic acid, or dicarboxylic acids such as anhydride, fumaric acid, maleic acid, and maleic anhydride.

The polyester resin of the present invention is preferably crosslinked with a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol. The crosslinking components include trimellitic anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and novolak. An oxyalkylene ether of a type phenol resin is preferred.

The following are examples of the vinyl-based monomer for producing the vinyl-based resin.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p -Methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene,
styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride; Vinyl halides such as vinyldene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate , Isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate Acrylates such as stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone Vinyl ketones such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides, such as: methyl maleate 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, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
anhydrides of β-unsaturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

If necessary, the polymer may be cross-linked with a cross-linkable monomer as exemplified below.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene; examples of the diacrylate compound linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds Examples of the acrylate include methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; including an aromatic group and an ether bond Examples of chain-linked diacrylate compounds include polyoxyethylene (2) -2,2
-Bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-
(Hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; polyester-type diacrylates include, for example, the trade name MANDA (Nippon Kayaku).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; Triallyl cyanurate and triallyl trimellitate;

These cross-linking agents can be used in combination with other monomer components 10
0.01 to 10 parts by weight (more preferably 0.03 to 5 parts by weight) can be used with respect to 0 parts by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of fixability and offset resistance to the resin for toner include an aromatic divinyl compound (particularly divinylbenzene), one aromatic group and one ether bond. And diacrylate compounds linked by a chain.

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid and anhydrides thereof; Examples of the monomer constituting the vinyl copolymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resins and polyester resins is used. Alternatively, a method obtained by polymerizing both resins is preferable.

Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include, for example, 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide;
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m- Trioil peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate,
Di-2-ethoxyethyl peroxycarbonate, di-
Methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Decanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butyl peroxyallyl carbonate,
t-amyl peroxy 2-ethylhexanoate, di-
t-butyl peroxyhexahydroterephthalate,
Di-t-butyl peroxyazelate and the like.

The ester wax used in the present invention has a slight polarity, unlike the polyolefin wax and the hydrocarbon release agent.

For this reason, when combined with the special binder resin of the present invention, it is more uniformly dispersed in the component (G) insoluble in ethyl acetate than the polyolefin hydrocarbon wax, and the dispersion state is more stable. Become In addition, due to the effect of the uniform dispersion, the toner is more efficiently softened when heat-fixed, and a better fixing property is obtained.

Further, by combining the special binder resin of the present invention with an ester wax, the negative sleeve ghost can be effectively suppressed. Although the reason is unknown, the interaction between the ethyl acetate-insoluble component (G) and the polar portion of the ester wax improves the charging characteristics of the ethyl acetate-insoluble component, thereby improving the negative sleeve ghost. It is supposed to be.

The ester wax used in the present invention refers to one having at least a long-chain alkyl or alkenyl moiety and an ester bonding moiety in its molecule.

Those having at least one alkyl or alkenyl moiety having 15 to 60 carbon atoms, more preferably 20 to 50 carbon atoms, are particularly preferred.

When the ester wax does not have an alkyl or alkenyl moiety having 15 or more carbon atoms, the molecular weight of the ester wax is small, so that the toner is easily fused to the latent image holding member and the storage stability is lowered. I do.

The ester wax contains 60 carbon atoms.
When the compound does not have the following alkyl or alkenyl moieties, the interaction between the polar group in the ester wax and the component (G) insoluble in ethyl acetate is reduced, and the effect of improving the negative sleeve ghost is reduced.

As for the ester bonding moiety, 1
It suffices if there are at least two or more, and two or more can be used.

Examples of the ester wax include alcohols and carboxylic acids having a relatively long chain alkyl or alkenyl obtained by synthesis, or natural alcohols having a relatively long chain alkyl or alkenyl,
An ester wax obtained by subjecting a carboxylic acid to a raw material condensation reaction can be used.

Further, a wax containing a natural ester wax component such as carnauba wax, candelilla wax and rice wax can also be used.

The ester wax contained in the toner of the present invention has a temperature of 70 to 140 ° C. in a DSC curve of the toner containing the wax measured by a differential scanning calorimeter.
It is preferred that the toner has an endothermic main peak in the region from the viewpoint of low-temperature fixability and offset resistance of the toner.

More preferably, the toner containing the ester wax preferably has an endothermic main peak in a temperature range of 75 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter. More preferably, the temperature is 80 to 1 in a DSC curve measured by a differential scanning calorimeter.
It is preferable to have an endothermic main peak and an endothermic subpeak or an endothermic shoulder in the region of 30 ° C. from the viewpoint of low-temperature fixing property, offset resistance and blocking resistance.

Further, D of the toner containing the ester wax contained in the present invention as measured by a differential scanning calorimeter.
In the SC curve, it is preferable that the half-width of the endothermic main peak is less than 2.5 ° C. When the half width of the endothermic main peak is less than 2.5 ° C., it is more preferable in view of the storage stability of the toner.

When the ester wax is used alone,
It is preferable to use 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of the binder resin.

When an ester wax is used in combination, the total amount of the ester wax is 0.1% per 100 parts by weight of the binder resin.
It is preferred to use up to 30 parts by weight, preferably 0.5 to 20 parts by weight.

The toner of the present invention preferably contains a hydrocarbon wax or a petroleum wax together with a specific binder resin and an ester wax. The presence of these waxes improves the pressure roller fouling that occurs in the fuser. The present inventor has conducted extensive studies on the pressure roller contamination phenomenon, and this phenomenon does not merely depend on the amount of toner to be offset, but the adhesion and release properties with the pressure roller are important factors. I found it.

The present inventors have paid attention to the point of the adhesiveness and the releasability, and as a result of further study, have found that the specific binder resin and the ester wax of the present invention, and further the hydrocarbon wax or the petroleum wax are used. By combining
It has been found that dirt on the pressure roller can be improved.

In the toner of the present invention, the component (G) insoluble in ethyl acetate contains the binder resin 100 contained in the toner.
When the amount is less than 2 parts by weight with respect to part by weight, the effect of improving the contamination of the pressure roller cannot be obtained.

When the content of the polyester resin component (Gp) is less than 40% by weight or more than 98% by weight relative to the component (G) insoluble in ethyl acetate, the component in which the polyester resin component (Sp) is soluble in ethyl acetate 2 for (S)
When the amount is less than 0% by weight, the effect of improving the contamination of the pressure roller cannot be obtained.

The hydrocarbon wax or petroleum wax having almost no polarity is mainly dispersed in the component (G) insoluble in ethyl acetate in the binder resin of the present invention.

The interaction of these waxes with the ester wax having a slight polarity in the toner of the present invention brings about a state in which the component (G) insoluble in ethyl acetate does not exist conventionally, The releasability from the pressure roller is improved. It is believed that this improves pressure roller contamination.

Specific examples of the hydrocarbon wax contained in the present invention include a low molecular weight alkylene polymer obtained by radical polymerization of alkylene such as ethylene and propylene under high pressure or a Ziegler catalyst under low pressure, and a high molecular weight alkylene polymer. A wax such as an alkylene polymer obtained by pyrolyzing an alkylene polymer, a distillation residue of a hydrocarbon obtained by the Age method from a synthesis gas composed of carbon monoxide and hydrogen, or a synthetic hydrocarbon obtained by hydrogenating the same. Used. Further, those separated by use of a press sweating method, a solvent method, vacuum evaporation or a separation crystallization method are more preferably used.

As the petroleum wax, wax separated from petroleum, such as paraffin wax, microcrystalline wax and petrolactam, is used.

The hydrocarbon wax and the petroleum wax in the present invention have substantially no functional groups. Substantially refers to those in which the number of functional groups is 0.1 or less per molecule.

The hydrocarbon wax or petroleum-based wax used in the present invention has a DSC curve measured by a differential scanning calorimeter of the toner containing the wax.
It is preferred that the toner has an endothermic main peak in a temperature range of 70 to 140 ° C. from the viewpoints of low-temperature fixability, offset resistance, and prevention of pressure roller contamination.

More preferably, a toner containing a hydrocarbon wax or a petroleum wax preferably has an endothermic main peak in a temperature range of 80 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter. More preferably, the toner containing the wax has a temperature of 90 to 1 on a DSC curve measured by a differential scanning calorimeter.
It is preferable to have an endothermic main peak and endothermic subpeak or an endothermic shoulder in the region of 30 ° C. from the viewpoints of low-temperature fixability, offset resistance, prevention of pressure roller contamination and offset resistance.

The hydrocarbon wax and the petroleum wax have a ratio Mw / weight average molecular weight (Mw) to number average molecular weight (Mn) determined from the molecular weight distribution measured by GPC.
Those having Mn of 1.0 to 3.0 are preferred. If hydrocarbon wax and petroleum wax meet this range,
The effect of pressure roller contamination is greater.

The content (Y) of the hydrocarbon wax or petroleum wax used in the present invention is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the binder resin. It is preferable to use parts.
Further, the content (X) of the ester wax and the content (Y) of the hydrocarbon wax or the petroleum wax preferably satisfy the following condition: X / Y = 0.02 to 50.

When X / Y is less than 0.02 or more than 50, the effect of improving the contamination of the pressure roller is reduced.

In the toner of the present invention, a charge control agent may be used as needed in order to further stabilize the chargeability. The charge control agent is 0.1 to 100 parts by weight of the binder resin.
It is preferred to use 10 parts by weight, preferably 0.2 to 5 parts by weight.

As the charge control agent, the following can be mentioned. For example, an organic metal complex, a chelate compound, and an organic metal salt are mentioned. Specific examples include a monoazo metal complex; a metal complex or a metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their anhydrides and esters, and phenol derivatives of bisphenol.

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, 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.

More specifically, as the magnetic material,
Iron (Fe_ThreeO_Four), Γ-iron sesquioxide (γ-Fe_TwoO_Three),acid
Zinc iron fossil (ZnFe_TwoO_Four), Yttrium iron oxide (Y_Three
Fe_FiveO₁₂), Cadmium iron oxide (CdFe_TwoO_Four),acid
Gadolinium iron (Gd_ThreeFe_Five-O₁₂), Iron oxide copper (C
uFe_TwoO_Four), Lead iron oxide (PbFe₁₂O₁₉), Iron oxide
Nickel (NiFe_TwoO_Four), Iron neodymium oxide (NdFe_Two
O_Three), Barium iron oxide (BaFe)₁₂O₁₉), Iron oxide
Gnesium (MgFe_TwoO_Four), Iron manganese oxide (MnF)
e_TwoO_Four), Lanthanum iron oxide (LaFe) O_Three), Iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc.
I can do it. The above magnetic materials may be used alone or in combination of two or more.
Use together. A particularly preferred magnetic material is ferric oxide
Or a fine powder of γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
μm (more preferably 0.1 to 0.5 μm) and 10 k
The magnetic properties upon application of the Oersted are coercive force of 20 to 150 Oersted, saturation magnetization of 50 to 200 emu / g (preferably 50 to 100 emu / g), and residual magnetization of 2 to 20 em.
u / g is preferred.

The magnetic material 1 was 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.

The toner of the present invention is preferably a magnetic toner containing magnetic iron oxide, and more preferably a magnetic iron oxide having a sphericity (Ψ) of 0.8 or more. The presence of magnetic iron oxide having a sphericity (Ψ) of 0.8 or more in the toner makes it easy for the magnetic iron oxide to be appropriately exposed to the surface of the toner particles, stabilizes the chargeability of the toner, and produces a negative sleeve ghost. Is considered to be effective in improving

The magnetic iron oxide used in the present invention preferably contains a silicon element. Further, the content of the silicon element in the magnetic iron oxide is preferably 0.2 to 4 based on the iron element.
And the ratio (B / A) of the content B of the silicon element present when the dissolution rate of the iron element of the magnetic iron oxide is up to 20% by weight and the total content A of the silicon element of the magnetic iron oxide. 100 is 44 to 84%, and the ratio of the content C of silicon existing on the surface of the magnetic iron oxide to the content A (C / A) × 100
Is more preferably 10 to 55%. When the magnetic iron oxide contains a silicon element, and more preferably exists so as to satisfy the above conditions, it is more effective in improving the negative sleeve ghost.

The magnetic iron oxide particles having a silicon element according to the present invention are produced, for example, by the following method.

After a predetermined amount of a silicate compound is added to the aqueous ferrous salt solution, an alkali such as sodium hydroxide is added in an amount equivalent to or more than the iron component to prepare an aqueous solution containing ferrous hydroxide. Air is blown in while maintaining the pH of the prepared aqueous solution at 7 or more (preferably 8 to 10), and the oxidation reaction of ferrous hydroxide is performed while heating the aqueous solution to 70 ° C. or more, and the core of the magnetic iron oxide particles is heated. First, a seed crystal is produced.

Next, an aqueous solution containing about 1 equivalent of ferrous sulfate based on the amount of the alkali added previously is added to the slurry-like liquid containing the seed crystals. The reaction of ferrous hydroxide is advanced while blowing air while maintaining the pH of the solution at 6 to 10 to grow magnetic iron oxide particles with the seed crystal as a core. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but it is preferable that the pH of the liquid is not less than 6. By adjusting the pH of the solution at the end of the oxidation reaction, it is preferable that a predetermined amount of the silicate compound is unevenly distributed on the surface layer and the surface of the magnetic iron oxide particles.

Examples of the silicic acid compound used for addition include commercially available silicates such as sodium silicate and silicic acids such as sol silicic acid generated by hydrolysis or the like. Other additives such as aluminum sulfate and alumina may be added as long as they do not adversely affect the present invention.

As the ferrous salt, iron sulfate generally produced as a by-product in the production of titanium sulfate, iron sulfate produced as a by-product of cleaning the surface of a steel sheet, and iron chloride can be used. .

A method for producing magnetic iron oxide by an aqueous solution method is as follows.
Generally, an iron concentration of 0.5 to 2 mol / liter is used from the viewpoint of preventing the viscosity from increasing during the reaction and the solubility of iron sulfate. Generally, the lower the concentration of iron sulfate, the smaller the particle size of the product tends to be. In addition, in the reaction, as the amount of air is larger and the reaction temperature is lower, the particles are easily atomized.

It is preferable that magnetic iron oxide particles having a silicic acid component are produced by the above-mentioned production method, and the magnetic iron oxide particles are used for toner.

The sphericity of the magnetic iron oxide is measured as follows. 100 or more magnetic iron oxide particles are randomly selected using an electron micrograph of the magnetic iron oxide, the ratio of the minimum length to the maximum length of each particle is determined, and then the calculated values are averaged.

Sphericity (Ψ) = minimum length (μm) / maximum length (μm)

In the present invention, the content C of the silicon element on the surface of the magnetic iron oxide particles can be determined by the following method. For example, about 3 liters of deionized water is placed in a 5 liter beaker and heated in a water bath to 50 to 60 ° C. About 300 g of about 25 g of magnetic iron oxide particles slurried with about 400 ml of deionized water
While washing with deionized water, add the deionized water together with the deionized water into a 5 liter beaker.

Then, while maintaining the temperature at about 60 ° C. and the stirring speed at about 200 rpm, a special grade sodium hydroxide was added to form a 1N sodium hydroxide solution to dissolve the silicon compound such as silicic acid on the surface of the magnetic iron oxide particles. Start. Sampling 20 ml 30 minutes after the start of dissolution,
Filter through a 0.1 μm membrane filter and collect the filtrate. The filtrate is subjected to quantitative determination of silicon element by plasma emission spectroscopy (ICP).

The content C of the silicon element corresponds to the concentration of the silicon element per unit weight (mg / liter) of the magnetic iron oxide in the aqueous sodium hydroxide solution.

In the present invention, the content of the silicon element (based on the iron element), the dissolution rate of the iron element, and the contents A and B of the silicon element in the magnetic iron oxide particles are determined by the following methods. Can be done. For example, put about 3 liters of deionized water in a 5 liter beaker at 45-50 ° C.
Heat in a water bath so that About 400ml
About 25 g of magnetic iron oxide slurried with deionized water is added to a 5 liter beaker together with the deionized water while washing with about 300 ml of deionized water.

Next, while maintaining the temperature at about 50 ° C. and the stirring speed at about 200 rpm, special grade hydrochloric acid is added to start dissolution. At this time, the magnetic iron oxide concentration was about 5 g / liter,
The hydrochloric acid aqueous solution is about 3N. From the start of dissolution, about 20 ml was sampled several times until it was completely dissolved and became transparent, and filtered with a 0.1 μm membrane filter.
Collect the filtrate. The filtrate is subjected to quantitative determination of iron element and silicon element by plasma emission spectroscopy (ICP).

The iron element dissolution rate for each sample is calculated by the following equation.

[0127]

(Equation 1)

The content and content of the silicon element for each sample are calculated by the following equations.

[0129]

(Equation 2)

The total content A of the silicon element in the magnetic iron oxide particles
Represents the concentration of silicon element per unit weight of the magnetic iron oxide particles after all are dissolved (mg / liter).

Content of Silicon Element B in Magnetic Iron Oxide Particles
Corresponds to the concentration of silicon element (mg / liter) per unit weight of the detected magnetic iron oxide particles when the dissolution rate of the magnetic iron oxide particles is 20%. The state in which the dissolution rate of the magnetic iron oxide particles is 20% is a state in which only the vicinity of the surface of the magnetic iron oxide is dissolved by hydrochloric acid. At this time, the silicon element content B exists near the surface of the magnetic iron oxide. Represents the amount of silicon element present.

The methods for measuring the contents A, B and C are as follows: (1) A magnetic iron oxide sample was divided into two parts, and while the contents and contents A and B of the silicon element were measured, the contents were measured. A method of separately measuring the amount C, and (2) measuring the content C of the sample of magnetic iron oxide, using the sample after the measurement, and then using the content B ′ (the amount obtained by subtracting the content C from the content B). ) And the content A ′ (the amount obtained by subtracting the content C from the content A).
Finally, a method of calculating the contents A and B may be used.

In addition to the magnetic iron oxide, carbon black, titanium white and other pigments and / or dyes can be used as the coloring agent. 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. 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. As pigments, mineral fast yellow, navel yellow,
Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, 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, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, 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 colorants may be used. Examples of the magenta coloring pigment include C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

Although the above pigments may be used alone,
It is more preferable to improve the sharpness by using a dye and a pigment in combination from the viewpoint of the image quality of a full-color image. Magenta dyes include C.I. I. Solvent Red 1,3,8,2
3,24,25,27,30,49,81,82,8
3,84,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,1
3, 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, 36, 3
7, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

Examples of the coloring pigment for cyan include 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 the following formula.

[0137]

Embedded image

The 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, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the nonmagnetic colorant used is 100
0.1 to 60 parts by weight, preferably 0.5 part by weight,
５０50 parts by weight.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner to improve the fluidity before and after the addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine powder titanium oxide, fine powder alumina, a silane coupling agent thereof, There are treated silica, treated titanium oxide, and treated alumina that have been surface-treated with a titanium coupling agent and silicone oil.

The toner of the present invention preferably contains hydrophobically treated silica, and the silica is preferably treated with a coupling agent, more preferably treated with silicone oil. By containing such silica, the rise and stability of charging are improved, and the negative sleeve ghost is improved.

The silica used in the present invention includes, for example, a so-called dry method produced by the above-described phase oxidation of a silicon halide or a dry silica called fumed silica, and a so-called wet silica produced from water glass. Both can be used, but there are few silanol groups on the surface and inside the silica fine powder, and Na ₂ O, SO ₃ ⁻
Dry silica with less production residue such as is preferred. In the case of fumed silica, in the production process, for example, it is also possible to obtain a composite fine powder of silica and another metal oxide by using aluminum chloride, titanium chloride, and another metal halide together with a silicon halide.
In the present invention, they are also included.

Examples of the coupling agent include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, and benzyldimethylchloro. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethyldiethoxysilane Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3
-Divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, each of the terminal units having one hydroxyl group bonded to one silicon atom. Contained dimethylpolysiloxane.

Aminopropyltrimethoxysilane having a nitrogen atom, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylamino Propyltrimethoxysilane, dioctylaminopropyldimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ
-Propylphenylamine, trimethoxysilyl-γ-
A silane coupling agent such as propylbenzylamine may be used alone or in combination. As a preferred silane coupling agent, hexamethyldisilazane (HMD)
S).

The preferred silicone oil used in the present invention has a viscosity at 25 ° C. of 0.5 to 1000 cS.
t, preferably 1 to 1000 cSt, more preferably 10 to 200 cSt, for example, dimethyl silicone oil, methylphenyl silicone oil,
α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil are particularly preferred. As a method of silicone oil treatment,
For example, a method in which silica fine powder treated with a silane coupling agent is directly mixed with silicone oil using a mixer such as a Henschel mixer; a method in which silicone oil is sprayed on a base silica fine powder; After dissolving or dispersing the silicone oil in the mixture, adding silica fine powder and mixing to remove the solvent.

The silicone oil-treated silica is more preferably heated to 200 ° C. or more (more preferably 250 ° C. or more) in an inert gas after the silicone oil treatment to stabilize the surface coat.

In the present invention, silica treated in advance by a method of treating silica with a coupling agent and then treating it with silicone oil, or a method of treating silica with a coupling agent and silicone oil simultaneously is preferred.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of the fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used.

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 are melted, kneaded and kneaded using a hot kneader such as a kneader or an extruder. Then, the resins are mutually dissolved, and the melt-kneaded product is cooled and solidified, and then the solidified product is pulverized, and the pulverized product is classified to obtain the toner of the present invention.

The toner of the present invention preferably has a weight average particle diameter of 3 to 9 μm (more preferably, 3 to 8 μm) in terms of resolution and image density. And heat and pressure.

Further, in the present invention, when the volume average particle diameter (D _V ) of the toner is 2.5 μm or more, a decrease in image density hardly occurs, and a sufficient image density is obtained.
When the particle size is 0 μm or less, the volume average particle diameter (D _V ) of the toner is preferably 2.5 to 6.0 μm since the gradation of a halftone image is particularly improved.

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

The methods for quantifying the solvent-soluble components of the toner of the present invention and measuring other physical properties are described below.

(1) Quantification of Ethyl Acetate-Insoluble Component of Toner and Preparation of NMR Measurement Sample 4 g of the toner was precisely weighed, placed in a 500 ml beaker, added with 300 ml of ethyl acetate, and stirred at room temperature for about 5 hours using a magnetic stirrer. I do. After standing for about an hour,
Carefully separate the precipitate and the ethyl acetate solution by decantation. After the precipitate is washed with a small amount of ethyl acetate, the ethyl acetate-insoluble resin component is quantified by evaporating the ethyl acetate to dryness and quantifying the dissolved resin component.

The precipitate insoluble in ethyl acetate remaining in the beaker is added to 200 ml of chloroform in the beaker and stirred at room temperature for about 2.5 hours using a magnetic stirrer. After standing for about 1 hour, carefully float (insoluble components)
And the precipitated colorant (magnetic substance) are separated by decantation, and chloroform is evaporated to dryness. By the above operation, the quantitative determination of the component insoluble in ethyl acetate and the NMR measurement sample can be obtained.

(2) Insoluble and soluble components in ethyl acetate
NMR measurement of components Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 400 MHz Pulse condition: 5.0 μs Data point: 32768 Delay time: 25 sec. Frequency range: 10500 Hz Number of times of accumulation: 16 Measurement temperature: 40 ° C. Sample: 200 mg of measurement sample and 5 mm diameter sample
Put in a tube and use CDCl as solvent_Three(TMS0.0
5%) and dissolve this in a 40 ° C.
Prepare.

(3) Measurement of melting point of wax ASTM D3418-8 using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put 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 0 ° C.

In this heating process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.

Using the temperature of the endothermic main peak, the melting point of the wax and the half width of the peak are determined.

(4) Measurement of DSC Curve of Toner A DSC curve in the process of raising the temperature of the toner is measured in the same manner as the measurement of the melting point of the wax.

(5) Glass transition temperature (Tg) of binder resin
ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put 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 0 ° C.

In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 200 ° C. is obtained.

At this time, the intersection between the line of 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 in the present invention.

(6) Measurement of molecular weight distribution of wax Gel permeation chromatography (GPC) measuring apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

The measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

(7) Measurement of Molecular Weight Distribution of Binder Resin Material or Binder Resin of Toner The molecular weight of a chromatogram by GPC is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute.
When the sample is a binder resin material, a material obtained by passing the binder resin material through a roll mill (130 ° C., 15 minutes) is used. If the sample is a toner, dissolve the toner in THF
m, and the filtrate is used as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is 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 standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 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. An RI (refractive index) detector is used as the detector.

In order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
rs Co., Ltd. μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 8
06,807 are preferred.

(8) Measurement of molecular weight distribution (long-chain alkyl compound) (GPC measurement conditions) Apparatus GPC-150C (Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

(9) Measurement of acid value and OH value a) Regarding acid value A sample is precisely weighed, dissolved in a mixed solvent and water is added. This solution is subjected to potentiometric titration with 0.1 N-NaOH using a glass electrode to determine an acid value. (According to JIS K1557-1970)

B) OH value (hydroxyl value) The sample was precisely weighed in a 100 ml volumetric flask, and 5 ml of the acetylating reagent was correctly added thereto. Then 100 ℃ ± 5
Heat by immersing in a bath at ° C. After 1-2 hours, the flask is taken out of the bath, left to cool, water is added and shaken to decompose acetic anhydride. Further, in order to complete the decomposition, the flask is again heated in a 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 was N / 2 using a glass electrode.
Potentiometric titration is performed with a potassium hydroxide ethyl alcohol solution to determine the OH value (according to JIS K0070-1966).

(10) Measurement of ¹³ C-NMR (nuclear magnetic resonance) spectrum of binder resin Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 100.40 MHz Pulse condition: 5.0 μs (45 °) DEPT method Data point: 32768 Delay time: 25 sec. Frequency range: 10500 Hz Number of times of integration: 10000 times Measurement temperature: 110 ° C. Sample: 200 mg of a measurement sample is placed in a φ10 mm sample tube, and chloroform (CDC) is used as a solvent.
l ₃ ) is added and dissolved in a 55 ° C. constant temperature bath to prepare.

(11) Measurement of Particle Size Distribution Measurement of the particle size distribution of the toner of the present invention uses a Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter Inc.). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method,
To 100 to 150 ml of the electrolytic aqueous solution, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is approximately 1 to
The dispersion treatment was performed for 3 minutes, and the measurement apparatus used a 100 μm aperture as a 2 μm aperture.
The volume and number distribution of the toner were measured to calculate a volume distribution and a number distribution.

Then, the weight-based weight average particle diameter (D ₄ ) and volume average particle diameter (D _V ) obtained from the volume distribution according to the present invention (each median value of each channel is a representative value for each channel) I asked.

The developing step of the image forming method using the toner of the present invention will be described in detail.

The developing method using the toner of the present invention includes a method using a magnetic toner and a method using a non-magnetic toner.

First, a method using a magnetic toner will be described.

In FIG. 1, the substantially right half of the peripheral surface of the toner carrier 102 is always in contact with the toner reservoir in the toner container 106, and the toner near the surface of the toner carrier is moved to the surface of the toner carrier by the magnetic force inside the toner carrier. It is attached and held by the magnetic force of the generating means 103 and / or by the electrostatic force. When the toner carrying member 102 is rotated the magnetic toner layer of the toner carrying member surface is advice service as a thin layer T ₁ of the Components uniform thickness in the process of passing through the position of the toner regulating member 104.
The magnetic toner is charged mainly by frictional contact between the surface of the toner carrier and the magnetic toner in a toner reservoir in the vicinity of the toner carrier as the toner carrier 102 rotates.
The thin magnetic toner layer surface on 2 rotates toward the photoconductor 101 with the rotation of the toner carrier, and passes through the developing area A, which is the closest part between the photoconductor 101 and the toner carrier 102.
During this passage, the magnetic toner of the magnetic toner thin layer on the surface side of the toner carrier 102 is transferred to the photosensitive member 101 and the toner carrier 102.
It flies by a direct current and an alternating electric field generated by a direct current and an alternating voltage applied between the photoconductor 101 and reciprocates between the surface of the photoconductor 101 in the developing area A and the surface of the toner carrier 102 (gap α). Finally, the magnetic toner on the toner carrier 102 side is
The toner image T ₂ selectively shifts adhere according to the potential pattern of the latent image are sequentially formed on the surface of the first surface.

After passing through the developing area A, the surface of the toner carrier on which the magnetic toner is selectively consumed is placed in the toner container 106.
Receiving a resupply of the magnetic toner by re-rotating the toner reservoir, the magnetic toner thin layer T ₁ side of the toner carrying member 102 is transferred to the developing region portion A, repeating the development process is performed.

The toner regulating member used in the image forming method of the present invention has good image density and "negative sleeve ghost" when the toner regulating member is in contact with the surface of the toner carrier.

In the case of toner regulation in which the toner regulating member is in contact with the surface of the toner carrier, in the toner of the present invention, the charging characteristics of the toner are further improved, and the image density and "negative sleeve ghost" are further improved. I think it will be.

As the toner regulating member, a rubber elastic body such as silicone rubber, urethane rubber or NBR; a synthetic resin elastic body such as polyethylene terephthalate; a metal elastic body such as stainless steel or steel can be used. Further, even a complex thereof can be used. Preferably, a rubber elastic body is good.

Further, the material of the toner regulating member greatly affects the charging of the toner on the toner carrier. Therefore, an organic substance or an inorganic substance may be added to the elastic body, may be melt-mixed, or may be dispersed. For example, metal oxides, metal powders, ceramics, carbon allotropes, whiskers,
Examples include inorganic fibers, dyes, pigments, and surfactants. Furthermore,
For the purpose of controlling the chargeability of the toner, a material such as resin, rubber, metal oxide, or metal may be applied to a rubber, a synthetic resin, or a metal elastic body so that the material contacts the toner carrier. When durability is required for the elastic body and the toner carrier, it is preferable that a resin and a rubber be stuck to the metal elastic body so as to contact the toner carrier abutting portion.

When the toner is negatively chargeable, it is preferable that the toner is easily charged to a positive polarity, such as urethane rubber, silicone rubber, urethane resin, polyamide resin, and nylon resin. When the toner is positively chargeable, it is preferable that the toner be easily charged to a negative polarity such as silicone rubber, silicone resin, polyester resin, fluororesin, and polyimide resin, in addition to urethane rubber and urethane resin.

In the case where the contact portion of the toner carrier is a molded product such as a resin or rubber, a metal such as silica, alumina, titania, tin oxide, zirconia, zinc oxide, etc. It is also preferable to include an oxide, carbon black, and a charge control agent generally used for toner.

The base on the upper side of the toner regulating member is fixedly held on the toner container side, and the lower side is bent in the forward or reverse direction of the toner carrier against the elasticity of the toner regulating member. The toner is brought into contact with the surface of the toner carrier with an appropriate elastic pressure. 2 and 3 show examples of the image forming apparatus.

The contact pressure between the toner regulating member and the toner carrier is 0.98 N as the linear pressure in the toner carrier genera direction.
/ M (1 g / cm) or more, preferably 1.27 to 245
N / m (3 to 250 g / cm), more preferably 4.9
１１８118 N / m (5 to 120 g / cm) is effective.
If the contact pressure is less than 0.98 N / m (1 g / cm), it becomes difficult to apply the toner uniformly, causing fogging and scattering. The contact pressure is 245 N / m (250 g / c
If the value exceeds m), a large pressure is applied to the toner, and the toner tends to deteriorate, which is not preferable.

The gap α between the photosensitive member and the toner carrier is preferably set to, for example, 50 to 500 μm.

The layer thickness of the magnetic toner layer on the toner carrier is
It is preferable to make the gap smaller than the gap α between the photoconductor and the toner carrier, but it is also possible to use a mode in which a part of the toner layer contacts the surface of the photoconductor.

In the present invention, it is preferable that an electric field containing an AC component is applied between the toner carrier and the photosensitive member. Further, it is preferable that the peak-to-peak magnitude (Vpp) of the electric field at the nearest part of the AC component between the toner carrier and the photoconductor is 2 to 8 MV / m or more. Further, the frequency of the AC bias is 1.0 kHz or more.
5.0 kHz, preferably 1.5 kHz to 3.0 kHz
Used in As the waveform of the AC bias, a waveform such as a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be applied. In addition, asymmetrical AC biases having different times for applying the forward / reverse voltage can be used.

In the present invention, the toner carrier is made of metal,
Although materials such as ceramics are used, aluminum, SUS, and the like are preferable from the viewpoint of chargeability to the toner. The toner carrier can be used as it is withdrawn or cut.However, in order to control the toner transportability and triboelectricity, the toner carrier is polished, roughened in the circumferential or longitudinal direction, or blasted. Coating, etc. are performed. In the present invention, blast treatment may be performed, and shaped particles and irregular shaped particles are used as a blasting agent, and they may be used alone or in combination, and may be used as a blasting agent.

A form in which a coating layer containing conductive fine particles is formed on the surface of the toner carrier can also be used.

Examples of the conductive fine particles contained in the resin layer covering the surface of the toner carrier include conductive metal oxides such as carbon black, graphite, and conductive zinc oxide, and metal double oxides, alone or in combination of two or more. It is preferably used. Examples of the resin in which the conductive fine particles are dispersed include phenolic resins, epoxy resins, polyamide resins, polyester resins, polycarbonate resins,
Known resins such as polyolefin resin, silicone resin, fluorine resin, styrene resin, and acrylic resin are used. Particularly, a thermosetting or photocurable resin is preferable.

Next, an example of the case of performing development using a non-magnetic toner will be described.

FIG. 4 shows an apparatus for developing an electrostatic image formed on a photosensitive member. Reference numeral 401 denotes a photoconductor, and a latent image is formed by an electrophotographic process unit or an electrostatic recording unit (not shown). Reference numeral 402 denotes a toner carrier, which is formed of a non-magnetic sleeve made of aluminum, stainless steel, or the like.

As the toner carrier, a rough tube of aluminum or stainless steel may be used as it is, but preferably the surface is uniformly roughened by spraying glass beads or the like, mirror-finished, or coated with resin or the like. This is similar to that used in the method for developing a magnetic toner.

[0203] The toner 406 is stored in the toner container 403, and is supplied onto the toner carrier by the supply roller 404. The supply roller is made of a foam material such as polyurethane foam, and rotates in a forward or reverse direction at a relative speed other than 0 with respect to the toner carrier, and together with the toner supply, the developed toner (undeveloped) on the toner carrier. Toner). The toner supplied on the toner carrier is uniformly and thinly applied by the toner application blade 605.

The material of the blade, the abutting means, the material of the toner carrier, the distance between the photosensitive member and the toner carrier, the bias applied to the toner carrier, and the like are the same as those of the magnetic toner developing method.

[0205]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

Production of the Polymer of the Present Invention: (Production Example 1) (a) Production of Polyester Resin Composition with Low Crosslinking Degree

The above-mentioned raw materials were charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a thermometer and a stirrer. .

After completely dissolving 70 parts by weight of the obtained polyester resin in 100 parts by weight of xylene, styrene 2
3 parts by weight, 6 parts by weight of 2-ethylhexyl acrylate,
A solution prepared by dissolving 1 part by weight of acrylic acid and 1 part by weight of t-butyl hydroperoxide as a polymerization initiator in 30 parts by weight of xylene was added dropwise at a temperature of about 110 ° C. for about 1 hour under a nitrogen atmosphere. The temperature was maintained at that temperature for 6 hours to terminate the radical polymerization reaction, and the solvent was removed to obtain a resin composition (A) containing a polyester resin, a vinyl copolymer and a resin in which these were chemically reacted.

(B) Production of Highly Crosslinked Polyester Resin Composition Next, a polycondensation reaction was carried out in the same manner except that the following monomers were used to obtain a highly crosslinked polyester resin (B).
I got

(C) Production of binder resin 27 parts by weight of the highly crosslinked polyester resin (B) and 70 parts by weight of the resin composition (A) were mixed with xylene 200
2 parts by weight of styrene, 0.8 part by weight of 2-ethylhexyl acrylate, 0.2 part by weight of acrylic acid
1 part by weight, 0.01 part by weight of divinylbenzene and 0.05 part by weight of the above-mentioned polymerization initiator were added dropwise at a temperature of about 125 ° C. for about 1 hour in a nitrogen atmosphere. By maintaining the temperature for 5 hours and removing the solvent, the binder resin of the present invention comprising a highly crosslinked polyester resin, a slightly crosslinked polyester resin, a vinyl copolymer and a resin in which these are chemically reacted ( 1) was obtained.

In the binder resin (1) of the present invention, the fact that the vinyl copolymer and the polyester resin composition are chemically reacted can be verified by ¹³ C-NMR.

In general, the signal measured by ¹³ C-NMR of the ester group of the acrylate copolymerized with styrene is higher than that of the acrylate homopolymer due to the benzene ring of styrene toward the high magnetic field side. Several pp
The phenomenon of m shift is known. This phenomenon is the same when the polyester resin composition is present as an ester group. Here, we focused on the carbon of the carboxyl group of trimellitic acid.

The low cross-linking degree polyester resin composition of ¹³ C-
The NMR measurement results in FIG. 5, the measurement results of the same composition as that reacts with lightly crosslinked polyester resin composition of styrene and 2-ethylhexyl acrylate in Figure 6, the binder resin of the present invention (1) ¹³ C- FIG. 7 shows the NMR measurement results.

Table 1 shows the measurement results of the respective resin compositions.

[0215]

[Table 1]

(Production Examples 2 to 6) The binder resin (2) of the present invention was prepared by changing the type and composition of the monomers as shown in Tables 2, 3 and 6.
To (6) were obtained.

(Comparative Production Examples 1 to 6) Comparative binder resins (1) to (C) by changing the type and composition of the monomers as shown in Tables 4 to 6.
(6) was obtained.

(Production Example 1 of Magnetic Iron Oxide) Sodium silicate was added to an aqueous ferrous sulfate solution so that the content ratio of silicon element to iron element was 1.5% by weight. 1.0 to 1.1 equivalents of a sodium hydroxide solution,
An aqueous solution containing ferrous hydroxide was prepared.

The pH of the aqueous solution is 7 to 10 (for example, pH 9)
Air was blown while maintaining the temperature at 80 ° C. to perform an oxidation reaction at 80 to 90 ° C. to prepare a slurry liquid for generating seed crystals. Next, an aqueous solution of ferrous sulfate is added to the slurry liquid so as to have an equivalent amount of 0.9 to 1.2 equivalents relative to the initial alkali amount (sodium component of sodium silicate and sodium component of sodium hydroxide), and then the pH of the slurry solution is adjusted to 6 to 10. 10 (for example, pH 8)
The oxidation reaction was promoted while blowing air, and the pH was adjusted at the end of the oxidation reaction, and the silicic acid component was unevenly distributed on the surface of the magnetic iron oxide particles. The produced magnetic iron oxide particles were washed, filtered, and dried by a conventional method, and then the aggregated particles were crushed to obtain magnetic iron oxide (1).

(Production Example 2 of Magnetic Iron Oxide) A magnetic iron oxide (2) was obtained in the same manner as in Production Example 1 of magnetic iron oxide except that sodium silicate was not added.

(Production Example 3 of Magnetic Iron Oxide) In the magnetic iron oxide particles 1, the content ratio of silicon element to iron element was 3.5% by weight.
Further, fine silica powder was added thereto and mixed with a Henschel mixer to obtain magnetic iron oxide (3).

(Production Example 4 of Magnetic Iron Oxide) In the magnetic iron oxide particles 2, the content of the silicon element with respect to the iron element was 0.6% by weight.
The resulting mixture was mixed with a Henschel mixer to obtain magnetic iron oxide (4).

(Production Example 5 of Magnetic Iron Oxide) Sodium silicate was added so that the content of silicon element with respect to iron element was 0.8% by weight, and the conditions were changed so that silicon element was not present on the surface. Thus, a magnetic iron oxide (5) was obtained.

(Production Example 6 of Magnetic Iron Oxide) Octahedral (sphericity Ψ = 0.67) magnetic iron oxide (6) was obtained by adding no sodium silicate and changing the temperature and pH. Was.

Table 7 shows the physical property values of the magnetic iron oxides 1 to 6.

[Example 1]-100 parts by weight of binder resin (1) of the present invention-2 parts by weight of azo-based iron complex compound-100 parts by weight of magnetic iron oxide (1)-Ester wax shown in Table 10 5 parts by weight 2 parts by weight of polyethylene wax shown in Table 11

The above mixture was melt-kneaded with a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a jet mill, and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 6.7 μm and a volume average particle diameter of 5.8 μm.

The content of the components insoluble in ethyl acetate with respect to 100 parts by weight of the binder resin of this toner was determined. As a result, the resin composition excluding the mixed wax was 16 parts by weight. Furthermore, when the polyester resin components Gp and Sp contained in the binder resin component insoluble in ethyl acetate and the binder resin component dissolved therein were quantified by NMR, Gp = about 88% by weight,
Sp = about 63% by weight, ratio (Sp / Gp) = 0.7
When the amount of the succinic acid derivative represented by the formula (1-3) was determined, it was found that the component insoluble in ethyl acetate contained about 77% by weight of the whole charged amount.

The amount of wax contained in the component insoluble in ethyl acetate can be measured by DSC and quantified from the enthalpy of dissolution. As a result, it was found that about 72% by weight of the total wax was added to the toner. all right.

(Evaluation of Image Characteristics) This magnetic toner 100
1.2 parts by weight of hydrophobic dry silica (BET = 100 m ² / g) surface-treated with dimethyl silicone oil was externally added to the parts by weight with a Henschel mixer to obtain a toner.

Using this toner, an image durability test was performed with a Canon printer LBP-450 in which the toner regulating member of the developing device was in contact with the toner carrier, and the image density was compared with that before the durability test. I checked later. The image endurance test was performed on up to 5,000 sheets. Table 12 shows the results.
It was shown to.

(Evaluation of Fixing Property) Printer L manufactured by Canon
The fixing device of the BP430 was removed, and the temperature of the fixing device was changed to 120 ° C. and 200 ° C. using a fixing test device equipped with an external drive and a temperature control device for the fixing device. . In the test in which the fixing temperature was set to 120 ° C., a load of 4900 N / m ² was applied to the image, the fixed image was rubbed with soft thin paper, and the image density reduction rate before and after rubbing was evaluated (%). In the test in which the fixing temperature was set to 200 ° C., the transfer paper was visually observed to examine the occurrence of hot offset. The evaluation was performed according to the following criteria, and the evaluation results are shown in Table 12. A: No hot offset has occurred B: Minor hot offset has occurred C: Apparent hot offset has occurred

(Evaluation of negative sleeve ghost) As shown in FIG. 8 using a Canon printer LBP-450,
A solid black image in a block shape corresponding to one round of the toner carrier was printed, and an image having a continuous halftone solid image was printed below the solid black image. The image density difference of the negative sleeve ghost at that time was evaluated. Specifically, it is a value obtained by subtracting the image density of the area A from the image density of the area B in FIG. Table 12 shows the evaluation results.

(Pressurized Roller Stain) The temperature of the fixing unit of the Canon printer LBP-430 was changed to 170 ° C. to perform 100,000 prints, and dirt on the pressure roller of the fixing machine was visually observed. Then, pressure roller contamination was evaluated according to the following evaluation criteria. Table 12 shows the evaluation results. A: No dirt B: Minor dirt generation C: Dirt generation

(Evaluation of blocking resistance) 50 g of toner
Is placed in a container having a capacity of 100 ml and left in an environment of 50 ° C. for 7 days. Thereafter, the fluidity of the toner is visually confirmed,
Evaluation was made according to the following criteria. Table 12 shows the evaluation results. A: No change in fluidity of toner B: Slight agglomerates

Examples 2 to 6 Example 1 was repeated except that the binder resins (2) to (6) were used instead of the binder resin (1).
A toner was obtained in the same manner as described above. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Example 1
Table 12 shows the results of the evaluation performed in the same manner as described above.

[Examples 7 to 10] Toners were obtained in the same manner as in Example 1 except that the ester wax shown in Table 10 was used instead of the ester wax. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 12 shows the results of evaluation in the same manner as in Example 1.
Shown in

Example 11 A toner was obtained in the same manner as in Example 1 except that the polyethylene wax shown in Table 11 was used instead of the polyethylene wax. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 12 shows the results of evaluation in the same manner as in Example 1.
Shown in

Example 12 A toner was obtained in the same manner as in Example 1 except that the polyethylene wax shown in Table 11 was used instead of the polyethylene wax. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 12 shows the results of evaluation in the same manner as in Example 1.
Shown in

Example 13 A toner was obtained in the same manner as in Example 1, except that a hydrocarbon wax synthesized by the Age method shown in Table 11 was used instead of the polyethylene wax. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 12 shows the results of evaluation in the same manner as in Example 1.

Example 14 A toner was obtained in the same manner as in Example 1 except that polypropylene wax shown in Table 11 was used instead of polyethylene wax. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 1 shows the results of evaluation in the same manner as in Example 1.
It is shown in FIG.

[Examples 15 to 19] Toners were obtained in the same manner as in Example 1 except that magnetic iron oxides 2 to 6 shown in Table 7 were used instead of magnetic iron oxide 1. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 12 shows the results of evaluation in the same manner as in Example 1.

Example 20 Instead of hydrophobic dry silica treated with dimethyl silicone oil, hydrophobic dry silica (BE) surface-treated with hexadimethyldisilazane was used.
T: 180 m ² / g), and a toner was obtained in the same manner as in Example 1. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 12 shows the results of evaluation in the same manner as in Example 1.

Example 21 A toner was obtained in the same manner as in Example 1 except that no polyethylene wax was used. Table 8 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Table 12 shows the results of evaluation in the same manner as in Example 1.

Comparative Examples 1 to 6 Example 1 was repeated except that the comparative binder resins (1) to (6) were used instead of the binder resin 1.
A toner was obtained in the same manner as described above. Table 9 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Example 1
Table 13 shows the results of the evaluation performed in the same manner as described above.

Comparative Example 7 Example 1 was repeated except that only 7 parts by weight of the polypropylene wax shown in Table 11 was used instead of the polyester wax and the polyethylene wax.
A toner was obtained in the same manner as described above. Table 9 shows the analysis results of the ethyl acetate soluble and insoluble components of the obtained toner, and Example 1
Table 13 shows the results of the evaluation performed in the same manner as described above.

[0247]

[Table 2]

[0248]

[Table 3]

[0249]

[Table 4]

[0250]

[Table 5]

[0251]

[Table 6]

[0252]

[Table 7]

[0253]

[Table 8]

[0254]

[Table 9]

[0255]

[Table 10]

[0256]

[Table 11]

[0257]

[Table 12]

[0258]

[Table 13]

[0259]

According to the toner and the image forming method using the toner of the present invention, the ester wax is uniformly dispersed in the binder resin, the fixing property is good, the offset resistance, the blocking resistance, and the number of sheets It is excellent in durability and in that a negative sleeve ghost is unlikely to occur.

[Brief description of the drawings]

FIG. 1 shows an example of an image forming apparatus used in an image forming method of the present invention.

FIG. 2 is a partially enlarged view of an image forming apparatus used in the image forming method of the present invention.

FIG. 3 is a partially enlarged view of an image forming apparatus used in the image forming method of the present invention.

FIG. 4 shows an example of an image forming apparatus used in the image forming method of the present invention.

FIG. 5 shows an NMR spectrum of the polyester resin composition having a low degree of crosslinking.

FIG. 6 shows styrene and 2-ethylhexyl acrylate
Polymeric 3 shows an NMR spectrum.

FIG. 7 shows an NMR spectrum of the binder resin (1) of the present invention.

FIG. 8 shows a test example of a negative sleeve ghost.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 101 Latent image holding body 102 Toner carrier 103 Magnetic generating means 104 Toner regulating member 105 Stirring member 106 Toner container

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 9/08 365 371 375

Claims (58)

[Claims] 1. A toner containing at least a colorant, a binder resin and an ester wax, wherein the binder resin contains at least a reaction product of a vinyl copolymer and a polyester resin, (A) relative to 100 parts by weight of the binder resin, 2 to 60 parts by weight of the component (G) insoluble in ethyl acetate and 40 to 98 parts by weight of the component (S) soluble in ethyl acetate. (B) the content of the polyester resin component (Gp) in the component (G) insoluble in the ethyl acetate is 40 to 98% by weight, and (c) the component (S) soluble in the ethyl acetate. And (d) the content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate and the content of the polyester resin component (Sp) in the ethyl acetate. Insoluble components A toner characterized in that the ratio (Sp / Gp) to the content of the polyester resin component (Sp) in (S) is from 0.5 to 1. 2. The toner according to claim 1, wherein the toner contains a hydrocarbon wax or a petroleum wax. 3. The toner according to claim 1, wherein the binder resin contains a component (G) insoluble in ethyl acetate in an amount of 5 to 50% by weight based on the weight of the binder resin. 4. The toner according to claim 1, wherein the binder resin contains a component (G) insoluble in ethyl acetate in an amount of 10 to 40% by weight based on the weight of the binder resin. 5. The toner according to claim 1, wherein the binder resin contains a component (G) insoluble in ethyl acetate in an amount of 15 to 35% by weight based on the weight of the binder resin. 6. The toner according to claim 1, wherein the component (G) insoluble in ethyl acetate contains 50 to 95% by weight of a polyester resin component (Gp). 7. The toner according to claim 1, wherein the component (G) insoluble in ethyl acetate contains 60 to 90% by weight of a polyester resin component (Gp). 8. The component (S) soluble in ethyl acetate,
The toner according to any one of claims 1 to 7, comprising 25 to 85% by weight of a polyester resin component (Sp). 9. The component (S) soluble in the ethyl acetate,
8. The toner according to claim 1, comprising 30 to 80% by weight of a polyester resin component (Sp). 10. The content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate and the content of the polyester resin component (S) in the component (S) soluble in ethyl acetate.
The ratio (Sp / Gp) to the content of p) is 0.6 to 0.9.
The toner according to any one of claims 1 to 9, wherein 11. The content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate and the content of the polyester resin component (S) in the component (S) soluble in ethyl acetate.
The ratio (Sp / Gp) to the content of p) is 0.65 to 0.5.
The toner according to any one of claims 1 to 9, wherein 12. The toner according to claim 1, wherein the ester wax has at least one alkyl or alkenyl moiety having 15 or more carbon atoms. 13. The ester wax according to claim 1, wherein the ester wax has a melting point of 70 to 140 ° C. defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC). 13. The toner according to any one of the above items 12. 14. The ester wax according to claim 1, wherein the ester wax has a melting point of 75 to 135 ° C. defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC). 13. The toner according to any one of the above items 12. 15. The ester wax according to claim 1, wherein the melting point of the ester wax is from 80 to 130 ° C., which is defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC). 13. The toner according to any one of the above items 12. 16. The ester wax according to claim 1, wherein a half-width of an endothermic main peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) is less than 2.5 ° C. The toner according to any one of the above. 17. The melting point of the hydrocarbon wax and the petroleum-based wax defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) is 70 to 140 ° C.
17. The toner according to claim 2, wherein: 18. The melting point of the hydrocarbon wax and the petroleum-based wax specified by the endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) is 80 to 135 ° C.
17. The toner according to claim 2, wherein: 19. The hydrocarbon wax and the petroleum wax have a melting point of 90 to 130 ° C., which is determined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC).
17. The toner according to claim 2, wherein: 20. The toner according to claim 2, wherein Mw / Mn of the hydrocarbon wax and the petroleum wax is 1 to 3. 21. The toner according to claim 1, wherein the toner is a magnetic toner containing at least magnetic iron oxide. 22. The magnetic iron oxide has a sphericity (Ψ) of 0.8.
The toner according to claim 21, wherein: 23. The toner according to claim 21, wherein the magnetic iron oxide contains a silicon element. 24. A silicon element in which the magnetic iron oxide has a silicon element content of 0.1 to 10% by weight based on the iron element and the iron element dissolution rate of the magnetic iron oxide is up to 20% by weight. (B / A) × 100 between the content B of the magnetic iron oxide and the total content A of the silicon element of the magnetic iron oxide is 44 to 100%, and the content C of silicon present on the surface of the magnetic iron oxide is 24. The toner according to claim 23, wherein the ratio (C / A) * 100 to the content A is 10 to 95%. 25. A silicon element in which the magnetic iron oxide has a silicon element content of 0.2 to 4% by weight based on the iron element, and the iron element dissolution rate of the magnetic iron oxide is up to 20% by weight. (B / A) × 100 of the content B of the magnetic iron oxide and the total content A of the silicon element of the magnetic iron oxide is 44 to 84%, and the content C of silicon present on the surface of the magnetic iron oxide is 24. The toner according to claim 23, wherein the ratio (C / A) * 100 to the content A is 10 to 55%. 26. The toner according to claim 1, wherein the toner contains silica subjected to a hydrophobic treatment. 27. The toner according to claim 26, wherein said silica has been treated with silicone oil. 28. The toner has a weight average particle size of 3 to 9 μm.
The toner according to any one of claims 1 to 27, wherein: 29. The toner has a volume average particle size of 2.5 to 2.5.
The toner according to any one of claims 1 to 28, wherein the thickness is 6.0 µm. 30. A charging step of charging by a charging device to which an external voltage is applied; a step of forming an electrostatic charge image on the charged latent image holder; A developing step of forming an image by developing with the toner layer on the toner carrier whose layer thickness is regulated by a toner layer thickness regulating member for regulating the layer thickness of the toner layer formed on the toner carrier. Wherein the toner layer thickness regulating member is in pressure contact with the surface of the toner carrier via the toner layer to regulate the layer thickness of the toner layer formed on the toner carrier. The toner is a toner containing at least a colorant, a binder resin and an ester wax, wherein the binder resin contains at least a reaction product of a vinyl copolymer and a polyester resin, In the resin, (a) the binder resin contains 2 to 60 parts by weight of a component (G) insoluble in ethyl acetate and 40 parts by weight of a component (S) soluble in ethyl acetate based on 100 parts by weight of the binder resin. (B) the content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate is 40 to 98% by weight, and (c) the ethyl acetate The content of the polyester resin component (Sp) in the component (S) soluble in water is 20 to 90% by weight, and (d) the content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate. An image forming method, wherein the ratio (Sp / Gp) of the content to the content of the polyester resin component (Sp) in the component (S) soluble in ethyl acetate is 0.5 to 1. 31. The toner according to claim 3, wherein the toner contains a hydrocarbon wax or a petroleum wax.
0. The image forming method according to item 1. 32. The image forming apparatus according to claim 30, wherein the binder resin contains 5 to 50% by weight of a component (G) insoluble in ethyl acetate based on the weight of the binder resin. Method. 33. The image forming apparatus according to claim 30, wherein the binder resin contains a component (G) insoluble in ethyl acetate in an amount of 10 to 40% by weight based on the weight of the binder resin. Method. 34. The image forming apparatus according to claim 30, wherein the binder resin contains 15 to 35% by weight of a component (G) insoluble in ethyl acetate based on the weight of the binder resin. Method. 35. The component (G) insoluble in ethyl acetate,
35. The image forming method according to claim 30, wherein the polyester resin component (Gp) is contained in an amount of 50 to 95% by weight. 36. The component (G) insoluble in ethyl acetate,
35. The image forming method according to claim 30, wherein the polyester resin component (Gp) is contained in an amount of 60 to 90% by weight. 37. The component (S) soluble in said ethyl acetate
The image forming method according to any one of claims 30 to 36, wherein the toner contains 25 to 85% by weight of a polyester resin component (Sp). 38. The component (S) soluble in said ethyl acetate
The image forming method according to any one of claims 30 to 36, wherein the toner contains 30 to 80% by weight of a polyester resin component (Sp). 39. The content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate and the content of the polyester resin component (S) in the component (S) soluble in ethyl acetate.
The ratio (Sp / Gp) to the content of p) is 0.6 to 0.9.
39. The image forming method according to claim 30, wherein 40. The content of the polyester resin component (Gp) in the component (G) insoluble in ethyl acetate and the content of the polyester resin component (S) in the component (S) soluble in ethyl acetate.
The ratio (Sp / Gp) to the content of p) is 0.65 to 0.5.
39. The image forming method according to claim 30, wherein: 41. The image forming method according to claim 30, wherein the ester wax has at least one alkyl or alkenyl moiety having 15 or more carbon atoms. 42. The ester wax having a melting point of 70 to 140 ° C. defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC). 41. The image forming method according to any one of 41. 43. The ester wax having a melting point of 75 to 135 ° C. defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC). 41. The image forming method according to any one of 41. 44. The ester wax according to claim 30, wherein the melting point of the ester wax is from 80 to 130 ° C. as defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC). 41. The image forming method according to any one of 41. 45. The ester wax according to claim 30, wherein a half-width of an endothermic main peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) is less than 2.5 ° C. The image forming method according to any one of the above. 46. The hydrocarbon wax and the petroleum-based wax have a melting point of 70 to 140 ° C. defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC).
The image forming method according to any one of claims 31 to 45, wherein: 47. The hydrocarbon wax and the petroleum-based wax have a melting point of 80 to 135 ° C. defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC).
The image forming method according to any one of claims 31 to 45, wherein: 48. The hydrocarbon wax and the petroleum-based wax have a melting point of 90 to 130 ° C. defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC).
The image forming method according to any one of claims 31 to 45, wherein: 49. The image forming method according to claim 31, wherein Mw / Mn of the hydrocarbon wax and the petroleum wax is 1 to 3. 50. The image forming method according to claim 30, wherein the toner is a magnetic toner containing at least magnetic iron oxide. 51. The magnetic iron oxide has a sphericity (鉄) of 0.8.
The image forming method according to claim 50, wherein: 52. The image forming method according to claim 50, wherein the magnetic iron oxide contains a silicon element. 53. A silicon element in which the content of silicon element in the magnetic iron oxide is 0.1 to 10% by weight based on the iron element, and the solubility of iron element in the magnetic iron oxide is up to 20% by weight. (B / A) × 100 between the content B of the magnetic iron oxide and the total content A of the silicon element of the magnetic iron oxide is 44 to 100%, and the content C of silicon present on the surface of the magnetic iron oxide is 53. The image forming method according to claim 52, wherein the ratio (C / A) * 100 to the content A is 10 to 95%. 54. A silicon element in which the content of the silicon element in the magnetic iron oxide is 0.2 to 4% by weight based on the iron element, and the solubility of the iron element in the magnetic iron oxide is up to 20% by weight. (B / A) × 100 between the content B of the magnetic iron oxide and the total content A of the silicon element of the magnetic iron oxide is 44 to 84%, and the content C of silicon present on the surface of the magnetic iron oxide is 53. The image forming method according to claim 52, wherein the ratio (C / A) * 100 to the content A is 10 to 55%. 55. The image forming method according to claim 30, wherein the toner contains silica subjected to a hydrophobic treatment. 56. The image forming method according to claim 55, wherein said silica is treated with silicone oil. 57. The toner has a weight average particle diameter of 3 to 9 μm.
The image forming method according to any one of claims 30 to 56, wherein: 58. The toner has a volume average particle size of 2.5 to 2.5.
58. The thickness is 6.0 μm.
The image forming method according to any one of the above.