JP2001175031A - Electrostatic charge image developing toner, image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which does not stain even a recorded image, a high-speed image forming device which uses the toner, does not form a diffused image or the like and gives high image quality and an image forming method. SOLUTION: In the electrostatic charge image developing toner comprising a bonding resin, a colorant, a releasing agent and an electric charge controlling agent, the bonding resin is based on a vinyl copolymer containing a styrene monomer and a (meth)acrylic ester monomer in constituent units, the molecular weight distribution of the copolymer has maximum values of the distribution in the low molecular weight range of 3,000-50,000 and in the high molecular weight range of 10×104-500×104, the molecular weight P1 at which the maximum value of the low molecular weight side is present and the molecular weight P2 at which the maximum value of the high molecular weight side is present satisfy the relation of 100<=P2/P1<=300 and the polymerization reaction of the bonding resin is carried out in the presence of the releasing agent.

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 image of a heat-melt fixing type in electrophotography, electrostatic recording, electrostatic printing and the like (hereinafter sometimes simply referred to as "toner"). The present invention relates to an image forming method and an image forming apparatus.

[0002]

2. Description of the Related Art As a method for fixing a toner image to a sheet such as paper, a so-called hot-melt fixing method for fixing a toner image by melting the toner by heat is often used.

[0003] The hot-melt fixing system is roughly classified into a flash fixing system which is a non-contact fixing system, and a heat roll and heat belt fixing system which is a contact fixing system. Among them, the heat roll and heat belt fixing methods fuse the toner by bringing the heat transfer member into contact with the toner image, so high thermal efficiency can be expected.Therefore, especially for electrophotographic copying machines and printers that output images at high speed. It is valid.

However, in the fixing method using a heat roll and a heat belt, since the heat transfer member comes into direct contact with the melted toner image, a part of the toner image adheres to and transfers to the heat transfer member, and is transferred to the next fixing sheet. An offset phenomenon, which is transferred and contaminates an image, is likely to occur.

Alternatively, when the heat transfer member comes into contact with the toner image, a contact charging phenomenon occurs, causing a phenomenon in which the heat transfer member is charged. Disturbance in the image caused by electrostatically repelling or attracting the unfixed toner image before contacting the heat member, that is, so-called image dust tends to occur. This phenomenon appears more prominently in an image forming apparatus that fixes at high speed.

In order to prevent the above-mentioned offset phenomenon, supply of a release oil to a fixing roll and introduction of an offset preventing agent to a toner have been conventionally performed. However, in the supply of the release oil, the structure of the fixing device is complicated and the size of the fixing device is increased. In addition, it is difficult to stably supply the oil, and thus sufficient offset suppression cannot be achieved. Introducing an anti-offset agent into the toner is relatively effective in preventing the offset, but on the other hand, it has a problem of inhibiting the charging of the toner, so that it is easy to cause image dust, and a high-quality image is always obtained. I can't do that.

[0007] Therefore, attempts have been made to introduce a charge control agent into the toner in order to solve the charge inhibition of the toner. However, because of the chargeability of the charge control agent, it is difficult to uniformly disperse the charge control agent in the toner, so that a sufficient charge-imparting effect cannot be obtained, and the chargeability also deteriorates the dispersion of the release agent. As a result, there is a problem that the expected offset suppressing effect cannot be sufficiently obtained.

[0008]

The charging performance is stable, and even if it is used for a long time in a fixing device of a heat-fusion type, it does not contaminate the heat roller, the pressure roller and the like in contact with the recording material, and therefore the recorded image is not contaminated. And a high-quality and high-speed image forming apparatus and an image forming method using the toner for developing an electrostatic image which does not contaminate the toner. In addition, the present invention provides a toner for developing an electrostatic image, an image forming apparatus, and an image forming method, which are excellent in the fixing property of thick paper.

[0009]

The object of the present invention is attained by adopting one of the following constitutions.

[1] In an electrostatic image developing toner comprising at least a binder resin, a colorant, a release agent, and a charge control agent, the binder resin is composed of a styrene monomer and a (meth) acrylate ester. The main component is a vinyl copolymer containing a monomer as a constituent unit, and the molecular weight distribution of the copolymer is at least as low as 3,000 to 50,000, and the molecular weight is 10 × 10 ⁴ to Each of the molecular weights P1 having the maximum value of the molecular weight distribution on the high molecular weight side of 500 × 10 ⁴ and having the maximum value on the low molecular weight side and the molecular weight P2 having the maximum value on the high molecular weight side satisfy 100 ≦ P2 / P1 ≦ 300. A toner for developing an electrostatic charge image, which is a binder resin satisfying the above-mentioned relationship, and further comprising performing a polymerization reaction of the binder resin in the presence of a release agent.

[2] The weight average molecular weight is 1 × 10 ⁴ -1
The toner for developing an electrostatic image according to [1], comprising a styrene-olefin block copolymer of 0 × 10 ⁴ .

[3] The release agent is a paraffinic or polyolefinic compound, and the charge control agent is Al, B,
The toner for developing an electrostatic image according to [1] or [2], which is a metal-containing charge control agent containing at least one of Ti, Co, and Fe.

[4] The toner for developing an electrostatic charge image according to [1], [2] or [3], comprising a compound represented by the following general formula (A) as a charge control agent.

[0014]

Embedded image

In the formula, R ₁ and R ₄ represent a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (a condensed ring) ). M represents at least one metal among Al, B, Ti, Co, and Fe, and X ^{n +} represents a cation. n represents an integer.

[5] Using the electrostatic image developing toner according to [1], [2], [3] or [4], a fixed heat generating member and a rotatable cylindrical transfer member around the heat generating member. An image forming apparatus using a heat roll fixing device including a heat member.

[6] The toner for developing an electrostatic image according to [1], [2], [3] or [4] is used to form a rotatable cylindrical member and a heating member disposed near the surface thereof. An image forming apparatus using a heat roll fixing device having the above configuration.

[7] The method according to [5] or [6], wherein a hot roll having a surface coated with a coating layer having a thickness of 10 to 200 μm and containing polyperfluoroalkyl ether as a main component is used. Image forming apparatus.

[8] The surface roughness Ra of the hot roll is 0.1
The image forming apparatus according to [7], which is in a range of from 1.0 to 1.0 μm.

[0020]

[9] Heat composed of a fixed heat generating member and a belt-shaped heat transfer member that can circulate around the heat generating member using the toner according to [1], [2], [3] or [4]. An image forming apparatus, wherein an image is formed by melting the toner using a belt fixing device and fixing the toner on an image holding member.

[10] A heat belt whose surface is coated with a coating layer having a thickness of 10 to 200 μm and containing polyperfluoroalkyl ether as a main component is used.

The image forming apparatus according to [9].

[11] The surface roughness Ra of the heat belt is 0.
The image forming apparatus according to [10], which is in a range of 1 to 1.0 μm.

[12] Any one of [5] to [11]
13. An image forming method, comprising: forming an output image using the image forming apparatus according to any one of the first to sixth aspects.

Heretofore, it has been known that the charge control agent must properly maintain the dispersion state in the toner particles. The relationship with the molecular weight of the binder resin has also been discussed. On the other hand, the dispersibility of the release agent in the binder resin is also a problem, and it has been known that the releasability differs depending on the dispersion state (for example, see JP-A-8-106).
174 and 10-123753).

However, in a toner containing both a charge control agent and a release agent, it is extremely difficult to find conditions such as mixing and kneading that can sufficiently exhibit both performances. Met.

The inventors have found that even if one of the performances is satisfactory,
It was inferred that the performance of the other was insufficient, probably because both were not contained in the binder resin in the proper dispersed state. In addition, the production conditions for providing appropriate dispersibility for both are extremely limited, and as is usually the case, simply mixing a charge control agent and a release agent with a binder resin and kneading the mixture will result in an appropriate It was determined that the conditions could not be found.

That is, it is not sufficient that both are simply dispersed sufficiently. The dispersed particle diameter has an appropriate value, and a particle having a certain particle diameter is dispersed in an appropriate state in toner particles. Is indispensable for performance. Furthermore, when each of them is separately dispersed, a method that can improve the dispersibility of one of them cannot be adopted even if the method can improve the dispersibility of the other.

The present invention has been made as a result of a study from the above viewpoint. In the present invention, the molecular weight and the molecular weight distribution of the binder resin and the styrene-olefin block copolymer described below can be determined from the molecular weight in terms of styrene measured by GPC.

Here, the molecular weight measurement method by GPC is as follows.
In the present invention, it is a measurement by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent.

That is, 1 ml of THF is added to 0.5 to 5 mg, more specifically, 1 mg of a measurement sample, and the mixture is sufficiently dissolved by stirring at room temperature using a magnetic stirrer or the like. Then, pore size 0.45-0.50μ
After treatment with a membrane filter of m, the mixture is injected into GPC. The GPC measurement conditions were as follows: the column was stabilized at 40 ° C., THF was flowed at a flow rate of 1 ml per minute, and 1 mg / m 2
About 100 ml of a sample having a concentration of 1 is injected and measured.

The column is preferably used in combination with a commercially available polystyrene gel column. For example, Shodex GPC KF-801, 80 manufactured by Showa Denko KK
2, 803, 804, 805, 806, 807, and TSKgel G1000H, G manufactured by Tosoh Corporation
2000H, G3000H, G4000H, G5000
H, G6000H, G7000H, TSK guard
column and the like.

As a detector, a refractive index detector (IR
Detector) or a UV detector. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodispersed polystyrene standard particles. It is preferable to use about 10 polystyrenes for preparing a calibration curve.

In the present invention, the release agent needs to be present at the time of polymerization of the binder resin. The release agent may be present in the polymerization reaction apparatus before the start of polymerization of the binder resin. Either a method in which a mold agent is added or a method in which the mold agent is added to a reactor during the polymerization reaction can be used.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds, production methods and the like according to the present invention will be further described below.

1. Binder Resin Used in the Present Invention The binder resin used in the present invention is not particularly limited as long as it is generally called a styrene-acrylic resin.

That is, specific examples of the monomer constituting the resin include the following, and a styrene monomer and a (meth) acrylate monomer can be used in combination.

As styrene monomers, styrene, o-
Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, Styrene such as pn-decylstyrene and pn-dodecylstyrene or a styrene derivative can be used.

On the other hand, (meth) acrylate monomers are roughly classified into two groups, (meth) acrylate monomers and acrylate monomers. Examples of the monomer include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, and methacrylic acid. There are methacrylate derivatives such as lauryl acrylate, phenyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate.

Examples of the acrylate monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and t-acrylate.
There are acrylate derivatives such as butyl, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate.

2. Toner Production Method In the present invention, a known production method including a melt-kneading step can be applied to the toner production method. Specifically, a colorant and a charge control agent are added to a resin to which a release agent and, if necessary, a styrene-olefin block copolymer are added at the time of the polymerization described above, and a sufficiently mixed toner raw material is melt-kneaded. Then, after mixing the colorant and the charge control agent in the resin, the mixture is cooled, pulverized, and classified to obtain colored resin particles.

Further, a toner is obtained by adding various fine particles and a lubricant as an external additive to the surface.

Here, the particle diameter of the toner of the present invention is preferably 3 to 9 μm in terms of volume average particle diameter. The volume average particle size of these toners can be measured using a Coulter Multisizer or the like. In the Coulter Multisizer, an aperture having an aperture diameter of 100 μm is used.
3 shows the results measured using the particle size distribution in the range of ４０40 μm.

Further, as the toner, the amount of fine powder toner of 3.0 μm or less is preferably 20% by number or less in the number distribution, more preferably 10% by number or less of 2.0 μm or less.

3. Colorant As the colorant, a known inorganic or organic colorant can be used. Specific colorants are exemplified below. As the black colorant, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite are also used.

Further, as a coloring agent for magenta or red, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I.
I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48; 1, C.I. I. Pigment Red 53; 1, C.I. I. Pigment Red 5
7; 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 13
9, C.I. I. Pigment red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166,
C. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222, and the like.

Examples of the coloring agent for orange or yellow include C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 1
2, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15,
C. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I.
I. Pigment Yellow 138, and the like.

As the colorant for green or cyan, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15; 2, C.I. I. Pigment Blue 15;
3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7, and the like.

These coloring agents can be used alone or in combination as needed. The amount of the colorant added is 1 to 20 with respect to the entire toner (100 parts by mass).
It is good to set to the mass part, preferably the range of 2 to 15 mass parts.

4. Release Agent As the release agent, known materials can be used as long as the polymerization of the binder resin is not hindered.

Specifically, 1-hexadecanol, 1-
Heptadecanol, stearyl alcohol, 1-nonadecanol, 1-eicosanol, 1-docosanol, 1
-Higher alcohol compounds such as tricosanol, 1-tetracosanol, and seryl alcohol; higher fatty acid compounds such as palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, behenic acid, tricosanoic acid, and lignoceric acid; Fatty acid ester compounds composed of higher alcohols and higher fatty acids, linoleamide, ricinoleamide, erucamide,
Fatty acid amide compounds such as oleic acid amide, eicosenoic acid amide, erucic acid amide, palmitoleic acid amide, vegetable waxes such as carnauba wax, candelilla wax, polyolefin compounds such as Fischer-Tropsch wax, polyethylene and polypropylene, eicosan And pentacosane, triacontan, tetracontan, pentacontan, hexacontan, heptaconsan, and the like. Furthermore, these release agents may be used alone or in combination.

Of these, paraffinic and polyolefinic compounds can be preferably used. Among them, n-paraffin having 21 to 105 carbon atoms is preferably used as the paraffin-based compound. As the polyolefin-based compound, preferably, the weight average molecular weight is 1,000 to 5,000.
It is good to use a low molecular weight polypropylene in the range.

These release agents can be used alone or in combination of two or more as necessary. Further, the amount of the release agent added is based on the entire toner (100 parts by mass).
It is preferable to set it in the range of 0.1 to 20 parts by mass.

In the present invention, a styrene-olefin block copolymer can be used as a dispersing aid for the release agent.

In the present invention, a block copolymer represented by the following structural formula (where A is a styrene component and B is a polyolefin component) can be used.

For example, AB, ABA or AB⊥
B-A, etc., and ⊥ indicates that this portion is further branched.

Examples of such a block copolymer include SBS (a block copolymer of styrene-butadiene-styrene), SIS (a block copolymer of styrene-isoprene-styrene), and SPS (a block copolymer of styrene-propylene-styrene). Block copolymer), SEBS (styrene-ethylene-butylene-styrene block copolymer), ESBS (epoxidized SBS) and the like. These block copolymers can be obtained, for example, by a living polymerization method.

However, when a double bond remains in the obtained block copolymer, the double bond is eliminated by hydrogenation.
Alternatively, a reduction operation may be added. Further, the block copolymer has a weight average molecular weight of 10,000 to 10
0000, particularly preferably 20,000 to 80,00
It is good to use the thing of 0.

If necessary, a release agent can be further added in the kneading step. Known materials such as natural wax such as carnauba wax, synthetic wax, and petroleum wax such as polyethylene and polypropylene can be used.

5. Charge control agent Various known charge control agents can be used. Specific examples include a nigrosine dye, a metal salt of naphthenic acid or a higher fatty acid, an alkoxylated amine, a quaternary ammonium salt compound, an azo metal complex, a metal salt of salicylic acid, and a metal complex thereof. Preferred metals to be contained are Al, B, Ti, Co, F
and at least one kind of e. Particularly preferred are the following metal complexes of oxyacid derivatives and benzylic acid derivatives.

[0060]

Embedded image

[0061]

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6. External Additive A so-called external additive can be added to the toner of the present invention for the purpose of improving fluidity, chargeability and cleaning property. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles, and lubricants can be used.

Conventionally known inorganic fine particles can be used. Specifically, silica, titanium, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic. Specifically, as silica fine particles, for example, commercial products R-805, R-976, R-974, and R-97 manufactured by Nippon Aerosil Co., Ltd.
2, R-812, R-809, HVK- manufactured by Hoechst
2150, H-200, commercial product TS- manufactured by Cabot Corporation
720, TS-530, TS-610, H-5, MS-
5 and the like.

As the titanium fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., and commercially available products MT-100S, MT-100B and MT-5 manufactured by Teika Co., Ltd.
00BS, MT-600, MT-600SS, JA-
1. Commercial products TA-300SI, TA-
500, TAF-130, TAF-510, TAF-5
10T, commercial products IT-S, IT-OA manufactured by Idemitsu Kosan Co., Ltd.
IT-OB, IT-OC and the like can be mentioned.

Examples of the alumina fine particles include commercially available products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and a commercially available product TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. As this, a homopolymer such as styrene or methyl methacrylate or a copolymer thereof can be used.

Examples of the lubricant include salts of zinc, aluminum, copper, magnesium, calcium and the like of stearic acid, salts of zinc, manganese, iron, copper, magnesium and the like of oleic acid, zinc, copper, magnesium and calcium of palmitic acid. Metal salts of higher fatty acids such as salts of linoleic acid such as zinc and calcium, and salts of ricinoleic acid such as zinc and calcium.

The addition amount of these external additives is preferably 0.1 to 5% by mass based on the toner. As a method of adding the external additive, various known mixing devices such as a Turbula mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer can be used.

7. Developer The toner of the present invention may be used as a one-component developer or a two-component developer.

When used as a one-component developer, a non-magnetic one-component developer or a toner containing magnetic particles of about 0.1 to 0.5 μm in a toner to form a magnetic one-component developer can be used. Can be used. The particle size of the magnetic particles is measured by an electron microscope.

Further, it can be used as a two-component developer by mixing with a carrier. In this case, as the magnetic particles of the carrier, conventionally known materials such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Particularly, ferrite particles are preferable. The magnetic particles have a volume average particle size of 15 to 100 μm, more preferably 25 to 80 μm.
μm is preferred.

The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution analyzer “HELOS” equipped with a wet disperser (SYMPATIC (SYMPIC)).
(ATEC)).

The carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin-dispersed carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, but, for example, an olefin resin, a styrene resin, a styrene-acrylic resin, a silicone resin, an ester resin, or a fluorine-containing polymer resin is used. The resin for forming the resin dispersion type carrier is not particularly limited, and a known resin can be used. For example, a styrene-acrylic resin, a polyester resin, a fluororesin, a phenol resin, or the like is used. be able to.

The amount of the carrier to be added is preferably set in a mass ratio of carrier: toner = 1: 1 to 20: 1.

8. Thermal fixing device, image forming method, and image forming apparatus The toner of the present invention is fixed by an image forming method and an image forming apparatus including a fixing step by a heat fixing device.

FIG. 1 is a cross-sectional view showing an example of a fixing device (also referred to as a fixing device) used in the present invention. The fixing device shown in FIG. 1 includes a heating roll 10 and a pressure roll 20 which is in contact with the heating roll 10. And In FIG. 1, T is a toner image formed on a recording material 8 (transfer paper which is also referred to as an image support).

The heating roll 10 has a core metal 11 on which a coating layer 12 made of silicone rubber is formed, and includes a heating member 13 composed of a linear heater.

The metal core 11 is made of a metal selected from aluminum, iron and copper or an alloy thereof.
Its inner diameter is 10 to 50 mm.

The core metal 11 has a thickness of 0.1 to 2 mm.
It is determined in consideration of the balance between the demand for energy saving (thinning) and the strength (depending on the constituent materials). For example, 0.
In order to maintain the same strength as the iron core of 57 mm with the aluminum core, the wall thickness must be 0.8 mm.
mm.

The thickness of the coating layer 12 is 0.2 mm or more. Preferably it is 0.5 to 10 mm, more preferably 1.0 to 5 mm. When the thickness is less than 0.2 mm, the fixing nip cannot be increased, and the effect of soft fixing cannot be exhibited. As the heating member 13, a halogen heater can be suitably used.

In addition, as shown in FIG. 2, not only one heating member but also a plurality of heating members can be included so that the heat distribution area can be changed according to the size (width) of the passing paper. It may be. The heating roll 15 shown in FIG. 2 has a halogen heater 1 for heating a central region of the roll surface.
6A, and a halogen heater 16B and a halogen heater 16C for heating the end region of the roll surface.

According to the heating roll 15 as shown in FIG. 2, when passing narrow paper, only the halogen heater 16A is energized, and when passing wide paper,
Further, the halogen heater 16B and the halogen heater 1
6C may be energized.

Returning to FIG. 1, the pressure roll 20
1 is provided with a coating layer 22 made of rubber on the surface thereof.
The rubber of the coating layer is not particularly limited, and urethane rubber, silicone rubber, and the like can be used, and more preferably, heat-resistant silicone rubber.
As the silicone rubber, the same material as that of the coating layer 12 can be used.

The core 21 is made of a metal such as aluminum or iron or an alloy thereof.

The thickness of the coating layer 22 is 0.2 mm or more. Preferably it is 0.5 to 10 mm, more preferably 1.0 to 5 mm. If the thickness is less than 0.2 mm, the fixing nip cannot be increased, and the effect of soft fixing may not be exhibited.

The silicone rubber or rubber constituting the coating layers 12 and 22 has an Asker C hardness of 35 to 75, preferably 40 to 50, and silicone sponge rubber can be preferably used. When the Asker C hardness is less than 35, the rubber is too soft, and there is a problem in durability. If it exceeds 75, the rubber is too hard, and it becomes difficult to apply pressure uniformly.

The contact load (total load) between the heating roll 10 and the pressure roll 20 is usually 40 to 350 N,
Preferably 50 to 300 N, more preferably 50 to 2
50N. The contact load is defined in consideration of the strength of the heating roll 10 (the thickness of the cored bar 11).
In the case of a heating roll having a core bar made of 3 mm of iron, the heating roll is preferably set to 250 N or less. If the contact load is less than 40 N, the pressure becomes insufficient and sufficient fixing performance cannot be obtained. On the other hand, if it exceeds 350 N, the roll will be overloaded.

From the viewpoints of offset resistance and fixability, the nip width is preferably 4 to 8 mm, and the surface pressure of the nip is preferably 0.6 to 1.5 × 10 ⁵ Pa. .

As an example of the fixing conditions by the fixing device shown in FIG. 1, the fixing temperature (the surface temperature of the heating roll 10) is 130 to 240 ° C., and the fixing linear velocity is 80 to 640 mm.
/ Sec.

The fixing device used in the present invention may be provided with a fixing unit cleaning mechanism as necessary. In this case, as a method of supplying the silicone oil to the upper roll of the fixing unit, a method of supplying and cleaning with a pad, a roll, a web, or the like impregnated with the silicone oil can be used.

As the silicone oil, those having high heat resistance are used, and polydimethyl silicone, polyphenylmethyl silicone, polydiphenyl silicone and the like are used. Since those having a low viscosity have a large outflow during use, those having a viscosity at 20 ° C. of 1 to 100 Pa · s are preferably used.

In particular, the present invention is remarkably effective in a system using a fixed amount of silicone oil. In this case, the supply amount of the silicone oil is not particularly limited, but the amount of the silicone oil attached to paper or the like after fixing at about 0.1 to 5.0 μg / cm ² may be small. Further, it is preferable as an area where there is no difficulty in writing with an oil-based pen such as a ball-point pen due to silicone oil adhering to paper, and on the other hand, there is no problem of fixing offset.

Further, in order to prevent the end region of the roll surface from being overheated, the fixing device may be provided with a cooling fan or the like for the end region.

In the above description, a fixing device using a heating roll and a pressure roll has been described. However, in the present invention, a heat belt type fixing device or a device having a preheating mechanism can be preferably used. .

In any method, the surface roughness Ra of the hot roll or the belt is preferably in the range of 0.1 to 1.0 μm. This is the determined surface roughness. The outermost surface of the heat roll or the belt is preferably coated with a coating layer having a thickness of 10 to 200 [mu] m containing a fluororesin, especially polyperfluoroalkyl ether as a main component. In addition, even when the coating layer is already applied to the surface as described above,
This layer is further provided thereon.

Next, an example of the image forming method and the image forming apparatus of the present invention will be described. FIG. 3 is a schematic configuration diagram of an image forming apparatus showing an embodiment of the present invention. Reference numeral 4 denotes a photosensitive member, which is a typical example of the electrostatic latent image forming member in the present invention. An organic photoconductor (OPC), which is a photoreceptor layer, is formed on the outer peripheral surface of a drum substrate made of aluminum, and rotates at a predetermined speed in the direction of the arrow. In this embodiment, the photoconductor 4 has an outer diameter of 60 mm.

In FIG. 3, the semiconductor laser light source 1 emits exposure light based on information read by a document reading device (not shown). This is distributed by a polygon mirror 2 in the direction perpendicular to the paper surface of FIG. 3, and is irradiated on the photoreceptor surface via an fθ lens 3 for correcting image distortion to form an electrostatic latent image. The photoreceptor is uniformly charged in advance by the charger 5 and starts rotating clockwise in synchronization with the timing of image exposure.

The electrostatic latent image on the photoreceptor surface is developed by the developing device 6, and the formed developed image is transferred to the recording material 8 conveyed at a proper timing by the operation of the transfer device 7. Further, the photoconductor 4 and the recording material 8 are separated by a separator (separation pole) 9, and the toner image is transferred and carried on the recording material 8, guided to the fixing device 100, and fixed.

The untransferred toner remaining on the photoreceptor surface is
It is cleaned by a cleaning device 25 of a cleaning blade type, and residual charges are removed by a pre-charging exposure (PCL) 26, and is uniformly charged again by the charger 5 for the next image formation.

The cleaning blade 27 has a thickness of 1
It is made of a rubber-like elastic body of about 30 mm, and urethane rubber is most often used.

[0101]

Next, embodiments of the present invention will be described specifically, but of course the present invention is not limited to these embodiments.

Example 1 Preparation of Binder Resin Toluene 900 was placed in a separable flask having a capacity of 3 liters.
g of styrene having a weight average molecular weight of 1.5 million.
n-butyl acrylate-methyl methacrylate (St
/ BA / MMA) copolymer 350 g, weight average molecular weight 7
Ten thousand styrene / hydrogenated isoprene / styrene (SIS) triblock copolymer (50 g) and 150 g of dopentacontan (52 carbon atoms) as a release agent were added and mixed and dispersed. Thereafter, the gas phase was replaced with nitrogen gas, and the temperature was raised to the boiling point of toluene.

While stirring with the reflux of toluene, 950 g of styrene and 200 parts of methyl methacrylate were added.
g, 60 g of n-butyl acrylate, and 90 g of azobisisobutyronitrile were added dropwise over 2.5 hours to perform solution polymerization. After completion of the dropwise addition, the mixture was aged for 30 minutes while stirring at the reflux temperature of toluene.
The toluene was removed by reducing the pressure while increasing the temperature to 0 ° C. Thereafter, the resin composition obtained by cooling was coarsely pulverized by a hammer mill so as to pass a mesh diameter of 2 mm, thereby obtaining a binder resin P-1.

The molecular weight distribution of the obtained binder resin P-1 is represented by G
As a result of measurement by PC, it was confirmed that the compound had local maximum values at the positions of molecular weight of 10,000 and 1.5 million.

Preparation of Toner The above-mentioned “Chemical Formula 3” was added to the binder resin P-1 prepared above.
A metal complex compound of a benzylic acid derivative represented by the formula “K-
1) 2% by mass and 10% by mass of carbon black were charged and stirred and mixed with a Henschel mixer. Thereafter, melt kneading was performed with a twin screw extruder, and the obtained melt kneaded material was cooled, coarsely pulverized with a hammer mill, and further finely pulverized with a mechanical pulverizer (Turbo Mill; manufactured by Turbo Kogyo Co., Ltd.). Thereafter, the particles were classified by air pressure using a Microplex to obtain colored particles C-1.

To the obtained colored particles C-1, 0.6% by mass of silica fine particles and 0.5% by mass of titania fine particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-1 was obtained. The particle size of the obtained toner particles T-1 is measured by a laser diffraction type particle size distribution analyzer (HE).
(LOS; manufactured by Sympatech Co., Ltd.), it was confirmed that the 50% particle size by volume was 7.2 μm.

Preparation of Developer The obtained toner particles T-1 and a silicone-coated carrier (volume-based 50% particle size = 60 μm) in which magnetite particles are coated with a silicone resin have a toner concentration of 5% by mass. And mixed with a W cone mixer to obtain a developer D-1 used for evaluation.

Performance Evaluation Evaluation of Fixable Temperature Region The hot roll fixing device of the Konica 7050 high-speed digital copying machine manufactured by Konica Co., Ltd. was modified so that the hot roll temperature could be set arbitrarily. Thereafter, the obtained developer D-1 was mounted on a copying machine, and a fixed image was produced while changing the hot roll temperature from 130 ° C. to 240 ° C. in steps of 10 ° C. In outputting the fixed image, A4 size plain paper (weighing 65 g / m ² ) and thick paper (weighing 130 g / m ² ) were used.

The fixing strength of the obtained fixed image was fixed using a method according to the mending tape peeling method described in Chapter 9, Section 1.4 of "Basic and Application of Electrophotographic Technology: Edited by the Electrophotographic Society". It was evaluated by rate. Specifically, after producing a solid fixed image of 2.54 cm square with a toner adhesion amount of 0.6 mg / cm ² , a scotch mending tape (Sumitomo 3)
(Manufactured by M Corporation) before and after peeling, and the residual ratio of the image density was determined as the fixing ratio. A Macbeth reflection densitometer RD-918 was used to measure the image density.
% Is defined as the fixing temperature. Here, the case where the fixable temperature range is 90 ° C. or more was evaluated as ◎ (excellent), the case where the temperature was 60 ° C. or more was evaluated as ○ (good), the case where the temperature was 30 ° C. or more was evaluated as Δ (practical), and the case where the temperature was less than 30 ° C. was evaluated as × (bad).

[0110] 2. Offset Occurrence Evaluation In a low temperature and low humidity environment of 10 ° C. and 20% RH, a developer D-1 was mounted on a high-speed digital copying machine Konica 7050 manufactured by Konica Corporation, and A3 size plain paper (weighing 65 g / m ² ), 1000 continuous copies were made, and the presence or absence of occurrence of offset was evaluated by directly visually observing the hot roll surface on the image and after the 1000 copies. Here, オ フ セ ッ ト (good) when no occurrence of an offset is observed on the image and on the surface of the heat roll, and Δ (practicable) when the offset is not generated on the image but on the heat roll. A case in which the image was stained by offset was determined to be x (bad).

3. Evaluation of image dust generation In a low-temperature and low-humidity environment of 10 ° C. and 20% RH, A3 size plain paper (weighing 65 g) conditioned with Konica Corporation's high-speed digital copier Konica 7050 equipped with developer D-1 / M ² ), continuous 1000 copies were made, and the fine line image in the obtained image was observed under magnification with a microscope to evaluate the presence or absence of toner dust around the fine line.

Here, when there is no occurrence of dust in the enlarged observation, it is indicated by ○ (good), when the number of dust generation is 10 / mm ² or less, Δ (practical), X (poor) was determined.

Table 2 shows the evaluation results.
It was confirmed that good fixing performance was obtained by using No. 1.

Example 2 Based on the resin composition P-1 prepared in Example 1, 3% by mass of polypropylene (Viscol 660P; softening point: 145 ° C .; manufactured by Sanyo Chemical Co., Ltd.), and benzyl represented by the above “Chemical Formula 3” 2% by mass of a metal complex compound “K-2” of an acid derivative and 10% by mass of carbon black were added, and the mixture was stirred and mixed with a Henschel mixer. Thereafter, colored particles C-2 were obtained in the same manner as in Example 1.

To the obtained colored particles C-2, 0.6% by mass of silica fine particles and 0.5% by mass of titania fine particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-2 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Example 3 A binder resin P-3 was produced in the same manner as in Example 1, except that 150 g of polypropylene (weight average molecular weight 1500) was used instead of using dopentacontan. When the molecular weight distribution of the obtained binder resin P-3 was measured by GPC, it was confirmed that the binder resin P-3 had local maximum values at the positions of 10,000 and 1.5 million.

2% by mass of a metal complex compound “K-1” of a benzylic acid derivative represented by “Chemical Formula 3” and 10% by mass of carbon black were added to the binder resin P-3, and the mixture was charged into a Henschel mixer. To mix. After that, colored particles C-3 were obtained in the same manner as in Example 1.

To the obtained colored particles C-3, 0.6% by mass of silica fine particles and 0.5% by mass of titania fine particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-3 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Example 4 Preparation of Resin Composition Toluene 900 was placed in a separable flask having a capacity of 3 liters.
g of styrene having a weight average molecular weight of 1.5 million.
n-butyl acrylate-methyl methacrylate (St
/ BA / MMA) copolymer 250 g, weight average molecular weight 5
Styrene / hydrogenated propylene / styrene (S
PS) 50 g of a ternary block copolymer and 150 g of pentatetracontane (45 carbon atoms) were charged and mixed and dispersed. Thereafter, the gas phase was replaced with nitrogen gas, and the temperature was raised to the boiling point of toluene.

While stirring with the reflux of toluene, 900 g of styrene and 150 g of methyl methacrylate were added.
g, 60 g of n-butyl acrylate, and 90 g of azobisisobutyronitrile were added dropwise over 1.5 hours to perform solution polymerization. After dropping, the mixture was aged for 20 minutes while stirring at the reflux temperature of toluene.
The toluene was removed by reducing the pressure while raising the temperature to ° C.

Thereafter, the resin composition obtained by cooling was coarsely pulverized by a hammer mill so as to pass a mesh diameter of 2 mm to obtain a binder resin P-4. When the molecular weight distribution of the obtained binder resin P-4 was measured by GPC, it was confirmed that the binder resin P-4 had local maximum values at the positions of the molecular weight of 6,000 and 1.5 million.

Preparation of Toner To a binder resin P-4, 2% by mass of K-2 represented by a metal complex compound of a benzylic acid derivative “Chemical Formula 3” and 10% by mass of carbon black were added, and a Henschel mixer was added. And mixed by stirring. Thereafter, melt kneading was performed with a twin screw extruder, and the obtained melt kneaded material was cooled, coarsely pulverized with a hammer mill, and further finely pulverized with a mechanical pulverizer (Turbo Mill; manufactured by Turbo Kogyo Co., Ltd.). Thereafter, the particles were classified by air classification using a Microplex to obtain colored particles C-4.

To the obtained colored particles C-4, 0.6% by mass of silica fine particles and 0.5% by mass of titania fine particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-4 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Example 5 3% by mass of polypropylene (Viscol 550P; manufactured by Sanyo Chemical Co., Ltd.) based on the binder resin P-4 prepared in Example 4
2% by mass of a metal complex compound “K-1” of a benzylic acid derivative and 10% by mass of carbon black were charged and mixed by stirring with a Henschel mixer. Thereafter, colored particles C-5 were obtained in the same manner as in Example 1.

To the obtained colored particles C-5, 0.6% by mass of silica fine particles and 0.5% by mass of titania fine particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-5 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Example 6 A binder resin P-6 was produced in the same manner as in Example 4 except that 150 g of polypropylene (weight average molecular weight 1500) was used instead of using pentatetracontan.
The molecular weight distribution of the obtained binder resin P-6 was measured by GPC. As a result, it was confirmed that the binder resin P-6 had local maximum values at the positions of molecular weight of 6,000 and 1.5 million.

To the binder resin P-6 thus prepared, 2% by mass of a metal complex compound "K-1" of a benzylic acid derivative and 10% by mass of carbon black were added, and the mixture was stirred and mixed with a Henschel mixer. Thereafter, colored particles C-6 were obtained in the same manner as in Example 1.

With respect to the colored particles C-6, 0.6% by mass of silica fine particles and 0.5% by mass of titania fine particles were added.
External addition was performed by mixing with a Henschel mixer to obtain toner particles T-6. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Example 7 Preparation of resin composition Toluene 900 was placed in a separable flask having a capacity of 3 liters.
g, and a weight average molecular weight of 1,000,000 styrene-n
-Butyl acrylate-methyl methacrylate (St /
(BA / MMA) copolymer, 300 g, styrene / hydrogenated propylene / styrene (SPS) triblock copolymer (weight average molecular weight: 50,000), 50 g, and hentetracontane (carbon number: 41), 150 g, were mixed and dispersed. Was. afterwards,
The gas phase was replaced with nitrogen gas, and the temperature was raised to the boiling point of toluene.

While stirring with the reflux of toluene, 780 g of styrene and 210 g of methyl methacrylate were added.
g, 60 g of n-butyl acrylate, and 90 g of azobisisobutyronitrile were added dropwise over 2 hours to perform solution polymerization. After completion of the dropwise addition, the mixture was aged for 30 minutes while stirring at the reflux temperature of toluene.
The pressure was reduced while increasing the temperature to remove toluene.

Thereafter, the resin composition obtained by cooling was coarsely pulverized by a hammer mill until the resin composition passed a mesh diameter of 2 mm to obtain a binder resin P-7. The molecular weight distribution of the obtained binder resin P-7 was measured by GPC. As a result, it was confirmed that the binder resin P-7 had local maximum values at the positions of 8,000 and 1,000,000.

Preparation of Toner 2% by mass of a metal complex compound “K-1” of a benzylic acid derivative and 10% by mass of carbon black were added to the prepared binder resin P-7, and stirred with a Henschel mixer. Mixed. Thereafter, melt kneading was performed by a twin-screw extrusion kneader, and the obtained melt kneaded product was cooled, coarsely pulverized by a hammer mill, and further finely pulverized by a mechanical pulverizer (Turbo Mill; manufactured by Turbo Industries) Thereafter, the particles were subjected to air classification using a Microplex to obtain colored particles C-7.

To the colored particles C-7, 0.6% by mass of silica fine particles and 0.5% by mass of fine titania particles were added.
External mixing was performed by mixing with a Henschel mixer to obtain toner particles T-7. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Example 8 To the binder resin P-7 produced in Example 7, 3% by mass of polypropylene (Viscol 660P; manufactured by Sanyo Chemical Co., Ltd.) and a metal complex compound "K-1" of a benzylic acid derivative were added.
% By mass and 10% by mass of carbon black, and mixed by stirring with a Henschel mixer. Thereafter, colored particles C-8 were obtained in the same manner as in Example 7.

To the obtained colored particles C-8, 0.6% by mass of silica fine particles and 0.5% by mass of titania fine particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-8 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Example 9 A binder resin P-9 was produced in the same manner as in Example 1 except that 150 g of polypropylene (weight average molecular weight 1500) was used instead of using dopentacontan. When the molecular weight distribution of the obtained binder resin P-9 was measured by GPC, it was confirmed that the binder resin P-9 had local maximum values at the positions of 8,000 and 1,000,000.

To the prepared binder resin P-9, 2% by mass of a metal complex compound “K-2” of a benzylic acid derivative and 10% by mass of carbon black were added, and the mixture was stirred and mixed with a Henschel mixer. Thereafter, in the same manner as in Example 1, colored particles C-9 were obtained.

To the obtained colored particles C-9, 0.6% by mass of silica fine particles and 0.5% by mass of fine particles of titania were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-9 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Comparative Example 1 Preparation of Binder Resin Toluene 900 was placed in a separable flask having a capacity of 3 liters.
g, and 350 g of a styrene-n-butyl acrylate-methyl methacrylate (St / BA / MMA) copolymer having a weight average molecular weight of 600,000 and 150 g of dopentacontane (52 carbon atoms) are added and mixed and dispersed. Was. Thereafter, the gas phase was replaced with nitrogen gas, and the temperature was raised to the boiling point of toluene. While stirring with the reflux of toluene, 820 g of styrene and methyl methacrylate 1 were added.
Solution polymerization was performed while a mixed solution of 40 g, 40 g of n-butyl acrylate, and 60 g of azobisisobutyronitrile was dropped over 2.5 hours. After completion of the dropwise addition, the mixture was aged for 30 minutes while stirring at the reflux temperature of toluene.
The toluene was removed by reducing the pressure while increasing the temperature to 180 ° C. Thereafter, the resin composition obtained by cooling was coarsely pulverized by a hammer mill so as to pass a mesh diameter of 2 mm, thereby obtaining a binder resin P-11. When the molecular weight distribution of the obtained binder resin P-11 was measured by GPC, it was confirmed that the binder resin P-11 had local maximum values at the positions of 10,000 and 600,000.

Preparation of Toner and Developer Based on the prepared binder resin P-11, 2% by mass of a chromium complex diazo compound “K-6” represented by Chemical Formula 4 and 10% by mass of carbon black were added. And mixed with a Henschel mixer. Thereafter, melt kneading is performed by a twin screw extruder, and the obtained melt kneaded material is cooled, coarsely pulverized by a hammer mill, and finely pulverized by a mechanical pulverizer (turbo mill: Turbo Kogyo). Colored particles C-11 were obtained by air classification using a Microplex.

To the obtained colored particles C-11, 0.6% by mass of silica fine particles and 0.5% by mass of fine titania particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-11 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Comparative Example 2 Preparation of Binder Resin Toluene 900 was placed in a separable flask having a capacity of 3 liters.
g of styrene having a weight average molecular weight of 1.2 million.
n-butyl acrylate-methyl methacrylate (St
(/ BA / MMA) copolymer (360 g) and dopentacontan (carbon number: 52) 150 g were charged and mixed and dispersed. Thereafter, the gas phase was replaced with nitrogen gas, and the temperature was raised to the boiling point of toluene. While stirring with the toluene refluxing, 750 g of styrene and 250 parts of methyl methacrylate were added.
g, n-butyl acrylate 80 g, and a mixed solution of azobisisobutyronitrile 90 g were dropped over 1 hour to perform solution polymerization. After completion of the dropwise addition, the mixture was aged for 30 minutes while stirring at the reflux temperature of toluene.
The pressure was reduced while increasing the temperature to remove toluene.

Thereafter, the resin composition obtained by cooling was coarsely pulverized by a hammer mill until the resin composition passed a mesh diameter of 2 mm to obtain a binder resin P-12. The molecular weight distribution of the obtained binder resin P-12 was measured by GPC. As a result, it was confirmed that the binder resin P-12 had local maximum values at the positions of 3,000 and 1.2 million.

Preparation of Toner and Developer A colored particle C-12 was obtained in the same manner as in Comparative Example 1 for the binder resin P-12. Based on the obtained colored particles C-12, silica fine particles 0.6% by mass, titania fine particles 0.5
% By mass and mixed with a Henschel mixer to perform an external addition process to obtain toner particles T-12. Or later,
The preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Comparative Example 3 Preparation of Binder Resin Toluene 900 was placed in a separable flask having a capacity of 3 liters.
g of styrene having a weight average molecular weight of 1,000,000.
n-butyl acrylate-methyl methacrylate (St
(BA / MMA) copolymer (350 g) was charged and mixed and dispersed. Thereafter, the gas phase was replaced with nitrogen gas, and the temperature was raised to the boiling point of toluene. The solution polymerization was carried out while dropping a mixed solution of 880 g of styrene, 180 g of methyl methacrylate, 50 g of n-butyl acrylate, and 80 g of azobisisobutyronitrile over 2 hours while stirring with the reflux of toluene occurring. After completion of the dropwise addition, the mixture was aged for 30 minutes while stirring at the reflux temperature of toluene.
The toluene was removed by reducing the pressure while increasing the temperature to 180 ° C.

Thereafter, the resin composition obtained by cooling was coarsely pulverized by a hammer mill so as to pass through a mesh diameter of 2 mm, thereby obtaining a binder resin P-13. The molecular weight distribution of the obtained binder resin P-13 was measured by GPC. As a result, it was confirmed that the binder resin P-13 had local maximum values at the positions of 80,000,000 and 1,000,000.

Preparation of Toner and Developer A colored particle C-13 was obtained in the same manner as in Comparative Example 1 for the binder resin P-13. Based on the obtained colored particles C-13, silica fine particles 0.6% by mass, titania fine particles 0.5
% By mass and mixed by a Henschel mixer to perform an external addition process, thereby obtaining toner particles T-13. Or later,
The preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Comparative Example 4 3% by mass of polypropylene (Viscol 660P; manufactured by Sanyo Chemical Co., Ltd.) and 2% by mass of a chromium complex diazo compound “K-6” were added to the binder resin P-13 obtained in Comparative Example 3. And 10% by mass of carbon black, and stirred and mixed with a Henschel mixer. Thereafter, colored particles C-14 were obtained in the same manner as in Comparative Example 1.

To the obtained colored particles C-14, 0.6% by mass of silica fine particles and 0.5% by mass of fine titania particles were added, and the mixture was mixed with a Henschel mixer to perform an external addition treatment. T-14 was obtained. Thereafter, the preparation of the developer and the performance evaluation were performed in the same manner as in Example 1.

Table 1 shows the contents of Examples 1 to 9 and Comparative Examples 1 to 4, and Table 2 shows the evaluation results.

[0151]

[Table 1]

[0152]

[Table 2]

From the evaluation results, it can be seen that the characteristics of Examples 1 to 9 in the present invention are extremely superior to Comparative Examples 1 to 4.

Examples 11 to 19 and Comparative Examples 11 to 14 Performance evaluation was performed in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 4, except that the fixing device used for performance evaluation was changed to a heat belt fixing device. went.

[0155]

[Table 3]

The results were almost the same as those shown in Table 2 above. Examples 21 to 29 and Comparative Examples 21 to 24 Examples 1 to 9 except that the fixing device used for performance evaluation was changed to a heat roll fixing device having a heating member near the roll surface.
The performance was evaluated in the same manner as in Comparative Examples 1 to 4.

[0157]

[Table 4]

The results were almost the same as those shown in Table 2 above.

[0159]

As described above, according to the present invention, even if the charging performance is stable and it is used for a long time in a heat fusing type fixing device, the portion in contact with the recording material, such as a heat roller and a pressure roller, is not contaminated. And a high-quality and high-speed image forming apparatus and an image forming method using the toner for developing an electrostatic image which does not contaminate the toner. In addition, the present invention provides a toner for developing an electrostatic image, an image forming apparatus, and an image forming method, which are excellent in the fixing property of thick paper.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a fixing device used in the present invention.

FIG. 2 is an explanatory diagram showing an example of a heat distribution pattern of a heating roll constituting a fixing device used in the present invention.

FIG. 3 is a schematic configuration diagram of an image forming apparatus according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Heating roll 11 Core metal 12 Coating layer 13 Heating member 15 Heating roll 16A Halogen heater 16B Halogen heater 16C Halogen heater 20 Pressure roll 21 Core metal 22 Coating layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/20 103 G03G 9/08 346 365

Claims (12)

[Claims] At least a binder resin, a colorant, a release agent,
In a toner for developing an electrostatic image composed of a charge controlling agent, the binder resin is mainly composed of a vinyl copolymer containing a styrene monomer and a (meth) acrylate monomer as constituent units. The copolymer has a maximum molecular weight distribution on the low molecular weight side with a molecular weight distribution of at least 3,000 to 50,000 and on the high molecular weight side with a molecular weight of 10 × 10 ^{4 to} 500 × 10 ^4. , The molecular weight P1 having the maximum value on the low molecular weight side, and the molecular weight P having the maximum value on the high molecular weight side
2 is a binder resin satisfying the relationship of 100 ≦ P2 / P1 ≦ 300, and the polymerization reaction of the binder resin is performed in the presence of a release agent. 2. A weight average molecular weight of 1 × 10 ⁴ to 10 × 1.
0 ⁴ is styrene - The toner according to claim 1, characterized in that it comprises an olefin block copolymer. 3. The release agent is a paraffin-based or polyolefin-based compound, and the charge control agent is Al, B, Ti,
The electrostatic image developing toner according to claim 1, wherein the toner is a metal-containing charge control agent containing at least one of Co and Fe. 4. The electrostatic image developing toner according to claim 1, further comprising a compound represented by the following general formula (A) as a charge control agent. Embedded image (Wherein, R ₁ and R ₄ represent a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring) ).
M represents at least one metal among Al, B, Ti, Co, and Fe, and X ^{n +} represents a cation. n represents an integer. ) 5. A fixed heat generating member using the electrostatic image developing toner according to claim 1, and a cylindrical heat transfer member rotatable therearound. An image forming apparatus using a heat roll fixing device. 6. A hot roll fixing device comprising the electrostatic charge image developing toner according to claim 1, comprising a rotatable cylindrical member and a heat generating member disposed near the surface thereof. An image forming apparatus using a container. 7. A hot roll having a surface coated with a coating layer having a thickness of 10 to 200 μm and containing polyperfluoroalkyl ether as a main component is used.
Or the image forming apparatus according to 6. 8. A hot roll having a surface roughness Ra of 0.1-1.
The image forming apparatus according to claim 7, wherein the distance is in a range of 0 μm. 9. A heat belt fixing device using the toner according to claim 1, and comprising a fixed heat generating member and a belt-shaped heat transfer member circulating around the heat generating member. An image forming apparatus for forming an image by fusing the toner and fixing the toner on an image holding member. 10. The image forming apparatus according to claim 9, wherein a heat belt whose surface is coated with a coating layer having a thickness of 10 to 200 μm and containing polyperfluoroalkyl ether as a main component is used. 11. The heat belt has a surface roughness Ra of 0.1 to 0.1.
The image forming apparatus according to claim 10, wherein the distance is in a range of 1.0 μm. 12. An image forming method, comprising: forming an output image using the image forming apparatus according to claim 5. Description: