JPH08314300A - Electrostatic charge image developing toner, image forming method and color image record - Google Patents

Abstract

PURPOSE: To make it possible to obtain images free from odd feel even with the images in which graph parts, such as graphic images, and character parts coexist by fixing toner images by a thermal means, thereby forming the images exhibiting the specific glossiness behavior. CONSTITUTION: The min. step. at which the toner images are fixable by thermal means is defined as Tmin and the max. temp. as Tmax . The toner images are fixed on an image carrier at the temp. T existing within this temp. range and are so formed that the glossiness G(T) of the images exhibits the glossiness behavoir satisfying the relation of the following equation, where (T, G(T))=(Tmin , 0) are assumed as the origin. The glossiness G(T) when Tmin <=Tmin +30 is [(T-Tmin)/30]+1<=G(T)<=[(T-Tmin )/5]+30. The glossiness G(T) when Tmin+30<Tmin +120 is [T-Tmin )/5]-4<=G(T)<=[7(T-Tmin )/10]+15 and G(T)<=50.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image suitable for heat fixing, an image recording method and a color image recorded material, which are used in electrophotography, electrostatic recording, magnetic recording and the like. .

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, US Pat. No. 2,297,691 and JP-B-42-23910 are known.
Although a number of methods such as those described in Japanese Patent Publication No. 43-24748 and Japanese Patent Publication No. 43-24748 are known, in general,
First, an electric latent image is formed on a photoconductor by various means using a photoconductive substance, then the latent image is developed with a toner, and the toner is transferred to a transfer material such as paper as necessary. After transferring the image, the toner image is fixed by heating, pressure, heating and pressurizing, solvent vapor or the like to obtain an image recorded matter such as a copy. The toner remaining on the photoconductor without being transferred is cleaned by various methods, and the above developing process is repeated.

Further, a method of forming a general full-color image by electrophotography will be described. First, a photosensitive member of a photosensitive drum is uniformly charged by a primary charger, and a laser beam modulated by a magenta image signal of an original is modulated. Image exposure is carried out to form an electrostatic latent image on the photosensitive drum.
Next, the electrostatic latent image is developed by a magenta developing device containing magenta toner to form a magenta toner image. Next, the magenta toner image developed on the photosensitive drum is transferred to the transfer material conveyed by the transfer charger.

On the other hand, the photosensitive drum after the development of the electrostatic latent image is discharged by the discharging charger, is cleaned by the cleaning means, and is charged again by the primary charger. The cyan toner image is formed in the same manner as the case of forming the magenta toner image, and further, the cyan toner image is transferred to the transfer material on which the magenta toner image is transferred. Further, the yellow color and the black color are sequentially performed in the same manner as described above, and the four color toner images are transferred to the transfer target material. Finally, the transfer material having the four color toner images is fixed by the action of heat and pressure by the fixing roller to form a full color image.

In recent years, the copying apparatus as described above has been used not only as a general-purpose copying machine for copying original documents but also as a printer as a computer output or a personal copying field for individuals. I'm beginning to be hurt. Furthermore, in addition to the fields represented by such laser beam printers, the development of plain paper faxes using the basic engine is also rapidly developing.

For this reason, there has been a strict pursuit of smaller size, lighter weight, higher speed, higher image quality, and higher reliability, and machines have various points and are composed of simpler elements. Is coming. As a result, the performance required of the toner becomes higher, and if the improvement of the performance of the toner cannot be achieved, a better machine cannot be established. In addition, the demand for color copying has been rapidly increasing with various copying needs in recent years, and higher image quality, higher resolution, etc. are desired in order to more faithfully copy an original color image. From these viewpoints, the toner used in the method for forming a color image needs to have good meltability when heat is applied to the toner, and good color mixing property, and has a low softening point and a low melt viscosity. It is preferable to use a toner having a high melt property. That is, by using such a sharp melt toner, it is possible to widen the color reproduction range of the copy and obtain a color copy faithful to the original image.

However, in recent years, such a color copying apparatus has been rapidly used as a printer function as a computer output in order to use a graphic image processed by a personal computer or the like for presentation. There is. On this occasion,
Regardless of when outputting a pictorial image, when outputting a so-called graphic image in which a graph and the characters that explain it are arranged, when using a toner with a high sharp-melting property as in the conventional case, the graph part and the character part are Has a problem that the output image is hard to see and hard to read because the glossiness becomes too large.

On the other hand, there is a means of reducing the sharp melt property as a toner and considerably suppressing the glossiness of a fixed image, but in this case, the readability of the graphic image as described above is low. Although it is certain that the image will be improved, it is not satisfactory in terms of gradation, brightness, saturation, etc. in pictorial images. Furthermore, a transparency film (hereinafter, referred to as “OHP”) using an overhead projector (hereinafter referred to as “OHP”)
When abbreviated as OHT), the agglomeration of light coming from the projector increases due to the presence of toner particles that are not completely dissolved even after fixing, and the transparency of the projected image due to insufficient color mixing. There is a problem in that it leads to a decrease in color, a decrease in brightness, and a decrease in color sharpness. In particular, when the reflective OHP is used, this adverse effect is further increased as compared with the case where the transmissive OHP is used.

[0009]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide an image recorded matter which solves the above problems of the prior art. That is, an electrostatic charge image developing toner capable of providing an image having no discomfort even in an image in which a graph portion and a character portion are mixed, such as a graphic image, an image forming method using the toner, and a color image recorded matter are provided. Especially. Another object of the present invention is a toner for developing an electrostatic charge image, which can be satisfactorily fixed without applying a large amount of oil to a fixing roller or without applying any oil to the fixing roller,
And to provide an image recording method using the same.
Still another object of the present invention is to provide a toner for developing an electrostatic charge image capable of obtaining a high-quality full-color OHT image having excellent transparency.
And to provide an image recording method using the same.

[0010]

The above object can be achieved by the present invention described below. That is, the present invention provides an image forming method for fixing an image recorded matter by thermal means after forming a toner image on an image bearing member with a toner containing at least a binder resin, a colorant and a release agent, When the minimum temperature at which the toner image can be fixed by the thermal means is T _min and the maximum temperature is T _max , the toner image on the image carrier is fixed at a temperature T within this temperature range, and an image is formed. The glossiness G (T) of the image measured by making incident light incident on the carrier surface at an incident angle of 75 degrees is (T, G
The image forming method is characterized by forming so as to exhibit glossiness behavior satisfying the relationship of the following formula when (T)) = (T _min , 0) is assumed to be the origin. Fixing temperature T is T _min
Gloss G within the range of ≦ T ≦ T _min +30
(T) is [(T−T _min ) / 30] + 1 ≦ G (T) ≦ [(T−T
_min ) / 5] +30 The glossiness G (T) when the fixing temperature T is within the range of T _min +30 <T ≦ T _min +120 is [(T−T _min ) / 5] −4 ≦ G ( T) ≦ [7 (T−T
_min ) / 10] +15 and G (T) ≦ 50

[0011]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, when an image exhibits a specific glossiness behavior as described below, a graph portion such as a graphic image is displayed. It has been found that even in an image in which character portions are mixed, an image having no discomfort is provided, a high-quality full-color OHT image having excellent transparency is provided, and further, transferability of a transferred material is also excellent. Further, in order to obtain an image showing a specific glossiness behavior, at least 1
It has been found that it is best to contain a high molecular weight component of 0,000 ≦ Mw ≦ 1,000,000, and the present invention has been completed.

That is, when a toner image formed on the image bearing member by a toner containing at least a binder resin, a colorant and a releasing agent is fixed on the image bearing member by a thermal means, heat is applied. The minimum temperature at which a toner image can be fixed by a mechanical means is T _min , and the maximum temperature is T
_{When the} toner image is fixed on the image carrier at a temperature T within the temperature range of _max , the surface of the image carrier is measured by making incident light incident on the surface of the image carrier at an incident angle of 75 degrees. When the glossiness G (T) of the image-recorded matter exhibits the glossiness behavior satisfying the relationship of the following formula, an excellent image-recorded matter satisfying the above-mentioned object is obtained. (T, G (T)) =
Assuming that (T _min , 0) is the origin, first, when the fixing temperature T is within the range of T _min ≦ T ≦ T _min +30, the glossiness G (T) is [(T−T _min ) / 30] + 1 ≦ G (T) ≦ [(T−T
_min ) / 5] +30 More preferably, [(T-T _min ) / 30] + 1≤G (T) ≤ [(T-T _min ) /
6] It is desired to show gloss behavior in the range of +20. In the formula, T: temperature at which the toner image is fixed by thermal means G (T): Gloss degree of the toner image fixed at the temperature T is G
(T) T _min : minimum temperature at which a toner image can be fixed by thermal means

That is, when the inclination of the straight line when (T-T _min ) is taken as the x-axis is less than 1/30, the image gloss at the time of fixing is too low. However, the characteristics required for a high definition image such as high brightness and high saturation cannot be obtained. When the slope of the straight line exceeds 1/5, more preferably 1/6, the change in image glossiness with temperature is too large. For example, when an A3 portrait image is formed, before and after the fixed image. Differences in glossiness occur at the edges, and along with that, the brightness, saturation, etc. also fluctuate greatly, resulting in an image that gives a sense of discomfort, and high image quality cannot be achieved.

Further, the fixing temperature T is T _min +30 <T ≦
When it is within the range of T _min +120, the glossiness G (T)
, [(T-T _min ) / 5] -4 ≤ G (T) ≤ [7 (T-T _min )
/ 10] +15 and G (T) ≤ 50, and more preferably [(T-T _min ) / 3] -8 ≤ G (T) ≤ [5 (T-T
_min ) / 6] and G (T) ≦ 50.

That is, when the inclination of the straight line when (T-T _min ) is taken as the x-axis is less than ⅕, the toner cannot be completely melted when OHP is used, and the transparency is diffused due to diffused reflection of light. The color recognition of the projected image is remarkably deteriorated because the mixing property is remarkably lowered and the mixing property is insufficient. If the slope of the straight line exceeds 7/10, or if the G (T) value is 50
If it exceeds, when fixing an unfixed image in which a large amount of toner is transferred to the transfer material, the completely melted toner layer is cooled immediately after fixing and the volume shrinkage of the resin is remarkably large. Curl is generated at the edge portion of the fixed image, and accordingly, the transportability of the fixed image during double-sided fixing is extremely deteriorated, and a high-quality double-sided image cannot be obtained.

Further, in the present invention, 100,000 ≦ Mw ≦ 1,000,0 is contained in the binder resin constituting the toner.
By including the high molecular weight component of 00 in the binder resin, the above-described glossiness behavior can be obtained. The reason for this is that if the release agent in the toner composition contained in the production of the toner is present together with the specific high molecular weight component as described above, it is melted when the toner image is fixed by the heating means, This molten release agent enters the polymer chains in the binder resin in a state where the high molecular weight component that has begun to melt to a certain extent is frayed.
This is because the plasticizing effect of the high molecular weight component occurs in the fixing temperature range up to the temperature exceeding ℃. Further, at this time, the molecular chain of the high molecular weight component whose plasticization is promoted is likely to be broken, and the melt viscosity of the entire binder resin of the toner is also lowered. The gloss behavior is also achieved due to this decrease in melt viscosity.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The toner for developing an electrostatic image of the present invention has at least a weight average molecular weight Mw of 100,000 ≦ Mw ≦ 1,50 in the binder resin of the toner containing at least a binder resin, a colorant and a release agent.
It is characterized by the fact that it contains a high molecular weight component of 10,000. Then, the toner image is fixed on the image bearing member by a thermal means using the toner for developing the electrostatic charge image to form an image recorded matter. At this time, the minimum temperature at which the toner image can be fixed by thermal means is T
_{When the} toner image is fixed as an image on the image carrier at a temperature T within this temperature range, where _{min is} the maximum temperature and T _max is the maximum temperature, incident light is incident on the surface of the image carrier at an incident angle of 75 degrees. The measured glossiness G (T) of the image has a constant glossiness behavior.

The high molecular weight component contained in the binder resin, which is a constituent of the electrostatic image developing toner of the present invention, has a molecular weight of 100,000≤Mw≤1,500,000. Any of them may be used, but more preferably, a high molecular weight component of 150,000 ≦ Mw ≦ 800,000 is desired. Particularly, in the case of color toner, those having 180,000 ≦ Mw ≦ 700,000 are used. When Mw is less than 100,000, when the fixing temperature T is in the range of T _min ≦ T ≦ T _min +30,
G (T)> [1/5 (T-T _min )] + 30,
Further, the gloss increases rapidly with the fixing temperature, and uniform image glossiness cannot be obtained.

When Mw exceeds 1,500,000, T _min +30 <T ≦ T _min +120,
G (T) <[1/5 (T-T _min )]-4, and the image is too low-gloss and a high-definition image cannot be obtained.

In the invention, 100,000 ≦ Mw ≦
The reason why the above effect is obtained by including 1,500,000 high molecular weight components in the binder resin is as described above, and the release agent in the toner composition is the above high molecular weight components. When the toner image is fixed by the heating means, the releasing agent melts into the frayed polymer chains that have started to melt to some extent when the toner image is fixed by the heating means, and as a result, fixing starts. 3 from the point
This is because the plasticizing effect of the high molecular weight component occurs in the fixing temperature range exceeding 0 ° C. Further, at this time, the molecular chain of the high molecular weight component whose plasticization is promoted is likely to be broken, so that the melt viscosity of the entire binder resin of the toner is also lowered, which causes the above-described glossiness behavior.

In the present invention, the amount of the above high molecular weight component added to the toner is 100 parts by weight of the binder resin.
The amount is 1 to 50 parts by weight, more preferably 3 to 30 parts by weight. If the addition amount is less than 1 part by weight, the effect of exhibiting the above specific glossiness behavior is not exhibited, and
When the addition amount exceeds 50 parts by weight, for example, in the case of a polymerization toner in which a raw material mixture is directly polymerized to obtain a toner, it not only takes time to dissolve the polymer in the monomer system, However, the granulation property also deteriorates, and a product having a wide particle size distribution is produced.

The release agent used in the toner for developing an electrostatic image of the present invention includes, for example, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax, and modified products thereof (for example, oxidation). Products, graft-treated products, etc.), higher fatty acids and metal compounds thereof, amide waxes, ester waxes and the like. Further, the amount of these releasing agents added is such that the mixture of the binder resin, the colorant, and the wax is melt-kneaded, cooled and ground, and then classified to obtain toner particles. When a toner for developing a charge image is produced, it is preferably added in an amount of 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the binder resin.

On the other hand, the electrostatic charge image development of the present invention is carried out in a toner production method in which the toner particles are directly produced by polymerizing a mixture containing at least a polymerizable monomer, a colorant and a release agent. In the case of producing a toner for use in the toner, since the polarity of the releasing agent which is usually used is lower than that of the binder resin in comparison with the case of the dry toner production method described above, a large amount of toner is present inside the toner particles in the polymerization method in an aqueous medium. Since the release agent can be easily encapsulated and a large amount of the release agent can be generally used as compared with the above dry toner manufacturing method, it is particularly effective for the offset prevention effect at the time of fixing.

When the toner for developing an electrostatic image of the present invention is produced by a polymerization toner production method for directly obtaining toner particles, 5 parts of a releasing agent are added to 100 parts by weight of a polymerizable monomer. It is desirable to use in the range of -40 parts by weight, more preferably 10-30 parts by weight. If the addition amount of the release agent is less than the respective lower limit, the offset prevention effect tends to decrease, and if it exceeds the upper limit, the blocking resistance effect decreases, and the offset resistance effect tends to be adversely affected, and the drum fusion, It is not preferable because sleeve fusion easily occurs. Furthermore,
Polymerized toner is not preferable because a toner having a wide particle size distribution tends to be produced.

As the release agent used in the present invention, the release agents having the following structural formulas are preferably used from the viewpoints of fixability and transparency.

<Structural Formula 1 of Release Agent> (A, b: an integer of 0 to 4 and a + b = 4, R1, R2: an organic group having an integer of 1 to 40 carbon atoms, the carbon number difference between R1 and R2 is 3 or more, m and n are integers from 0 to 25, and m and n are 0 at the same time.
Never be)

<Structural Formula 2 of Release Agent> (A, b: integers from 0 to 3 and 1 ≦ a + b ≦
3, R1, R2: an organic group having an integer of 1 to 40 carbon atoms, the difference in carbon number between R1 and R2 is 3 or more, R3: a hydrogen atom, an organic group having 1 or more carbon atoms. However, a
When + b = 2, one of R3 is an organic group having a carbon number of 1 or more, k: an integer of 1 to 3, m, n: an integer of 0 to 25, and m and n are 0 at the same time.
Never be)

<Structural Formula 3 of Release Agent> (A, b: integers from 0 to 4 and a + b = 4,
b ≠ 0, R1: an organic group having an integer of 1 to 40 carbon atoms, m, n: an integer of 0 to 25, and m and n are 0 at the same time.
Never be)

<Structural Formula 4 of Release Agent> (R1 and R3 are organic groups having 6 to 32 carbon atoms,
R1 and R3 may be the same or different. R2 represents an organic group having 1 to 20 carbon atoms)

<Structural Formula 5 of Release Agent> (R1, R3: an organic group having 6 to 32 carbon atoms,
R1 and R3 may or may not be the same _{as, R2: -CH 2 CH 2 OC} 6 H 4 OCH 2 CH 2 -, or _{- (CH (CH 3) CH} 2 O) -C 6 H 4 C (CH ₃ ) ₂ C ₆ H ₄
-(OCH ₂ CHCH ₃ ) _n- having these modified bisphenol skeletons, or-
(CH ₂ CH ₂ ) _n- , and n represents an integer of 1 to 10)

More specifically, the following releasing agents can be mentioned, but the present invention is not limited thereto.

Release agent 1 CH ₃ (CH ₂ ) ₂₀ COO (CH ₂ ) ₂₁ CH ₃

Release agent 2 CH ₃ (CH ₂ ) ₁₆ COO (CH ₂ ) ₂₁ CH ₃

Release agent 3 CH ₃ (CH ₂ ) ₃₉ COO (CH ₂ ) ₁₇ CH ₃

Release agent 4 CH ₃ (CH ₂ ) ₂₀ COO (CH ₂ ) ₁₇ CH ₃

Release agent 5

Release agent 6

Release agent 7

Release agent 8

Release agent 9

Release agent 10

Release agent 11

Release agent 12

In the present invention, the molecular weight distribution of the releasing agent as described above is measured by GPC under the following conditions. -Apparatus: GPC-150C (manufactured by Waters) -Column: GMH-HT 30 cm 2 (manufactured by Tosoh Corporation) -Temperature: 135 ° C-Solvent: o-dichlorobenzene (0.1% ionol added) -Flow rate: 1.0 ml / min-Sample: 0.45 ml of 0.15% sample is injected. The molecular weight distribution is measured under the above conditions. When calculating the molecular weight of the sample, a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is calculated. In addition, Mark-
It is calculated by polystyrene conversion using a conversion formula derived from the Houwink viscosity formula.

The weight average molecular weight (Mw) of the above-mentioned releasing agent used in the present invention is 350 or more and 4,000 or less,
The number average molecular weight (Mn) is preferably 200 or more and 4,000 or less, and more preferably Mw is 400 or more and 3,500 or less and Mn is 250 or more and 3,500 or less. Mw is less than 350, Mn is 2
If it is less than 00, the blocking resistance of the toner is significantly deteriorated, which is not preferable. Also, Mw is 4,000,
When Mn exceeds 4,000, the crystallinity of the release agent itself is developed and the transparency of OHT images and the like is significantly deteriorated, which is not preferable.

The melting point of the above releasing agent used in the present invention is preferably in the range of 30 to 150 ° C, more preferably 50 to 90 ° C. If the melting point is lower than 30 ° C., the blocking resistance of the toner, the prevention of sleeve contamination when copying a large number of sheets, and the prevention of contamination of the photosensitive member are likely to deteriorate, which is not preferable. If the melting point is higher than 150 ° C., excessive energy is required for uniform mixing with the binder resin in the toner production method by the pulverization method, and on the other hand, in the toner production method by the polymerization method, the use of the high boiling point solvent is required. In addition, a pressure-resistant reaction vessel under high pressure is required, which makes the apparatus extremely complicated, which is not preferable.

The solubility parameter (SP) value of the release agent used in the toner for developing an electrostatic image of the present invention is determined by the method of Fedors [Poly] which utilizes the chemical conversion of atomic groups.
m. Eng. Sci. , 14 (2) 147 (197)
4)] is used. The SP value of the release agent used in the present invention obtained by such a method is preferably in the range of 7.6 to 9.7. A release agent having an SP value of less than 7.6 has a poor compatibility with the binder resin used, and as a result, it is difficult to obtain a good dispersion in the binder resin. Is easily adhered to the developing sleeve, and the charge amount of the toner easily changes, which is not preferable. Further, background fog and density fluctuations during toner replenishment are likely to occur. In the present invention, the SP value is 9.
When a release agent exceeding 7 is used, blocking between toner particles tends to occur when the toner is stored for a long period of time. Further, since the compatibility with the binder resin is too good, it is difficult to form a sufficient release layer between the fixing member and the binder resin layer of the toner during fixing, and the offset phenomenon is likely to occur, which is not preferable.

The melt viscosity of the release agent used in the present invention is
A method of measuring with VP-500 manufactured by HAAKE using a cone plate type rotor (PK-1) at 135 ° C. may be mentioned. The melt viscosity of the release agent at 135 ° C is
Preferably 1 to 300 cPs, more preferably 3 to 50
The range is cPs. When the melt viscosity is lower than 1 cPs, the sleeve is apt to be contaminated by mechanical shearing force when the toner layer is thinly coated on the sleeve by a blade or the like in the non-magnetic one-component developing method. Further, also in the two-component developing method, when the toner is developed using the carrier, damage is likely to occur due to a shearing force between the toner and the carrier, so that the external additive is buried and the toner is crushed. Three
When the melt viscosity is more than 00 cPs, the viscosity of the dispersoid is too high when the toner is produced by using the polymerization method, and it is not easy to obtain a toner having a fine particle diameter having a uniform particle diameter. It tends to be a toner with a wide distribution.

The hardness of the release agent used in the present invention can be measured by, for example, Shimadzu dynamic ultra-fine hardness tester (DUH-).
200) and the like. As a measurement condition, using a Vickers indenter, under a load of 0.5 g,
The Vickers hardness is obtained by analyzing the dents on the sample held for 12 seconds after being displaced by 10 μm at a load speed of 9.67 mg / sec. As the sample, a pre-melted sample is molded into a cylindrical shape having a thickness of 5 mm using a mold having a diameter of 20 mmφ. The hardness of the resulting release agent used in the present invention is preferably 0.3 to 5.0, more preferably 0.5 to 3.0.

The toner containing a release agent having a Vickers hardness of less than 0.3 is easily crushed at the cleaning portion of the copying machine in the case of copying a large number of sheets, and toner fusion is likely to occur on the drum surface. Black streaks tend to occur on the image, which is not preferable. Further, when multiple image samples are stored in piles, the toner is transferred to the back surface, so-called show-through easily occurs, which is not preferable. Vickers hardness is 5.0
A toner containing a release agent exceeding 5 is not preferable because a fixing device used during heat fixing requires an excessive pressing force, and the fixing device needs to have an excessive strength design. When a fixing device with a normal pressing force is used, the offset resistance tends to decrease, which is not preferable.

Examples of the method for producing the release agent preferably used in the present invention include, for example, a synthesis method by an oxidation reaction, a synthesis from a carboxylic acid and its derivative, an ester group introduction reaction represented by a Michael addition reaction, and a carboxylic acid compound. It can be produced by a method utilizing a dehydration condensation reaction from a phenol compound with an alcohol compound, a reaction from an acid halide with an alcohol compound, a transesterification reaction, or the like. As the catalyst, general acid catalysts and alkaline catalysts used in the esterification reaction such as zinc acetate and titanium compounds are used. After that, it may be highly purified by a recrystallization method, a distillation method or the like.

Examples of the binder resin used in the electrostatic image developing toner of the present invention include the following resins. For example, polystyrene, poly-p-chlorostyrene, homopolymers of styrene such as polyvinyltoluene and its substitution products; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers. , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrene-based copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol Resin, natural resin modified Nord resins, natural resin modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane, polyamide resins, furan resins, epoxy resins,
Xylene resin, polyvinyl butyral, tempen resin,
Examples include coumarone indene resin and petroleum-based resin. Among them, a particularly preferable binder resin is a styrene-based copolymer or a polyester resin.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate,
Duplex such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. Carboxylic acid having a bond or a substituted product thereof; Dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like; a substituted product thereof; vinyl chloride, vinyl acetate, vinyl benzoate, etc. Such as vinyl esters; ethylene-based olefins such as ethylene, propylene and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone;
Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; these vinyl monomers may be used alone or in combination of two or more.

The weight average molecular weight Mw used in the toner for developing an electrostatic image of the present invention is 100,000≤Mw≤.
As the high molecular weight component of 1,500,000, the above-mentioned various materials can be used. The number average molecular weight of the THF-soluble component of the binder resin used in the present invention is 3,000.
It is preferably 0 to 1,000,000. Further, the styrene-based polymer or the styrene-based copolymer may be crosslinked, or may be a mixed resin thereof.

The cross-linking agent for the binder resin is mainly 2
A compound having one or more polymerizable double bonds may be used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate,
A carboxylic acid ester having two double bonds such as 1,3-butadiol dimethacrylate; a divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and a compound having three or more vinyl groups; These are used alone or as a mixture. The addition amount is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

The electrostatic image developing toner of the present invention may contain a charge control agent. Examples of the charge control agent that controls the toner to be negatively charged include the following substances. For example,
Organic metal compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Further, urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-
Examples thereof include methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, nonmetal carboxylic acid compounds, and the like.

Further, there are the following substances as charge control agents for controlling the toner to be positively charged. For example, modified products of nigrosine and fatty acid metal salts, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like 4
Primary ammonium salts, onium salts such as phosphonium salts which are analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdenum) Acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; dibutyltin oxide,
Diorgano tin oxides such as dioctyl tin oxide and dicyclohexyl tin oxide; diorgano tin borates such as dibutyl tin borate, dioctyl tin borate and dicyclohexyl tin borate; these can be used alone or in combination of two or more.
Of these, charge control agents such as nigrosine type and quaternary ammonium salts are particularly preferably used.

These charge control agents are preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the resin component in the toner. . Examples of the colorant contained in the toner for developing an electrostatic image of the present invention include black pigments such as carbon black, aniline black and acetylene black.

Examples of magenta pigments include red lead yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, brilliant carmine 3
B, carmine 6B, manganese purple, fast violet B, methyl violet lake, rhodamine lake, alizakun lake, red iron oxide, quinacridone, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1, 52, 53, 54, 55, 57, 58, 60, 6
3, 64, 68, 81, 83, 87, 88, 89, 9
0, 112, 114, 122, 123, 163, 20
2, 206, 207, 209; C.I. I. Pigment violet 19, C.I. I. Violet 1, 2, 10, 1
3, 15, 23, 29, 35 and the like.

Examples of cyan pigments include C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bad Blue 6, C.I. I. Acid Blue 45, Indanthrene Blue, Navy Blue, Cobalt Blue, Alkali Blue Lake, Biclear Blue Lake, Phthalocyanine Blue, Earth Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final yellow green G
Etc.

Examples of yellow pigments include naphthol yellow, high the yellow, yellow lead, cadmium yellow, mithral fast yellow, navel yellow, permanent yellow NCG, tartrazine lake, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, 97, 120, 127, 174, 17
6, 180, 191, C.I. I. Bad Yellow 1, 3,
20 etc. are mentioned. These pigments are used in an amount necessary for maintaining the optical density of the fixed image, but in the present invention, 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, relative to 100 parts by weight of the resin. It is desirable to add in the range of parts by weight.

Examples of the dye used as the colorant in the present invention include the followings. Examples of magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Disperse Violet 1, C.I. I. Basic Red 1, 2,
9, 12, 13, 14, 15, 17, 18, 22, 2
3, 24, 27, 29, 32, 34, 35, 36, 3
7, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25,2
6, 27, 28, C.I. I. Direct Red 1, 4,
C. I. Acid Red 1, C.I. I. Mordant Red 30 and the like can be mentioned.

Examples of cyan dyes include C.I. I. Direct Blue 1, 2, C.I. I. Acid Blue 9, 15,
C. I. Basic Blue 3, 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic greens 4, 6 and the like can be mentioned. These dyes are preferably added in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the resin.

Further, the electrostatic image developing toner of the present invention is
Further, it may contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material can also serve as a coloring agent. In the present invention, examples of the magnetic material contained in the magnetic toner include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel; or aluminum, cobalt and copper of these metals;
Examples thereof include alloys of metals such as lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

The average particle size of these ferromagnetic materials is preferably 2 μm or less, preferably about 0.1 to 0.5 μm. The amount of these magnetic materials contained in the toner is about 20 to 200 parts by weight with respect to 100 parts by weight of the resin component.
Particularly preferably, it is desirable to use it in the range of 40 to 150 parts by weight. As for the physical properties of the magnetic material used in the present invention, the magnetic characteristics at the application of 10 kOe are the coercive force (H _c ).
20 to 300 Oe, saturation magnetization (σ _s ) 50 to 200 em
It is preferable to use those having u / g and remanent magnetization (σ _r ) of 2 to 20 emu / g.

Further, various additives added for the purpose of imparting toner characteristics have a volume average particle size of the toner particles of 1 / n from the viewpoint of durability in the toner or when added to the toner.
The particle size is preferably 5 or less. Here, the particle size of the additive means the average particle size thereof obtained by observing the surface of the toner particles with an electron microscope. Examples of additives for the purpose of imparting these characteristics include the following.

Examples of the fluidity-imparting agent include metal oxides such as silicon oxide, aluminum oxide and titanium oxide, carbon black and carbon fluoride. It is more preferable to use a hydrophobized material. Examples of the abrasive include metal oxides such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide and chromium oxide, nitrides such as silicon nitride, carbides such as silicon carbide, calcium sulfate, barium sulfate and calcium carbonate. And the like.

Examples of the lubricant include vinylidene fluoride, polytetrafluoroethylene and other fluorine-based resin powders, zinc stearate, calcium stearate and other fatty acid metal salts, and the like. Examples of the charge control agent include metal oxides such as tin oxide, titanium oxide, zinc oxide, silicon oxide and aluminum oxide, and carbon black. These additives are 0.1 to 100 parts by weight of toner particles.
It is used in an amount of 10 parts by weight, preferably 0.1 to 5 parts by weight. These additives may be used alone or in combination.

The toner for developing an electrostatic image of the present invention is usually
It can be used as either a one-component developer or a two-component developer. For example, in the case of a magnetic toner in which a magnetic material is contained in the toner as the one-component developer, there is a method of transporting and charging the magnetic toner by using a magnet incorporated in the developing sleeve.
When a non-magnetic toner containing no magnetic material is used, there is a method in which a blade and a fur brush are used to forcibly triboelectrically charge the developing sleeve, and the toner is adhered onto the developing sleeve for conveyance.

On the other hand, when used as a commonly used two-component type developer, a carrier is used together with the toner of the present invention, and the carrier is used as a developer. The carrier used in the present invention is not particularly limited, but is mainly composed of a single or composite ferrite state composed of iron, copper, zinc, nickel, cobalt, manganese, and chromium elements. From the viewpoint that saturation magnetization and electric resistance can be controlled over a wide range, the carrier shape is also important.For example, spherical, flat, or irregular shape is selected, and further, the fine structure of the carrier surface state, for example, surface irregularity It is also preferable to control

In general, a method is used in which carrier core particles are previously formed by firing and granulating the above-mentioned inorganic oxide, and then the resin is coated with a resin. From the viewpoint of reducing the load, a method of kneading the inorganic oxide and the resin, pulverizing and classifying the resin to obtain a low-density dispersed carrier, and further, kneading the inorganic oxide and the monomer directly in an aqueous medium Turbid polymerization
It is also possible to use a method of obtaining a polymerized carrier for obtaining a true spherical dispersion carrier. A system in which the surface of the carrier is coated with a resin or the like is particularly preferable. 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 and applying the coating material to adhere it to a carrier, a method of simply mixing with a powder, or the like can be applied.

The substance adhered to the surface of the carrier varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metallic compound of ditertiary butyl salicylic acid, Styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin,
It is suitable to use a basic dye and its lake, fine silica powder, fine alumina powder, etc. alone or in combination, but the invention is not limited thereto.

The treatment amount of the above compounds is generally 0.1 to 30% by weight, preferably 0.1% by weight, based on the total amount of the carrier.
It is preferably in the range of 5 to 20% by weight. It is preferable that the carrier has an average particle diameter of 10 to 100 μm, preferably 20 to 50 μm.

A particularly preferred embodiment of the carrier is ferrite, the surface of which is a combination of resins such as fluororesin and styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin; polytetrafluoroethylene and styrene. -Methyl methacrylate resin; Fluorine-based copolymer and styrene-based copolymer;
90:10 to 20:80, preferably 70:30 to
A mixture of 30:70, a silicone resin or the like, 0.01 to 5% by weight, preferably 0.1 to 1
The coated ferrite carrier having the above-mentioned average particle diameter after being coated by weight% may be mentioned. Examples of the fluorine-based copolymer include vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10), and examples of the styrene-based copolymer include styrene--2-ethylhexyl acrylate (20 : 80-80: 2
0), styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60: 5-30: 30-10-5)
0) can be mentioned.

The coated ferrite carrier as described above is
The particle size distribution is sharp, and the toner of the present invention has a preferable triboelectrification property, and further has an effect of improving electrophotographic characteristics. When a two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is 2 to 15% by weight, preferably 4 to 1% by weight as the toner concentration in the developer.
At 3% by weight, good results are usually obtained. If the toner concentration is 2% by weight or less, the image density is low and it becomes unpractical, and if it is 15% by weight or more, fog and scattering in the machine are increased, and the useful life of the developer is shortened, which is not preferable.

Further, the carrier used in the present invention preferably has the following magnetic characteristics. That is, the magnetization intensity (σ ₁₀₀₀ ) at 1000 Oe after magnetic saturation is required to be 30 to 300 emu / g. In order to achieve higher image quality, it is preferably 100 to 250 emu / g.
If it is higher than 300 emu / g, it becomes difficult to obtain a high-quality toner image. Further, if it is less than 30 emu / g, the magnetic restraining force is also reduced and carrier adhesion is likely to occur.

As for the carrier shape, SF1 indicating the degree of roundness is 180 or less, and SF2 indicating the degree of unevenness is 25.
It is preferably 0 or less. The values of SF1 and SF2 are defined by the following formulas, and LUZEX II manufactured by Nireco
Measured at I. SF1 = [(maximum length of carrier) ² / area] × (π / 4) SF2 = [(peripheral length of carrier) ² / area] × (1/4)
π)

When the toner for developing an electrostatic charge image of the present invention is produced by a pulverization method, the pulverized toner is produced by first forming a binder resin, a high molecular weight component, a release agent, and a pigment or dye as a colorant. According to the above, a magnetic material, a charge control agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then melt-kneaded by using a heat kneader such as a heating roll, a kneader or an extruder. A metal compound, a pigment, a dye, and a magnetic material are dispersed or dissolved in a resin in which the resins are mutually compatible, and after cooling and solidification, pulverization and classification are performed to obtain the toner of the present invention. Thereafter, if necessary, the desired additive can be externally added by sufficiently mixing it with a mixer such as a Henschel mixer to obtain the toner for developing an electrostatic image according to the present invention.

The polymerized toner obtained by directly polymerizing the toner for developing an electrostatic charge image of the present invention is manufactured by the following method. That is, in the polymerizable monomer, a high molecular weight component, a release agent, a colorant, if necessary, a charge control agent,
A polymerization initiator, and other additives are added, and the monomer system that is uniformly dissolved or dispersed by a homogenizer or an ultrasonic disperser is stirred in a dispersion medium containing a dispersion stabilizer or an emulsifier or a homomixer. Disperse with a homogenizer and granulate. After that, stirring may be performed to such an extent that the dispersion stabilizer acts to maintain the monomer-based particle state and prevents the precipitation of the monomer-based particles. The polymerization temperature is set to 40 ° C. or higher, generally 50 to 90 ° C. to carry out the polymerization. Further, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers, by-products, etc. which may cause odor during toner fixing, the latter half of the reaction or the end of the reaction. The aqueous medium may be partially distilled off later. After the completion of the reaction, the produced toner particles are washed, collected by filtration and dried. In the suspension polymerization method, usually, 300 to 3 parts by weight of water is added to 100 parts by weight of the monomer system.
It is preferred to use 000 parts by weight as the dispersion medium.

The particle size of the toner is preferably such that the weight average particle size in Coulter Counter Model TA-II (manufactured by Coulter Electronics Co.) is 0.1 to 12 μm, and the particle size distribution has a variation coefficient in the weight average size of 8 to 40%. , And the shape has an SF1 value of 10 indicating the degree of roundness.
0 <SF1 <150, the SF2 value representing the degree of unevenness is
It is preferable that 100 <SF2 <200.

Examples of the polymerizable monomer used when directly obtaining the toner by the polymerization method include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and p-methoxy. Styrene-based monomers such as styrene and p-ethylstyrene; methyl acrylate, ethyl acrylate, acrylate n-butyl, isobutyl acrylate, acrylate n-propyl, acrylate n-
Octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, -2-acrylic acid
Acrylic esters such as chloroethyl and phenyl acrylate; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, methacryl Methacrylic acid esters such as 2-ethylhexyl acid acid, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile,
Examples include monomers such as acrylamide. These monomers may be used alone or in combination.

Further, a polymer or copolymer having a polar group may be added as an additive to the monomer of the polymerization toner used in the present invention. The polar polymers and copolymers that can be used in this case include the following. For example, polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; copolymers with styrene-unsaturated carboxylic acid esters and the like, nitrile monomers such as acrylonitrile;
Halogen-containing monomers such as vinyl chloride; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; other polymers such as unsaturated dibasic acids, unsaturated dibasic acid anhydrides, nitro monomers and styrene Examples thereof include copolymers with system monomers and the like, polyesters, epoxy resins and the like.

The polymerization initiator used at this time is
For example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′ -Azobis-4-methoxy-2,
Azo-based or diazo-based polymerization initiators such as 4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, Dixyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl oxide,
2,2-bis (4,4-t-butylperoxycyclohexyl) propane, tris- (t-butylperoxy)
Peroxide-based initiators such as triazine and polymeric initiators having a peroxide in the side chain; persulfates such as potassium persulfate and ammonium persulfate; hydrogen peroxide and the like are used.

The above-mentioned polymerization initiator is preferably added in an amount of 0.5 to 20 parts by weight of the polymerizable monomer, and may be used alone or in combination. Known crosslinking agents and chain transfer agents may be added, and the preferable addition amount is 0.001 to 15 parts by weight.

In the present invention, emulsion polymerization, dispersion polymerization,
A polymerization toner is produced by a suspension polymerization, a seed polymerization, a polymerization method using salting out, or the like, and any appropriate stabilizer is used as a dispersion medium used at this time. As the stabilizer in this case, for example, as the inorganic compound, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate,
Examples thereof include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch, polyacrylamide, polyethylene oxide, poly (hydroxystearic acid-g-methacrylic acid). Methyl-eu-methacrylic acid) copolymers and nonionic or ionic surfactants are used.

When the emulsion polymerization method is used, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, and a nonionic surfactant are used as stabilizers. It is preferable to use 0.2 to 30 parts by weight of these stabilizers per 100 parts by weight of the polymerizable monomer.
When an inorganic compound is used among these stabilizers, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be formed in a dispersion medium and used.

Further, because of the fine dispersion of these stabilizers,
0.001-0.1 parts by weight of surfactant may be used. This promotes the desired action of the above dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, and stearin. Examples thereof include potassium acidate and calcium oleate.

As the colorant used in the polymerization toner in the present invention, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant.
It is preferably used after being subjected to surface modification, for example, a hydrophobic treatment that does not inhibit polymerization. In particular, since many dyes and carbon black have a polymerization inhibitory property, caution is required when using them. A preferred method for surface-treating a dye system is a method of preliminarily polymerizing a polymerizable monomer in the presence of these dyes, and the obtained colored polymer is added to the monomer system. In addition to carbon black, the carbon black may be treated with a substance that reacts with the surface functional groups of carbon black, such as polyorganosiloxane.

In the present invention, the evaluation method of toner fixability, offset resistance, and color mixture area of the image recorded matter is as follows. First, a suitable external additive is added to the toner of the present invention in an appropriate amount to obtain a developer. An unfixed image of the obtained developer is produced by a commercially available copying machine. At this time, when the toner is black toner, the fixing property and the offset property are evaluated by a 40 mmφ heat roller external fixing device having no oil application function. In the case of mono-color toner or full-color toner, there is no oil application function 4
In addition to the 0 mmφ heat roller external fixing device, a 40 mmφ heat roller external fixing device was used to apply a small amount of oil evenly to the fixing roller (for example, oil amount 0.02 g / A4 size). The fixed image for the evaluation of the transparency, the transparency and the image is obtained.

At this time, as the roller material, a fluorine-based material is used for both the upper and lower parts. As for the fixing conditions, when the transfer material is SK paper (manufactured by Nippon Paper Industries Co., Ltd.), the nip is 6.5 mm and the process speed is 105 mm.
/ Sec and the transfer material is an OHT sheet (CG3300 /
(Manufactured by 3M), the nip is 6.5 mm, the process speed is 35 mm / sec, and the temperature is adjusted every 5 ° C. within a temperature range of 100 to 250 ° C.

Fixing property The fixing property is obtained by applying a load of 50 g / cm ² to a fixed image (including an image subjected to low-temperature offset), and applying a sillbon paper (Lenz
Cleaning Paper "dasper"
(R) ”(Ozu Paper Co., Ltd.) is rubbed, and the temperature at which the density decrease rate before and after rubbing is less than 10% is the fixing start point.

Offset resistance For offset resistance, the temperature at which offset does not appear visually is taken as the low temperature offset start point, and the highest temperature without offset is taken as the high temperature offset end point.

Glossiness Furthermore, the gloss value was measured for the image in the non-offset area by using a specular glossiness measuring instrument PG-3D (manufactured by Nippon Color Co., Ltd.). Tables 1 and 2 show the low temperature offset starting point (T
_low ), minimum fixing temperature T _min , T _min +30, high temperature offset end point (maximum fixing temperature T _max ), fixing temperature TG _max showing the maximum gloss value, G (T _min ), G (T _min +30),
The values of G (T _max ), G (TG _max ), non-offset region, transmittance, and haze are shown.

[0094]

The present invention will be described in more detail below with reference to examples. The present invention is not limited to the embodiments.

Example 1 500 g of a 0.1 M Na ₃ PO ₄ aqueous solution was added to 750 g of ion-exchanged water and heated to 60 ° C., and then a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) was used. 1,000 rp
It was stirred at m. Add 1.0M-CaCl ₂ solution 7
5 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . Meanwhile, styrene 170 g, n-butyl acrylate 30 g, copper phthalocyanine pigment 18 g, di-t-butyl salicylate metal compound 2 g, release agent (1) 40 g, high molecular weight resin (weight average molecular weight Mw = 600,000) 24 g The formulation was heated to 60 ° C. and uniformly dissolved and dispersed at 10,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo). A polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (10 g) was dissolved in this to prepare a polymerizable monomer composition. The polymerizable monomer composition was added to the aqueous medium, and the temperature was 12,000 r with a TK homomixer at 60 ° C. in an N ₂ atmosphere.
The polymerizable monomer composition was granulated by stirring at pm for 12 minutes. Then, while stirring at 500 rpm using a paddle stirring blade, the temperature was raised to 70 ° C. and the reaction was carried out for 15 hours. After the completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then the polymer was filtered, washed with water and dried to obtain polymer particles.
To 100 parts by mass of the obtained particles, 1.2 parts by mass of hydrophobic titanium oxide fine particles having a BET specific surface area of 100 m ² / g was externally added to obtain a suspension-polymerized toner. The weight average particle diameter of the obtained cyan toner is 6.4 μm.
Met. To 6 parts by mass of this toner, 94 parts by weight of a ferrite carrier coated with a silicone resin was mixed to obtain a developer. Using this developer, a commercially available electrophotographic copying machine CLC700 (manufactured by Canon Inc.) was used to produce an unfixed image, and the fixability and OHT transparency were evaluated. The results are shown in Table 1.

Example 2 styrene 169 g n-butyl acrylate 31 g copper phthalocyanine pigment 22 g di-t-butyl salicylate metal compound 2 g mold release agent (5) 40 g high molecular weight resin (weight average molecular weight Mw = 350, 000) 20 g The same procedure as in Example 1 was carried out with the above formulation to obtain a polymerizable composition, and then a developer was obtained. Using the developer, the fixability and the OHT transparency were evaluated in the same manner as in Example 1. The weight average particle diameter of the obtained magenta toner was 6.5 μm. The results are shown in Table 1.

Example 3 styrene 171 g n-butyl acrylate 29 g copper phthalocyanine pigment 20 g di-t-butyl salicylate metal compound 4 g mold release agent (7) 40 g high molecular weight resin (weight average molecular weight Mw = 120, 000) 10 g The same procedure as in Example 1 was carried out with the above formulation to obtain a polymerizable composition, and then a developer was obtained. Using the developer, the fixability and the OHT transparency were evaluated in the same manner as in Example 1. The weight average particle diameter of the obtained yellow toner was 6.7 μm. The results are shown in Table 1.

Example 4 Styrene 172 g n-Butyl acrylate 28 g Grafted carbon black pigment 17 g Di-t-butyl salicylate metal compound 3 g Paraffin wax 40 g High molecular weight resin (weight average molecular weight Mw = 880,000) 22 g The same operation as in Example 1 was carried out with the above formulation to obtain a polymerizable composition and then a developer. Using the developer, the fixability and the OHT transparency were evaluated in the same manner as in Example 1. The weight average particle diameter of the obtained black toner was 6.2 μm. The results are shown in Table 1.

Example 5 styrene 175 g n-butyl acrylate 25 g magnetic iron oxide (average particle size = 0.21 μm, saturation magnetization = 70 emu / g, remanent magnetization = 10 emu / g, coercive force = 1 under 10 kOe) , 10 Oe) 95 g-di-t-butylsalicylic acid metal compound 3 g-Release agent (3) 40 g-High molecular weight resin (weight average molecular weight Mw = 780,000) 34 g The same procedure as in Example 1 was carried out with the above formulation. After obtaining the polymerizable composition, a developer was obtained. The fixability was evaluated using the developer. The weight average particle diameter of the obtained magnetic toner was 6.6 μm, and a commercially available electrophotographic copying machine NP8582 (manufactured by Canon Inc.) was used as an evaluation machine for producing an unfixed image.
It was adopted. The results are shown in Table 1.

Example 6 Polyester resin 1,000 g (bisphenol A diol-terephthalic acid-dodecenyl succinic acid-trimethyl acid condensate; molar ratio = 50: 40: 5: 5) magnetic iron oxide (average particle size) = 0.24 μm, under 10 kOe, saturation magnetization = 55 emu / g, remanent magnetization = 10 emu / g, coercive force = 1,20 Oe) 750 g-di-t-butylsalicylic acid metal compound 20 g-Polyethylene wax (PE190 / Sanyo Chemical Co., Ltd.) 50 g High molecular weight resin (weight average molecular weight Mw = 450,000) 330 g The above materials were premixed and then melt-kneaded by a twin-screw kneading extruder set to 130 ° C. The kneaded product was cooled, coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified by an air classifier to obtain a toner having a weight average particle diameter of 6.7 μm. 100 parts by mass of this toner and 1.2 parts by mass of the hydrophobic titanium oxide fine powder were mixed (externally added) to obtain a toner having the hydrophobic titanium oxide fine powder on the toner particle surface. Using this developer, a commercially available electrophotographic copying machine NP-8582 (manufactured by Canon Inc.) was used to produce an unfixed image, and the fixing property was evaluated by the same evaluation method as in Example 1. The results are shown in Table 1.

Example 7 Polyester resin 1,000 g (bisphenol A diol-terephthalic acid-dodecenyl succinic acid-trimellitic acid condensate; molar ratio = 50: 40: 5: 5) Copper phthalocyanine pigment 40 g Di- t-Butylsalicylic acid metal compound 20 g-Release agent (2) 50 g-High molecular weight resin (weight average molecular weight Mw = 470,000) 150 g After mixing the above materials, a developer was obtained in the same manner as in Example 6, The fixability and OHT transparency were evaluated. The weight average particle diameter of the obtained cyan toner was 6.2 μm. The results are shown in Table 1.

Example 8 styrene 165 g n-butyl acrylate 34 g copper phthalocyanine pigment 22 g di-t-butyl salicylate metal compound 3 g mold release agent (8) 40 g high molecular weight resin (weight average molecular weight Mw = 350, 000) 20 g The same procedure as in Example 1 was carried out with the above formulation to obtain a polymerizable composition, and then a developer was obtained. Using the developer, the fixability and the OHT transparency were evaluated in the same manner as in Example 1. The weight average particle diameter of the obtained magenta toner was 6.5 μm. The results are shown in Table 1.

In the same manner as in Example 1, magenta, yellow, and black toners were prepared from quinacridone pigment, disazo yellow pigment, and graft-treated carbon black pigment, and four-color toner of cyan toner of Example 1 was prepared. When a CLC700 (manufactured by Canon Inc.), which is a commercially available electrophotographic copying machine, was used to output a graphic full-color image, it was possible to obtain a low glossiness, easy-to-read, and comfortable feeling. The full-color OHT image at this time was excellent in transparency and high in quality.

Table 1

Comparative Example 1 To 740 g of ion-exchanged water, 490 g of a 0.1 M Na ₃ PO ₄ aqueous solution was added, and after heating to 60 ° C., 12 using a TK homomixer (manufactured by Tokushu Kika Kogyo). 1,000 rp
It was stirred at m. Add 1.0M-CaCl ₂ solution 7
7 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . Meanwhile, styrene 170 g, n-butyl acrylate 30 g, copper phthalocyanine pigment 17 g, di-t-butyl salicylate metal compound 2 g, release agent (12) 40 g, high molecular weight resin (weight average molecular weight Mw = 30,000) 36 g

The above formulation was heated to 60 ° C., and a TK homomixer (made by Tokushu Kika Kogyo) was used to obtain 10,000 rp.
m was uniformly dissolved and dispersed. In addition to this, the polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
0 g was dissolved to prepare a polymerizable monomer composition. The
The above polymerizable monomer composition is put into an aqueous medium, and 60
℃, N ₂ atmosphere, TK homomixer 1
The polymerizable monomer composition was granulated by stirring at 2,000 rpm for 12 minutes. After that, 500r using a paddle stirring blade
While stirring at pm, the temperature was raised to 70 ° C. and the reaction was carried out for 15 hours. After the completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then the polymer was filtered, washed with water and dried to obtain polymer particles. BET for 100 parts by mass of the obtained particles
1.2 parts by mass of hydrophobic titanium oxide fine particles having a specific surface area of 100 m ² / g according to the method was externally added to obtain a suspension-polymerized toner. The weight average particle diameter of the obtained cyan toner was 6.4 μm. To 6 parts by mass of this toner, 94 parts by weight of a ferrite carrier coated with a silicone resin was mixed to obtain a developer. Using this developer, an unfixed image was produced with a commercially available electrophotographic copying machine CLC700 (manufactured by Canon Inc.), and the fixability and OHT transparency were evaluated by the above methods. The results are shown in Table 2.

Comparative Example 2 High molecular weight resin (weight average molecular weight Mw = 1,510,000) 34 g Other than this, the weight average particle diameter was 6.
Commercially available electrophotographic copying machine C with 7 μm cyan toner
An unfixed image was produced by using LC700 (manufactured by Canon Inc.), and the fixability and the OHT transparency were evaluated by the above methods. The results are shown in Table 2.

Comparative Example 3 High molecular weight resin (weight average molecular weight Mw = 490,000) 102 g Other than this, in the same manner as in Example 6 except that the weight average particle size was 6.
3 μm black toner was obtained. Evaluation was performed in the same manner as in Example 6. The results are shown in Table 2.

Comparative Example 4 styrene 172 g n-butyl acrylate 28 g copper phthalocyanine pigment 21 g di-t-butyl salicylate metal compound 4 g mold release agent (1) 40 g high molecular weight resin (weight average molecular weight Mw = 40, 000) 1g.2,2'-azobis (2,4-dimethylvaleronitrile) 6g After obtaining the polymerizable composition as described above, a developer was obtained in the same manner as in Comparative Example 4 to obtain fixability, OHT. The transparency was evaluated.
The weight average particle diameter of the obtained magenta toner is 6.
It was 5 μm. The results are shown in Table 2.

Comparative Example 5 170 g of styrene 30 g of n-butyl acrylate Magnetic iron oxide (average particle size = 0.21 μm, 10 kOe, saturation magnetization = 70 emu / g, remanent magnetization = 10 emu / g, coercive force = 1 , 10 Oe) 98 g-di-t-butylsalicylic acid metal compound 3 g-Release agent (10) 40 g-High molecular weight resin (weight average molecular weight Mw = 1,800,000) 30 g The above-mentioned polymerizable composition was obtained. Thereafter, a developer was obtained in the same manner as in Comparative Example 1 and the fixability was evaluated. The weight average particle size of the obtained magnetic toner was 6.6 μm, and a commercially available electrophotographic copying machine NP was used as an evaluation machine for producing an unfixed image.
8582 (manufactured by Canon Inc.) was adopted. The results are shown in Table 2.
It was shown to.

Comparative Example 6 Polyester resin 1,000 g (bisphenol A diol-terephthalic acid-dodecenyl succinic acid-trimellitic acid condensate; molar ratio = 50: 40: 5: 5) Magnetic iron oxide (average particle size) = 0.24 μm, under 10 kOe, saturation magnetization = 55 emu / g, remanent magnetization = 10 emu / g, coercive force = 1,20 Oe) 750 g-di-t-butylsalicylic acid metal compound 20 g-Polyethylene wax (PE130 / Sanyo Chemical Co., Ltd.) 50 g High molecular weight resin (weight average molecular weight Mw = 130,000) 60 g The above materials were premixed and then melt-kneaded by a twin-screw kneading extruder set at 130 ° C. The kneaded product was cooled, coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified by an air classifier to obtain a toner having a weight average particle diameter of 6.7 μm. 100 parts by mass of this toner and 1.2 parts by mass of the hydrophobic titanium oxide fine powder were mixed (externally added) to obtain a toner having the hydrophobic titanium oxide fine powder on the toner particle surface. Using this developer, a commercially available electrophotographic copying machine NP-8582 (manufactured by Canon Inc.) was used to produce an unfixed image and the fixability was evaluated. The results are shown in Table 2.

Comparative Example 7 Polyester resin 1,000 g (bisphenol A diol-terephthalic acid-dodecenyl succinic acid-trimellitic acid condensate; molar ratio = 50: 40: 5: 5) Copper phthalocyanine pigment 45 g Di- t-Butylsalicylic acid metal compound 20 g-Release agent (1) 50 g-High molecular weight resin (weight average molecular weight Mw = 50,000) 18 g After mixing with a polymerizable composition, the same procedure as in Comparative Example 6 was performed. After obtaining the agent, the fixability and OHT transparency were evaluated.
The weight average particle diameter of the obtained cyan toner is 6.2.
μm. The results are shown in Table 2.

Table 2

[0114]

As described above, according to the present invention, an image having no discomfort can be obtained even in an image such as a graphic image in which a graph portion and a character portion are mixed, and the OHT
A full-color image excellent in transparency is provided. Furthermore,
According to the present invention, it is possible to perform fixing without substantially applying oil to the fixing roller.

Claims (5)

[Claims] 1. An image forming method for fixing an image recorded matter by a thermal means after forming a toner image on an image carrier with a toner containing at least a binder resin, a colorant and a release agent. When the minimum temperature at which the toner image can be fixed by the mechanical means is T _min and the maximum temperature is T _max , the toner image on the image carrier is fixed at a temperature T within this temperature range, and the image carrier is carried. Incident angle 75 to body surface
The glossiness G (T) of the image measured with incident light
Is formed so as to exhibit a glossiness behavior that satisfies the relationship of the following formula when (T, G (T)) = (T _min , 0) is assumed to be the origin. The fixing temperature T is T
Gloss G when _min ≤ T ≤ T _min +30
(T) is [(T−T _min ) / 30] + 1 ≦ G (T) ≦ [(T−T
_min ) / 5] +30 When the fixing temperature T is within the range of T _min +30 <T ≦ T _min +120, the gloss G (T) is [(T−T _min ) / 5] −4 ≦ G ( T) ≦ [7 (T−T
_min ) / 10] +15 and G (T) ≦ 50 2. An electrostatic charge image developing toner used in the image forming method according to claim 1, wherein the toner contains at least a binder resin, a colorant and a release agent. , At least a weight average molecular weight Mw of 100,000
A toner for developing an electrostatic charge image, comprising a high molecular weight component satisfying 0 ≦ Mw ≦ 1,500,000. 3. The electrostatic charge image developing according to claim 2, wherein a mixture containing at least a binder resin, a colorant and a releasing agent is melt-kneaded, cooled, pulverized and classified to prepare toner particles. toner. 4. The toner for developing an electrostatic charge image according to claim 2, wherein the toner particles are directly prepared by polymerizing a mixture containing at least a polymerizable monomer, a colorant and a release agent. 5. A color image recorded matter formed using the toner for developing an electrostatic image according to claim 2.