JP2002091080A - Toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which can realize low electric power consumption and quick printing and which has sufficient low temperature fixing property. SOLUTION: The toner is used for the image forming method by which an image is formed on a recording material by using a heating and pressurizing means having at least (1) a magnetic field generating means, (2) a rotary heating member having a heat generating layer which generates heat at electromagnetic induction and a release layer and (3) a rotary pressurizing member forming a nip with the rotary heating member, and by heating and fixing a toner image on the recording material while pressing the rotary heating member through the recording material by the rotary pressurizing member. The toner has toner particle containing at least a binder resin and coloring agent. The binder resin has a hybrid resin component having vinyl polymer units and polyester units. The melt viscosity of the toner at 120 deg.C ranges from 5×103 to 5×105 Pa.s.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, an electrostatic printing method or a toner jet recording method, and an image forming method using the toner.

[0002]

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

Various methods and apparatuses have been developed for the final step of fixing a toner image on a sheet as a transfer material. At present, the most common method is a compression heating method using a fixed heating heater via a heat roller or a heat-resistant film.

In the pressure heating method using a heat roller or a heat-resistant film, the surface of the heat roller or the heat-resistant film having a releasability from the toner is passed through the sheet while the toner image surface of the sheet is brought into contact with the surface under pressure. Thus, the toner image is fixed. In this method, since the surface of the heat roller or the heat-resistant film and the toner image on the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and Fixing can be performed.

In such a configuration, the fixing roller is formed in a hollow shape, and a heating element is held on a central axis of the fixing roller by holding means.

[0006] The heating element is formed of, for example, a tubular heating heater such as a halogen lamp, and generates heat when a predetermined voltage is applied. Since the halogen lamp is located at the center axis of the fixing roller, heat generated from the halogen lamp is uniformly radiated to the inner wall of the fixing roller, and the temperature distribution of the outer wall of the fixing roller becomes uniform in the circumferential direction. The outer wall of the fixing roller is heated until its temperature reaches a temperature suitable for fixing.

In this state, the fixing roller and the pressure roller rotate in opposite directions while being pressed against each other, and pinch the sheet to which the toner has adhered. At a pressure contact portion (hereinafter, referred to as a nip portion) between the fixing roller and the pressure roller, the toner on the sheet is melted by the heat of the fixing roller, and is fixed to the sheet by the pressure applied from both rollers.

However, in the above-described fixing device having a heating element composed of a halogen lamp or the like, since the fixing roller is heated using radiant heat from the halogen lamp,
After turning on the power, a relatively long time is required until the temperature of the fixing roller reaches a predetermined temperature suitable for fixing (hereinafter referred to as a warm-up time).

On the other hand, if a large amount of electric power is applied to the fixing roller in order to shorten the warm-up time, the power consumption of the fixing roller is increased, which is a countermeasure to the energy saving that is being actively promoted. Would.

Therefore, in order to enhance the value of a product such as a copying machine, energy saving of the fixing device (low power consumption) is required.
Attention has been paid more and more to achieve both compatibility with the improvement of user operability (quick print).

Japanese Patent Application Laid-open No. Sho 5
As disclosed in Japanese Patent Application Laid-Open No. 9-33787, an induction heating type fixing device using high frequency induction as a heating source has been proposed. In this induction heating fixing device, a coil is arranged concentrically inside a hollow fixing roller made of a metal conductor, and an induced eddy current is generated in the fixing roller by a high-frequency magnetic field generated by applying a high-frequency current to this coil. The fixing roller itself generates Joule heat by the skin resistance of the fixing roller itself. According to the fixing device of the induction heating system, the electric-heat conversion efficiency is extremely improved, so that the warm-up time can be reduced.

Further, by combining the coil with a core (magnetic field blocking member) made of a magnetic material, a high-frequency magnetic field can be efficiently generated. In particular, when a core having a T-shaped cross section is used, the amount of heat required for the fixing device can be generated with low power due to the effective concentration of the high-frequency magnetic field and the effect of shielding the magnetic field from a portion other than the heat generating portion. However, in the case of the above-described conventional technology, the following problems have occurred.

In the above-described induction heating type fixing device, in order to take advantage of the feature that the time required for the surface temperature of the fixing roller to reach an appropriate temperature for fixing at the time of starting the fixing device can be shortened, the fixing roller It is better that the heat capacity is as small as possible. Therefore, if a thin fixing roller is used, it is difficult to set the pressing force at the fixing nip portion high due to the rigidity of the fixing member, and it is difficult to set the fixing temperature low. Further, in this case, it is difficult to transfer heat in the rotation axis direction of the fixing roller. For example, when small-sized paper is continuously passed, the difference in the fixing roller temperature between the paper passing portion and the non-paper passing portion increases. Cheap. At this time, if the temperature is adjusted in the paper passing portion of the fixing roller, the temperature of the non-paper passing portion greatly exceeds the temperature suitable for fixing. Toner offset is likely to occur.

[0014] In order to solve such a problem, using a toner whose viscosity and glass transition point (Tg) have been lowered and softened,
A method for improving the low-temperature fixability can be considered. However, even in such a toner, under severe conditions such as high temperature and high humidity, storage stability is deteriorated, and photoreceptor contamination at the time of development occurs, which leads to deterioration of development performance.

For this reason, the performance required of the toner applied to such a fixing system is becoming higher than that of other fixing systems, and further improvement of the fixing performance and the anti-offset property is required. Required.

Heretofore, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resins have excellent low-temperature fixability, but also have the problem that offset phenomena easily occur at high temperatures.

Further, a vinyl copolymer such as a styrene resin is excellent in pulverizability at the time of toner production, and is excellent in hot offset resistance because it can be polymerized. However, when the molecular weight is lowered or the glass transition point is lowered to improve the low-temperature fixability, there is a problem that the blocking resistance and the developability deteriorate.

As described above, at present, there is no toner having sufficient performance to take advantage of the features of the above-described fixing device of the electromagnetic induction heating system.

[0019]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and an image forming method which solve the above-mentioned problems.

An object of the present invention is to provide a method for heating and fixing a toner image on a recording material by electromagnetic induction heating.
An object of the present invention is to provide a toner that has excellent low-temperature fixing properties and high-temperature offset resistance, and that maintains good developability even under high temperature and high humidity.

It is a further object of the present invention to provide an image forming method which realizes both energy saving (low power consumption) of a fixing device and improvement of user operability (quick print).

[0022]

The present invention provides (1) a magnetic field generating means, (2) a rotary heating member containing at least a heating layer and a release layer heated by electromagnetic induction, and (3) the rotary heating member. Using a heating and pressing means having at least a member and a rotary pressing member forming a nip, the toner image on the recording material is pressed while pressing the rotary pressing member via the recording material. And a toner applied to an image forming method for forming a fixed image on a recording material by heating and fixing the toner. The toner has toner particles containing at least a binder resin and a colorant. Has a hybrid resin component having a vinyl polymer unit and a polyester unit, and the melt viscosity at 120 ° C. of the toner is 5 × 10 ^{3 to} 5 × 10 ⁵ Pa · s. Characterized Tona On.

The present invention is also an image forming method for forming a fixed image on a recording material by heating and fixing a toner image on a recording material by a heating and pressing means. The toner has toner particles containing at least a binder resin and a colorant, and the binder resin has a hybrid resin component having a vinyl polymer unit and a polyester unit. The melt viscosity at 120 ° C. is 5 × 10 ^{3 to} 5 × 10 ⁵ Pa · s, and the heating means comprises (1) a magnetic field generating means, and (2) at least a heating layer and a release layer which are heated by electromagnetic induction. A heating / pressurizing means having at least a rotating heating member to be contained and (3) a rotating pressing member forming a nip with the rotating heating member, and rotating the rotating pressing member via a recording material. Press heating member While an image forming method for forming a fixed image on a recording material by heat-fixing the toner image on the recording material.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The toner of the present invention comprises (1) a magnetic field generating means, (2) a rotary heating member containing at least a heating layer and a release layer heated by electromagnetic induction, and (3) a rotary heating member. Using a heating and pressing means having at least a member and a rotary pressing member forming a nip, the toner image on the recording material is pressed while pressing the rotary pressing member via the recording material. Is applied to an image forming method of forming a fixed image on a recording material by heat fixing. In particular, the thickness of the heating layer of the rotary heating member is 0.01 to 20 mm, and the nip width formed by the rotary heating member and the rotary pressing member is 1 mm.
And a fixing speed of 10 to 500 mm / sec while pressing the rotary heating member at a linear pressure of 10 ³ to 10 ⁵ N / m via the recording material. It is suitably applied to an image forming method for fixing under heat and pressure.

In the fixing device having such a configuration, the electric-heat conversion efficiency is extremely improved, so that the warm-up time can be reduced. In addition, by combining a coil with a core made of a magnetic material, a high-frequency magnetic field can be obtained. This is preferable because the generation of heat can be efficiently performed, and the amount of heat required for the fixing device can be generated with low power.

In the fixing device of the present invention, in order to reduce the heat capacity of the fixing roller, it is preferable that the core of the fixing roller and the heat generating layer be thin. Therefore, the pressure applied to the fixing roller and the pressure roller is also set relatively small. As a toner used in such a fixing device, a toner that easily melts and fixes even under light pressure is preferable.

The resin of the present invention comprises a vinyl resin, a polyester resin, and a hybrid resin component having a vinyl polymer unit and a polyester unit. The “hybrid resin component” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester-based unit and a vinyl-based polymer unit obtained by polymerizing a monomer having a carboxylic ester group such as an acrylate ester are formed by a transesterification reaction.

Therefore, in the present invention, the vinyl polymer unit and the polyester unit of the hybrid resin component are

[0029]

Embedded image Are connected via

This is different from a simple mixture of two kinds of resins, and because two kinds of resins which are originally incompatible with each other are dispersed uniformly, it can be said that the resin makes use of the characteristics of both resins. . That is, it is possible to obtain a toner utilizing the sharp melt property of a polyester resin, which is advantageous in low-temperature fixability, and the high-temperature offset resistance and blocking resistance of a vinyl resin.

It has been found that the use of this hybrid resin can provide good low-temperature fixability, high-temperature offset resistance, and developability even in the fixing device of the present invention as described above.

In the binder resin of the present invention, the copolymerization ratio (mass ratio) of the vinyl monomer and the polyester monomer is preferably from 10/90 to 50/50. If the amount of the polyester-based monomer is less than 50% by mass, the melt viscosity of the toner increases, and the low-temperature fixability deteriorates. In such a state, the fixing set temperature must be increased or the pressure at the time of fixing must be set to a large value, resulting in adverse effects such as a slow first copy time. Further, when the polyester-based monomer is more than 90% by mass, when the temperature of the fixing member becomes non-uniform, a high-temperature offset tends to occur at a high temperature.

The binder resin of the present invention preferably contains 10 to 60% by mass of a THF insoluble matter. 10% by mass
If less than, the melt viscosity of the toner is small,
High-temperature offset is likely to occur. If the content is more than 60% by mass, the load in the melt-kneading process during the production of the toner is large, causing a problem in productivity, and the melt viscosity of the toner is increased, so that the low-temperature fixability is deteriorated.

The melt viscosity of the toner at 120 ° C. is preferably 5 × 10 ^{3 to} 5 × 10 ⁵ Pa · s. If the melt viscosity exceeds 5 × 10 ⁵ Pa · s, it does not melt sufficiently when passing through the fixing roller, and the low-temperature fixability deteriorates.
If it is less than 5 × 10 ³ Pa · s, high-temperature offset is likely to occur or contamination of the photoreceptor occurs.

Examples of the polyester-based monomer in the binder resin used in the present invention as described above include the following.

Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivative represented by the following formula (A), and formula (B) The diols shown are mentioned.

[0037]

Embedded image

[0038]

Embedded image

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

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

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-butylstyrene, p-tert-tributylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxy Styrene, p-chlorostyrene, 3,4-dichlorostyrene,
Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, odor Vinyl halides such as vinyl chloride and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate and isobutyl methacrylate Α-methylene fats such as n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Monocarboxylic acid esters: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic esters such as 2-chloroethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl Pyrrole, N-vinylcarbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic acid Unsaturated acid dibasic acid anhydrides such as anhydrides; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itacone Acid methyl half ester, alkenyl succinic acid methyl half ester,
Unsaturated dibasic acid half esters such as methyl fumarate half ester and mesaconic acid methyl half ester; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; acrylic acid, methacrylic acid, crotonic acid and cinnamic acid Α, β-unsaturated acids such as crotonic anhydride and cinnamic anhydride; anhydrides of the α, β-unsaturated acids and lower fatty acids; alkenylmalonic acid; Monomers having a carboxyl group, such as alkenyl glutaric acid, alkenyl adipic acid, and monoesters thereof, may be mentioned.

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

In the toner of the present invention, the polyester unit of the binder resin has a structure crosslinked with a trivalent or higher polycarboxylic acid or an anhydride thereof and / or a trivalent or higher polyhydric alcohol. Is what it is. As the trivalent or higher polycarboxylic acid or its anhydride, for example,
1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, and acid anhydrides or lower alkyl esters thereof; Examples of the polyhydric alcohol include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, and pentaerythritol.
Preferred are 1,2,4-benzenetricarboxylic acid and its anhydride.

In the toner of the present invention, the vinyl polymer unit of the binder resin may have a cross-linked structure cross-linked by a cross-linking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; and diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate and 1,3.
-Butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate,
Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and those obtained by replacing the acrylate of the above compounds with methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond include, for example, poly Oxyethylene (2) -2,2-bis (4-hydrodiphenyl) propane diacrylate, polyoxyethylene (4)-
2,2-bis (4-hydroxydiphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate; polyester-type diacrylates include, for example, the trade name MANDA (Nippon Kayaku).

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

These cross-linking agents can be used in combination with other monomer components 10
0.01 to 10.0 parts by mass (more preferably 0.03 to 5 parts by mass) can be used with respect to 0 parts by mass.

Among these crosslinking monomers, those which are preferably used from the viewpoint of fixing property and offset resistance to the binder resin include aromatic divinyl compounds (particularly divinylbenzene), chains containing an aromatic group and an ether bond. Diacrylate compounds tied together.

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

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

The polymerization initiator used for producing the vinyl copolymer of the present invention includes, for example, 2,2'-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4 -Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide; 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxydiisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, di- Isopropyl peroxydicarbonate, di-2-ethylhexylperoxycarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3- Methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Canoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxy isophthalate, t- Butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxy hexahydroterephthalate, di-t-butyl peroxyazelate are exemplified.

Examples of the method for producing the binder resin used in the toner of the present invention include the following production methods (1) to (6).

(1) A method in which a vinyl resin, a polyester resin, and a hybrid resin component are blended after each production, and the blend is a method in which the organic solvent is distilled off after dissolution and swelling in an organic solvent (for example, xylene). It is preferably produced by adding a wax in this blending step. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. Can be used.

(2) After the production of the vinyl polymer unit,
This is a method for producing a polyester unit and a hybrid resin component in the presence of this. The hybrid resin component is produced by reacting a vinyl-based polymer unit (a vinyl-based monomer can be added if necessary) with a polyester-based monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

(3) After the production of the polyester unit,
This is a method for producing a vinyl polymer unit and a hybrid resin component in the presence of this. The hybrid resin component is composed of a polyester-based unit (a polyester-based monomer can be added if necessary),
Alternatively, it is produced by a reaction with a vinyl polymer unit. Preferably, a wax is added in this step.

(4) After the production of the vinyl-based polymer unit and the polyester-based unit, the hybrid resin component is added by adding a vinyl-based monomer and / or a polyester-based monomer (alcohol, carboxylic acid) in the presence of these polymer units. Manufactured. Also in this case, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

(5) After the production of the hybrid resin component, a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) is added to carry out addition polymerization and / or
Alternatively, a vinyl-based polymer unit and a polyester-based unit are produced by conducting a polycondensation reaction. In this case, as the hybrid resin component, one produced by the production method of the above (2) to (4) can be used, and if necessary, one produced by a known production method can be used. Further, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

(6) By mixing the vinyl monomer and the polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing the addition polymerization and the condensation polymerization reaction, the vinyl polymer unit, the polyester unit and the hybrid resin component are formed. Manufactured. Further, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

In the above-mentioned production methods (1) to (5), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used as the vinyl-based polymer unit and / or the polyester-based unit.

Among the above-mentioned production methods (1) to (6), the production method (3) is particularly easy to control the molecular weight of the vinyl polymer unit and can control the production of the hybrid resin component. When a wax is added, the dispersion state is preferably controlled.

The above-mentioned binder resins may be used alone, or two or more kinds of binder resins having different softening points may be mixed and used. Such a system is preferable because the melt viscosity of the toner can be designed relatively easily.

The toner of the present invention may contain one or more waxes as a release agent, if necessary, and the wax is measured by a differential scanning calorimeter (DSC). The melting point defined by the endothermic peak temperature at the time of temperature rise is preferably from 60 to 130 ° C. Melting point 6
If the temperature is lower than 0 ° C., the viscosity of the toner is reduced, and high-temperature offset is likely to occur. If the melting point is higher than 130 ° C., the low-temperature fixability is deteriorated. The wax is preferably added in an amount of 1 to 20 parts by mass based on 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the desired release effect cannot be sufficiently obtained. If the amount exceeds 20 parts by mass,
Filming on the photoreceptor and surface contamination of a toner carrier such as a carrier and a sleeve occur, and the toner image is deteriorated, resulting in a practical problem.

Examples of such a wax include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; Block copolymers of these aliphatic hydrocarbon waxes; waxes mainly containing fatty acid esters such as carnauba wax, sasol wax and montanic acid ester wax; and some or all of fatty acid esters such as deoxidized carnauba wax. Deoxidized. Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a longer-chain alkyl group; prandic acid, eleostearic acid,
Unsaturated fatty acids such as vinaric acid; saturated alcohols such as stearic alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, melisyl alcohol, or long chain alkyl alcohols having a longer chain alkyl group; sorbitol Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate (commonly referred to as metal soaps); aliphatic hydrocarbon waxes and vinyl such as styrene and acrylic acid Waxes grafted with a series of monomers; partially esterified products of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; methyl having a hydroxyl group obtained by hydrogenation of vegetable fats and oils Ester compounds.

The wax may be added at the time of melt-kneading during the production of the toner, or may be added at the time of the production of the resin.

The toner of the present invention may be a magnetic toner or a non-magnetic toner. In the case of a magnetic toner, the following magnetic materials are used for charging,
It is preferable for reasons such as fluidity and uniformity of copy density.

As a magnetic material used also as a coloring agent,
Iron oxides such as magnetite, maghemite, ferrite, and magnetic iron oxides containing other metal oxides; Fe, C
metals such as o and Ni, or these metals and A
1, Co, Pb, Mg, Ni, Sn, Zn, Sb, B
Alloys with metals such as e, Bf, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof, and the like. Conventionally, ferric oxide (Fe ₃ O ₄ ), iron sesquioxide (γ-
Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), cadmium iron oxide (Cd ₃
Fe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ),
Iron oxide steel (CuFe ₂ O ₄ ), lead oxide (PbFe)
₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), iron neodymium (NdFe ₂ O ₃ ), barium iron oxide (BaFe ₁₂
O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), lanthanum iron oxide (LaFe)
O ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like are known. The above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials are fine powders of triiron tetroxide or gamma iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic properties at 795.8 kA / m applied are coercive force 1.6 to 12.0 kA / m saturation magnetization, 50 to 200 A
m ² / kg (preferably 50 to 100 Am ² / kg) and a remanent magnetization of ^{2 to 20} Am ² / kg are preferable.

The magnetic material is preferably added in an amount of 10 to 200 parts by mass based on 100 parts by mass of the binder resin.

When the toner of the present invention is used as a non-magnetic toner, any suitable pigment or dye can be used as a colorant.

As the dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I.
I. Direct Blue 2, C.I. I. Acid blue 9,
C. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I.
Basic Green 4, C.I. I. Basic Green 6
Etc. As pigments, graphite, cadmium yellow,
Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Red Lead Yellow, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red,
Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indanthrene Blue BC,
Chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a toner for forming a full-color image, the following colorants may be used. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,
11, 12, 13, 14, 15, 16, 17, 18, 1
9, 21, 22, 23, 30, 31, 32, 37, 3
8,39,40,41,48,49,50,51,5
2,53,54,55,57,58,60,63,6
4,68,81,83,87,88,89,90,11
2,114,122,123,163,202,20
6,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,13,1
5, 23, 29, 35 and the like.

Although the above magenta pigment may be used alone, it is more preferable to use a dye and a pigment together to improve the sharpness from the viewpoint of the quality of a full-color image. 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. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,1
8, 22, 23, 24, 27, 29, 32, 34, 3
5, 36, 37, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,
And basic dyes such as 25, 26, 27 and 28.

The coloring pigments for cyan include C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having the following structure.

[0074]

Embedded image

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

The coloring agent is based on 100 parts by mass of the resin component.
0.1 to 60 parts by mass is preferable, and more preferably 0.5 to 60 parts by mass.
５０50 parts by mass.

In the toner of the present invention, a charge control agent can be used if necessary in order to further stabilize the charge amount. As the negatively charged one, for example, an organic metal complex and a chelate compound are effective, and examples thereof include a monoazo metal complex; an acetylacetone metal complex; a metal complex of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid and a metal thereof. Examples include salts, anhydrides, esters and phenol derivatives such as bisphenol.

Examples of a substance which is controlled to have a positive charge include denatured products such as nigrosine and fatty acid metal salts; and quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate. And onium salts such as phosphonium salts, which are analogs thereof, and their lake pigments; triphenylmethane dyes and these lake pigments (phosphorotungstic acid, phosphomolybdate acid, phosphotungsten molybdate acid, Tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanide compound, etc.); metal salts of higher fatty acids; cyorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide;
Examples include organotin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate. These can be used alone or in combination of two or more. Of these, charge control agents such as nigrosine compounds and quaternary ammonium salts are particularly preferably used.

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

The preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halide, and is a so-called dry silica or fumed silica. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production step, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

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

AEROSIL (Aerosil Japan) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by subjecting a silica fine powder produced by vapor phase oxidation of the silicon halide compound to a hydrophobic treatment is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating with an organosilicon compound or the like which reacts with or physically adsorbs silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each having one to each of the terminal units. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. These are used alone or as a mixture of two or more.

The inorganic fine powder may be treated with silicone oil, or may be treated together with the above-mentioned hydrophobic treatment.

Preferred silicone oils include 25
Those having a viscosity at 30 ° C of 30 to 1000 centistokes are used, and for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil and the like are particularly preferable.

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

The preferred silicone oil used in the present invention has a viscosity at 25 ° C. of 0.5 to 10,000 centistokes, preferably 1 to 1,000 centistokes, and more preferably 10 to 200 centistokes. Silicone oil,
Methylfell silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil are particularly preferred. Examples of the method of silicone oil treatment include a method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; Or a method of dissolving or dispersing silicone oil in an appropriate solvent, adding silica fine powder, mixing and removing the solvent. The silicone oil-treated silica is more preferably heated to 200 ° C. or more (more preferably 250 ° C. or more) in an inert gas after the treatment of the silicone oil to stabilize the surface coat.

In the present invention, silica is previously added
It is preferable to use a method of treating with a silicone oil after treating with a coupling agent or a method of treating silica with a coupling agent and silicone oil simultaneously.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. It is preferable to use 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of the fluidity improver based on 100 parts by mass of the toner particles.

Further, an external additive other than the fluidity improver may be added to the toner of the present invention, if necessary.

For example, there are resin fine particles and inorganic fine particles which function as a charge auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent, a lubricant, and an abrasive. As such a lubricant, for example, a lubricant such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride, among which polyvinylidene fluoride is preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferred. Alternatively, a fluidity-imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferred. Alternatively, a small amount of a caking inhibitor, a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, or tin oxide, or fine particles of the opposite polarity can be used as a developability improver.

It is preferable to use 0.1 to 5 parts by weight of the resin fine particles, the inorganic fine powder, or the hydrophobic inorganic fine powder mixed with the toner based on 100 parts by weight of the toner.

The toner of the present invention can be used as a two-component developer by mixing with a carrier. The current value of the carrier is preferably adjusted to 20 to 200 μA by adjusting the degree of unevenness on the carrier surface and the amount of resin to be coated.

Examples of the resin for coating the carrier surface include styrene-acrylate copolymer, styrene-methacrylate copolymer, acrylate copolymer, methacrylate copolymer, silicone resin, and the like.
Fluorine-containing resin, polyamide resin, ionomer resin,
Polyphenylene sulfide resin or the like, or a mixture thereof can be used.

As the magnetic material of the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples include zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium.

To prepare the toner of the present invention, first, a binder resin, a colorant and / or a magnetic substance, a release agent, a charge control agent or other additives are mixed with a mixer such as a Henschel mixer or a ball mill. Mix well. The mixture is melted and kneaded using a hot kneader such as a kneader or an extruder to make the resins compatible with each other. Toner can be obtained. Further, the fluidity improver and / or other external additives are sufficiently mixed with the toner by a mixer such as a Henschel mixer to obtain a toner having the fluidity improver and / or other external additives on the surface of the toner particles. Can be.

The following are generally used as toner production apparatuses, but are not limited thereto.

(1) Example of crushing apparatus for toner production Apparatus name Manufacturer Maker Counter Jet Mill Hosokawa Micron Micron Jet Hosokawa Micron IDS Mill Nippon Pneumatic Industries PJM Jet Pulverizer Nippon Pneumatic Industries Cross Jet Mill Kurimoto Iron Works ur Max Date Cao engineering · SK jet-O-mill Seishin enterprise-Cryptron Kawasaki Heavy Industries, turbo mill turbo industrial and Inomizer Hosokawa Micron (2) toner manufacturing mixing device for example apparatus name manufacturer, Henschel mixer manufactured by Mitsui Mining Super mixer Kawata-Ribocone Okawara Works ・ Nauta Mixer Hosokawa Micron ・ Spiral Pin Mixer Taiheiyo Kiko ・ Redige Mixer Matsubo ・ Turbulizer Hosokawa Micron ・ Sa Black Mix Hosokawa Micron (3) for producing a toner classifier example device name manufacturer & classy Le Seishin Enterprise Micron crush fire Seishin Enterprise-spare Dick crush fire Seishin Enterprise Turbo crush Fire Nisshin Engineering micron separator by Hosokawa Micron-Turboplex (ATP ) Hosokawa Micron-TSP Separator Hosokawa Micron-Elbow Jet Nippon Steel Mining-Dispersion Separator-Nippon Pneumatic-YM Micro Cut Yasukawa Shoji (4) Example of kneading equipment for toner production Equipment name Manufacturer -KRC Kneader Kurimoto Iron Works-Bus Co. Kneader Buss ・ TEM extruder TOSHIBA MACHINE ・ TEX twin screw kneader Nippon Steel Works ・ PCM kneader Ikekai Iron Works ・ Three roll mill Inoue Manufacturing mixing roll mill Inoue Manufacturing & kneader Inoue Seisakusho, KNEADEX Mitsui Mining & MS-type pressure kneader Moriyama Seisakusho-Nida Ruder Moriyama Seisakusho, a Banbury mixer by Kobe Steel (5) Toner manufacturing sieving apparatus example device name manufacturer Ultra Sonic Koei Sangyo ・ Resonasive Tokuju Kogyo ・ Vibra Sonic System Dalton ・ Soniclean Shinto Kogyo ・ Gyro Shifter Tokuju Kogyo ・ Many manufacturers of circular vibrating sieves ・ Turbo Screener Turbo Kogyo ・ Micro Shifter Makino Sangyo

The toner of the present invention preferably has a weight average particle size of 3 to 9.5 μm in view of image density and resolution.

Next, a preferred fixing device used in the image forming method of the present invention will be described. However, the materials, shapes, three-dimensional configurations, and the like described in the embodiments are not intended to limit the scope of the present invention only to them unless otherwise specified.

FIG. 1 is a schematic configuration diagram of an example of an image forming apparatus according to an embodiment of the present invention.

The fixing roller 1 is constituted by providing, for example, a layer of PTFE or PFA as a release layer 12 on a core metal cylinder 111 (heating layer) made of iron in order to enhance the releasability of the surface.

The pressure roller 2 comprises a hollow cored metal 14 and an elastic layer 1 which is a heat-resistant rubber layer having a surface release property formed on the outer peripheral surface thereof.
5

Bearings are formed at both ends of the pressure roller 2, and are rotatably attached to a fixing unit frame (not shown).

The fixing roller 1 and the pressure roller 2 are rotatably supported, so that only the fixing roller 1 is driven.

The pressure roller 2 is in pressure contact with the surface of the fixing roller 1 and is arranged so as to be driven to rotate by frictional force at a pressure contact portion (nip portion). The pressing force and the nip width at that time are arbitrarily set and configured in consideration of use conditions and the like.

The temperature sensor 6 is disposed so as to be in contact with the surface of the fixing roller 1, and the power supply to the exciting coil 3 as the exciting means is increased or decreased based on the detection signal of the temperature sensor 6, so that the temperature of the fixing roller 1 is increased. Automatic control is performed so that the surface temperature becomes a predetermined constant temperature.

The conveyance guide 7 is arranged at a position for guiding the transfer material 16 conveyed while carrying the unfixed toner image 8 to a pressure contact portion (nip portion) between the fixing roller 1 and the pressure roller 2. The separation claw 10 is disposed in contact with or close to the surface of the fixing roller 1 to prevent the transfer material 16 from being wound around the fixing roller 1.

The exciting coil 3 is formed by winding a conductive wire around a central projection of a magnetic core 4 (hereinafter referred to as a core) having a T-shaped cross section.
In order to have a structure along the inner peripheral surface of the fixing roller,
It is provided outside the holder 5 made of a heat-resistant resin such as PPS, PEEK, and phenol resin.

An alternating current is applied to this exciting coil,
The magnetic field induced thereby is guided to the core 4 as a magnetic field interrupting unit having a high magnetic permeability to generate a magnetic flux and an eddy current on the inner surface of the fixing roller 1 as a heating unit. As a result, Joule heat is generated.

In order to increase the heat generation, the number of turns of the exciting coil 3 is increased, the core 4 is made of ferrite or permalloy having a high magnetic permeability and a low residual magnetic flux density, or the frequency of the alternating current is increased. good.

The core 4 has a T-shaped cross section extending in the direction of the rotation axis of the fixing roller 1.
The magnetic field generated by the excitation is cut off, and the magnetic field is concentrated toward the heating unit.

With the above configuration, the surface temperature of the fixing roller 1 is adjusted to a predetermined temperature which is optimal for fixing.

In the above description, the case where the fixing roller is used as the heating member has been described. However, it is of course possible to adopt a configuration made of a thin metal film instead of the fixing roller.

The methods for measuring the physical properties of the toner and raw materials of the present invention are described below. The embodiments described below are also based on this method.

(1) Measurement of tetrahydrofuran (THF) -insoluble content 0.5 to 1.0 g of a sample was weighed (W ₁ g), and a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.) was put into the soxhlet extractor. After extracting with 200 ml of THF as a solvent for 10 hours, evaporating the soluble component solution extracted with the solvent, vacuum drying at 100 ° C. for several hours, and weighing the amount of the THF soluble component (W ₂ g). The weight of the residual combustion ash in the toner is determined (W ₃ g). The residual ash from combustion is determined by the following procedure. About 2.0 g of a sample is placed in a 30-ml magnetic crucible precisely weighed in advance and precisely weighed, and the weight (Wa) g of the sample is precisely weighed. Put the crucible in an electric furnace, about 900
The mixture was heated at 3 ° C. for 3 hours, allowed to cool in an electric furnace, allowed to cool in a desiccator at room temperature for 1 hour or more, and then accurately weighed the crucible mass. From this, the residual combustion ash (Wb) g is determined.

(Wb / wa) × 100 = residual ash content (% by mass)

From the content, the weight of the residual combustion ash in the sample is determined. The THF-insoluble content is obtained from the following equation.

[0123]

(Equation 1)

In the case of a binder resin, the THF-insoluble matter may be determined from the following equation.

[0125]

(Equation 2)

FIG. 2 shows an example of a Soxhlet extraction apparatus. The THF 22 contained in the container 21 is heated and vaporized by the heater 23, and the vaporized THF is led to the cooler 25 through the pipe 24. The cooler 25 is constantly cooled by cooling water 26. The THF cooled and liquefied by the cooler 25 accumulates in the storage unit 28 having the cylindrical filter paper 27, and when the liquid level of THF becomes higher than the middle pipe 29, the THF is discharged from the storage unit to the container 21. The toner contained in the cylindrical filter paper is extracted by the circulating THF.

(2) Measurement of acid value Measurement is carried out according to the measurement method described in JIS K0070-1992. Measuring device: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics Co., Ltd.) Device configuration: 120 ml of toluene and 30 ml of ethanol
Use a mixed solvent of Measurement temperature: 25 ° C. Sample preparation: 0.5 g of a sample is added to 120 ml of toluene and dissolved by stirring at room temperature (about 25 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to make a sample solution.

(3) Measurement of Melt Viscosity of Toner Measuring apparatus: Flow tester CFT-500 (manufactured by Shimadzu Corporation) Measurement conditions: Die diameter; 1 mm Die length: 1 mm Load: 10 kg Heating rate: 6 ° C./min Sample preparation : About 2 g of toner on a pellet having a diameter of 1 cm is used.

[0129]

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

(Production of Resin 1) Terephthalic acid: 2.2 parts by weight Trimellitic anhydride: 1.7 parts by weight Dodecenylsuccinic acid: 1.7 parts by weight PO-BPA: 3.0 parts by weight EO -BPA: 1.3 parts by mass The above polyester monomer was charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device. Polycondensation reaction was performed while heating to 210 ° C. according to the method to obtain a polyester resin. Next, in 50 parts by mass of xylene, the polyester resin (100 parts by mass) obtained here, 8.8 parts by mass of styrene, and 1.1 parts of 2-ethylhexyl acrylate.
A part by weight and 0.001 part by weight of divinylbenzene were added and heated to 110 ° C. to dissolve and swell. Under a nitrogen atmosphere, a solution prepared by dissolving 1 part by mass of t-butyl hydroperoxide as a radical polymerization initiator in 10 parts by mass of xylene was added dropwise over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. The pressure was reduced while heating, and the solvent was removed to obtain Resin 1 having a softening point of 135 ° C.

(Production of Resin 2) Terephthalic acid: 1.7 parts by weight Trimellitic anhydride: 1.7 parts by weight Dodecenylsuccinic acid: 2.2 parts by weight PO-BPA: 3.0 parts by weight EO -BPA: 1.3 parts by mass-Styrene: 5.2 parts by mass-2-EHA: 0.7 parts by mass In the method for producing resin 1, the polyester monomer was changed to the above monomer, and the presence of wax 1 shown in Table 2 Resin 2 having a softening point of 130 ° C. was obtained in the same manner except that the polycondensation was performed below.

(Production of Resins 3 to 7) In the production method of Resin 1, a resin as shown in Table 2 was obtained in the same manner except that the monomers shown in Table 1 were used and the degree of polymerization was changed. Was.

(Production of Comparative Resins 1 ′ to 3 ′) In the production method of Resin 1, the monomers shown in Table 1 were used to prepare
Comparative resins 1 ′ to 3 ′ as shown in Table 2 were obtained in the same manner except that the degree of polymerization was changed.

Example 1 Resin 2: 70 parts by mass Resin 7: 30 parts by mass Magnetic iron oxide: 100 parts by mass (average particle size 0.2 μm, Hc 9.5 kA / m, σs = 8)
1 Am ² / kg, σr = 11 Am ² / kg) Monoazo iron complex: 2 parts by mass

The above mixture was melt-kneaded with a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a jet mill, and the obtained fine powder was classified by an air classifier to obtain a toner 1 having a weight average particle diameter of 7 μm.

To 100 parts by mass of this toner, 1.0 part by mass of silica subjected to hydrophobizing treatment and oil treatment and 4.0 parts by mass of strontium titanate were externally added by a Henschel mixer to obtain an externally added toner.

The above toner was measured by ¹³ C-NMR to confirm that the vinyl polymer, the polyester resin, and the hybrid resin component having the vinyl polymer unit and the polyester unit were present in the toner. confirmed.

In the toner, a hybrid resin component having a vinyl-based polymer unit and a polyester-based unit can be verified by detecting a signal of a newly formed ester bond by ¹³ C-NMR.

In general, the signal measured by ¹³ C-NMR of the ester group of the acrylate copolymerized with styrene is several ppm higher than that of the acrylate homopolymer due to the benzene ring of styrene. The phenomenon of shifting is known. This is the same in the case of the hybrid resin component obtained by transesterification of the alcohol component of the acrylate with the alcohol component of the polyester, and the effect of the benzene ring contained in the polyester unit introduced by the transesterification is also affected. The signal is detected as a signal on the higher magnetic field side than the acrylate of the vinyl polymer unit.

Examples of ¹³ C-NMR results of the toner containing the polyester resin, styrene-2-ethylhexyl acrylate and the hybrid resin component are shown in FIGS.

The ¹³ C-NMR measurement of the toner of Example 1 was performed. The toner of Example 1 contained a vinyl polymer, a polyester resin, a vinyl polymer unit, and a polyester unit. It was confirmed that a hybrid resin component existed.

In addition, Examples 2 to 7 and Comparative Examples 1 to 4 described later.
It was confirmed that the toner of No. 1 also contained a hybrid resin component.

The following evaluation was performed using this externally added toner.

(1) Low-temperature fixability test The fixing unit of the digital copying machine GP215 manufactured by Canon Inc. was tested using a heating layer having a thickness of 0.5 mm, a nip width of 8 mm, and a linear pressure of 18000.
The fixing device of the present invention was modified as shown in FIG. 1 at N / m and a fixing speed of 100 mm / sec, and a fixing image of the evaluation toner was obtained by changing the fixing temperature. 4 on the obtained image
The density reduction rate is measured by measuring the densities before and after rubbing when rubbing 5 times with a load of 900 N / m ² (50 g / cm ² ). The temperature at which the density reduction rate is 20% or less is defined as the minimum fixing temperature.

(2) Hot offset test An unfixed image of the evaluation toner is used. Using the same machine as in the above test, the unfixed image is passed while changing the fixing temperature. At that time, it is visually determined that the toner is offset to the fixing roller, and the generated temperature is defined as a hot offset occurrence temperature.

(3) Image Extraction Test under High Temperature and High Humidity Using the same machine as in the above test, under high temperature and high humidity (temperature 30)
(80.degree. C., 80% humidity). The image density was measured with a Macbeth densitometer (manufactured by Macbeth) using a SPI filter to measure the reflection density.
The image density of (φ) was measured. Initial image density and 1
The difference ΔD in image density after the image output of 100,000 sheets was measured and evaluated.

As a result of performing the tests (1) to (3) on Example 1, good results as shown in Table 4 were obtained.

[Examples 2 to 7] In Example 1, Table 4
The toners 2 to 7 were obtained in the same manner except that the raw materials shown in
I got As a result of evaluation in the same manner as in Example 1, good results as shown in Table 4 were obtained.

[Comparative Examples 1-4] In Example 1, Table 4
Comparative Toners 1 to 4 were obtained in the same manner, except that the raw materials were changed to the following. As a result of evaluation in the same manner as in Example 1, results as shown in Table 4 were obtained.

[0150]

[Table 1]

[0151]

[Table 2]

[0152]

[Table 3]

[0153]

[Table 4]

[0154]

According to the present invention, by combining the image forming method having the above-described structure with the toner, it has excellent low-temperature fixability and high-temperature offset resistance from low to high speeds, and has low power consumption. It is possible to provide a toner and an image forming method that can achieve compatibility with quick printing.

[Brief description of the drawings]

FIG. 1 is a schematic configuration sectional view of a fixing device according to an embodiment of the present invention.

FIG. 2 is an explanatory diagram showing an example of a Soxhlet extraction device.

FIG. 3 shows the results of ¹³ C-NMR measurement of the polyester resin.

FIG. 4. Styrene-2-ethylhexyl acrylate
^The result of ¹³ C-NMR measurement is shown.

FIG. 5 shows ¹³ C of a toner containing a hybrid resin component
-Shows the results of NMR measurement.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Rotary heating member (fixing roller) 2 Rotating pressure member (pressure roller) 3 Excitation coil (magnetic field generating means) 4 Core 5 Holder 6 Temperature sensor 7 Transport guide 8 Toner image 10 Separation claw 11 Heat generation layer 12 Release layer 13 Fixed image 14 Hollow core 15 Elastic layer 16 Transfer material (recording material)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/20 107 G03G 9/08 101 325 331 F-term (Reference) 2H005 AA01 AA02 AA08 AB06 CA04 CA08 CA12 CA17 CA18 CA26 CB07 CB13 EA03 EA07 FA06 FB01 2H033 AA30 AA32 AA49 BA58 BB18 BB28 BB33 BB34 BB37 CA36

Claims (24)

[Claims] 1. A magnetic field generating means, (2) a rotary heating member containing at least a heating layer and a release layer heated by electromagnetic induction, and (3) a nip with the rotary heating member. A heating and pressurizing means having at least a rotating and pressing member, and heating and fixing the toner image on the recording material while pressing the rotating and heating member via the recording material with the rotating and pressing member. A toner applied to an image forming method for forming a fixed image, wherein the toner has toner particles containing at least a binder resin and a colorant, and the binder resin has a vinyl polymer unit and A toner comprising a hybrid resin component having a polyester unit, wherein the toner has a melt viscosity at 120 ° C. of 5 × 10 ^{3 to} 5 × 10 ⁵ Pa · s. 2. The toner according to claim 1, wherein the binder resin contains a vinyl resin, a polyester resin, and a hybrid resin component. 3. A structure in which the polyester resin and the polyester unit of the binder resin are crosslinked with a trivalent or higher polyhydric carboxylic acid or an anhydride thereof and / or a trivalent or higher polyhydric alcohol. 2. The method according to claim 1, wherein
Or the toner according to 2. 4. The binder resin according to claim 1, wherein the vinyl resin and the vinyl polymer unit of the binder resin have a structure crosslinked by a crosslinking agent having two or more vinyl groups.
The toner according to any one of the above. 5. The vinyl resin unit and the polyester unit of the hybrid resin component are represented by the following formula: 5. The method according to claim 1, wherein the connection is made through
The toner according to any one of the above. 6. The hybrid resin component is a copolymer formed by a transesterification reaction between a polyester-based unit and a vinyl-based polymer unit obtained by polymerization of a monomer having a carboxylic acid ester group. The toner according to any one of claims 1 to 5, wherein 7. The binder resin according to claim 1, wherein the binder resin contains a vinyl monomer unit and a polyester monomer unit in a mixing ratio (mass ratio) of 10/90 to 50/50. The toner according to any one of the above. 8. The toner according to claim 1, wherein the binder resin contains a THF-insoluble content of 10 to 60% by mass. 9. The method according to claim 1, wherein the toner is a differential scanning calorimeter (DS).
The toner according to any one of claims 1 to 8, wherein the toner contains a wax having a melting point of 60 to 130 ° C defined by an endothermic peak temperature at the time of temperature rise measured in C). 10. The toner according to claim 1, wherein the toner contains a magnetic powder as the colorant. 11. The toner according to claim 1, wherein the toner is externally added with a hydrophobic fine inorganic powder.
0. The toner as described in any one of 0 above. 12. The heating layer of the rotary heating member has a thickness of 0.1 mm.
01 to 20 mm, a nip width formed by the rotary heating member and the rotary pressing member is 1 to 20 mm, and a linear pressure of 10 ³ to 10 ^{5 is applied} to the rotary heating member via a recording material.
Fixing speed 1 while pressing the rotating pressure member at N / m
The toner according to any one of claims 1 to 11, wherein the toner is used in an image forming method for fixing a toner image under heat and pressure under a condition of 0 to 500 mm / sec. 13. An image forming method for forming a fixed image on a recording material by heating and fixing a toner image on the recording material by heating and pressing means, wherein the toner forming the toner image is at least a binder resin. And a toner particle containing a colorant. The binder resin has a hybrid resin component having a vinyl polymer unit and a polyester unit, and the toner melts at 120 ° C. The viscosity is 5 × 10 ^{3 to} 5 × 10 ⁵ Pa · s, and the heating means includes: (1) a magnetic field generating means; and (2) a rotary heating method including at least a heating layer and a release layer heated by electromagnetic induction. A heating and pressurizing means having at least a rotary pressing member forming a nip with the rotary heating member, and pressing the rotary heating member via a recording material. While The image forming method of forming a fixed image on a recording material by heat-fixing the toner image on the recording material. 14. The image forming method according to claim 13, wherein the binder resin contains a vinyl resin, a polyester resin, and a hybrid resin component. 15. A structure in which the polyester resin and the polyester unit of the binder resin are crosslinked with a trivalent or higher polyhydric carboxylic acid or an anhydride thereof and / or a trivalent or higher polyhydric alcohol. The image forming method according to claim 13, wherein: 16. The binder resin according to claim 13, wherein the vinyl resin and the vinyl polymer unit of the binder resin have a structure crosslinked with a crosslinking agent having two or more vinyl groups. 2. The image forming method according to 1., 17. The vinyl polymer unit and the polyester unit of the hybrid resin component are represented by the following formula: The image forming method according to any one of claims 13 to 16, wherein the image forming method is coupled via a link. 18. The hybrid resin component is a copolymer formed by a transesterification reaction between a polyester-based unit and a vinyl-based polymer unit obtained by polymerization of a monomer having a carboxylic acid ester group. The image forming method according to claim 13. 19. The binder resin according to claim 13, wherein the binder resin contains a vinyl monomer unit and a polyester monomer unit in a mixing ratio (mass ratio) of 10/90 to 50/50. The image forming method according to any one of the above. 20. The method according to claim 13, wherein the binder resin contains 10 to 60% by mass of a THF-insoluble component.
20. The image forming method according to any one of claims 1 to 19. 21. The method according to claim 1, wherein the toner is a differential scanning calorimeter (DS).
21. The image forming method according to claim 13, further comprising a wax having a melting point of 60 to 130 [deg.] C. defined by an endothermic peak temperature at the time of temperature increase measured in C). 22. The image forming method according to claim 13, wherein said toner contains a magnetic powder as said colorant. 23. The image forming method according to claim 13, wherein the toner is externally added with a hydrophobic fine inorganic powder. 24. The heating layer of the rotary heating member has a thickness of 0.5 mm.
01 to 20 mm, a nip width formed by the rotary heating member and the rotary pressing member is 1 to 20 mm, and a linear pressure of 10 ³ to 10 ^{5 is applied} to the rotary heating member via a recording material.
Fixing speed 1 while pressing the rotating pressure member at N / m
24. The image forming method according to claim 13, wherein the toner image is heated and pressurized and fixed under a condition of 0 to 500 mm / sec.