JP3230009B2 - Heat fixing toner for developing an electrostatic image, image fixing method, image forming apparatus, and resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
The present invention relates to a toner for forming an image by developing an electrostatic image, such as electrostatic printing, a toner image fixing method using the toner, an image forming apparatus, and a resin composition.

[0002]

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

Various methods and techniques have been developed for the final step of fixing the toner image on a sheet such as paper. Currently, the most common method is a pressure heating method using a heating roller.

In the pressure heating method using a heating roller, fixing is performed by allowing the toner image surface of the sheet to be fixed to pass through the surface of a heating roller having a surface formed of a material having a releasable property with respect to the toner while contacting the surface under pressure. Things. In this method, since the surface of the heating roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Very effective in high-speed electrophotographic copying machines. However, in the above method, a part of the toner image adheres to the fixing roller surface because the surface of the heating roller and the toner image come into contact with each other under pressure in a molten state.
The sheet is transferred and re-transferred to the next sheet to be fixed, causing a so-called offset phenomenon, which may stain the sheet to be fixed. Preventing toner from adhering to the surface of the heat fixing roller is an essential condition in the heat roller fixing method.

Therefore, at present, it is desired to develop a binder resin for toner having a wide fixing temperature range and high offset resistance.

There have been many studies and commercialization of two-color copying machines and full-color copying machines. For example, “Journal of the Society of Electrophotography,” Vol 22, No. 1 (1983) and "Journal of the Institute of Electrophotography", Vol. 1, P. 52 (198
As described in 6), there are reports of color reproducibility and gradation reproducibility.

However, full color electrophotography which is not practically compared with the real thing such as a television, a photograph, and a color print, and which is regarded as a color image which is more beautifully processed than the real thing, is now considered. The images are not always satisfactory.

Color image formation by full-color electrophotography generally reproduces all colors using three color toners of three primary colors, yellow, magenta, and cyan, or four colors including black. . In the general method, first, an electrostatic latent image is formed on a photoconductive layer by passing light from a document through a color separation light transmission filter having a complementary color relationship with the color of the toner. Next, the toner is held on the support through a development and transfer process. Next, the above-described steps are sequentially performed a plurality of times, the toner is superimposed on the same support while the registration is being performed, and a final full-color image is obtained through a fixing step.

In full-color electrophotography, a binder resin for color toner is used to form a full-color image by performing development a plurality of times using a plurality of types of toners having different colors and superposing a toner layer on the same support. Necessary conditions to be met include the following. (1) In order that the fixed toner does not diffusely reflect light and hinder color reproduction, the toner needs to be in a state of almost complete melting such that the shape of the toner particles cannot be determined. (2) Since the toner layer is laminated, the binder resin must be transparent so as not to hinder the different colors of the lower toner layer.

As described above, for a monocolor copying machine, a binder resin for a toner having a wide fixing temperature range and high offset resistance is required. For a full-color copying machine, not only the fixing temperature range is wide but also the transparency of the resin is high. It is required that the fixing surface becomes flat when fixed. As described above, the transparency of the resin and the smoothness of the fixing surface are determined not only when the toner image is fixed on a non-translucent transfer material such as paper and the reflected image is viewed, but also when the translucent material such as an OHP sheet is used. The quality of the transmitted light image viewed by fixing the toner image on the transfer material is greatly affected.

Further, in recent years, from a mono-color copying machine to a full-color copying machine, many requirements such as high speed, reduction of heat-up time of a heating roller, and reduction of power consumption are required.

In order to satisfy these requirements, a toner binder which can be fixed at a low temperature and has a wide fixing area, excellent transparency and a flat fixing surface when fixed as described above. Requires resin.

On the other hand, a method using a pressure fixing toner is also conceivable. However, in this method, when used as a full-color toner for reproducing colors by superimposing three or four colors, the binder resin cannot be melted, so that the color mixing property is poor. Bad, dull images with poor saturation. Therefore, in the fixing step, heat must be applied to such an extent that the binder resin can be melted and mixed.

It is possible to lower the melt viscosity of the binder resin for toner only for the purpose of fixing at a low temperature. For example, there is a method of lowering the molecular weight or the glass transition temperature of the resin. However, this method deteriorates the storage stability of the toner, and tends to cause phenomena such as blocking between toners and fusion to a developing drum.

In order to increase the fixing temperature of a conventional vinyl polymer, Japanese Patent Application Laid-Open Nos. 58-14148 and 58-7
2948, JP-A-59-174855-6, JP-A-60-123855, JP-B-52-3
Nos. 304-5, JP-B-57-52574 and JP-B-58-8505 disclose methods using an anti-offset agent. These methods are auxiliary, and are particularly useful for monocolor toners. Has a problem in that the transparency is impaired, and when used as a full-color toner, the color mixing property deteriorates.

JP-A-56-158340, JP-A-58-86558, JP-A-58-203453, JP-A-59-88748, and JP-A-59-2
26358, JP-A-60-45259, JP-A-60-45261, JP-A-60-46566
Japanese Patent Application Publication No. 60-24111 and Japanese Patent Publication No. 60-2411 disclose a binder resin for toner having a low molecular weight component and a high molecular weight component. The use of these resins made it possible to extend the fixing temperature to some extent, but the presence of high molecular weight components such as gels caused problems such as reduced grindability and excessively high melt viscosity during hot kneading. In particular, when used as a full-color toner, there is a problem that the smoothness of the fixing surface at the time of fixing is impaired, so that the color mixing property is deteriorated.

US Pat. No. 4,925,765 describes a negative solid block toner using an AB type, BAB type or ABA type block copolymer as a charge control agent.

In the block copolymer, a copolymer composed of an acrylic monomer or a copolymer composed of a methacrylic monomer is used for the A segment, and styrene; substituted styrene; butadiene; A copolymer made of acrylic and / or a monomer selected from the group consisting of acrylic is used.

When such a block copolymer is used as a binder resin for a toner, since the A segment is an acrylic copolymer or a methacrylic copolymer, the pulverizability during the production of the toner is reduced. It is conceivable that the particle size distribution of the inferior toner becomes broad and the toner has poor environmental stability.

Therefore, it is extremely difficult to simultaneously fix at a low temperature, expand the fixing temperature range, and simultaneously satisfy the toner characteristics such as storage stability, fluidity, durability, transparency, and smoothness of the fixing surface. .

On the other hand, the fixing roller is roughly classified into a silicone rubber roller and a fluorine-based roller.

When a silicone rubber roller is used as a fixing roller, regardless of whether or not a release oil is applied.
High-temperature offset is likely to occur by repeated use. In the silicon rubber roller, since the smoothness and cleanliness of the roller surface are not impaired at the beginning of use, a certain degree of releasability is maintained. However, when full-color copying is repeated, the image area is large like a full-color image, and the toner holding amount on the support is much larger than that of a black-and-white image, the releasability of the roller surface gradually decreases. The degree of reduction is several times that of black-and-white copying. As a result, after a few thousand to tens of thousands of full-color copies have been made, a toner film or particulate attachment is formed on the roller surface, and the toner upper layer on the image surface is peeled off when the full-color image passes through the heat roller. A so-called high-temperature offset occurs.

Fluorine-based rollers generally have good durability, but are liable to spread the toner by pressure, and therefore have the drawback of lowering the resolving power in a copy image and making the background stain more conspicuous. In order to improve these drawbacks, rubber coated with a PFA (perfluoroalkoxy resin) tube of 100 to 300 μm (Japanese Patent Publication No. 58-43)
740). When these rollers are used, the reduction in the resolving power of the copied image due to the toner expansion is improved.

However, in general, when a fluorine-based roller is used as a fixing roller, the pressure roller includes, for example, as disclosed in Japanese Patent Application Laid-Open No. 61-89845 by the present applicant.
A core metal whose outer peripheral surface is covered with a relatively thick elastic material layer such as rubber is used.

In this case, as shown in FIG. 5, the direction in which the toner is discharged from the fixing roller after fixing is performed in a direction perpendicular to the line connecting the centers of the fixing roller and the pressure roller is the fixing roller side.

For this reason, even if the fixed image passes through the nip portion where the fixing roller and the pressure roller are in contact,
So-called "twisting" dragged by the fixing roller
A phenomenon occurs, and an offset occurs. To prevent this, there is a method to attach a separation sheet for paper ejection.However, this separation sheet is in contact with the fixing roller, so that it damages and leaves streaks on the image surface. In a full-color copy of a photograph having a large area, the image quality is significantly reduced.

Although various measures have been tried with a fixing device and toner to solve or reduce this problem, it cannot be said that a satisfactory solution has yet been achieved.

The fixing device is made of a material having excellent surface releasability, or is devised by applying oil to a roller. A heat roller fixing device of a copying machine which is currently commercialized has some form of oil application. Most are doing. However, the application of a large amount of oil to increase the releasability causes undesired problems such as oil contamination of the sheet and an increase in cost.

As a toner, a method of adding a low molecular weight polyethylene or wax which sufficiently melts when heated to increase the releasability is also used. O of toner
Adverse effects such as loss of transparency of the HP image, instability of charging characteristics, and reduction of durability are also recognized, and it is difficult to say that the image is satisfactory.

In particular, a problem peculiar to full-color copying is that at least three colors, and preferably four colors, must be balanced in harmony, so that the fixing characteristics and the color reproducibility are not balanced. Must be

In principle, if there are three primary colors, yellow, magenta, and cyan, almost all colors should be able to be reproduced by the subtractive color mixing method. The full-color copying machine has a configuration in which three primary color toners are used in an overlapping manner. By this, ideally, all colors can be realized in all density ranges, but in reality, there are still points to be improved, such as the spectral reflection characteristics of the toner, the color mixing at the time of superimposing and fixing the toner, and the decrease in the saturation. have.

When a black color is obtained by superimposing three colors, as described above, three times more toner layer is formed on the transfer paper than in the case of a single color, so that the offset resistance becomes more difficult. Have.

[0033]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-fixable toner for developing an electrostatic image, an image fixing method, an image forming apparatus, and a resin composition which solve the above-mentioned problems. .

An object of the present invention is to provide a heat-fixable toner for developing an electrostatic image, an image fixing method, an image forming apparatus, and a resin composition that can be fixed at a low temperature and have a wide fixing temperature range.

An object of the present invention is to provide a heat-fixable toner for developing an electrostatic image, which has excellent storage stability and fluidity, does not cause aggregation, and has excellent impact resistance, an image fixing method, an image forming apparatus, and a resin composition. It is to provide things.

An object of the present invention is to provide a heat-fixable toner for developing an electrostatic image, which has good charging characteristics and has stable chargeability during use, and provides a clear and fog-free image. An object of the present invention is to provide an image forming apparatus and a resin composition.

An object of the present invention is to provide an electrostatic charge capable of forming a smooth fixed surface so that a fixed toner image does not irregularly reflect light and hinder color reproduction when used as a full-color toner. An object of the present invention is to provide a heat fixing toner for image development, an image fixing method, an image forming apparatus, and a resin composition.

An object of the present invention is to provide a full-color toner for developing an electrostatic image capable of obtaining a full-color image having color mixing properties which does not hinder the color tone of a toner layer having a different color tone under the toner layer. An object of the present invention is to provide a heat fixing toner, an image fixing method, an image forming apparatus, and a resin composition.

An object of the present invention is to provide an image fixing method in which a high-temperature offset is sufficiently prevented and a fixable temperature range is wide.

An object of the present invention is to provide an image fixing method in which the offset resistance is maintained even after repeated fixing.

[0041]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies, the domain particles dispersed in the matrix have an average particle size of 5 μm or less,
The resin P ₁ constituting the domain particles has a glass transition temperature Tg ₁ of 15 to 50 ° C., and the resin P ₂ constituting the matrix has a glass transition temperature T g of 55 to 80 ° C.
has a g _2, the resin P ₂ of the glass transition temperature Tg
_2, a glass transition higher domain 5 ° C. or higher than the temperature Tg ₁ of the resin P ₁ - has been found that can solve the above problems by using a resin composition having a matrix structure.

That is, the present invention relates to the above-mentioned resin composition, and further relates to a heat-fixable toner for developing an electrostatic image having toner particles containing a binder resin having the resin composition and a colorant. .

Further, according to the present invention, a transfer material supporting a toner image is passed through a fixing device having a rubber-like elastic layer on a cored bar and a heat roller fixing device having a pressure roller. An image fixing method for fixing the toner image on the fixing roller and discharging the transfer material to the pressure roller side from a direction perpendicular to a line connecting the center of the fixing roller and the pressure roller to fix the image. The present invention relates to an image fixing method using the toner having the above configuration as a toner for forming.

Further, the present invention provides a latent image carrier for carrying an electrostatic latent image, a charging means for charging the latent image carrier, and an electrostatic latent image on the charged latent image carrier. A latent image forming unit for forming, a developing unit for forming the electrostatic latent image and forming a toner image on the latent image carrier, and a developing unit for transferring the toner image from the latent image carrier to a transfer material Transfer means,
An image forming apparatus having a cleaning unit for removing toner remaining on the latent image carrier without being transferred and a fixing unit for fixing the toner image transferred to the transfer material by the action of heat and pressure. The image forming apparatus is characterized in that the developing means has the toner having the above configuration.

The present inventors have found out that the reason is based on the following.

A structure in which a resin having a high glass transition point Tg is used as a matrix and a resin having a low glass transition point Tg is used as domain particles generally has excellent blocking resistance and also has excellent blocking resistance. .

For a toner in which the binder resin has domain particles and a matrix, that is, a so-called domain-matrix structure, for example, in Japanese Patent Publication No. 57-6586, the domain particles have a glass transition temperature (Tg) of 30 ° C.
> And a soft and deformable polymer having a number average molecular weight (Mn) of 500 to 50,000, wherein the matrix is an amorphous polymer having a glass transition temperature (Tg) of 50 ° C <
m) 40 ° C. <crystalline polymer and number average molecular weight (M
n) A method for controlling the domain particle size by adding a dispersant such as a graft or a block polymer, which is a tenacious polymer having 1500 <is disclosed. In such a method, as shown in the exemplary substances described in the text, the polymers constituting the matrix and the domain particles are completely incompatible substances, and addition of a graft or a block polymer is indispensable to obtain a domain-matrix structure. is there. Therefore, it seems that a special method for controlling the domain particles and the matrix by the spray drying method-coacervation method is employed. The toner obtained by this method can certainly be fixed at a low temperature, but the particle size distribution of the toner produced by the spray drying method is broad, so that the image quality is poor due to fog and toner scattering. . In the spray drying method, a resin obtained by dissolving a resin of domain particles, a matrix, and a dispersant in a mutual solvent and adding a non-solvent (a selective solvent for a matrix component having a higher boiling point than the mutual solvent) is spray-dried. The toner is obtained by removing the mutual solvent to precipitate the soft polymer component and then removing the solvent from the matrix formed around the soft polymer component. When using this method, the combination of the resin and the solvent is limited (the resin is soluble in the first solvent, but not in the solvent to be added next, or the boiling point of the solvent must be low for spray drying. ), It is not easy to change the molecular weight or the composition of the resin, for example. It is also very difficult to use resins having similar compositions, considering that they are selectively precipitated in order. Since the polarity of the graft or block polymer serving as a dispersant for the formed domain particles is not so strong, the domain becomes large by long-term storage, and therefore, the blocking resistance becomes poor.

A method of blending a condensation resin such as polyester or epoxy resin for the purpose of fixing at a low temperature and a vinyl resin for the purpose of improving the offset at a high temperature is disclosed in
It is disclosed in Japanese Patent Publication No. 9-50060. In this method, a weight-average molecular weight of a macromolecular weight of 500,000 or more, and a vinyl resin having a relatively low polarity is melt-kneaded with a condensation resin such as polyester or epoxy resin,
In such mixing, the graft or block polymer may not be added, and even if domain particles are formed, it is very difficult to control the domain particle diameter more than that described above. Further, since the domain particles become larger due to long-term storage, the blocking resistance decreases.

A method of blending resins having different glass transition temperatures (Tg), molecular weights and / or compositions is disclosed in
6-159340, JP-A-58-106522, JP-A-63-214760, and JP-A-63-214760.
In these methods, domain particles are not formed, or even if they are formed, the particle size is large. If either one of the resins has a glass transition temperature (Tg) lower than 50 ° C., the blocking resistance becomes very poor.

Therefore, the present inventors have conducted intensive studies and as a result,
The inventors have invented a resin composition for a developer which does not cause the above-mentioned various problems and has excellent low-temperature fixability.

The resin composition of the present invention may be used at a temperature of 0 to 60 ° C.
An average particle size of 5μm or less domain particles having a glass transition temperature Tg ₁ of, 40 to 90 ° C. The glass transition temperature Tg ₂ of
Wherein Tg ₂ is 5 times greater than Tg ₁
The developer of the present invention has a domain-matrix structure having a high glass transition temperature relationship of not less than ° C., and uses a binder resin having the resin composition.

With the above configuration, a toner having excellent low-temperature fixability and excellent blocking resistance can be obtained.

The domain-matrix structure in the present invention includes, for example, the following forms (1) to (4).

A domain-matrix structure obtained by introducing a carboxyl group by using a resin having a carboxyl group in one of the resin forming the domain particles and the vinyl resin forming the matrix.

[0055] In this embodiment, when the resin forming the domain particles has a carboxyl group, by a glass transition temperature Tg ₁ is lower resin 5 ° C. or higher than the glass transition temperature Tg ₂ of the resin P ₂ forming the matrix The formed domain particles are associated by carboxyl groups,
It forms micelles very finely and stably.

The mixing ratio of the resin having a carboxyl group for forming the domain particles and the resin having no carboxyl group for forming the matrix is determined by the ratio of the resin having the carboxyl group for forming the domain particles. The compounding ratio is increased (when the resin having a carboxyl group has an acid, the resin having a carboxyl group: the resin having no carboxyl group is 6 to 9: Choose between 4-1)
Thereby, the domain-matrix structure is reversed, and the resin having a carboxyl group forms a matrix.

In this embodiment, a cross-linkable metal compound can be used. In the case where the cross-linkable metal compound is used, a part or all of the domain particles forming micelles become a microgel due to the cross-linkable metal compound at the time of toner formation. More excellent effects can be obtained with respect to fixability and blocking resistance.

A polyester resin having an unsaturated double bond is used as a resin forming a matrix, and a resin comprising a vinyl-based monomer having an unsaturated double bond is used as a resin forming a domain particle. A domain-matrix structure obtained by partially chemically bonding unsaturated double bonds of two kinds of resins having no or low compatibility with a resin forming domain particles.

In this embodiment, the glass transition temperature Tg ₂ of the resin P ₂ forming the matrix is 5 ° C. lower than the glass transition temperature Tg ₁ of the resin P ₁ forming the domain particles.
The unsaturated double bonds of the two types of resins, which are higher and have no or low compatibility between the resin P ₁ forming the domain particles and the resin P ₂ forming the matrix, are partially chemically bonded. Thereby, the domain particles are finely and stably dispersed in the matrix, so that excellent low-temperature fixability and blocking resistance can be obtained. In addition, the unsaturated double bonds of the resin forming the domain particles and the matrix are partially chemically bonded to each other, so that the domain particles do not appear on the toner surface due to pulverization during the production of the toner, thereby improving the fluidity. I do.

The resin forming the matrix has an acid value of 1
Using a polyester resin having substantially no carboxyl group of less than 5 and using a vinyl resin having an acid value of 15 or more in which a carboxyl group is introduced by acid-modifying a vinyl resin to a resin forming domain particles. Domain-matrix structure thereby obtained.

[0061] In this embodiment, a matrix high 5 ° C. or higher than the glass transition temperature Tg ₁ of the resin P ₁ having a glass transition temperature Tg ₂ of the resin P ₂ to form a domain particles forming the, and a carboxyl group by acid-modified Domain particles formed by the introduced resin are associated with carboxyl groups to form micelles, so that they are very finely and stably dispersed, so that excellent low-temperature fixability and blocking resistance can be obtained. In this embodiment, a crosslinkable metal compound can be used, and when used,
Since the resin forming the domain particles and the resin forming the matrix are crosslinked, the fluidity is further improved because the domain particles do not appear on the toner surface due to the pulverization during the production of the toner.

The resin forming the matrix has an acid value of 1
Using a polyester resin having 5 or more carboxyl groups, using a vinyl resin having a carboxyl group having an acid value of 15 or more as a resin forming domain particles, and forming a resin and domain particles forming a matrix with a crosslinkable metal compound. A domain-matrix structure obtained by partially or entirely cross-linking a resin to be formed.

In this embodiment, the glass transition temperature Tg ₂ of the resin P ₂ forming the matrix is 5 ° C. lower than the glass transition temperature Tg ₁ of the resin P ₁ forming the domain particles.
Or higher, and the compatibility no or low two resins of the resin P ₂ to form the resin P ₁ and matrix forming the domain particles is partially or entirely crosslinked, the domain particles, the matrix Since the particles are very finely and stably dispersed therein, excellent low-temperature fixability and blocking resistance can be obtained. Further, since the resin forming the domain particles and the resin forming the matrix are partially or completely crosslinked, the domain particles do not appear on the toner surface due to the pulverization during the production of the toner, so that the fluidity is further improved.

[0064] cause blocking even when high as the glass transition temperature Tg ₁ of the resin P ₁ to form a domain particles is less than 0 ℃ glass transition temperature Tg ₂ of the resin P ₂ to form a matrix, also the domain particles Resin P to be formed
_When the glass transition temperature Tg1 of ( ₁₎ exceeds 60 ° C., the fixability of the toner deteriorates. If the glass transition temperature Tg ₂ of the resin forming the matrix is lower than 40 ° C., blocking occurs. If the glass transition temperature Tg ₂ exceeds 90 ° C., the fixability of the toner deteriorates.
Therefore, the glass transition point Tg ₁ for forming the domain particles constituting the binder resin is preferably 15 to 50 ° C., and the glass transition point Tg _{2 for} the resin forming the matrix.
Is preferably 55 to 80 ° C. Furthermore, in order to further exhibit the effect in the present invention, the glass transition temperature Tg ₂ of the resin P ₂ is the glass transition temperature Tg ₁ of the resin P ₁
5 ° C. or more, preferably 10 ° C.
It is better to be higher than ℃.

In the above-mentioned embodiments, the acid value of the domain particles is preferably 15 or more. If the acid value is less than 15, the dispersion stability of the domain particles becomes poor, and the blocking resistance tends to decrease. If the acid value of the matrix exceeds 10, the compatibility with the domain particles increases, so that the dispersion stability of the domain particles is deteriorated and the blocking resistance tends to decrease.

In the above embodiment, it is desirable that the acid value of the resin forming the domain particles is 15 or more and the acid value of the resin forming the matrix is less than 15. If this condition is not satisfied, the dispersion stability of the domain particles is not sufficient, and the blocking resistance may be poor.

In the above embodiment, the domain resin and the matrix resin preferably have an acid value of 15 or more. When the acid value of the domain resin is less than 15, the dispersion stability of the domain particles is not sufficient and the blocking resistance may be poor, and when the acid value of the matrix resin is less than 15, the crosslink density of the domain resin and the matrix resin is low. It becomes low and becomes inferior in blocking resistance.

The weight ratio of the matrix resin to the resin forming the domain particles is preferably 5 to 300 parts by weight of the resin forming the domain particles per 100 parts by weight of the matrix resin. This is because if the amount of the resin forming the domain particles is less than 5 parts by weight, there is no effect of lowering the fixing temperature.
If the mixing is performed in excess of parts by weight, the blocking resistance may be poor.

The matrix can be formed from a resin having a carboxyl group by increasing the mixing ratio of the resin having a carboxyl group. Particularly, for example, as in the case of stearyl methacrylate such as stearyl methacrylate, It is preferable to use a resin having a long-chain aliphatic hydrocarbon in the side chain, since this form is more likely to occur.

In the binder resin used in the present invention, when a vinyl monomer is used as the resin constituting the domain resin, the following may be mentioned.

For example, 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, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o -Nitrostyrene, p-
Styrene derivatives such as nitrostyrene; ethylene and unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated diolefins such as butadiene and isoprene; vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl halides such as vinyl acetate, vinyl propionate, and vinyl benzoate; methacrylic acid and methyl methacrylate, ethyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n methacrylate Α-methylene aliphatic monocarboxylic esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate; acrylic acid and methyl acrylate, acrylic Acrylic esters such as ethyl, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone,
Vinyl ketones such as methyl isopropenyl ketone; N
N-vinyl compounds such as vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; acroleins. ,
Those obtained by polymerizing one or more of these monomers are used.

In the case where the binder resin used in the present invention contains a carboxyl group in the domain particles, the carboxyl group-containing vinyl monomer is used. Examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid, maleic acid, and monoesters thereof such as methyl, ethyl, butyl and 2-ethylhexyl. And one or more of these monomers are used together with the above-mentioned monomers. The content of such a carboxyl group-containing vinyl monomer is preferably based on a polymer that forms domain particles in order to reduce the domain particle diameter to 5 μm or less,
The content is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight.

Particularly, when an acid-modified polymer having an unsaturated double bond is used as the resin forming the domain particles, at least an acid-modifiable polymer such as an unsaturated diolefin such as butadiene and isoprene is used. A monomer having a saturated double bond is used. The amount of the monomer having an unsaturated double bond to be used is preferably 0.1 to 70 wt%, more preferably 0.3 to 55 wt%, based on the resin forming the domain particles.

Further, as an acid for modifying the domain resin in the binder resin used in the present invention, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid, maleic acid, and their acids Methyl,
Monoesters such as ethyl, butyl, 2-ethylhexyl, octyl, dodecyl, hexadecyl, and stearyl can be mentioned. After synthesizing a resin that forms domain particles by one or more of these, a method such as heat treatment in a solvent is used. To the unsaturated double bond.

The amount of acid for modifying the domain resin in the binder resin used in the present invention is 5 μm.
In order to achieve the following, preferably 0.1 to 50 wt%, more preferably 1 to 3 based on the polymer forming the domain.
The content of 0 wt% is preferably contained in the resin forming the domain particles.

Further, in order to chemically bond the matrix resin and the domain resin, a part of the double bond of the domain resin must be left. Therefore, in this case, the amount of acid for modifying the domain resin is desirably 95 mol% or less based on the amount of diolefin-based monomer.

In the binder resin used in the present invention, examples of the resin constituting the matrix include vinyl resins, polyester resins, phenol resins, and epoxy resins.

It is preferable to use a vinyl resin as the resin forming the matrix because the polarity is low and the dispersion stability of the domain particles is good.

As the vinyl resin forming the matrix, the same resin as the vinyl resin that can be used to form the domain particles can be used.

Further, the use of a carboxyl group-containing vinyl monomer for causing the resin forming the matrix to contain a carboxyl group, and the use of a monomer having an unsaturated double bond for forming an acid-modified polymer having an unsaturated double bond. For the use of acid and acid, the same monomer as the resin forming the domain particles can be used.

The amount of acid for modifying the matrix resin in the binder resin used in the present invention is 5 domain particles.
In order to reduce the particle size to μm or less, it is preferable that the resin is contained in a resin forming a matrix, preferably 0.1 to 50 wt%, more preferably 1 to 30 wt%, based on a polymer forming the matrix.

It is preferable to use a polyester resin as the resin forming the matrix, because the polyester resin is excellent in the fluidity of the toner and the rise of charge.

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

Alcohol components account for 45 to 55 mol% of all polyester resin components, and 55 to 45 mol% are acid components.

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, a bisphenol derivative represented by the following structural formula (A);

[0086]

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

Examples of the divalent carboxylic acid containing 50 mol% or more of the total acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipic acid, sebacic acid , Dicarboxylic acids such as azelaic acid or anhydrides thereof, and succinic acids or anhydrides thereof further substituted with an alkyl group having 6 to 18 carbon atoms; Examples include melitic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

Examples of those having an unsaturated double bond include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid and dodecenylsuccinic acid, and anhydrides thereof.

The particularly preferred alcohol component of the polyester resin in the practice of the present invention is a bisphenol derivative represented by the above formula (A), and the preferred acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, or succinic acid. , Trimellitic acid or anhydrides thereof, such as tricarboxylic acids, and those having an unsaturated double bond include fumaric acid, maleic acid, and maleic anhydride. The content of the acid having an unsaturated double bond is preferably 1% by weight or more, more preferably 5% by weight or more based on the total acid amount.

The heat fixing toner according to the present invention can be used for a one-component developer and a two-component developer used by being mixed with a carrier. it can.

In order to sufficiently exhibit the toner characteristics according to the present invention, when used for full color, the number average molecular weight (Mn) of the polymer of the domain particles used as the binder resin is preferably from 1500 to 40,000. , More preferably 3500 to 30000, a weight average molecular weight (M
w) is preferably 3,000 to 300,000, more preferably 5,000 to 100,000, and the number average molecular weight (Mn) of the matrix resin is preferably 1
500 to 20,000, more preferably 3000 to 100
00, the weight average molecular weight (Mw) is preferably 3000
50,000, more preferably 5,000 to 30,000. When used for a one-component system or a monocolor type, the number average molecular weight (Mn) of the polymer of the domain particles used as the binder resin is preferably 30.
00 to 150,000, more preferably 5000 to 100
000, preferably a weight average molecular weight (Mw) of 600
0 to 1,000,000, more preferably 10,000 to 70
0000, and the number average molecular weight (Mn) of the matrix resin is preferably 2,000 to 50,000,
The weight average molecular weight (Mw) is preferably 4,000 to 30,000, more preferably 6,000 to 250,000, and more preferably 10,000 to 150,000.

The polymer synthesized from the vinyl monomer may be a generally known method, for example, a method obtained by solution or suspension polymerization using a peroxide as an initiator. Polyester resins are also obtained by generally known condensation polymerization.

The method of causing the binder resin to have a domain-matrix structure by using the matrix resin and the domain resin obtained by this method, respectively, is to obtain a uniform and fine structure by merely dry blending and melt-kneading. Creating a domain-matrix structure is very difficult.

As a result of intensive studies by the present inventors, a uniform and fine domain-matrix structure was successfully obtained by the following method. Each of the polymerized resins is weighed at a specific ratio, heated and melted, and stirred and mixed in a solution state. Further, the mixture is heated, the temperature is raised, and the blend solution is compatible. After being made compatible, the mixture is rapidly cooled to obtain a blended resin. With this method, the domain diameter can be controlled to be small and uniform.

If the domain resin is polymerized using a non-polar solvent and then the matrix resin is polymerized in the presence of the domain resin, the domain resin is blended in a micro-dispersed state. Can be very small.

Conversely to this method, it is also possible to first polymerize the matrix resin and then polymerize the domain resin. As still another production method, there is a method in which a polymer dissolved in unreacted monomer taken out after stopping at a certain reaction rate by carrying out bulk polymerization is obtained by suspension or solution polymerization.
In this case, since the reaction rate of the carboxyl group-containing monomer is higher than that of other vinyl monomers, it may be used at the stage of bulk polymerization, but it is more preferable to synthesize the domain resin by solution polymerization after bulk polymerization of the matrix resin. The method is desirable.

Each of the polymerized resins is dissolved in a non-polar solvent (a polar solvent can be used to form a sea-island structure, but the domain diameter increases), and the solution is formed under heating and strong stirring. There is also a method of blending. In the present invention, it is very important to control the domain diameter to be small. Therefore, in the case of blending, it is effective to increase the stirring power at the time of blending, but it is possible to increase the compatibility between the matrix resin and the domain resin by setting the temperature to a high temperature, and thus to reduce the domain diameter. Can be. Remove the solvent in this state,
Quenching has made it possible to create a uniform and fine domain-matrix structure.

This domain diameter is determined by the dissociation state of the carboxyl group. Therefore, in the case of blending, an auxiliary agent that does not react with a small amount of alcohol such as water or methanol or a carboxyl group k and increases the dissociation of the carboxyl group is used, while increasing the temperature at the time of Brent and increasing the stirring power. The addition can further reduce the size.

The present inventors have also found that the more uniform the composition distribution of the monomer having a carboxyl group in the polymer, the smaller the domain diameter and the more uniform the distribution of the domain diameter. This means that the above-mentioned resin can be obtained by a method in which a monomer having a carboxyl group is added little by little during the polymerization of the domain resin.

[0101] Further, the resin P ₁ and P ₂ as a method of chemically bonding the resin P ₁ and, after dissolving the P ₂ in a suitable solvent, for example, only peroxides such as only benzoyl peroxide, residual A method of cross-linking double bonds, or
A method of crosslinking using a peroxide such as benzoyl peroxide or another radical polymerization initiator and a vinyl monomer or a divinyl crosslinking monomer (for example, divinylbenzene), or a resin, a colorant, a magnetic powder, A method in which a peroxide such as benzoyl peroxide and / or a vulcanizing agent and / or a vulcanization accelerator for rubber or plastics are mixed in advance when melt-kneading, and crosslinking is performed during melt-kneading. And the like.

As the crosslinkable metal compound used in the present invention, those containing the following metal ions can be used. Suitable one
Na ⁺ , Li ⁺ , K ⁺ , Cs
^+, Ag ^+, Hg ^+, include Cu ^+, the divalent metal ions ^{Be 2+, Mg 2+, Ca 2+} , Hg 2+, Sn 2+, P
b ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ and the like. The trivalent ions include Al ³⁺ , Sc ³⁺ , Fe ³⁺ ,
Co ³⁺ , Ni ³⁺ , Cr ³⁺ , γ ^{3+ and the} like. Among the compounds containing metal ions as described above, the more decomposable, the better the results. This is presumed to be due to the fact that the metal ion in the compound is more easily bonded to the carboxyl group in the polymer by the thermal decomposition in the decomposable one.

Among the crosslinkable metal compounds, the organometallic compounds are excellent in compatibility and decomposability with the polymer, and the crosslinking by the reaction with the metal compound proceeds more uniformly in the polymer, so that more excellent results can be obtained. . However, Na ⁺ , K ⁺ , and Li ⁺ are highly reactive even with hydroxides, and good results can be obtained.

Among the above organometallic compounds,
In particular, those containing an organic compound rich in vaporization and sublimation as a ligand and a counter ion are useful. Among the organic compounds forming a ligand or a counter ion with a metal ion, those having the above properties include, for example, salicylic acid, salicylamide, salicylamine, salicylaldehyde,
Salicylosalicylic acid, ditertiary butyl salicylic acid,
And β-diketones such as acetylacetone and propionacetone, and low-molecular carboxylate salts such as acetate and propionic acid.

A release agent can be used in the toner of the present invention for the purpose of improving the offset resistance.

The release agent used in the present invention has a melting start temperature of 40 ° C. or more, preferably 50 ° C. or more, and 50 to 250 ° C., preferably 7 to 70 ° C. as measured by DSC.
It may have at least two or more melting points between 0 and 200 ° C, or may be used as a mixture of two or more kinds having different melting points. This is because the melting start temperature of the release agent is 4
When the temperature is lower than 0 ° C., the blocking resistance is poor, and 50 to 2
This is because a material having a plurality of melting points at 50 ° C. can exert a releasing effect over a wide range from a low temperature to a high temperature. Further, more preferable use methods of the release agent for the binder resin used in the present invention include two types of release agents having different melting points and having no polar group and a release agent having a polar group. It is preferable to use a combination of the above.
This is because, when the binder resin of the present invention is used, most of the non-polar release agent is present in the matrix resin, and conversely, most of the release agent having a polar group is present in the domain resin. By doing, for the matrix resin,
This is because it also has a releasing effect on the domain resin. Therefore, there is no problem even if one kind of release agent is used as long as it can be present in the matrix resin and the domain resin and has a plurality of melting points between 50 and 250 ° C.

Examples of the releasing agent having no polar group used in the present invention include the following. Low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, aliphatic hydrocarbon wax such as paraffin wax, oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax, or block copolymer thereof; carnauba wax; Waxes mainly containing fatty acid esters such as sasol wax and montanic acid ester wax; and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. The following are examples of the releasing agent having a polar group used in the present invention. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandinic acid, eleostearic acid, and valinaric acid; Saturated alcohols such as silalcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide;
Saturated fatty acid bisamides such as ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N '
Unsaturated fatty acid amides such as dioleyl adipic amide and N, N'-dioleyl sebacic amide; aromatic bisamides such as m-xylene bisstearic amide and N, N'-distearyl isophthalic amide Metal salts of fatty acids such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soaps); grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid Waxes; partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils;
Is mentioned.

The amount of the release agent used in the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the binder resin. This is because when the amount of the release agent exceeds 20 parts by weight, the anti-blocking property and the high-temperature offset tend to decrease.
When the amount is less than the weight part, the releasing effect is small.

These release agents dissolve the resin in a solvent,
It can be contained in the binder resin by a method of adding and mixing while raising the temperature of the resin solution and stirring, or a method of mixing at the time of kneading.

It is also possible for the metal complex to have charge controllability of toner particles. Such metal complexes include:
An azo metal complex represented by the following general formula [I] is exemplified.

[0110]

Embedded image Next, specific examples of the complex are shown.

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image Alternatively, a basic organic acid metal complex represented by the following general formula [II] can also be used in the present invention.

[0116]

Embedded image Next, specific examples of the complex represented by the general formula [II] are shown.

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image These metal complexes can be used alone or in combination of two or more.

The amount of the metal complex added to the toner particles depends on the type of the binder resin of the toner, whether or not the carrier is used, or the pigment for coloring the toner, and the reactivity of the metal complex with the binder resin. And, preferably, 0.01 to 20 parts by weight, more preferably 0.0 to 20 parts by weight, based on 100 parts by weight of the binder resin.
5 to 10 parts by weight is good.

The metal complex is reacted with the binder resin at the time of melt-kneading, or after the binder resin is dissolved in an appropriate solvent, the metal complex is added, and the reaction is performed by setting reaction conditions such as raising the temperature. be able to.

In the present invention, when a larger amount of charge is required than when the above-mentioned charge control agent is used, the conductive fine powder is held on the surface of the toner, and the fine powder is placed on the surface of the toner at a distance of 0.1 mm from the surface. By embedding to the inside more than 05μm,
The charge amount of the toner can be improved.

According to such a configuration, upon contact between the developer and the charge-imparting material, the conductive fine powder in the outermost shell of the developer and the charge-imparting material are frictionally charged, and the charge transferred from the charge-imparting material is transferred to the conductive material. The toner reached the charge control agent inside the developer through the fine powder, and as a result, a charge amount required for development was obtained, and was particularly remarkable under high temperature and high humidity.

As a method for holding the conductive fine powder on the toner surface, the conductive fine powder is electrostatically adhered to the surface of the toner particles by, for example, light stirring, and then a mechanical impact force is applied thereto. Thus, the fine powder can be brought into a state where it is driven into the surface of the toner particles.

This conductive fine powder has an average particle size of 2
It is preferably at most 1 μm, particularly preferably at most 1 μm. When the average particle size is larger than 2 μm, OH
When fixed to P, the light transmittance deteriorates.

In order for these fine powders to exert their effects, it is necessary that a part of the fine powder be held in a state of being exposed from the surface of the toner particles. Specifically, it is necessary that the toner particles be embedded and held to a depth of 0.05 μm or more from the surface of the toner particles. As shown in FIG. 1, the ratio (D / R) of the length D of the portion embedded in the toner particles 1 to the particle size R of the conductive fine powder 2 is 0.025 to 0.025.
It is in a state of 0.95. This state can be easily confirmed by observing the interface of the flakes of the developer particles with a transmission electron microscope or the like.

In the present invention, it is preferable that a portion of 1% to 50% of the surface area of the toner particles is covered with the implanted conductive fine powder. If it exceeds this range, the fixability deteriorates. On the other hand, if it is smaller than this range, the effect of injecting charges from the charge imparting material to the charge control agent inside the toner particles is not exhibited.

Examples of such conductive fine powder include metal oxides such as titanium oxide, aluminum oxide and zirconium oxide, strontium titanate, and titanium nitride.

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

Regarding the colorant irrespective of the one-component developer or the two-component developer, carbon black, titanium white and any other pigments and / or dyes can be used.

For example, when the toner according to the present invention is used as a magnetic color toner, C.I. I.
Direct Red 1, C.I. I. Direct Red 4,
C. 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 is an example. As pigments, graphite, cadmium yellow, mineral fast yellow,
Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Red Lead Yellow, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue,
Indanthrene Blue BC, chrome green, chromium oxide, pigment green B, malachite green lake, and final yellow green G.

When the toner according to the present invention is used as a toner for a two-component full color developer, the following pigments and dyes can 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, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, and 35.

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

Other coloring pigments include cyan coloring pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid blue 45 or a phthalocyanine skeleton having a structure represented by the following structural formula (C),
Copper phthalocyanine pigments having five substituents are exemplified.

[0139]

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

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

The toner according to the present invention does not limit the negative charging property and the positive charging property. When producing a negatively chargeable toner, it is preferable to add a charge control agent to the toner for the purpose of stabilizing the negative charge characteristics. Examples of the negative charge control agent include a carboxyl group such as phenolic resin, polymethacrylic acid, a copolymer of styrene and acrylic acid, a copolymer of styrene and methacrylic acid, and a maleic acid-added styrene-butadiene copolymer. And resins having a carboxyl group or -OH group at the polymer chain end by condensation polymerization, such as polyester resin and polyester.

In the case where a polyester resin is used as the binder resin matrix, it is preferable to use a negatively chargeable toner in view of the charging characteristics of the matrix in view of the characteristics.

When a positively chargeable toner is prepared, it is preferable to add a positively chargeable charge control agent to the toner. Examples include a positive charge control nigrosine compound, a triphenylmethane compound, a rhodamine dye, and polyvinyl pyridine. When a color toner is prepared, a binder resin containing 0.1 to 40 mol%, preferably 1 to 30 mol% of an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate having a positive charge as a monomer is contained. Or a colorless or light-colored positive charge control agent that does not affect the color tone of the toner. Examples of the colorless or light-colored positive charge control agent include quaternary ammonium salts represented by the following structural formulas (D) and (E).

[0144]

Embedded image

[0145]

Embedded image Among the quaternary ammonium salts represented by the above structural formulas (D) and (E), particularly the following structural formulas (D-1) and (D-2)
Use of the positive charge control agent represented by (E-1) and (E-1) is preferable because it shows good chargeability with little dependence on the environment.

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image In the case of using positively charged aminocarboxylic acid esters such as dimethylaminomethyl methacrylate as a binder resin component in a positively chargeable toner, a positive charge control agent or negative charge control agent is required. Use according to. In the case of a negatively chargeable toner, the amount of the negative charge control agent used is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

In the case of not using an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate having a positive charge characteristic as a resin component in a positively chargeable toner, a positive charge control agent is added to 100 parts by weight of the binder resin. On the other hand, preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight.
It is good to use parts by weight. When aminocarboxylic acid-containing esters are used, a positive charge control agent and / or a negative charge control agent may be added to 100 parts by weight of the binder resin, if necessary, for the purpose of providing good chargeability with little environmental dependency. Preferably, 0 to 10 parts by weight, more preferably 0 to 8 parts by weight is used.

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

The flow improvers used in the present invention include:
Any material can be used as long as the fluidity can be increased before and after the addition by adding to the colorant-containing resin particles.

Fluororesin resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and lead stearate; metal oxides such as zinc oxide powder; For example, silica fine powders such as wet-process silica, dry-process silica, and treated silica obtained by subjecting the silica to a surface treatment with a treating agent such as a silane coupling agent, a titanium coupling agent, or silicon oil.

Preferred flow improvers are fine powders produced by vapor phase oxidation of silicon halide compounds, so-called dry silica or fumed silica, which is produced by a conventionally known technique. It is. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is utilized, and a basic reaction formula is represented by the following formula.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl In this production process, by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide, a composite fine powder of silica and another metal oxide is obtained. It is also possible to obtain and include them.

The fluidity improver has an average primary particle size of preferably from 0.001 to 2 μm, more preferably
It is preferable to use silica fine powder in the range of 0.002 to 0.2 µ.

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

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

The method of imparting hydrophobicity is provided by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs silica fine powder.

As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane and benzyldimethylchlorosilane. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate,
Vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule Siloxane units of 1
And dimethylpolysiloxane containing hydroxyl groups bonded to individual Si. These are used alone or as a mixture of two or more.

The treated silica fine powder has a particle size of 0.0
It is preferable to use one in the range of 03 to 0.1 µ. Commercially available products include Taranox-500 (Talco) and AEROSIL R-972 (Nippon Aerosil).

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

[0163]

Embedded image

[0164]

Embedded image

[0165]

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

[0166]

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

Viscosity at 25 ° C. Amine Equivalent Trade name (cps) SF8417 (manufactured by Toray Silicone Co., Ltd.) 1200 3500 KF393 (manufactured by Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (manufactured by Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (manufactured by Shin-Etsu Chemical Co., Ltd.) 250 7600 KF861 (Shin-Etsu Chemical) 3500 2000 KF862 (Shin-Etsu Chemical) 750 1900 KF864 (Shin-Etsu Chemical) 1700 3800 KF865 (Shin-Etsu Chemical) 90 4400 KF369 (Shin-Etsu Chemical) 20 320 KF 383 (Shin-Etsu Chemical) 20 320 X-22-3680 (Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-3810B (Shin-Etsu Chemical Co., Ltd.) Shin-Etsu Chemical Co., Ltd. ) 1300 1700 It is noted that the amine equivalent, equivalent weight per amine (g / e
qiv) is the value obtained by dividing the molecular weight by the number of amines per molecule.

It is preferable that these silica fine particles treated with a coupling agent or silicone oil containing an amino group are further subjected to a hydrophobic treatment with the aforementioned organosilicon compound before use.

In the case where the toner according to the present invention is used for a two-component developer, the carrier used to sufficiently exhibit the effect plays an important role. As the carrier used in the present invention, for example, metals such as surface-oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, and alloys or oxides thereof and ferrites can be used. There are no special restrictions on the manufacturing method.

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

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

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

In a particularly preferred embodiment, Cu—Zn—
Fe ternary ferrite whose surface is made of, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin, polytetrafluoroethylene and styrene-methyl methacrylate resin, and fluorine-based copolymer and styrene-based copolymer. A carrier coated with a mixture of a fluorine resin and a styrene resin,
The mixing ratio is preferably 90:10 to 20:80,
More preferably 70:30 to 30:70, the mixture is coated on 0.01 to 5% by weight, preferably 0.1 to 1% by weight carrier particles, based on the carrier,
A carrier which is a coated ferrite carrier having the above-mentioned average particle size in which carrier particles of 50 mesh pass and 400 mesh-on are 70% by weight or more is exemplified. Examples of the fluorine-based copolymer include a vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10), and examples of the styrene-based copolymer include a styrene-2-ethylhexyl acrylate copolymer ( 20: 80-80: 2
0), styrene-2-ethylhexyl acrylate-methyl methacrylate copolymer (20-60: 5-30: 10)
To 50). The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectric charging properties to the toner of the present invention, and has the effect of further improving electrophotographic properties.

When the above-mentioned carrier is mixed with the toner according to the present invention to prepare a two-component developer, the mixing ratio is 2 to 15% by weight, preferably 4 to 13% by weight, as the toner concentration in the developer. Good results are obtained with the percentage by weight.
If the toner density is less than 2%, the image density is low and practically difficult. If the toner density is more than 15%, fog and scattering in the machine are increased, and the useful life of the developer is shortened.

The measuring method used in the present invention will be described below.

(1) Measurement of glass transition temperature Tg In the present invention, the measurement is performed using a differential thermal analyzer (DSC measuring apparatus), DSC-7 (manufactured by PerkinElmer). Measurement sample is 5 to 20 mg, preferably 10 mg
Is weighed precisely.

The measurement sample was placed in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 200 ° C. In this heating process, an endothermic peak in a temperature range of 40 to 100 ° C. is obtained. The intersection of the line at the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is determined by the glass transition temperature Tg according to the present invention.
And

(2) Measurement of Molecular Weight In the present invention, the molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and TH was used as a solvent at this temperature.
F (tetrahydrofuran) at a flow rate of 1 ml per minute,
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 the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6 × 10
² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ ,
It is appropriate to use 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and 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.
μs-styragel 500, 10 ³ ,
Combination of 10 ⁴ and 10 ⁵ and showa Denko
x KF-80M, KF-801, 803, 804,
805, KA-802, 803, 804, 80
5 combinations or TSKgel G1 made by Toyo Soda
000H, G2000H, G2500H, G3000
H, G4000H, G5000H, G6000H, G7
A combination of 000H and GMH is preferred.

(3) Acid value The acid value is important as it accurately indicates the progress of esterification in a short time. In general, the esterification check starts at the 80th acid value and ends as needed between 20 and 50 positions. Here, the acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the carboxyl group contained in 1 g of the resin. Therefore, the acid value indicates the number of terminal groups. The measuring method is as follows.

Samples 2 to 10 g in 200 to 300 ml
Weighed in an Erlenmeyer flask, and methanol: toluene = 3
About 50 ml of a 0:70 mixed solvent is added to dissolve the resin.
If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, a standardized N / 1
Titrate with a potassium hydroxide-alcohol solution and determine the acid value from the consumption of the alcohol potassium solution by the following calculation.

Acid value = KOH (ml number) × N × 56.1 /
Sample weight (where N is a factor of N / 10 KOH) (4) Average particle size of domain particles In the present invention, the average particle size of domain particles is measured, for example, under the following conditions. About 0.1 g of the binder resin is placed on a glass plate and dissolved with a hot plate. After dissolving the binder resin, 2-3 drops of rhodamine dye dissolved in ethanol are dropped. As soon as the dye is applied, cover glass is covered from above and a thin layer sample of binder resin / rhodamine is made while holding down. (When the resin forming the domain particles is composed of a polymer having a carboxyl group and the resin forming the matrix is composed of a polymer having no carboxyl group, the rhodamine dye dissolved in ethanol is attracted to the carboxyl group. When the resin forming the matrix is composed of a polymer having a carboxyl group and the resin forming the domain particles is composed of a polymer having no carboxyl group, ethanol is used. The rhodamine dye dissolved in is selectively colored in the matrix.When a vinyl resin is used as the resin forming the domain particles and a polyester is used as the resin forming the matrix, the matrix using the polyester is Domain using vinyl resin Are strongly colored than particles.) This was observed with an optical microscope (X100
0) Randomly take a photograph of at least four fields of view. Particles that can be visually identified in these photographed photographs are measured for particle diameter. The average value of the particle diameters measured by the above method is obtained (number average) according to the following equation to obtain the average particle diameter d of the domain particles.

(D ₁ + d ₂ +... + D _n ) / n = d In the case where it cannot be seen by this method, osmic acid or ruthenic acid is used as a dye, and the domain is dyed in the same manner as described above. Thereafter, there is a method in which a slice is formed, the dispersion state of the domain is observed with a transmission electron microscope, and the average particle diameter of the domain is measured by the same method as described above.

(5) Measurement of Friction Charge Amount FIG. 2 is an explanatory view of a friction charge amount measuring device. First, a mixture of particles to be measured and magnetic particles used as a developer is prepared. The mixing ratio is 5 parts by weight with respect to 95 parts by weight of magnetic particles in the case of toner and colorant-containing fine particles, and 2 parts by weight with respect to 98 parts by weight of magnetic particles in the case of a fluidity imparting agent. .

The particles to be measured and the magnetic particles are placed in a measuring environment and left for 12 hours or more, then put into a polyethylene bottle, and sufficiently mixed and stirred.

Next, a conductive screen 3 of 500 mesh (which can be appropriately changed to a size that does not allow magnetic particles to pass) is provided on the bottom.
A mixture of particles and magnetic particles whose frictional charge is to be measured is placed in a metal measuring container 32 having a metallic cover 3.
Do 4. At this time, the weight of the entire measurement container 32 is weighed and W
₁ (g). Next, in the suction device 31 (at least the portion in contact with the measurement container 32 is at least an insulator), suction is performed from the suction port 37 and the air volume control valve 36 is adjusted to adjust the pressure of the vacuum gauge 35 to 250 mmAq. In this state, suction is sufficiently performed (about 2 minutes) to remove toner by suction. Electrometer 3 at this time
The potential of No. 9 is set to V (volt). Here, reference numeral 38 denotes a capacitor having a capacity of C (μF). Further, the weight of the whole measurement container after suction is weighed to be W ₂ (g). This triboelectric charge amount T (μc / g) is calculated as in the following equation.

T (μc / g) = C × V / (W ₁ −W ₂ ) The present inventors have found that in a fixing device including a fixing roller and a pressure roller, the discharge direction when white paper is passed is It has been found that the offset resistance can be further improved by combining the developer using the resin composition of the present invention so that the pressure roller is closer to the pressure roller side in the vertical direction of the line connecting the center of the fixing roller and the pressure roller. .

By using this fixing device and the developer of the present invention, a copied image having good color reproducibility can be obtained, and the durability of the fixing roller can be greatly increased.

The fixing device used in the present invention may be configured such that when white paper is passed, the discharge direction is on the pressure roller side with respect to the vertical direction of the line connecting the fixing roller and the center of the pressure roller. In addition, the offset resistance can be further improved (see FIG. 4).

As a method for setting the discharge direction to the pressure roller side, for example, the hardness of the pressure roller is set higher than the hardness of the fixing roller. As a method of increasing the pressure roller hardness,
(I) a method of using an elastic body having a higher hardness than that of the fixing roller to be attached to the cored bar, and (ii) when using the same elastic body as the fixing roller, by making the elastic body layer thickness of the fixing roller thinner to form a roller. Hardening method; a method in which the diameter of the fixing roller is made larger than the diameter of the pressure roller.

Furthermore, by mounting the heating device not only on the fixing roller side but also on the pressure roller side, it is possible to further improve the offset resistance as compared with the case where the heating device is mounted only on the fixing roller side.

As a fixing device incorporating these methods, for example, a roller having a single layer of an RTV or LTV having a silicone rubber elastic body as a fixing roller, or an HTV layer provided as a lower layer in order to reduce rubber swelling due to fixing oil. And a two-layer structure in which an RTV or LTV layer is provided as an upper layer to improve the wetting with the fixing oil. The rubber hardness (JIS-A) of the fixing roller is preferably
30 to 70 degrees, more preferably 35 to 60 degrees (when two layers are combined), the layer thickness is preferably 0.5 to 5 mm, and more preferably 1.0 to 3. 5m
m is good and the rubber hardness of the pressure roller is preferably 40
Degree or more, more preferably 50 degree or more.

The diameter of the fixing roller cannot be so large because the miniaturization of the copying machine is required. When the diameter of the fixing roller is reduced, the nip cannot be sufficiently taken, so that the toner does not melt sufficiently, so that the color mixing property is deteriorated, or the fixing speed has to be reduced in order to increase the color mixing property.
Therefore, the diameter of the fixing roller and the pressure roller is 4
0 to 80 mmφ is preferred.

Next, referring to FIGS. 6 to 9, an example of an image forming apparatus for developing a latent image on a negatively charged latent image carrier using a one-component developer having a positively charged magnetic toner will be described. The image forming method and apparatus of the present invention will be described below, but the image forming method and apparatus of the present invention include not only a one-component developer but also a two-component developer using a carrier.

Numeral 102 denotes a charging roller which is a charging means brought into contact with the latent image carrier 101 at a predetermined pressure.
The conductive rubber layer 102b is formed on the metal core 102a as shown in FIG.
And a surface layer 102 which is a release coating on its peripheral surface.
c is provided. The conductive rubber layer is 0.5 to 10 mm
(Preferably 1 to 5 mm). The surface layer 102c is a releasable film, and the provision of the releasable film prevents the softener from the conductive rubber layer 102b from seeping out into a portion in contact with the latent image carrier 101, which is a member to be charged. In order to Therefore, when the softener adheres to the photoreceptor, image flow due to lowering of the resistance of the photoreceptor and a decrease in charging ability due to filming of residual toner on the photoreceptor can be prevented, and a decrease in charging efficiency can be suppressed.

Further, by using a conductive rubber layer for the charging roller, sufficient contact between the charging roller and the photosensitive member can be maintained, and no charging failure occurs.

The thickness of the release coating is preferably within 30 μm (preferably 10 to 30 μm). The lower limit of the thickness of the releasable coating is considered to be about 5 μm if the coating is free of peeling and burrs.

[0199] Nylon resin PVDF is used for the release coating.
(Polyvinylidene fluoride) and PVDC (polyvinylidene chloride) can be used. As the photosensitive layer of the latent image carrier 101, OPC, amorphous silicon, selenium, or ZnO can be used. In particular, when amorphous silicon is used for the photoconductor, the softener for the conductive rubber layer 102b is more softened than when the other is used.
Even if it adheres to the photosensitive layer of No. 01, the image flow becomes severe, so that the effect of the insulating coating on the outside of the conductive rubber layer is great.

It is also preferable to form a high-resistance layer between the conductive rubber layer and the surface layer of the release coating to prevent leakage to the photoreceptor, for example, a hydrin rubber layer with small environmental fluctuation.
One. Reference numeral 115 denotes a power supply unit for applying a voltage to the charging roller 102, which applies a predetermined voltage to the charging roller 10
The second core metal 102a is supplied.

Reference numeral 103 denotes a transfer charger as transfer means. A predetermined bias is applied from the constant voltage power supply 114 to the transfer charger. The bias condition is that the current value is 0.1
And a voltage value (absolute value) of 500 to 400 μA.
It is preferably 0V.

A latent image carrier 101 is charged by a charging roller 102 as a charging unit having a power supply unit (voltage applying unit) 115.
The surface of the OPC photoreceptor is charged to, for example, a negative polarity, and is exposed by light image exposure as the latent image forming means 105 to form an electrostatic latent image. One-component development having the positively-charged magnetic toner of the present invention held in a developing device 109 provided with an iron magnetic blade 111 and a non-magnetic developing sleeve 104 as a toner carrier that contains a magnet 140. The latent image is developed with an agent 110. As the developing sleeve 104, a stainless sleeve (SUS304) having a plurality of spherical trace depressions having a diameter of 50 mm is used. In the developing section, an alternating bias, a pulse bias, and / or a DC bias are applied from the bias applying unit 112 between the conductive substrate of the latent image carrier 101 and the developing sleeve 104. When the transfer paper P is conveyed and arrives at the transfer section, the latent image carrier 101 is charged by charging the transfer paper P from the back surface (the surface opposite to the latent image carrier side) of the transfer paper P by the voltage applying means 114. Is electrostatically transferred onto the transfer paper P. Latent image carrier 101
The transfer paper P separated from the recording paper P is subjected to a fixing process for fixing a toner image on the transfer paper P by a heating / pressing roller fixing device 107 as a fixing unit.

The developer 110 remaining on the latent image carrier 101 after the transfer process is removed by a cleaning device 108 having a cleaning blade. After the cleaning process, the latent image carrier 101 is gradually charged by the erase exposure 106,
The process starting from the charging process by the charger 102 is repeated again.

FIG. 8 is a partially enlarged view of FIG. 6 for explaining the developing step. The latent image carrier 101 has an OPC photosensitive layer and a conductive substrate and moves in the direction of the arrow. The non-magnetic cylindrical developing sleeve 104, which is a developer carrier, rotates so as to advance in the same direction as the surface of the latent image carrier 101 in the developing section. Inside the developing sleeve 104, a multi-pole permanent magnet 140 (magnet roll) as a magnetic field generating means is arranged so as not to rotate. The multi-pole permanent magnet 140 has a magnetic pole N ₁ = 500 to 900 gauss and a magnetic pole N ₂ = 600 to 11
00 gauss, magnetic pole S ₁ = 800 to 1500 gauss, and preferably set to magnetic pole S ₂ = 400 to 800 gauss. The developer 110 in the developing device 109 is the developing sleeve 1
04, the surface of the developing sleeve 104 and the developer 1
Due to friction with the developer 10, the developer 110 is given a positive triboelectric charge. Further, a magnetic doctor blade 111 made of iron is placed close to the cylindrical surface of the developing sleeve 104 (at an interval of 50 μm to 500 μm), and
By arranging it at one of the 40 magnetic pole positions,
Reduce the thickness of the toner layer 200 (30 μm to 300 μm).
m) and uniformly regulate the latent image carrier 1 in the developing section.
01 and the toner layer 2 thinner than the interval between the developing sleeve 104
00 is formed so as not to contact the latent image carrier 101. The rotational speed of the developing sleeve 104 is adjusted so that the surface speed of the developing sleeve 104 is substantially the same as or close to the speed of the surface of the latent image carrier 101. The opposing magnetic poles may be formed by using permanent magnets instead of iron as the magnetic doctor blade 111. In the developing section, the developing sleeve 104 and the latent image carrier 1
Alternatively, an AC bias or a pulse bias may be applied from the bias power supply 112 serving as a bias unit to the surface of the optical disc 01. As the bias condition, V
pp = 1500-2300V, f = 900-1600
(Hz) and DC = −10 as a DC bias
It is preferably 0 to -350V. The developer 11 in the developing section formed at and near the nearest portion between the developing sleeve (toner carrier) 104 and the latent image carrier 101
In the transition of 0, the electrostatic force of the electrostatic image bearing surface of the latent image carrier 101 and the reciprocating motion between the developing sleeve 104 and the latent image carrier 101 by the action of an AC bias or a pulse bias. The developer 110 transfers to the latent image carrier 101 side.

Instead of the magnetic doctor blade 111 as the toner layer regulating member, an elastic blade made of an elastic material such as silicon rubber is used, and the elastic blade is pressed against the surface of the latent image carrier 101 to thereby form the toner layer. The toner layer having a predetermined layer thickness may be formed on the developing sleeve 104 by regulating the layer thickness of the toner layer 200.

As the photosensitive layer of the latent image carrier 101, OPC
Insulating drum for electrostatic recording, α-Se,
A photosensitive drum having a photoconductive insulating material layer such as CdS, ZnO ₂ , and α-Si can be appropriately selected and used in accordance with development conditions.

FIG. 9 is a view showing an embodiment of another charging means in place of the charging roller shown in FIG. 7, and the charging means is a blade-shaped contact charging member 102 '. This blade-shaped contact charging member 102 'also has the same layer configuration as the charging roller 102, and is a metal supporting member 102' to which a voltage is supplied.
a, the conductive rubber member 102'b supported by the metal support member 102'a, and the conductive rubber member 10
It is composed of a surface layer 102 ′ c, which is a release coating provided on the portion of the 2′b that is in contact with the latent image carrier 101, and can provide the same effects as the charging roller 102.

In the above-described example, a roller-shaped or blade-shaped charging member is used. However, the present invention is not limited to this, and the present invention can be applied to other shapes.

The charging means 102 can be used as a transfer means by bringing it into contact with the latent image carrier 101 via the transfer paper P.

In the above image forming method and apparatus,
Instead of a charging unit for charging the surface of the latent image carrier 101 to a negative polarity (or a positive polarity), a charger that charges the surface of the latent image carrier 101 by general corona charging can be used.

[0211] When the above-described means for performing corona charging is used, the generation of ozone increases, so it is preferable to mount an ozone filter or the like.

[0212]

The present invention will be described in detail with reference to the following examples, which do not limit the present invention in any way. Parts and percentages are by weight unless otherwise indicated.

Resin Production Example 1 (Resin Blend of Resin) <Polymerization of Resin for Domain> Styrene: 92 g n-butyl acrylate: 78 g Monobutyl maleate (half ester): 15 g + 15 g (after 4 hours) Benzoyl peroxide: 15 g Toluene: 500 g A polymerization reaction is carried out at 85 ° C. for 10 hours using the above raw materials.
In order to make the composition distribution in the polymer uniform, 15 g of monobutyl maleate was added and reacted in two portions, that is, at the start of polymerization and 4 hours after the start of polymerization. As a result, the number average molecular weight (Mn) was 4600 and the weight average molecular weight (Mw) was 13
000, glass transition temperature (Tg) 31.9 ° C, acid value 5
A copolymer (resin a) of 7.0 was obtained. <Polymerization of resin for matrix> Styrene: 243 g n-butyl acrylate: 57 g Benzoyl peroxide: 22.5 g Toluene: 750 g A polymerization reaction is carried out at 85 ° C. for 16 hours using the above raw materials.
As a result, the number average molecular weight (Mn) was 5400, the weight average molecular weight (Mw) was 15,000, and the glass transition temperature (Tg) was 5
A copolymer (resin b) having 8.5 ° C. and an acid value of 0 was obtained.

Next, the polymers after the polymerization reaction and drying were weighed so that the ratio of (resin a) to (resin b) was 3: 7, and (resin a) and (resin b) were mixed. I do. The temperature of the mixed solution was set to 150 ° C., rapidly stirred, and then rapidly cooled.
A binder resin (1) is obtained. The domain average particle size of the binder resin (1) was 2 μm. Table 1 shows each physical property value.

Resin Production Example 2 (Polymerization in the Presence of Resin) <Polymerization of Resin for Domain> Styrene: 104 g n-butyl acrylate: 66 g Monobutyl maleate (half ester): 30 g Benzoyl peroxide: 15 g Toluene: 500 g The polymerization reaction was carried out at 85 ° C. for 10 hours using
Number average molecular weight (Mn) 5300, weight average molecular weight (M
w) 16000, glass transition temperature (Tg) 42.8 ° C,
A copolymer having an acid value of 60.0 was obtained. Then, as follows:
The matrix resin was polymerized in this resin solution. <Polymerization of resin for matrix> Styrene: 165 g n-butyl acrylate: 35 g Benzoyl peroxide: 15 g Toluene: 500 g The above raw materials were added to the resin solution, and further, 85 ° C. × 16.
An hr polymerization reaction is performed. As a result, the number average molecular weight (Mn)
A copolymer having 5700 and a weight average molecular weight (Mw) of 15,000 was obtained. This was dried to obtain a binder resin (2). The domain average particle diameter of the binder resin (2) was 1.5 μm. The resin obtained by polymerizing only the matrix resin had a number average molecular weight (Mn) of 6300, a weight average molecular weight (Mw) of 14,000, and a glass transition temperature (Tg) of 59.0.
° C and the acid value was 0. Table 1 shows each physical property value.

Resin Production Examples 3 to 8 The binder resins (3) to (8) were prepared in the same manner as in Resin Production Examples 1 and 2, except that the initiator amount and the monomer amount ratio in Resin Production Examples 1 and 2 were changed. ) Was synthesized.

Table 1 shows the physical properties of the synthesized binder resins (3) to (8) and the production method used.

Comparative Resin Production Examples 1 to 6 Polymers were obtained by a solution polymerization method. The obtained polymers shown in Table 2 were used as comparative binder resins A, B, D, and E, and the two kinds of obtained polymers (resin: I and resin: II) shown in Table 2 were subjected to solution blending. Thus, comparative binder resins C and F were obtained.

Table 2 shows the monomer compositions and physical properties of the comparative binder resins A to F.

[0220]

[Table 1]

[0221]

[Table 2] Example 1 Binder resin (1) 100 parts Styrene-methacrylic acid copolymer 5.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts The above materials were melt-kneaded by a roll mill and cooled. Thereafter, coarse pulverization, fine pulverization and classification were performed to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

[0222] As the carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 6.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine. As a result, the fixing temperature range in which color mixing is possible is 120 to 22.
It was 0 ° C.

Using this two-component developer, CLC-50
At 0, an image output test was performed. As a result, 1.
There was no offset to the fixing roll even after copying 100,000 sheets, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained. OHP
Even when a film was used, the transparency of the toner image was very favorable. The toner was allowed to stand in a hot air dryer at 45 ° C. for one day, and the blocking state of the toner was observed. However, no change was observed and the toner had good fluidity. Table 3 shows the results.

Examples 2 to 4 and Comparative Examples 1 to 3 Example 1 was repeated except that the binder resin (1) was replaced with binder resins (2) to (4) and comparative binder resins A to C. A two-component developer was prepared in the same manner as described above, and the same test was conducted. Table 3 shows the results.

[0226]

[Table 3] Example 5 Resin of Resin Synthesis Example (5) 100 parts Magnetic iron oxide 70 parts Nigrosine 2 parts The above materials were melt-kneaded by a roll mill, cooled, coarsely ground, finely ground and classified to obtain a black magnetic toner. . A one-component developer was prepared by externally adding 0.6 part of positively charged hydrophobized dry silica as a flow improver to 100 parts of the black magnetic toner.

This one-component developer was used in a copier N
An unfixed image was obtained using P-4835, and this was subjected to a fixing test with an external fixing machine. As a result, the fixable area is 12
0-250 ° C. Further, an image output test was performed using this one-component developer and a copying machine. As a result, 10
Even after 10,000 copies, there was no offset to the fixing roll, and a good image without fogging or scattering was obtained. When the blocking resistance was observed in the same manner as in Example 1, it was good. Table 4 shows the results.

Examples 6 to 8 and Comparative Examples 4 to 6 Example 5 was repeated except that the binder resin (5) was replaced with binder resins (6) to (8) and comparative binder resins DF. A one-component developer was prepared in the same manner, and a test was conducted in the same manner.
Table 4 shows the results.

[0229]

[Table 4] Resin Production Example 9 (Melting Blend of Resin) <Polymerization of Resin for Domain> Styrene: 88 g n-butyl acrylate: 76 g Monobutyl maleate (half ester): 15 g + 15 g (after 4 hours) Benzoyl peroxide: 10 g Toluene: 500 g Is used to carry out a polymerization reaction at 85 ° C. for 10 hours.
In order to make the composition distribution in the polymer uniform, 15 g of monobutyl maleate was added and reacted in two portions, that is, at the start of polymerization and 4 hours after the start of polymerization. As a result, the number average molecular weight (Mn) was 5200 and the weight average molecular weight (Mw) was 13
500, glass transition temperature (Tg) 32.4 ° C, acid value 5
0.0 copolymer (resin c) was obtained. <Polymerization of matrix resin> Styrene: 246 g n-butyl acrylate: 48 g Benzoyl peroxide: 20.5 g Toluene: 750 g A polymerization reaction is carried out at 85 ° C. for 16 hours using the above raw materials.
As a result, the number average molecular weight (Mn) was 5700, the weight average molecular weight (Mw) was 14600, and the glass transition temperature (Tg) was 5
A copolymer (resin d) having 9.5 ° C. and an acid value of 0 was obtained.

Next, after the polymerization reaction, the dried polymers were weighed so that the ratio of (resin c) to (resin d) was 3: 7, and (resin c) and (resin d) were weighed. Mix
After the temperature was raised to 160 ° C., the mixture was melt-stirred and mixed, then cooled,
A binder resin (9) is obtained. The domain average particle diameter of the binder resin (9) was 2.6 μm. Table 5 shows the physical property values.

Resin Production Example 10 (Polymerization in the Presence of Resin) <Polymerization of Resin for Matrix> Styrene: 163 g n-butyl acrylate: 28 g Benzoyl peroxide: 13 g Toluene: 500 g Using the above raw materials, a polymerization reaction was carried out at 85 ° C. for 10 hours. Do
Number average molecular weight (Mn) 5800, weight average molecular weight (M
w) 15300, glass transition temperature (Tg) 60.0 ° C.,
A copolymer having an acid value of 0 was obtained. Next, the domain resin was polymerized in this resin solution as follows. <Polymerization of resin for domain> Styrene: 105 g n-butyl acrylate: 77 g Monobutyl maleate (half ester): 32 g Benzoyl peroxide: 15 g Toluene: 500 g The above raw materials were added to the resin solution, and further 85 ° C. × 16.
An hr polymerization reaction is performed. As a result, the number average molecular weight (Mn)
A copolymer having a weight average molecular weight (Mw) of 5600 and 15,000 was obtained. This was dried to obtain a binder resin (10). The domain average particle diameter of the binder resin (10) was 1.2 μm. The resin obtained by polymerizing only the domain resin has a number average molecular weight (Mn) of 5300, a weight average molecular weight (Mw) of 15,000, and a glass transition temperature (Tg) of 39.5.
° C and an acid value of 53.0. Table 5 shows the physical property values.

Resin Preparation Examples 11 and 12 Binder resins (11) and (12) were prepared in the same manner as in Resin Preparation Examples 9 and 10, except that the amounts of the initiator and the monomers in Resin Preparation Examples 9 and 10 were changed. Was synthesized.

Table 5 shows the physical property values of the synthesized binder resins (11) and (12) and the production methods used.

Comparative Resin Production Examples 7 to 9 Polymers were obtained by a solution polymerization method. The obtained polymers shown in Table 6 were used as comparative binder resins G and H, and the two kinds of obtained polymers (resin: I and resin: II) shown in Table 6 were melt-blended to obtain comparative binder resins. A resin I was obtained.

Table 6 shows the monomer compositions and physical properties of the comparative binder resins GI.

[0236]

[Table 5]

[0237]

[Table 6] Example 9 Binder resin (9) 100 parts Styrene-methacrylic acid copolymer 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts The above materials were melt-kneaded by a roll mill and cooled. Thereafter, coarse pulverization, fine pulverization and classification were performed to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

As the carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 5.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine. The fixing roller has two layers of silicon rubber composed of RTV / HTV, and has a rubber layer thickness of 2.0 mm and a hardness of 4 mm.
The fixing roller has a diameter of 5 degrees and a fixing roller diameter of 40 mm. The pressure roller is a fluorine rubber roller having a hardness of 50 degrees.
A rubber layer having a thickness of 1.0 mm and a pressure roller diameter of 40 mm was used. The heating device was attached to both the fixing roller and the pressure roller, and in the blank paper passing test, the paper discharging direction was the pressure roller side.

With this fixing device, the fixing temperature range in which colors can be mixed was 115 to 220 ° C. Using this two-component developer, an image output test was performed using CLC-500.

As a result, there was no offset to the fixing roll even after copying 20 thousand sheets in the single color mode, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained. Even when an OHP film was used, the transparency of the toner was very favorable. The toner was allowed to stand in a hot air dryer at 45 ° C. for one day, and the blocking state of the toner was observed. However, no change was observed and the toner had good fluidity. Table 7 shows the results.

Examples 10 to 12 and Comparative Examples 7 to 9 Except that the binder resin (9) was replaced with the binder resins (10) to (12) and the comparative binder resins (G) to (I). A two-component developer was prepared in the same manner as in Example 9, and a test was conducted in the same manner. Table 7 shows the results.

Example 13 The fixing device used in Example 9 was used as a fixing roller and an RTV
/ HTV silicone rubber layer, rubber layer thickness 2.0
mm, hardness 65 degrees, fixing roller diameter 40 mm, fluorine rubber as pressure roller, hardness 50 degrees,
A rubber layer thickness of 1.0 mm and a pressure roller diameter of 40 mm are used, and the heating device is attached only to the fixing roller. In the blank paper passing test, replace the fixing device with the direction of discharging the white paper on the fixing roller side. A test was conducted in the same manner as in Example 9 except for the above. Table 7 shows the results.

[0244]

[Table 7] Resin Production Example 13 (Resin Blend) <Polymerization of Resin for Domain> Styrene: 94 g n-butyl acrylate: 82 g Monobutyl maleate (half ester): 15 g + 15 g (after 4 hours) Benzoyl peroxide: 12 g Toluene: 500 g Is used to carry out a polymerization reaction at 85 ° C. for 10 hours.
In order to make the composition distribution in the polymer uniform, 15 g of monobutyl maleate was added and reacted in two portions, that is, at the start of polymerization and 4 hours after the start of polymerization. As a result, the number average molecular weight (Mn) was 4800 and the weight average molecular weight (Mw) was 13
300, glass transition temperature (Tg) 32.1 ° C, acid value 5
0.0 copolymer (resin e) was obtained. <Polymerization of resin for matrix> Styrene 240 g n-butyl acrylate 60 g Benzoyl peroxide 21.5 g Toluene 750 g A polymerization reaction is carried out at 85 ° C. for 16 hours using the above raw materials.
As a result, the number average molecular weight (Mn) was 5200, the weight average molecular weight (Mw) was 14300, and the glass transition temperature (Tg) was 5
A copolymer (resin f) having 7.2 ° C. and an acid value of 0 was obtained.

Next, the polymer after the polymerization reaction and drying was weighed so that the ratio of (resin e) to (resin f) was 3: 7, and (resin e) and (resin f) were mixed. I do. The temperature of the mixed solution was raised to 160 ° C., rapidly stirred, and then rapidly cooled.
A binder resin (13) is obtained. The domain average particle size of the binder resin (13) was 2.2 μm. Table 8 shows the physical property values.

Resin Production Example 14 (Polymerization in the Presence of Resin) <Polymerization of Resin for Domain> Styrene: 108 g n-butyl acrylate: 70 g Monobutyl maleate (half ester): 34 g Benzoyl peroxide: 15 g Toluene: 500 g The polymerization reaction was carried out at 85 ° C. for 10 hours using
Number average molecular weight (Mn) 5600, weight average molecular weight (M
w) 16500, glass transition temperature (Tg) 41.5 ° C,
A copolymer having an acid value of 62.0 was obtained. Then, as follows:
The matrix resin was polymerized in this resin solution. <Polymerization of resin for matrix> Styrene: 168 g n-butyl acrylate: 32 g Benzoyl peroxide: 15 g Toluene: 500 g The above raw materials were added to the resin solution, and further, 85 ° C. × 16.
An hr polymerization reaction is performed. As a result, the number average molecular weight (Mn)
Thus, a copolymer having a weight average molecular weight (Mw) of 6,200 was obtained. This was dried to obtain a binder resin (14). The domain average particle size of the binder resin (14) was 1.3 μm. The resin obtained by polymerizing only the matrix resin had a number average molecular weight (Mn) of 6,500, a weight average molecular weight (Mw) of 15,500, and a glass transition temperature (Tg) of 60.1.
℃, the acid value was 0. Table 8 shows the physical property values.

Resin Preparation Examples 15 and 16 Binder resins (15) and (16) were prepared in the same manner as in Resin Preparation Examples 15 and 16 , except that the initiator amount and the monomer ratio in Resin Preparation Examples 13 and 14 were changed. Was synthesized.

Table 8 shows the physical property values of the synthesized binder resins (15) and (16) and the production method used.

Comparative Resin Production Examples 10 to 12 Polymers were obtained by solution polymerization. The obtained polymers shown in Table 9 were used as comparative binder resins J and K, and the obtained two kinds of polymers (resin: I and resin: II) shown in Table 9 were subjected to solution blending to obtain comparative binder resins. A resin L was obtained.

Table 9 shows the monomer compositions and physical properties of the comparative binder resins J to L.

[0251]

[Table 8]

[0252]

[Table 9] Example 14 Binder resin (13) ... 100 parts Chromium complex of di-tert-butylsalicylic acid ... 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) ... 5.0 parts The above materials were melt-kneaded by a roll mill. After cooling, coarse pulverization, fine pulverization and classification were performed to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

As the carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 5.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine. The fixing roller has two layers of silicone rubber composed of RTV / HTV, and has a rubber layer thickness of 1.8 mm and a hardness of 4 mm.
A fixing roller having a diameter of 0 ° and a fixing roller diameter of 40 mm was used.
A rubber layer having a thickness of 1.3 mm and a pressure roller diameter of 40 mm was used. The heating device was attached to both the fixing roller and the pressure roller, and in the blank paper passing test, the paper discharging direction was the pressure roller side.

With this fixing device, the fixing temperature range in which colors can be mixed was 110 to 220 ° C. Using this two-component developer, an image output test was performed using CLC-500.

As a result, even after copying 250,000 sheets in the single color mode, there was no offset to the fixing roll, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained. Even when an OHP film was used, the transparency of the toner was very favorable. When left in a hot air dryer at 45 ° C. for one day, the toner blocking state was observed, but no change was observed.
It had good flowability. Table 10 shows the results.

Examples 15 to 17 and Comparative Examples 10 to 12 Example 14 and Example 14 were repeated except that the binder resin (13) was replaced with binder resins (14) to (16) and comparative binder resins J to L. Similarly, a two-component developer was prepared and tested in the same manner. Table 10 shows the results.

Example 18 The fixing device used in Example 14 was replaced with a fixing roller by RT.
V / HTV silicone rubber two layers, rubber layer thickness
0 mm, hardness 65 degrees, fixing roller diameter 40 mm, fluorine rubber as a pressure roller, hardness 50
Temperature, rubber layer thickness 1.0 mm, pressure roller diameter 40 mm, and the heating device is attached only to the fixing roller, and in the blank paper passing test, the white paper is discharged to the fixing roller side in the fixing roller side. The test was performed in the same manner as in Example 14 except that the substitution was performed. Table 10 shows the results.

[0259]

[Table 10] Resin Production Example 17 (Melting Blend of Resin) <Polymerization of Resin for Domain> 92 parts of styrene 78 parts of n-butyl acrylate 15 parts of monobutyl maleate (half ester) +15 parts (after 4 hours) Benzoyl peroxide 15 parts Toluene 500 parts Using the above raw materials, a polymerization reaction is performed at 85 ° C. for 10 hours.
In order to make the composition distribution in the polymer uniform, 15 parts of monobutyl maleate were added and reacted in two parts, one at the start of polymerization and four hours after the start. As a result, the number average molecular weight (Mn) was 5,000 and the weight average molecular weight (Mw) was 13
000, glass transition temperature (Tg) 32.0 ° C, acid value 5
A copolymer (resin g) of 6.0 was obtained. <Polymerization of matrix resin> Styrene 243 parts N-butyl acrylate 57 parts Benzoyl peroxide 22.5 parts Toluene 750 parts Using the above-mentioned raw materials, a polymerization reaction is carried out at 85 ° C for 16 hours.
As a result, the number average molecular weight (Mn) was 5500, the weight average molecular weight (Mw) was 15,000, and the glass transition temperature (Tg) was 5
A copolymer (resin h) having a temperature of 9.0 ° C. and an acid value of 0 was obtained.

Next, the polymer after the polymerization reaction and the drying was weighed so that the ratio of (resin g) to (resin h) was 3: 7, and (resin g) and (resin h) were measured. Mix.
After the temperature was raised to 150 ° C. and the mixture was vigorously stirred, it was rapidly cooled to obtain a binder resin (17).

The domain average particle size of the binder resin (17) was 1.5 μm. Table 11 shows the physical property values.

Resin Production Example 18 (Polymerization in the Presence of Resin) <Polymerization of Matrix Resin> Styrene 165 parts N-butyl acrylate 35 parts Benzoyl peroxide 15 parts Toluene 500 parts Polymerization reaction at 85 ° C. for 10 hours using the above raw materials. Do
Number average molecular weight (Mn) 5800, weight average molecular weight (M
w) 15000, glass transition temperature (Tg) 60.5 ° C,
A copolymer having an acid value of 0 was obtained. Next, the domain resin was polymerized in this resin solution as follows. <Polymerization of resin for domain> Styrene 104 parts N-butyl acrylate 66 parts Monobutyl maleate 30 parts Benzoyl peroxide 15 parts Toluene 500 parts The above raw materials were added to the resin solution, and further 85 ° C × 16.
An hr polymerization reaction is performed. As a result, the number average molecular weight (Mn)
A copolymer having 5400 and a weight average molecular weight (Mw) of 16,000 was obtained. This was dried to obtain a binder resin (18). The domain average particle diameter of the binder resin (18) was 0.5 μm. The number average molecular weight (Mn) of the resin obtained by polymerizing only the domain resin was 5500, and the weight average molecular weight (M
w) 14000, glass transition temperature (Tg) 38.0 ° C.,
The acid value was 54.0. Table 11 shows the physical property values.

Resin Preparation Examples 19 and 20 Binder resins (19) and (20) were prepared in the same manner as in Resin Preparation Examples 17 and 18, except that the initiator amount and the monomer amount ratio in Resin Preparation Examples 17 and 18 were changed. Was synthesized.

Table 11 shows the physical property values of the synthesized binder resins (19) and (20) and the production methods used.

Comparative Resin Production Examples 13 to 18 Polymers were obtained by solution polymerization. The obtained polymers shown in Table 12 were used as comparative binder resins M, N, P and Q.
The two polymers obtained (resin: I and resin: I
I) was subjected to melt blending to obtain comparative binder resins O and R.

Table 12 shows the monomer compositions and physical properties of the comparative binder resins M to R.

[0267]

[Table 11]

[0268]

[Table 12] Example 19 Binder resin (17) 100 parts Di-tert-butylsalicylic acid chromium complex 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts Calcium laurate (106, 125, 142, 160) 2.0 ° C, peak melting point, melting start temperature 80 ° C) Low molecular weight polyethylene wax 2.0 parts (melting point 123 ° C, melting start temperature 75 ° C) The above materials are melt-kneaded by a roll mill, cooled, and coarsely pulverized. , Pulverized and classified to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

As the carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 6.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine.

As a result, the fixing temperature range in which color mixing is possible is 12
5-220 ° C.

Using this two-component developer and toner, C
An image output test was performed using LC-500.

As a result, there was no offset to the fixing roll even after copying 20 thousand sheets in the single color mode, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

When an OHP film was used, the transparency of the toner image was very favorable.

The toner was allowed to stand in a hot air dryer at 45 ° C. for one day, and the blocking state of the toner was observed. No change was observed, and the toner had good fluidity. Table 13 shows the results.

Example 20 A binder resin (17) was added to a binder resin (18), and a release agent (low molecular weight polyethylene wax) was added to 2 parts of ethylenebislauric amide (melting point: 102/52 ° C., melting start temperature: 90).
C) and a two-component developer was prepared in the same manner as in Example 19 except that the low-molecular weight polyethylene was replaced by 2 parts, and a test was conducted in the same manner. Table 13 shows the results.

Comparative Examples 13 to 15 Two-components were prepared in the same manner as in Example 19, except that the binder resin (17) was replaced with comparative binder resins M to O, and that no release agent (low molecular weight polyethylene wax) was used. A system developer was prepared and tested similarly. Table 13 shows the results.

[0278]

[Table 13] Example 21 Binder resin (19) 100 parts Magnetic iron oxide 70 parts Nigrosine 2 parts Low molecular weight polyethylene (melting point 110 ° C., melting start temperature 95 ° C.) 2 parts Ethylene bislauric amide 2 parts The above raw materials are melt-kneaded by a roll mill. After cooling, the mixture was coarsely ground, finely ground and classified to obtain a black magnetic toner. A one-component developer was prepared by externally adding 0.6 part of positively charged hydrophobized dry silica as a flow improver to 100 parts of the black magnetic toner.

The one-component developer was used in a copier N
An unfixed image was obtained using P-4835, and this was subjected to a fixing test with an external fixing machine. As a result, the fixable area is 13
0-250 ° C. Further, an image output test was performed using the one-component developer and the copying machine. As a result, even after 100,000 copies were made, there was no offset to the fixing roll, and a good image free of fog and unevenness was obtained.

When the blocking resistance was observed in the same manner as in Example 19, the result was good. Table 14 shows the results.

Example 22 The binder resin (19) was replaced with the binder resin (20), and the release agent (low molecular weight polyethylene) was 2 parts of low molecular weight polypropylene (melting point 150 ° C., melting start 110 ° C.) and number average Linear alkyl alcohol having a molecular weight of 700 (melting point 105
(C, 70 ° C. at the start of melting) A one-component developer was prepared in the same manner as in Example 21 except that 2 parts were used, and the same test was conducted. Table 14 shows the results.

Comparative Examples 16 to 18 One-component systems were prepared in the same manner as in Example 21 except that the binder resin (19) was replaced with comparative binder resins P to R, and that no release agent (low molecular weight polyethylene) was used. A developer was prepared and tested similarly. Table 14 shows the results.

[0283]

[Table 14] Resin Production Example 21 (Melt Blend of Resin) <Polymerization of Domain Resin> Styrene 96 parts N-butyl acrylate 74 parts Monobutyl maleate (half ester) 15 parts +15 parts (after 4 hours) Benzoyl peroxide 14 parts Toluene 500 parts Using the above raw materials, a polymerization reaction is performed at 85 ° C. for 10 hours.
In order to make the composition distribution in the polymer uniform, 15 parts of monobutyl maleate were added and reacted in two parts, one at the start of polymerization and four hours after the start. As a result, the number average molecular weight (Mn) was 5200 and the weight average molecular weight (Mw) was 13
000, glass transition temperature (Tg) 31.5 ° C, acid value 5
2.0 copolymer (resin i) was obtained. <Polymerization of resin for matrix> Styrene 249 parts N-butyl acrylate 51 parts Benzoyl peroxide 22.8 parts Toluene 750 parts Using the above-mentioned raw materials, a polymerization reaction is carried out at 85 ° C for 16 hours.
As a result, the number average molecular weight (Mn) was 5800, the weight average molecular weight (Mw) was 15500, and the glass transition temperature (Tg) was 6
A copolymer (resin j) having 0.5 ° C. and no acid value was obtained.

Next, the polymers after the polymerization reaction and drying were weighed so that the ratio of (resin i) to (resin j) was 3: 7, and (resin i) and (resin j) were mixed. I do. After the temperature was raised to 150 ° C. and the mixture was vigorously stirred, it was rapidly cooled to obtain a binder resin (21).

The average domain particle size of the binder resin (21) was 2.0 μm. Table 15 shows each physical property value.

Resin Production Example 22 (Polymerization in the Presence of Resin) <Polymerization of Resin for Matrix> Styrene 162 parts N-butyl acrylate 33 parts Benzoyl peroxide 15 parts Toluene 500 parts Polymerization reaction at 85 ° C. × 10 hours using the above raw materials Do
Number average molecular weight (Mn) 6100, weight average molecular weight (M
w) 16000, glass transition temperature (Tg) 61.8 ° C,
A copolymer having an acid value of 0 was obtained. Next, the domain resin was polymerized in this resin solution as follows. <Polymerization of Domain Resin> Styrene 108 parts n-butyl acrylate 72 parts monobutyl maleate (half ester) 27 parts benzoyl peroxide 15 parts toluene 500 parts The above-mentioned raw materials were added to the resin solution, and further 85 ° C. × 16.
An hr polymerization reaction is performed. As a result, the number average molecular weight (Mn)
A copolymer having a weight average molecular weight (Mw) of 5,900 was obtained. This was dried to obtain a binder resin (22). The domain average particle size of the binder resin (22) was 1.0 μm. The resin obtained by polymerizing only the domain resin has a number average molecular weight (Mn) of 5600, a weight average molecular weight (Mw) of 13800, and a glass transition temperature (Tg) of 36.5.
° C and an acid value of 48.0. Table 15 shows each physical property value.

Comparative Resin Production Examples 19 to 21 Polymers were obtained by a solution polymerization method. The obtained polymers were used as comparative binder resins S and T, and the obtained two polymers were melt-blended to obtain comparative binder resins U.

Table 16 shows the monomer compositions and physical properties of the comparative binder resins S to U.

[0289]

[Table 15]

[0290]

[Table 16] Example 23 Binder resin (21) 100 parts Di-tert-butylsalicylic acid chromium complex 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts Calcium laurate (106, 125, 142, 160) 2.0 parts at ℃ with melting peak, melting start temperature 80 ° C) Low molecular weight polyethylene wax 2.0 parts (melting point 123 ° C, melting start temperature 75 ° C) After pulverization, fine pulverization and classification, a blue toner was obtained. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

As the carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 5.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine.

The fixing roller has two layers of silicon rubber composed of RTV / HTV and has a rubber layer thickness of 1.8 m.
m, hardness of 40 degrees, fixing roller diameter of 40 mm, and fluorine roller as a pressure roller.
Hardness 50 degrees, rubber layer thickness 1.3 mm, pressure roller diameter 40
mm. Further, the heating device was attached to both the fixing roller and the pressure roller, and in the blank paper passing test, the discharge direction was toward the pressure roller.

As a result, the fixing temperature range where color mixing is possible is 11
0-220 ° C.

Using this two-component developer, CLC-50
At 0, an image output test was performed.

As a result, there was no offset to the fixing roll even after copying 40,000 sheets in the single color mode, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

When an OHP film was used, the transparency of the toner was very favorable.

The toner was allowed to stand in a hot-air dryer at 45 ° C. for one day, and the blocking state of the toner was observed. No change was observed, and the toner had good fluidity. Table 17 shows the results.

Example 24 The binder resin (21) was replaced with the binder resin (22), and the release agent (low molecular weight polyethylene wax) was replaced with 2 parts of ethylenebislauric amide (melting point: 102 ° C., 152 ° C., melting start). A two-component developer was prepared and tested in the same manner as in Example 23 except that the temperature was changed to 90 ° C.) and 2 parts of low molecular weight polyethylene was used. Table 17 shows the results.

Comparative Examples 19 to 22 Same as Example 23 except that the binder resin (21) was replaced with comparative binder resins S to U and that no release agent (low molecular weight polyethylene wax) was used. A two-component developer was prepared, and a test was conducted in the same manner. Table 17 shows the results.

Example 25 The fixing device used in Example 23 was replaced with a fixing roller by RT.
V / HTV silicone rubber two layers, rubber layer thickness
0 mm, hardness 65 degrees, fixing roller diameter 40 mm, fluorine rubber as a pressure roller, hardness 50
Temperature, rubber layer thickness 1.0 mm, pressure roller diameter 40 mm, and the heating device is attached only to the fixing roller, and in the blank paper passing test, the white paper is discharged to the fixing roller side in the fixing roller side. The test was performed in the same manner as in Example 23 except that the substitution was made. Table 17 shows the results.

[0302]

[Table 17] Resin Production Example 23 (Resin Blend of Resin) <Polymerization of Resin for Domain> Styrene 120 g Stearyl methacrylate 80 g Benzoyl peroxide 15 g Toluene 500 g Using the above raw materials, a polymerization reaction was performed at 85 ° C. for 10 hours. As a result, the number average molecular weight (Mn) was 5000, the weight average molecular weight (Mw) was 11,000, and the glass transition temperature (Tg).
A copolymer (resin k) having an acid value of 0 at 33.0 ° C. was obtained. <Polymerization of Resin for Matrix> Styrene 105 g n-butyl acrylate 65 g monobutyl maleate (half ester) 30 g benzoyl peroxide 15 g toluene 500 g Using the above raw materials, a polymerization reaction was performed at 85 ° C. for 16 hours. As a result, the number average molecular weight (Mn) was 5200, the weight average molecular weight (Mw) was 13500, and the glass transition temperature (Tg).
A copolymer (resin 1) having 61.0 ° C. and an acid value of 60.0 was obtained.

Next, the polymer-toluene solution after the polymerization reaction was weighed so that the ratio of (Resin k) to (Resin 1) was 3: 7, and (Resin k) and (Resin 1) were weighed. Was mixed with a solution, stirred vigorously, and then dried to obtain a binder resin (23).

The average domain particle size of the binder resin (23) was 3.0 μm. Table 18 shows the physical property values.

Resin Production Example 24 (Polymerization in the Presence of Resin) <Polymerization of Resin for Matrix> Styrene 105 g n-butyl acrylate 65 g monobutyl maleate (half ester) 30 g benzoyl peroxide 15 g toluene 500 g Using the above raw materials, 85 ° C. × 16 hr polymerization reaction,
Number average molecular weight (Mn) 6000, weight average molecular weight (M
w) 14000, glass transition temperature (Tg) 62.0 ° C.,
A copolymer having an acid value of 62.5 was obtained. Then, as follows:
The domain resin was polymerized in this resin solution. <Polymerization of Domain Resin> Styrene 120 g Stearyl methacrylate 80 g Benzoyl peroxide 15 g Toluene 500 g The above raw materials were added to the resin solution, and further, 85 ° C. × 16.
An hr polymerization reaction is performed. As a result, the number average molecular weight (Mn)
A copolymer having 5800 and a weight average molecular weight (Mw) of 13500 was obtained. This was dried to obtain a binder resin (24).

The domain average particle size of the binder resin (24) was 3.5 μm.

The resin obtained by polymerizing only the domain resin had a number average molecular weight (Mn) of 5200, a weight average molecular weight (Mw) of 12000, and a glass transition temperature (Tg) of 34.0.
° C and the acid value was 0. Table 18 shows the physical property values.

Resin Production Examples 25 and 26 Binder resins (25) and (26) were produced in the same manner as in Resin Production Examples 23 and 24, except that the amounts of the initiator and the monomers in Resin Production Examples 23 and 24 were changed. Was synthesized.

Table 18 shows the physical property values of the synthesized binder resins (25) and (26) and the production methods used.

Comparative Resin Production Examples 22 to 27 Polymers were obtained by a solution polymerization method. The obtained polymers shown in Table 19 were used as comparative binder resins V, W, Y and Z.
The two polymers obtained (resin: I and resin: I
I) is subjected to melt blending to obtain comparative binder resins X and AA
I got

Table 19 shows the monomer compositions and physical properties of the comparative binder resins V to X and AA.

[0312]

[Table 18]

[0313]

[Table 19] Example 26 Binder Resin (13) 100 parts Di-tert-butylsalicylic acid chromium complex 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts The above materials were melt-kneaded by a roll mill and cooled. , Coarse pulverization, fine pulverization and classification to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

[0314] As the carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 6.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine.

As a result, the fixing temperature range where color mixing is possible is 13
0-220 ° C.

Using this two-component developer, CLC-50
At 0, an image output test was performed.

As a result, there was no offset to the fixing roll even after copying 20 thousand sheets in the single color mode, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

When an OHP film was used, the transparency of the toner image was very favorable.

The toner was allowed to stand in a hot-air dryer at 45 ° C. for one day, and the blocking state of the toner was observed. No change was observed, and the toner had good fluidity. The results are shown in Table 20.

Example 27 and Comparative Examples 22 to 24 In the same manner as in Example 26 except that the binder resin (23) was replaced with the binder resin (24) and the comparative binder resins V to X, a two-component system was used. A developer was prepared and tested similarly. The results are shown in Table 20.

[0322]

[Table 20] Example 28 Resin of Resin Synthesis Example (25) 100 parts Magnetic iron oxide 70 parts Di-tert-butylsalicylic acid chromium complex 2 parts The above-mentioned raw materials were melt-kneaded by a roll mill, cooled, coarsely ground, finely ground and classified to black. A magnetic toner was obtained. To one hundred parts of the black magnetic toner, 0.6 part of hydrophobized dry silica was externally added as a flow improver to prepare a one-component developer.

This one-component developer was used in a copier N
An unfixed image was obtained using P-8580, and this was subjected to a fixing test using an external fixing machine. As a result, the fixable area is 12
0-240 ° C. Further, an image output test was performed using the one-component developer and the copying machine. As a result, even after 100,000 copies were made, there was no offset to the fixing roll, and a good image free of fog and unevenness was obtained.

[0324] As in Example 26, the anti-blocking property was good. The results are shown in Table 21.

Example 29 and Comparative Examples 25 to 28 One example was prepared in the same manner as in Example 28 except that the binder resin (25) was replaced with the binder resin (26) and the comparative binder resins Y, Z and AA. Component developers were prepared and tested similarly. The results are shown in Table 21.

[0326]

[Table 21] Resin Production Example 27 (Resolution Blend of Resin) <Polymerization of Resin for Domain> Styrene 120 g n-butyl acrylate 80 g benzoyl peroxide 15 g toluene 500 g Using the above raw materials, a polymerization reaction was performed at 85 ° C. for 10 hours. As a result, the number average molecular weight (Mn) was 4600, the weight average molecular weight (Mw) was 12000, and the glass transition temperature (Tg).
A copolymer (resin m) having an acid value of 0 at 32.0 ° C. was obtained. <Polymerization of Matrix Resin> Styrene 170 g Butadiene 30 g Benzoyl peroxide 15 g Toluene 500 g Using the above raw materials, a polymerization reaction was performed at 85 ° C. for 16 hours,
After the reaction, 20 g of maleic anhydride was added to cause an addition reaction to the unsaturated portion of butadiene, and then a small amount of water was added to open the ring.

As a result, the number average molecular weight (Mn) was 700
0, a copolymer (resin n) having a weight average molecular weight (Mw) of 21,000, a glass transition temperature (Tg) of 60.0 ° C., and an acid value of 42.0 was obtained.

Next, the polymer-toluene solution after the polymerization reaction was weighed so that the ratio of (resin m) to (resin n) was 3: 7, and (resin m) and (resin n) were weighed. Was mixed with a solution, stirred vigorously, and then dried to obtain a binder resin (27).

The average particle size of domains of the binder resin (27) was 2.5 μm. Table 22 shows the physical property values.

Resin Production Example 28 (Polymerization in the Presence of Resin) The same amount of monomer as in Resin Production Example 27 was used to polymerize the domain resin, and then the matrix resin was mixed at a quantitative ratio of 50.
The polymerization was carried out in the presence so as to be / 50. After the completion of the polymerization reaction, 20 g of maleic anhydride was added to carry out an addition reaction, and then a small amount of water was added to open the ring to obtain a binder resin (28).

At this time, a small amount of the domain resin was sampled and measured. As a result, the number average molecular weight (Mn) was 500.
0, weight average molecular weight (Mw) 12000, glass transition temperature (Tg) 33 ° C., and acid value 0. As a result of polymerizing the matrix resin under the same conditions and adding maleic acid, the number average molecular weight (Mn) was 6800, the weight average molecular weight (Mw) was 21,000, and the glass transition temperature (Tg) was 5
The acid value was 9.5 ° C and the acid value was 41.0. This binder resin (2
The domain average particle size of 8) was 3.5 μm. Table 22 shows the physical property values.

Resin Preparation Examples 29 and 30 Binder resins (29) and (30) were prepared in the same manner as in Resin Preparation Examples 27 and 28, except that the amounts of the initiator and the monomers in Resin Preparation Examples 27 and 28 were changed. Was synthesized. Table 22 shows the physical property values of the synthesized binder resins (29) and (30) and the production methods used.

Comparative Resin Production Examples 28 to 33 Polymers were obtained by a solution polymerization method. The obtained polymers shown in Table 23 were used as comparative binder resins BB, CC, EE and FF, and the two kinds of obtained polymers shown in Table 23 (resin: I and resin: II) were melt-blended. B for comparison
D and GG were obtained.

Table 23 shows the monomer compositions and physical properties of the comparative binder resins BB to GG.

[0335]

[Table 22]

[0336]

[Table 23] Example 30 Binder resin (27) 100 parts Aluminum complex of di-tert-butylsalicylic acid 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts The above materials were melt-kneaded by a roll mill, and cooled. , Coarse pulverization, fine pulverization and classification to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

Thereafter, a two-component developer was prepared in the same manner as in Example 26, and a fixing test was performed.

As a result, the fixing temperature range where color mixing is possible is 13
0-220 ° C.

Using this two-component developer, CLC-50
At 0, an image output test was performed.

As a result, there was no offset to the fixing roll even after copying 20 thousand sheets in the single color mode, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

When an OHP film was used, the transparency of the toner image was very favorable.

The toner was allowed to stand in a hot-air dryer at 45 ° C. for one day, and the blocking state of the toner was observed. No change was observed, and the toner had good fluidity. The results are shown in Table 24.

Example 31 and Comparative Examples 28 to 30 The binder resin 27 was replaced with the binder resin 28 and the comparative binder resins BB to D.
A two-component developer was prepared and tested in the same manner as in Example 30 except that D was used instead. Table 2 shows the results
It is shown in FIG.

[0344]

[Table 24] Example 32 Binder resin (29) 100 parts Magnetic iron oxide 70 parts Di-tert-butylsalicylic acid chromium complex 2 parts The above materials were melt-kneaded by a roll mill, cooled, coarsely ground, finely ground, and classified to obtain a black magnetic toner. I got To one hundred parts of the black magnetic toner, 0.6 part of hydrophobized dry silica was externally added as a flow improver to prepare a one-component developer.

This one-component developer was used in a copier N
An unfixed image was obtained using P-8580, and this was subjected to a fixing test using an external fixing machine. As a result, the fixable area is 13
0-240 ° C. Further, an image output test was performed using the one-component developer and the copying machine. As a result, even after copying 100,000 sheets, there was no offset to the fixing roll, and a good image without fog or scattering was obtained.

The anti-blocking property was observed in the same manner as in Example 26, but it was good. The results are shown in Table 25.

Example 33 and Comparative Examples 31 to 33 A one-component system was prepared in the same manner as in Example 32 except that the binder resin (29) was replaced with the binder resin (30) and the comparative binder resins EE to GG. A developer was prepared and tested similarly. The results are shown in Table 25.

[0348]

[Table 25] Resin Production Example 31 (Crosslinking in Resin Solution) <Polymerization of Domain Resin> Styrene 140 g Butadiene 60 g Benzoyl peroxide 15 g Toluene 500 g Using the above raw materials, a polymerization reaction was performed at 85 ° C. for 15 hours. As a result, the number average molecular weight (Mn) was 5200, the weight average molecular weight (Mw) was 13,000, and the glass transition temperature (Tg).
A copolymer (resin o) at 31.0 ° C. was obtained. <Resin for matrix> Ethylene glycol, propoxylated bisphenol, terephthalic acid and fumaric acid were condensed. As a result, the number average molecular weight (Mn) was 4000, the weight average molecular weight (Mw) was 18,000, and the glass transition temperature (Tg)
A polyester (resin p) at 60.0 ° C. was obtained.

Next, each of (resin o) and (resin p) is weighed so that the ratio of (resin o) to (resin p) becomes 3: 7, and (resin o) and (resin p) are mixed with a solution. Here, 0.1 g of benzoyl peroxide was further added, and the temperature of the mixed solution was reduced to 80 g.
C. and reacted for 5 hours to obtain a binder resin (31).

The domain average particle diameter of the binder resin (31) was 2.8 μm. Table 26 shows the physical property values.

Resin Production Example 32 (Resin for Crosslinking During Kneading) The resin blended in Resin Production Example 31 without crosslinking was dried to obtain a binder resin (32). This binder resin (3
The domain average particle size of 2) was 2.0 μm. Table 26 shows the physical property values.

Resin Preparation Examples 33 and 34 Binder resins (33) and (34) were prepared in the same manner as in Resin Preparation Examples 31 and 32 except that the amounts of the initiator and the monomers in Resin Preparation Examples 31 and 32 were changed. Was synthesized.

Table 26 shows the physical properties of the synthesized binder resins (33) and (34) and the production methods used.

Comparative Resin Production Examples 34 to 39 Polymers were obtained by a solution polymerization method. The obtained polymers shown in Table 27 were used as comparative binder resins HH, II, KK and LL, and the two kinds of obtained polymers (resin: I and resin: II) shown in Table 27 were subjected to solution blending. B for comparison
J and MM were obtained. Table 27 shows the monomer compositions and physical properties of comparative binder resins HH to MM.

[0355]

[Table 26]

[0356]

[Table 27] Example 34 Binder resin (31) 100 parts Aluminum complex of di-tert-butylsalicylic acid 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts The above materials were melt-kneaded by a roll mill, and cooled. , Coarse pulverization, fine pulverization and classification to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

As a carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 6.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine.

As a result, the fixing temperature range where color mixing is possible is 13
0-210 ° C.

Using this two-component developer, CLC-50
At 0, an image output test was performed.

As a result, there was no offset to the fixing roll even after copying 20 000 sheets in the single color mode, and a full-color image faithfully reproducing the fog-free original color chart was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

When an OHP film was used, the transparency of the toner image was very favorable.

When left in a hot-air dryer at 45 ° C. for 1 day, the toner was observed for a blocking state. No change was observed and the toner had good fluidity. The results are shown in Table 28.

Example 35 The same procedures as in Example 34 were carried out except that the binder resin (31) was replaced with the binder resin (32), and that 0.3 parts of benzoyl peroxide and 0.1 part of zinc oxide were added. Cross-linking was performed during kneading to prepare a two-component developer, and a test was conducted in the same manner. The results are shown in Table 28.

Comparative Examples 34 to 36 A two-component developer was prepared in the same manner as in Example 34, except that the binder resins (31) were replaced with comparative binder resins HH to JJ, and the same tests were conducted. Was. The results are shown in Table 28.

[0366]

[Table 28] Example 36 Binder resin (33) 100 parts Magnetic iron oxide 70 parts Di-tert-butylsalicylic acid chromium complex 2 parts The above materials were melt-kneaded by a roll mill, cooled, coarsely ground, finely ground, and classified to obtain a black magnetic toner. I got A one-component developer was prepared by externally adding 0.6 part of positively charged hydrophobized dry silica as a flow improver to 100 parts of the black magnetic toner.

The one-component developer was used in a copying machine N manufactured by Canon Inc.
An unfixed image was obtained using P-8580, and this was subjected to a fixing test using an external fixing machine. As a result, the fixable area is 13
0-230 ° C. Further, an image output test was performed using the one-component developer and the copying machine. As a result, even after 100,000 copies were made, there was no offset to the fixing roll, and a good image free of fog and unevenness was obtained.

The anti-blocking property was good as in Example 34, and the result was good. The results are shown in Table 29.

Example 37 The procedure of Example 36 was repeated, except that the binder resin (33) was replaced with the binder resin (34) and 0.3 parts of benzoyl peroxide and 0.2 part of zinc oxide were added. Then, crosslinking was performed at the time of kneading to prepare a one-component developer, and the same test was conducted. The results are shown in Table 29.

Comparative Examples 37 to 39 A one-component developer was prepared in the same manner as in Example 36 except that the binder resin (33) was replaced with comparative binder resins KK to MM, and the same test was conducted. Was. The results are shown in Table 29.

[0371]

[Table 29] Resin Production Example 35 (Resolution Blend of Resin) <Polymerization of Resin for Domain> Styrene 140 g Butadiene 60 g Benzoyl peroxide 15 g Toluene 500 g Using the above raw materials, a polymerization reaction was performed at 85 ° C. for 10 hours. After the reaction, 20 g of maleic anhydride was added to carry out an addition reaction. Thereafter, a small amount of water was added to open the ring. As a result, the number average molecular weight (Mn) was 4800, and the weight average molecular weight (Mw) was
A copolymer (resin q) having 13000, a glass transition temperature (Tg) of 33.5 ° C., and an acid value of 41.0 was obtained. <Resin for matrix> Ethylene glycol, propoxylated bisphenol, terephthalic acid and fumaric acid were condensed. As a result, the number average molecular weight (Mn) was 3700, the weight average molecular weight (Mw) was 16,000, and the glass transition temperature (Tg).
A polyester (resin r) having an acid value of 8.5 at 59.5 ° C. was obtained.

Next, (resin q) and (resin r) were weighed so that the ratio of (resin q) to (resin r) was 3: 7, and (resin q) and (resin r) were mixed in a solution. Further, 0.1 g of benzoyl peroxide was added, the temperature of the mixed solution was raised to 80 ° C., and a reaction was carried out for 5 hours to obtain a binder resin (35).

In the binder resin (35), the domain average particle size was 1.0 μm. Table 32 shows the physical property values.

Resin Production Example 36 (Resin for Crosslinking during Kneading) In Resin Production Example 35, a solution-blended resin without crosslinking was dried to obtain a binder resin (36). This binder resin (3
In 6), the domain average particle size was 0.8 μm.
Table 30 shows the physical property values.

Resin Preparation Examples 37 and 38 Resin Preparation Examples (35) and (36) except that the initiator amount and the monomer amount ratio in Resin Preparation Examples 35 and 36 were changed.
Binder resins (37) and (38) were synthesized in the same manner as described above.

Table 30 shows the physical properties of the synthesized binder resins (37) and (38) and the production methods used.

Comparative Resin Production Examples 40 to 45 Polymers were obtained by solution polymerization. The obtained polymers shown in Table 33 were used as comparative binder resins NN, OO, QQ and RR, and the two kinds of obtained polymers (resin: I and resin: II) shown in Table 33 were subjected to solution blending. B for comparison
P and SS were obtained. Table 31 shows the monomer compositions and physical properties of the comparative binder resins NN to SS.

[0378]

[Table 30]

[0379]

[Table 31] Example 38 Binder resin (35) 100 parts Aluminum complex of di-tert-butylsalicylic acid 4.0 parts Copper phthalocyanine pigment represented by structural formula (C) 5.0 parts The above materials were melt-kneaded by a roll mill, and cooled. , Coarse pulverization, fine pulverization and classification to obtain a blue toner. To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

Thereafter, a two-component developer was prepared in the same manner as in Example 31, and a fixing test was performed. As a result, the fixing temperature range where color mixing was possible was 130 to 220 ° C.

Using this two-component developer, CLC-50
At 0, an image output test was performed. As a result, 2.
There was no offset to the fixing roll even after copying 100,000 sheets, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

When an OHP film was used, the transparency of the toner image was very favorable.

The toner was allowed to stand in a hot-air dryer at 45 ° C. for one day, and the blocking state of the toner was observed. No change was observed, and the toner had good fluidity. The results are shown in Table 32.

Example 39 Example 39 was repeated except that the binder resin (35) was replaced with the binder resin (36) and 0.3 parts of benzoyl peroxide and 0.1 part of zinc oxide were added. Cross-linking was performed during kneading to prepare a two-component developer, and a test was conducted in the same manner. The results are shown in Table 32.

Comparative Examples 40 to 42 A two-component developer was prepared in the same manner as in Example 38, except that the binder resin (35) was replaced with comparative binder resins NN to PP, and a test was conducted in the same manner. Was. The results are shown in Table 32.

[0386]

[Table 32] Example 40 Binder resin (37) 100 parts Magnetic iron oxide 70 parts Di-tert-butylsalicylic acid chromium complex 2 parts The above materials were melt-kneaded by a roll mill, cooled, coarsely ground, finely ground, and classified to obtain a black magnetic toner. I got A one-component developer was prepared by externally adding 0.6 part of positively charged hydrophobized dry silica as a flow improver to 100 parts of the black magnetic toner.

This one-component developer was used in a copier N
An unfixed image was obtained using P-8580, and this was subjected to a fixing test using an external fixing machine. As a result, the fixable area is 13
0-230 ° C. Further, an image output test was performed using the one-component developer and the copying machine. As a result, even after copying 100,000 sheets, there was no offset to the fixing roll, and a good image without fog or scattering was obtained.

When the blocking resistance was observed in the same manner as in Example 34, it was good. The results are shown in Table 33.

Example 41 The same procedure as in Example 40 was carried out except that the binder resin (37) was replaced with the binder resin (38), and that 0.3 part of benzoyl peroxide and 0.2 part of zinc oxide were added. Crosslinking was performed during kneading to prepare a one-component developer, and the same test was conducted.
The results are shown in Table 33.

Comparative Examples 43 to 45 A one-component developer was prepared in the same manner as in Example 40 except that the binder resin (37) was replaced with comparative binder resins QQ to SS, and the same test was conducted. Was. The results are shown in Table 33.

[0391]

[Table 33] Resin Production Example 39 (Resin Blend) <Polymerization of Resin for Domain> Styrene 90g n-butyl acrylate 80g Monobutyl maleate (half ester) 15g + 15g (after 4 hours) Benzoyl peroxide 15g Toluene 500g Using the above raw materials, 85 A polymerization reaction was carried out at 10 ° C for 10 hours. Monobutyl maleate is used at the start of polymerization and 4 hours after the start of polymerization in order to make the composition distribution in the polymer uniform.
The mixture was added and reacted 15 g at a time. As a result, the number average molecular weight (Mn) was 4700, and the weight average molecular weight (Mw) was
A copolymer (resin s) having 12000, a glass transition temperature (Tg) of 30.5 ° C. and an acid value of 62.5 was obtained. <Matrix resin> Ethylene glycol, propoxylated bisphenol, terephthalic acid, dodecenyl succinic acid, and trimellitic acid were condensed. As a result, the number average molecular weight (Mn) was 5600 and the weight average molecular weight (Mw) was 2000.
0, glass transition temperature (Tg) 62.0 ° C., acid value 30.0
(Resin t) was obtained.

Next, the polymer-toluene solution after the polymerization reaction was weighed so that the ratio of (resin s) to (resin t) was 3: 7, and (resin s) and (resin t) were weighed. Was mixed with the solution. The temperature of the mixed solution was adjusted to 80 ° C., 1.5 g of zinc acetate was added, and the mixture was vigorously stirred and then dried to obtain a binder resin (39).

[0393] The domain average particle diameter of the binder resin (39) was 3.0 µm. Table 34 shows the physical property values.

Resin Production Example 40 (Resin for Crosslinking During Kneading) The resin blended in Resin Production Example 39 without crosslinking was dried to obtain a binder resin (40). This binder resin (4
The domain average particle size of 0) was 2.5 μm. Table 34 shows the physical property values.

Resin Preparation Examples 41 and 42 Binder resins (41) and (42) were prepared in the same manner as in Resin Preparation Examples 39 or 40, except that the amounts of the initiator and the monomers in Resin Preparation Examples 39 or 40 were changed. Was synthesized.

Table 34 shows the physical property values of the synthesized binder resins (41) and (42) and the production methods used.

Comparative Resin Production Examples 46 to 51 Polymers were obtained by a solution polymerization method. The obtained polymers shown in Table 37 were used as comparative binder resins TT, UU, WW and XX, and the two kinds of obtained polymers (resin: I and resin: II) shown in Table 35 were subjected to solution blending. B for comparison
V and YY were obtained. Table 35 shows the monomer compositions and physical properties of comparative binder resins TT to YY.

[0398]

[Table 34]

[0399]

[Table 35] Example 42 Binder Resin (39) 100 parts Copper phthalocyanine pigment represented by Structural Formula (C) 5.0 parts The above materials were melt-kneaded by a roll mill, cooled, coarsely ground, finely ground, classified, and blue toner. I got To 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.2 part of aluminum oxide fine powder were externally added.

A two-component developer was prepared in the same manner as in Example 34, and a fixing test was performed. As a result, the fixing temperature range where color mixing was possible was 130 to 210 ° C.

Using this two-component developer, CLC-50
At 0, an image output test was performed. As a result, 2.
There was no offset to the fixing roll even after copying 100,000 sheets, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

Even when an OHP film was used, the transparency of the toner image was very favorable.

The toner was allowed to stand in a hot-air dryer at 45 ° C. for one day, and the state of blocking of the toner was observed. As a result, no change was observed and the toner had good fluidity. The results are shown in Table 36.

Example 43 Binder resin (40) 100 parts Di-tert-butylsalicylic acid chromium complex 4 parts Copper phthalocyanine pigment represented by the structural formula (C) 5.0 parts Cross-linking was performed during kneading to prepare a two-component developer, and the test was performed in the same manner. The results are shown in Table 36.

Comparative Examples 46 to 48 A two-component developer was prepared in the same manner as in Example 42, except that the binder resins (39) were replaced with comparative binder resins TT to VV, and a test was conducted in the same manner. Was. The results are shown in Table 36.

[0406]

[Table 36] Example 44 Binder resin (41) 100 parts Magnetic iron oxide 70 parts The above raw materials were melt-kneaded by a roll mill, cooled, coarsely ground, finely ground and classified to obtain a black magnetic toner. A one-component developer was prepared by externally adding 0.6 part of positively charged hydrophobized dry silica as a flow improver to 100 parts of the black magnetic toner.

This one-component developer was used in a copier N
An unfixed image was obtained using P-8580, and this was subjected to a fixing test using an external fixing machine. As a result, the fixable area is 14
0-220 ° C. Further, an image output test was performed using the one-component developer and the copying machine. As a result, even after 100,000 copies were made, there was no offset to the fixing roll, and a good image free of fog and unevenness was obtained.

The anti-blocking property was good as in Example 34, and the result was good. The results are shown in Table 37.

Example 45 The same as Example 44 except that the binder resin (41) was replaced with the binder resin (42), and that 4 parts of an azo metal complex represented by the complex [I] -1 were added. To perform cross-linking during kneading,
A one-component developer was prepared and tested similarly. The results are shown in Table 37.

Comparative Examples 49 to 51 A one-component developer was prepared in the same manner as in Example 44, except that the binder resin (41) was replaced with comparative binder resins WW to YY, and the same test was conducted. Was. The results are shown in Table 37.

[0411]

[Table 37] Resin Production Example 43 (Resin solution blend) <Polymerization of resin for domain> 92 parts of styrene 78 parts of n-butyl acrylate 15 parts of monobutyl maleate (half ester) +15 parts (after 4 hours) Benzoyl peroxide 15 parts Toluene 500 parts Using the above raw materials, a polymerization reaction was carried out at 85 ° C for 10 hours. In order to make the composition distribution in the polymer uniform, 15 parts of monobutyl maleate were added and reacted in two portions, at the start of the polymerization and 4 hours after the start. As a result, the number average molecular weight (Mn) was 4600 and the weight average molecular weight (Mw) was 1
3000, glass transition temperature (Tg) 31.9 ° C, acid value 5
A copolymer (resin u) of 7.0 was obtained. <Polymerization of resin for matrix> 243 parts of styrene 57 parts of n-butyl acrylate 22.5 parts of benzoyl peroxide Toluene 750 parts A polymerization reaction was carried out at 85 ° C for 16 hours using the above raw materials. As a result, the number average molecular weight (Mn) was 5400, the weight average molecular weight (Mw) was 15,000, and the glass transition temperature (Tg).
A copolymer (resin v) having 58.5 ° C. and an acid value of 0 was obtained.

Next, the polymer-toluene solution after the polymerization reaction and drying was weighed so that the ratio of (resin u) to (resin v) was 3: 7, and (resin u) and (resin v) were measured. Was mixed with the solution. The temperature of the mixed solution was set to 150 ° C., the mixture was vigorously stirred, and then rapidly cooled to obtain a binder resin (43). The domain average particle diameter of the binder resin (43) was 2 μm. Table 38 shows each physical property value.

Resin Production Example 44 (Polymerization in the Presence of Resin) <Polymerization of Domain Resin> Styrene 104 parts N-butyl acrylate 66 parts Monobutyl maleate (half ester) 30 parts Benzoyl peroxide 15 parts Toluene 500 parts The polymerization reaction was carried out at 85 ° C. for 10 hours using
Number average molecular weight (Mn) 5300, weight average molecular weight (M
w) 16000, glass transition temperature (Tg) 42.8 ° C,
A copolymer having an acid value of 60.0 was obtained. Then, as follows:
The matrix resin was polymerized in this resin solution. <Polymerization of matrix resin> Styrene 165 parts N-butyl acrylate 35 parts Benzoyl peroxide 15 parts Toluene 500 parts The above-mentioned raw materials were added to the resin solution, and further, 85 ° C × 16.
An hr polymerization reaction is performed. As a result, the number average molecular weight (Mn)
A copolymer having 5700 and a weight average molecular weight (Mw) of 15,000 was obtained. This was dried to obtain a binder resin (44). The binder resin (44) had an acid value of 19.0 and a domain average particle size of 1.5 μm. The number average molecular weight (Mn) of the resin obtained by polymerizing only the matrix resin is 6300,
The weight average molecular weight (Mw) was 14,000, the glass transition temperature (Tg) was 59.0 ° C., and the acid value was 0. Table 3 shows each physical property value.
FIG.

Resin Preparation Examples 45 and 46 Binder resins (45) and (46) were prepared in the same manner as in Resin Preparation Examples 43 or 44, except that the initiator and the monomer ratio were changed. Synthesized.

Table 38 shows the physical properties of the synthesized binder resins (45) and (46) and the production methods used.

[0416]

[Table 38] Example 46 Binder resin (43) 100 parts Styrene-methacrylic acid copolymer 5 parts Copper phthalocyanine pigment represented by Structural formula (C) 5 parts The above raw materials are melt-kneaded by a roll mill, cooled, coarsely ground, and finely ground. And classified to obtain a blue toner. For 100 parts of this blue toner, 0.5 part of silica fine powder treated with hexamethyldisilazane as a flow improver and 0.7 part of strontium titanate fine powder (average particle size: 0.37 μm) as conductive fine particles are used. Mix and mix with Henschel mixer.

As a carrier, styrene-acryl 2
Cu-Zn-Fe-based ferrite carrier coated with 0.5% by weight of -ethylhexyl-methyl methacrylate (copolymer weight ratio: 50:20:30) based on the carrier (average particle size: 45 µm, 250 mesh pass, 400 mesh on 87 weight) %) And the toner concentration is 6.0% by weight.
Thus, a two-component developer was prepared by mixing with the blue toner having the above external additive.

Using this two-component developer, an unfixed image was developed and transferred only with a Canon full-color copying machine CLC-500, and a fixing test was performed with an external fixing machine.

As a result, the fixing temperature range where color mixing is possible is 12
0-220 ° C.

A temperature of 30 ° C. and a temperature of 30 ° C.
An image output test was performed by CLC-500 in an environment with a humidity of 75%.

As a result, there was no offset to the fixing roll even after copying 1,000,000 sheets in the single color mode, and a full-color image faithfully reproducing the original color chart without fog was obtained. The toner transportability in the copying machine was good, and a stable image density was obtained.

When an OHP film was used, the transparency of the toner image was very favorable.

When the toner was allowed to stand in a hot air dryer at 45 ° C. for one day and the blocking state of the toner was observed, no change was observed at all, and the toner had good fluidity. The results are shown in Table 39.

Examples 47 and 48 A two-component developer was prepared in the same manner as in Example 46 except that the binder resin (43) was replaced with the binder resins (44) and (45), respectively. The test was performed. Table 3 shows the results
It is shown in FIG.

Example 49 Except that the binder resin (43) was replaced by the binder resin (46) and that 0.7 parts of strontium titanate fine powder was replaced by 0.7 parts of titanium nitride having an average particle diameter of 1 μm. Example 46
A two-component developer was prepared in the same manner as described above, and the same test was conducted. The results are shown in Table 39.

[0426]

[Table 39] Examples 50 and 51 Two-component as in Examples 46 and 49 except that the Henschel mixer, which is a means for mixing the toner and the external additive used in Examples 46 and 49, was replaced with a hybridizer (Nara Machinery). A system developer was prepared and tested similarly. The results are shown in Table 40.

[0427]

[Table 40]

[0428]

Since the resin composition having a domain-matrix structure of the present invention has the above-described constitution, the resin composition, a developer for developing an electrostatic image using the resin composition, and the electrostatic charge The toner image fixing method and the image forming apparatus using the developer for image development have the following effects. Low-temperature fixing is possible and the fixing temperature range is wide. It has excellent storage stability and fluidity, does not cause aggregation, and has excellent impact resistance. It has good charging characteristics, has stable chargeability during use, and provides clear and fog-free images. The toner image fixed by using the full-color toner does not irregularly reflect light and can form a smooth fixing surface without hindering color reproducibility. A full-color image having color mixing properties and not hindering the color tone of the toner layer having a different color tone under the toner image can be obtained. High-temperature offset is sufficiently prevented, and a wide fixing temperature range can be obtained. The anti-offset property can be maintained even by repeated fixing paper passing.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing a state in which conductive fine particles are held on a toner surface.

FIG. 2 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount used in the present invention.

FIG. 3 is a diagram illustrating an example of a configuration cross section of the image forming apparatus according to the present invention.

FIG. 4 is a diagram illustrating a relationship between the positions of a fixing roller and a pressure roller in a fixing unit when a transfer material discharge direction is a pressure roller side.

FIG. 5 is a diagram illustrating a positional relationship between a fixing roller and a pressure roller in a fixing unit when a transfer material discharge direction is a fixing roller side.

FIG. 6 is an explanatory view schematically showing an embodiment of the image forming apparatus of the present invention.

FIG. 7 is an explanatory view schematically showing an embodiment of a charging unit according to the present invention.

FIG. 8 is a partially enlarged view of FIG. 6 for explaining a developing step.

FIG. 9 is an explanatory view schematically showing another embodiment of the charging means according to the present invention.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03G 15/01 G03G 9/08 321 15/20 102 331 361 (31) Claimed priority number Japanese Patent Application No. 3-19198 (32) Priority Date January 21, 1991 (1991.1.21) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-19199 (32) Priority date January 21, 1991 Date (1991.1.12) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-27772 (32) Priority date January 30, 1991 (1991.1.130) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-167386 (32) Priority date June 13, 1991 (1991.6.13) (33) Priority claim Country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-167388 (32) Priority date June 13, 1991 (1991.13.13) (33) Priority claim country Japan ( P) (56) References JP-A-2-29664 (JP, A) JP-A-2-881 (JP, A) JP-A-2-275962 (JP, A) JP-A-1-15659 (JP, A) JP-A-59-26741 (JP, A) JP-A-2-256061 (JP, A) JP-A-2-163751 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08-9/09

Claims (28)

(57) [Claims] 1. A heat-fixable toner for developing an electrostatic image, comprising a binder resin having a resin composition having a domain-matrix structure and toner particles containing a colorant, wherein the resin composition having the domain-matrix structure is provided. Is
Has a resin P ₂ constituting the resin P ₁ and matrix constituting the domain particles, the resin P ₁ has a glass transition temperature Tg ₁ of 15 to 50 ° C., the resin P ₂ is 55
Has a 80 ° C. glass transition temperature Tg ₂ of the resin P ₂
The glass transition temperature Tg ₂ of higher 5 ° C. or higher than the glass transition temperature Tg ₁ of the resin P _1, the domain particles, 5 [mu] m
A heat-fixable toner for developing an electrostatic image, having the following average particle size. 2. The resin P ₁ constituting the domain particles,
Has a carboxyl group, resin P ₂ constituting the matrix has substantially to claim 1, wherein the non heated for developing electrostatic images according carboxyl group
Fixing toner. 3. The resin P constituting the domain particles ₁ Is
A resin having an acid value of 15 or more and constituting the matrix;
P _Two Has an acid value of 10 or less.
3. The heat-fixable toner for developing an electrostatic image according to item 2. 4. The toner according to claim 1, wherein the resin composition comprises
The compound according to claim 2 or 3, wherein the compound contains a genus compound.
The heat-fixable toner for developing an electrostatic image according to the above. 5. The resin P constituting the domain particles ₁ Is
The matrix has substantially no carboxyl group.
Resin P _Two Has a carboxyl group
The heating for developing an electrostatic image according to claim 1, wherein
Fixing toner. 6. A polymer having substantially the carboxyl group.
Resin P ₁ And a resin P having the carboxyl group _Two With
The mixing ratio is as follows P ₁ : P _Two = 6-9: 4-1 6. The electrostatic charge image according to claim 5, wherein
Heat fixing toner for image. 7. The resin P ₁ constituting the domain particles,
Has been the polymer synthesized from a vinyl monomer, the resin P ₂ constituting the matrix to claim 5, characterized in that it has an acid added to the acid-modified polymer after being synthesized from a vinyl monomer Heat fixation for electrostatic image development as described
Gender toner. 8. The toner according to claim 1, wherein the resin composition and the crosslinkable gold
The compound according to any one of claims 5 to 7, comprising a genus compound.
The heat-fixable toner for developing an electrostatic image according to any one of the above. 9. The resin P constituting the domain particles ₁ Is
Has unsaturated double bond synthesized from vinyl monomer
Having a polymer which constitutes the matrix
P _Two Has a polyester having an unsaturated double bond
And the resin P ₁ And P _Two The unsaturated double bonds of
2. The method according to claim 1, wherein the compound is partially chemically bonded.
The heat-fixable toner for developing an electrostatic image according to the above. 10. The resin P constituting the domain particles
₁ Has an acid value of 15 or more and constitutes the matrix.
Resin P _Two Has an acid value of less than 15
The heat-fixable toner for developing an electrostatic image according to claim 9. 11. The resin P constituting the domain particles
₁ Is a vinyl monomer having an acid value of 15 or more and
Having a polymer having an unsaturated double bond synthesized from
And the resin P constituting the matrix _Two Has an acid value of 15
Less than and having an unsaturated double bond
The electrostatic charge according to claim 1, wherein
Heat fixing toner for image development. 12. The resin P constituting the domain particles
₁ Has an acid value of 15 or more and constitutes the matrix.
Resin P _Two Has an acid value of 10 or less
A heat-fixable toner for developing an electrostatic image according to claim 11. 13. The toner according to claim 1, wherein the resin composition is
12. The composition according to claim 11, which contains a metal compound.
13. The heat-fixable toner for developing an electrostatic image according to item 12. 14. The toner according to claim 1, wherein the resin composition is
Contains a metal compound and constitutes the domain particles
Resin P ₁ Is a vinyl-based monomer having an acid value of 15 or more and
Having a polymer having a carboxyl group synthesized from
And the resin P constituting the matrix _Two Is the acid value
Having a carboxyl group and at least 15
Having a stell and the resin P ₁ And P _Two Is the crosslinkable gold
Genus compound It is noted that some or all of the
The heat fixing property for developing an electrostatic image according to claim 1,
Ner. 15. The glass transition temperature Tg ₂ of the resin P ₂ constituting the matrix is higher than the glass transition temperature Tg ₁ of the resin P ₁ constituting the domain particles by 10 ° C. or more. 15. The heat-fixable toner for developing an electrostatic image according to any one of items 14 to 14 . 16. The resin composition, heat fixing toner for developing an electrostatic image according to any one of claims 1 to 15, characterized by containing a release agent. 17. The release agent has a melting onset temperature of 40 ° C. or more, and has at least two or more melting points between 50 and 250 ° C. as measured by DSC, or has a different melting point. 17. The toner according to claim 16 , comprising at least one kind of release agent, wherein the release agent is contained in the toner particles in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin. Heat-fixable toner for developing electrostatic images. 18. The electrostatic charge image developing device according to claim 1, wherein a conductive fine powder is embedded and held in the surface of the toner particles to a depth of 0.05 μm or more from the surface. Heat fixing toner. 19. A transfer material supporting a toner image,
The toner image is fixed on the transfer material by passing through a fixing roller having a rubber-like elastic layer on a cored bar and a heat roller fixing device having a pressure roller, and the fixing roller is connected to the center of the pressure roller. In an image fixing method in which the transfer material is discharged to a pressure roller side from a direction perpendicular to the line to fix the image, the toner for forming the toner image has a binder having a resin composition having a domain-matrix structure. heating fixability toner to have a toner particle containing a resin and a colorant
Dea is, the domain - resin composition having a matrix structure,
Has a resin P ₂ constituting the resin P ₁ and matrix constituting the domain particles, the resin P ₁ has a glass transition temperature Tg ₁ of 15 to 50 ° C., the resin P ₂ is 55
Has a 80 ° C. glass transition temperature Tg ₂ of the resin P ₂
The glass transition temperature Tg ₂ of higher 5 ° C. or higher than the glass transition temperature Tg ₁ of the resin P _1, the domain particles, 5 [mu] m
An image fixing method having the following average particle size. As claimed in claim 20 wherein said heat fixing toner according to claim 2
Image fixing method according to claim 19, characterized by using either a heat fixing property <br/> toner according to to 18. 21. A latent image carrier for carrying an electrostatic latent image, charging means for charging the latent image carrier, and means for forming an electrostatic latent image on the charged latent image carrier. Latent image forming means, developing means for forming the electrostatic latent image and forming a toner image on the latent image carrier, transfer means for transferring the toner image from the latent image carrier to a transfer material, An image forming apparatus comprising: a cleaning unit for removing toner remaining on the image carrier without being transferred; and a fixing unit for fixing the toner image transferred to the transfer material by the action of heat and pressure. The developing means has a heat-fixable toner having a binder resin having a resin composition having a domain-matrix structure and a toner particle containing a colorant, and the resin composition having a domain-matrix structure is
Has a resin P ₂ constituting the resin P ₁ and matrix constituting the domain particles, the resin P ₁ has a glass transition temperature Tg ₁ of 15 to 50 ° C., the resin P ₂ is 55
Has a 80 ° C. glass transition temperature Tg ₂ of the resin P ₂
The glass transition temperature Tg ₂ of higher 5 ° C. or higher than the glass transition temperature Tg ₁ of the resin P _1, the domain particles, 5 [mu] m
An image forming apparatus having the following average particle diameter. 22. As the heat fixing toner according to claim 2
22. The image forming apparatus according to claim 21 , wherein the heat fixing toner for developing an electrostatic image according to any one of the above items 18 to 18 is used. 23. A method of forming a heat fixing toner for developing an electrostatic image.
In a resin composition having a domain-matrix structure used as a landing resin, the resin composition has a resin P ₁ constituting domain particles and a resin P ₂ constituting a matrix, and the resin P ₁ It has a glass transition temperature Tg ₁ of 15 to 50 ° C., and the resin P ₂ has a glass transition temperature of 55 to 8
0 has a glass transition temperature Tg ₂ of ° C., a glass transition temperature Tg ₂ of the resin P ₂ has a glass transition temperature T of the resin P ₁
A resin composition, which is higher than g ₁ by 5 ° C. or more and the domain particles have an average particle size of 5 μm or less. 24. Resin P constituting said domain particles
₁ Has a carboxyl group, and the matrix is
Constituent resin P _Two Has a substantially carboxyl group
24. The resin composition according to claim 23, wherein
object. 25. A resin P constituting the domain particles
₁ Has an acid value of 15 or more and constitutes the matrix.
Resin P _Two Has an acid value of 10 or less
The resin composition according to claim 24. 26. Resin P constituting the domain particles
₁ Has substantially no carboxyl group,
Resin P that constitutes Rix _Two Has a carboxyl group
The resin composition according to claim 23, wherein
object. 27. A method having substantially the carboxyl group.
No resin P ₁ And a resin P having the carboxyl group _Two When
The following proportions P ₁ : P _Two = 6-9: 4-1 28. The resin composition according to claim 26, wherein:
object. 28. Resin P constituting said domain particles
₁ Has a polymer synthesized from a vinyl monomer,
Resin P constituting the matrix _Two Is a vinyl monomer
Having an acid-modified polymer synthesized from
28. The resin composition according to claim 27, wherein: