JP3122861B2 - Heat fixing developer and heat fixing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic printing,
The present invention relates to a developer and a fixing method used in a fixing method for fixing a visible image formed with a developer to a recording material in magnetic recording or the like.

[0002]

2. Description of the Related Art Conventionally, as a method for fixing a visible image of a developer (toner) to a recording material, a pressure roller having an elastic layer and a heating roller maintained at a predetermined temperature and pressing against the heating roller is used. Accordingly, a hot roll fixing method in which a recording material holding an unfixed toner visible image is heated while being nipped and conveyed is often used.

A belt fixing system described in US Pat. No. 3,578,797 is also known.

However, in the above-described heat roller fixing which has been frequently used, (1) there is a so-called wait time during which the image forming operation is prohibited until the heat roller reaches a predetermined temperature.

(2) The optimum temperature of the heating roller is set in order to prevent defective fixing due to the fluctuation of the temperature of the heating roller due to the passage of the recording material or other external factors and the transfer of toner to the heating roller, ie, the so-called offset phenomenon. In order to achieve this, the heat capacity of the heating roller or the heating element must be increased, which requires a large amount of electric power and causes a rise in the temperature inside the image forming apparatus.

(3) Since the temperature of the roller is low, when the recording material is discharged through the heating roller, the recording material and the toner on the recording material are cooled slowly, so that the toner has high tackiness. In addition, offset or paper jam due to entrainment of the recording material may occur in combination with the curvature of the roller.

(4) Since the high-temperature heating roller is directly in contact with the hand, there is a problem in safety and a protection member is required.

Further, even in the belt fixing system described in US Pat. No. 3,578,797, the above-mentioned problems (1) and (2) of heat roll fixing have not been fundamentally solved.

JP-A-63-313182 filed by the present applicant
In Japanese Patent Laid-Open No. 2 (1993) -207, a toner having a short wait time and low power consumption is heated by a fixing device that heats a toner-visible image via a heat-resistant sheet moved by a low-heat-capacity heating element heated in a pulsed manner and fixes it on a recording material. An image forming apparatus has been proposed. Similarly, Japanese Patent Application Laid-Open No.
In the fixing device for heating and fixing a visible image of a toner to a recording material via a heat-resistant sheet, the offset phenomenon is caused by the heat-resistant sheet having a heat-resistant layer and a release layer or a low-resistance layer. There has been proposed a fixing device that effectively prevents the fixing device.

However, in order to realize a fixing method that has a short wait time and low power consumption while achieving excellent fixability of a toner-visible image to a recording material, prevention of offset, and the like, a fixing device as described above is used. In addition, the characteristics of the toner are greatly affected.

Conventionally, in order to prevent the toner from adhering to the surface of the fixing roller, a method of adding a wax such as low molecular weight polyethylene or polypropylene which sufficiently melts when heated to increase the releasability of the toner has been used. ,
While effective in preventing offset, the cohesiveness of the toner increases, the charging characteristics become unstable, and the durability tends to decrease. Therefore, various attempts have been made to improve the binder resin as another method.

For example, a method is known in which the glass transition temperature (Tg) and the molecular weight of the binder resin in the toner are increased to improve the melt viscoelasticity of the toner. However, in such a method, when the offset phenomenon is improved, the fixing property becomes insufficient, and the fixing property at a low temperature required for high-speed development and energy saving, that is, the low-temperature fixing property is inferior. .

In general, in order to improve the low-temperature fixability of a toner, it is necessary to decrease the viscosity of the toner at the time of melting to increase the adhesion area with a fixing base material. Is required to be low.

That is, since the low-temperature fixing property and the offset preventing property have contradictory aspects, it is very difficult to develop a toner that simultaneously satisfies these functions.

In order to solve this problem, for example, Japanese Patent Publication No. 51-23354 discloses a toner comprising a vinyl polymer which is appropriately crosslinked by adding a crosslinking agent and a molecular weight modifier. Japanese Patent No. 6805 discloses a toner having a wide molecular weight distribution such that the ratio between the weight average molecular weight and the number average molecular weight of the α, β unsaturated ethylenic monomer as a constitutional unit is 3.5 to 4.0. Further, a blend-type toner or the like in which Tg, molecular weight, gel content, and the like of a vinyl polymer are combined has been proposed.

Certainly, the toner according to these proposals has a lower fixing temperature (the lowest temperature at which fixing can be performed) and an offset temperature (a temperature at which offset starts to occur) as compared with a toner made of a single resin having a narrow molecular weight distribution. Although the temperature range that can be fixed is widened, if sufficient anti-offset performance is given, the fixing temperature cannot be lowered sufficiently. There was the problem of becoming.

In place of these vinyl resins, a toner obtained by crosslinking an polyester resin, which is essentially superior to vinyl resins in terms of low-temperature fixability, and further adding an offset preventing agent, is also a special feature. Kaisho 57-20855
No. 9 proposes this. This is excellent in both low-temperature fixing property and offset prevention property, but has a problem in productivity (pulverizability) as a toner.

Further, Japanese Patent Application Laid-Open No. 56-116043 discloses that a vinyl monomer is polymerized in the presence of a reactive polyester resin, and is polymerized through a crosslinking reaction, an addition reaction and a grafting reaction in the course of polymerization. Although a toner using such a resin has been proposed and has been improved in terms of pulverizability, the functions of the resins cannot be sufficiently utilized in terms of low-temperature fixability and offset prevention.

Further, two types of polyester resin and gel content are simply different (gelation degree of 80% or more and gelation degree of 1
(Less than 0%), a toner using a resin blended with a vinyl resin has been proposed in Japanese Patent Publication No. 1-10663. The toner has good low-temperature fixability, but has an anti-offset property and a pulverizability. Not enough yet. Even if the proportion of the vinyl resin having a gelation degree of 80% or more is increased for the purpose of improving the offset resistance, the anti-offset property is improved, but the low-temperature fixability is significantly reduced. Gelation degree 1
Sufficient pulverizability cannot be satisfied only by containing less than 0% of a vinyl resin.

On the other hand, in order to satisfy the physical properties required for the toner as described above, crosslinking is performed by reacting a polymer having a carboxylic acid with a metal compound in a binder resin (Japanese Patent Laid-Open No. Sho 57-79). No. 178249, 57-17
No. 8250), or a binder having a vinyl resin monomer and a more specific monoester compound as essential constitutional units and a polyvalent metal compound are reacted and cross-linked via a metal (Japanese Patent Application Laid-Open No. 61-1986). No. 110155, 61-110
156).

Further, JP-A-63-214760, JP-A-63-217362, JP-A-63-217363, and JP-A-6-217363.
In Japanese Patent Application Laid-Open No. 3-217364, two low molecular weight and high molecular weight
Having a molecular weight distribution that is divided into groups, the carboxylic acid group contained on the low molecular weight side reacts with the polyvalent metal ion to form a crosslink (a dispersion of the metal compound is added to the solution obtained by solution polymerization, and the mixture is heated. However, in either case, the reaction between the binder and the metal compound or the dispersion of the metal compound in the binder is not sufficient, and the physical properties required for the toner, particularly Properties and offset resistance have not been satisfied. In addition, since it is necessary to mix a large amount of the metal compound with the binder resin, the compounded metal compound shows a catalytic action on the binder resin depending on conditions, and the binder resin is easily gelled, and as a result, the metal compound is mixed. However, it is difficult to determine the manufacturing conditions for obtaining a desired toner, and even if the manufacturing conditions can be determined, there is a problem that reproducibility is hardly obtained.

Further, Japanese Patent Application Laid-Open No. 2-168246,
JP-A-235069 discloses that the low molecular weight component and the high molecular weight component in the binder resin are further polarized, and that the high molecular weight component contains a carboxyl group, so that the offset resistance can be improved and the excess produced during toner production can be improved. It is disclosed that the deterioration of the developability due to the pulverization phenomenon is prevented.However, as a result of our investigation, although the performance is improved with respect to the fixing property and the offset resistance, it is described in the specification. With an acid amount of about a certain degree, the dispersion state of each component inside the developer including the binder resin becomes insufficient, and uneven distribution of each component inside the developer and release to the outside of the developer occur, It becomes difficult to obtain stable developability. Further, when the developer in such a state is used in a heat fixing method having a fixing film applied to the present invention, problems such as fixation to the fixing film and breakage of the fixing film occur. As a result of our intensive studies,
This phenomenon becomes more remarkable as the weight average molecular weight (Mw) / number average molecular weight (Mn), which is considered to indicate the degree of polarization of the binder resin, increases. Especially when Mw / Mn ≧ 40,
Although the fixing property and the anti-offset property can be satisfied to some extent, serious problems arise in matching with the developing property and the fixing method as described above.

Further, the various properties required for the above-mentioned toners are often reciprocal to each other, and it is more and more desirable in recent years to satisfy both of them with high performance. Research has been conducted on comprehensive responses that include characteristics, but there is still not enough.

[0024]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to solve the above-mentioned problems, and to realize an offset phenomenon with substantially no or very short wait time and low power consumption. In addition, the present invention provides a novel heat-fixing method in which a developer image is well fixed on a recording material.

Another object of the present invention is to provide a heat fixing developer preferably used in the heat fixing method provided in the present invention.

Still another object of the present invention is to provide a heat fixing method which does not use a high-temperature rotating roller and does not require a heat-resistant special bearing.

Still another object of the present invention is to provide a heat fixing method which is excellent in safety or does not require a protective member by having a fixing device structure which does not directly touch the high temperature member. is there.

Still another object of the present invention is to provide a good image without the fixing member being affected by fixation, flaws and the like by the developer.

[0029]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies, by specifying the molecular weight of the binder resin composed of a polymer and the polar group capable of forming a cross-linking bond possessed by the polymer, it has an extremely wide fixable temperature range and the reproducibility of fine lines It was found that a stable and good developed image could be formed, and the present invention was completed.

That is, the present invention relates to a heat fixing developer obtained by subjecting a mixture having at least a binder resin, a colorant and a metal-containing compound to a hot-melt kneading step.
(A) the binder resin is a mixture of a high molecular weight polymer and a low molecular weight polymer, and (b) the chromatogram of the binder resin measured by GPC has a molecular weight of 2,000 to 30,
(C) only the high molecular weight polymer has a polar group capable of forming a crosslink bond by reaction with a metal-containing compound. (D) the acid value of the polymer-side component constituting the maximum value existing in the range of molecular weight of 800,000 to 3,000,000 is larger than 1.0 mgKOH / g, and (e) the binder resin is an alkali. The present invention relates to a heat-fixing developer which has been processed.

Further, the present invention provides a recording material for developing a visible image of a developer by using a fixedly supported heating element and a pressing member which is in pressure contact with the heating element and is in close contact with the heating element via a film. A developer used in a fixing method for heat-fixing, which contains at least a binder resin, a colorant and a metal-containing compound, and (a) the binder resin comprises a high molecular weight polymer and a low molecular weight (B) a chromatogram of the binder resin measured by GPC,
Having at least one maximum in each of the molecular weight ranges of 2,000 to 30,000 and 800,000 to 3,000,000,
(C) only the high molecular weight polymer has a polar group capable of forming a cross-linking by reaction with a metal-containing compound,
(D) The acid value of the polymer side component constituting the maximum value existing in the molecular weight range of 800,000 to 3,000,000 is 1.0 mgKOH /
g) and (e) the binder resin has been subjected to an alkali treatment.

Further, according to the present invention, a heating member fixedly supported and a pressing member which is in pressure contact with the heating member and which is in close contact with the heating member via a film are used to form a visible image of a developer on a recording material. Wherein the developer contains at least a binder resin, a colorant and a metal-containing compound, and (a) the binder resin comprises a high molecular weight polymer and a low molecular weight polymer. (B) G of the binder resin
The chromatogram measured by PC has a molecular weight of 2,0.
(C) a polarity in which only the high-molecular-weight polymer can form a cross-linking by reaction with a metal-containing compound; (D) the acid value of the polymer side component constituting the maximum value present in the region of the molecular weight of 800,000 to 3,000,000 is larger than 1.0 mgKOH / g,
(E) The present invention relates to a heat fixing method, wherein the binder resin is subjected to an alkali treatment.

The present inventors consider the reason why the developer according to the present invention exerts the effects of the present invention as follows.

That is, the binder resin of the developer according to the present invention is a mixture of a high molecular weight polymer and a low molecular weight polymer, and only this high molecular weight polymer is developed by adding a reactive polar group. Through a hot-melt kneading step during the production of the agent, a sufficient crosslinking reaction with the metal-containing compound is performed.
In particular, when a binder resin having a low melt viscosity is used, the components constituting the developer can enjoy a stronger and more uniform shearing force than before, due to a thickening effect by a cross-linking reaction. In addition to the improved dispersibility, the anti-offset property and the stabilization of the developing property are realized more than before, and also, in the heat fixing method having the fixing film used in the present invention, good matching is shown. I think it is.

By not including a reactive polar group in the low molecular weight polymer, the competitiveness of the low molecular weight polymer in the crosslinking reaction can be suppressed, and only the high molecular weight polymer can be efficiently crosslinked. It is considered that deterioration of fixability due to cross-linking and inadvertent addition of a metal-containing compound are prevented beforehand, and further lower temperature fixing and stabilization of developability are possible, and it is thought that the developer of the present invention has been obtained. .

The above effects become more remarkable as the molecular weight distribution of the binder resin becomes more polarized into a high molecular component and a low molecular component. In particular, when the maximum value of the molecular weight of the polymer side component exceeds 800,000, the mobility in the binder resin is significantly reduced.
It is preferable that a polar group capable of forming a certain amount or more of a crosslink bond is contained, and the polar group is not contained in the low molecular weight polymer.

In order to achieve the object of the present invention, the binder resin used in the present invention has two peaks in a GPC chromatogram, and has a minimum value between the two peaks as shown below. The starting point is divided into a high molecular weight side peak portion and a low molecular weight side peak portion.

The two peaks in the GPC chromatogram of the polymer according to the present invention mean a large peak in the GPC chromatogram, and a low molecular weight peak based on a minimum value between the two peaks. The portion refers to the range of lower molecular weight from the position of the minimum value, and further, the high molecular side peak portion based on the minimum value between the two peaks is the range of the higher molecular weight from the position of the minimum value. Say

The polymer component constituting the low molecular weight peak in the GPC chromatogram of the binder resin used in the developer according to the present invention has a maximum value in the range of 2,000 to 30,000. , Its weight average molecular weight (M
w) and the number average molecular weight (Mn) are 3 or less, and the polymer component constituting the peak on the polymer side has a maximum value in the range of 800,000 to 3,000,000, and Mw / Mn is It is preferably 4 or less.

The binder resin according to the present invention has a Mw / M
n is preferably 40 or more. Mw / Mn <40
However, sufficient fixability and offset resistance cannot be obtained.

Further, the polymer side component constituting the binder resin contains a reactive polar group in an acid value (mgKOH / g) range of more than 1.0. More preferably, it is 5.0 or more, still more preferably 10.0 or more. Acid value ≦ 1.
In the case of 0, a sufficient crosslinked structure cannot be constructed,
Various problems are caused by the deterioration of the offset resistance and the decrease in the dispersibility of each component in the developer.

The glass transition temperature of the binder resin is from 55 to 70 ° C., preferably from 60 to 60 ° C., from the viewpoint of the storage stability of the developer.
６５65 ° C. and the glass transition temperature is lower than 55 ° C.,
Deterioration due to blocking of the developer in a high-temperature atmosphere and hot offset in a high-temperature region occur. On the other hand, when the temperature exceeds 70 ° C., the overall fixability is adversely affected.

Further, the mixing ratio of the high molecular weight component and the low molecular weight component also greatly affects the fixing characteristics of the developer. If the hot offset occurs and exceeds 45%, the fixability in a low temperature range deteriorates. Therefore, in the present invention, the ratio of the high molecular weight to the entire binder resin needs to be 15 to 45%, and preferably needs to be restricted to the range of 20 to 40%.

In the present invention, the molecular weight of the peak of the chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and the sample concentration was 0.05 to 0.6% by weight. Inject 50-200 μl of the THF sample solution of the resin adjusted to above and measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. Standard polystyrene samples for preparing a calibration curve include, for example, Pressure Chemical C
o. Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As a column, 10 ³ -4 × 10
^In order to accurately measure the molecular weight region of ^6, a plurality of commercially available polystyrene gel columns may be combined. For example, μ-styragel 500, 1 manufactured by Waters, Inc.
0 ³ , 10 ⁴ , 10 ⁵ , and Shodex KF-80M and KF-802, 803 manufactured by Showa Denko KK
804, 805 combination or T made by Toyo Soda
SKgel G1000H, G2000H, G2500
H, G3000H, G4000H, G5000H, G6
A combination of 000H, G7000H, and GMH is preferred.

The weight ratio of the low molecular weight component to the high molecular weight of the binder resin according to the present invention is determined by the area of the low molecular weight peak portion and the high molecular weight peak portion based on the minimum value between the peaks of the chromatogram of GPC. Calculate from the ratio.

The polymer component having a polar group capable of forming a cross-linking bond of the present invention generally has a carboxyl group, a carbonyl group, an ether group, a thioether group, an amino group, an amide group, a hydroxyl group and the like. Among them, a polymer containing a carboxyl group shows the best reactivity. Examples of the carboxyl group-containing monomer for synthesizing the vinyl polymer include acrylic acid, methacrylic acid, α-ethylacrylic acid, acrylic acid such as crotonic acid and α- or β-alkyl derivatives thereof, fumaric acid,
There are unsaturated dicarboxylic acids such as maleic acid and citraconic acid and monoester derivatives thereof, and such a monomer can be used alone or as a mixture and copolymerized with other monomers to produce a desired polymer. . Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid.

The carboxyl group-containing monomer usable in the present invention includes, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate,
Monoesters of α, β-unsaturated dicarboxylic acids such as monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc .; monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, Monoesters of alkenyl dicarboxylic acids such as monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate and monobutyl n-butenyladipate; monomethyl phthalate, monoethyl phthalate, monobutyl phthalate and the like And monoesters of aromatic dicarboxylic acids.

The above-mentioned carboxyl group-containing monomer may be added in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, based on all monomers constituting the polymer side of the binder resin.

The reason why the dicarboxylic acid monoester monomer is selected as described above will be described later in detail, but is that a suspension polymerization method is preferable as a resin production method. This is because, in the suspension polymerization, it is not appropriate to use an acid monomer having a high solubility in an aqueous suspension, and it is preferable to use an ester having a low solubility in an ester.

Examples of the comonomer for obtaining the high-molecular component of the binder resin used in the developer of the present invention and the monomer for obtaining the low-molecular component are as follows.

For example, styrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof; ethylene , Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Stearyl, meta Phenyl acrylic acid, dimethylaminoethyl methacrylate, alpha-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl methacrylate;
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, propyl acrylate,
Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds of vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; used alone or in combination of two or more.

Of these, a combination of monomers that will result in a styrene copolymer and a styrene acrylic copolymer is preferred.

If necessary, a crosslinking monomer may be added to the polymer side peak component.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used.

The binder resin used in the present invention needs to be a polymer cross-linked with a cross-linkable monomer as exemplified below in order to achieve the object of the present invention.

Aromatic divinyl compounds, for example, divinylbenzene, divinylnaphthalene, etc .; diacrylate compounds linked by an alkyl chain; for example, ethylene glycol diacrylate, 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 methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond , Such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds instead of methacrylate Diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2) -2,2-bis ( - hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku) . As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

These cross-linking agents are used in combination with other monomer components 10
It is preferable to use 0.001 to 1% by weight, preferably 0.03 to 0.01% by weight, based on 0% by weight.

Among these crosslinkable monomers, those which are preferably used in the developer resin from the viewpoint of fixing properties and anti-offset properties include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. And diacrylate compounds linked by a chain containing the same.

As a method for producing the binder resin according to the present invention, a high molecular weight polymer and a low molecular weight polymer are separately synthesized by a solution polymerization method, then they are mixed in a solution state, and then the solvent is removed. Alternatively, a low-molecular-weight polymer obtained by melt-kneading with an extruder or the like, and a low-molecular-weight polymer obtained by a solution polymerization method or the like are dissolved in a monomer constituting a high-molecular-weight polymer, and suspension polymerization is performed. A two-stage polymerization method for drying and obtaining a binder resin is exemplified. However, the dry blending method has problems in uniform dispersion and compatibility, and the two-stage polymerization method has many advantages in uniform dispersibility and the like, but increases the amount of low molecular weight to higher than high molecular weight. In the presence of low molecular weight components, not only is it difficult to synthesize the desired high molecular weight components desired in the present invention, but also there are drawbacks such as unnecessary low molecular weight components being by-produced. The solution blending method is most suitable for application to the present invention.

As a method for synthesizing the low molecular weight component of the binder resin according to the present invention, a known method can be used. However, in the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control. In that regard, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature, It is preferable to obtain a low molecular weight compound in the resin composition used in the present invention. In particular, the solution polymerization method under a pressurized condition is effective in minimizing the amount of the initiator used and minimizing the influence of the initiator residue.

On the other hand, as a polymerization method which can be used in the present invention as a method for synthesizing the high molecular weight component of the binder resin according to the present invention, an emulsion polymerization method or a suspension polymerization method can be mentioned.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
There is an advantage as a method for producing a binder resin for a toner because it is easy to mix with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. To avoid this inconvenience, suspension polymerization is advantageous.

In suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. There is an appropriate amount in terms of the amount of a monomer relative to an aqueous solvent, and generally 0.05 to 1 based on 100 parts by weight of an aqueous solvent. Used in parts by weight. The polymerization temperature is suitably from 50 to 95 ° C, but should be appropriately selected depending on the initiator used and the intended polymer.

In the present invention, as an initiator used for synthesizing a high molecular weight polymer, any initiator which is insoluble or hardly soluble in water can be used. Examples thereof include benzoyl peroxide and tert-butyl. Peroxyhexanoate or the like is used alone or in combination at 0.05 to 0.5 part by weight based on 100 parts by weight of the monomer.

In the present invention, the carboxylic acid groups and carboxylic acid ester sites in the copolymer obtained by the above method are subjected to an alkali treatment to be saponified. That is, it is preferable that the carboxylic acid group or the carboxylic acid ester moiety is changed to a polar functional group by reacting with a cation component of an alkali. Even if the polymer side component of the binder resin contains a carboxyl group that reacts with the metal-containing compound, the efficiency of the cross-linking reaction with the metal-containing compound decreases when the carboxyl group is dehydrated, that is, in a ring-closed state. Because you do.

This alkali treatment may be carried out after the production of the binder resin, by introducing it as an aqueous solution into the solvent used at the time of polymerization and stirring. Examples of the alkali that can be used in the present invention include Na, K, Ca, Li, Mg, and Ba.
Hydroxides of alkali metals and alkaline earth metals such as;
There are hydroxides of transition metals such as Zn, Ag, Pb, and Ni; hydroxides of quaternary ammonium salts such as ammonium salts, alkylammonium salts, and pyridium salts. Particularly preferred examples include NaOH and KOH. .

In the present invention, the saponification reaction does not need to be carried out over all of the carboxylic acid groups and carboxylic acid ester sites in the copolymer. I just need to change.

The amount of the alkali used in the saponification reaction is difficult to determine unequivocally depending on the type of the polar group in the binder resin, the dispersion method, the type of the constituent monomers, and the like. What is necessary is just 02-5 times equivalent. When the amount is less than 0.02 equivalent, the saponification reaction is not sufficient, and the number of polar functional groups generated by the reaction decreases, and as a result, the subsequent metal crosslinking reaction becomes insufficient.
On the other hand, when the amount exceeds 5 times equivalent, the functional group such as a carboxylic acid ester site is adversely affected by hydrolysis of the ester, generation of a salt by a saponification reaction, and the like.

When an alkali treatment having an acid value of 0.02 to 5 equivalents is performed, the residual cation ion concentration after the treatment is included in the range of 5 to 1000 ppm, which is preferable for defining the amount of alkali. Can be used.

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

Among the reactive metal compounds, the organometallic compounds are excellent in compatibility and dispersibility with the polymer, and the crosslinking by the reaction with the metal compound proceeds more uniformly in the polymer, so that more excellent results are obtained. .

Among the reactive organometallic compounds as described above, those containing an organic compound having a high vaporization or sublimation property as a ligand or a counter ion are particularly useful. Among the organic compounds forming a ligand or a counter ion with a metal ion, those having the above properties include, for example, salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicylosalicylic acid, ditert-butylsalicylic acid And salicylic acid and derivatives thereof, for example, β-diketones such as acetylacetone and propionacetone, and low-molecular carboxylic acid salts such as acetate and propionic acid.

It is also possible for the metal complex to have charge controllability of toner particles. As such a metal complex, there is an azo-based metal complex represented by the following general formula [I].

[0077]

Embedded image

Next, specific examples of the complex will be shown.

[0079]

Embedded image

[0080]

[0081]

[0082]

[0083]

[0084]

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

[0086]

Next, specific examples of the complex will be shown.

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

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

The amount of the metal complex to be added to the toner particles varies depending on the type of the toner binder, whether or not the carrier is used in combination, the pigment for coloring the toner, and the reactivity of the metal complex with the binder. 0.01 to 100% by weight of binder, including unreacted ones
It is 20% by weight, preferably 0.1 to 10% by weight.

Further, by reacting the above metal complex with the binder at the time of melt-kneading, compared with the case where it is added at the time of synthesizing the binder, the metal complex is more decomposed and reactive, and has higher compatibility with the binder or dispersibility in the binder. There is an advantage that the toner is excellent and a stable chargeability is obtained as a toner.

In the present invention, the metal compound as a cross-linking component can have charge controllability as a toner. However, if necessary, a charge control agent can be separately used. Conventionally known negative or positive charge control agents are used.

Today, charge control agents known in the art include the following:

The following substances control the toner to be negatively charged.

For example, organic metal complexes and chelate compounds are effective and include the above-mentioned monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

The following substances control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium analogs thereof Onium salts such as salts and lake pigments thereof. Triphenylmethane dyes and their lake pigments. (As a rake agent,
Metal salts of higher fatty acids, such as phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and ferrocyanide; metal complexes of acetylacetone. Diorganotin oxides such as dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate;
And diorganotin borates such as dicyclohexyl tin borate. These can be used alone or in combination of two or more. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity and durability, it is preferable to add silica fine powder.

The fine silica powder used in the present invention is BE
The specific surface area by nitrogen adsorption measured by the T method is 30 m ² / g
Those within the above range (especially 50 to 400 m ² / g) give good results. It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight of silica fine powder with respect to 100 parts by weight of the toner.

The silica fine powder used in the present invention may be, if necessary, silicone varnish, various modified silicone varnish, or the like for the purpose of hydrophobicity, charge control, etc.
It is also preferable to use a treatment agent such as silicone oil, various modified silicone oils, a silane coupling agent, a silane coupling agent having a functional group, or another organosilicon compound, or a combination treatment with various treatment agents.

As other additives, for example, lubricants such as Teflon, zinc stearate and polyvinylidene fluoride are preferable, and polyvinylidene fluoride is particularly preferable. Or an abrasive such as cerium oxide, silicon carbide, strontium titanate,
Among them, strontium titanate is preferable. Alternatively, for example, a fluidity imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferable. Anti-caking agent,
Alternatively, for example, a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide, and tin oxide, or white and black fine particles of opposite polarity can be used in a small amount as a developability improver.

For the purpose of improving the releasability at the time of hot roll fixing, a wax-like substance such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, carnauba wax, sasol wax, paraffin wax, etc. was added to 100% by weight of a binder resin. 0.5 ~
Adding about 10% by weight to the toner is also a preferred embodiment of the present invention.

Further, when the toner of the present invention is used as a two-component developer, it is used by mixing with a carrier powder.
In this case, the mixing ratio of the toner and the carrier powder is 0.1 to 50% by weight as a toner concentration, preferably 0.5 to 1%.
0% by weight, more preferably 3 to 5% by weight is desirable.

As the carrier that can be used in the present invention, all known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder and nickel powder, glass beads, etc. Those treated with a resin, a vinyl-based resin, a silicon-based resin, or the like can be given.

Further, the toner of the present invention can be used as a magnetic toner by further containing a magnetic material. In this case, the magnetic material also serves as a colorant. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; or aluminum, cobalt, copper, lead, magnesium, and tin of these metals. Zinc, antimony,
Examples include alloys of metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic materials have an average particle of 0.1 to 2
μm, and preferably about 0.1 to 0.5 μm.
The amount is preferably about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, based on 100 parts by weight of the resin component.

The magnetic characteristics when 10K Oersted is applied are such that the coercive force is 20 to 150 Oersted, the saturation magnetization is 50 to 150 Oersted.
Desirable is 200 emu / g and residual magnetization of 2 to 20 emu / g.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. Toner colorants are well known and include, for example, pigments such as carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengalara, phthalocyanine blue, and indanthrene blue. These are used in amounts necessary and sufficient to maintain the optical density of the fixed image.
0.1 to 20 parts by weight, preferably 2 to 10 parts by weight per part by weight
Good addition amount by weight. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes and the like.
0.1 to 20 parts by weight, preferably 0.1 part by weight, per 0 parts by weight.
The addition amount of 3 to 3 parts by weight is good.

To prepare the toner for developing an electrostatic image according to the present invention, a binder resin, a metal compound, a pigment or dye as a colorant, a magnetic substance, a charge control agent, and other additives as necessary are used. After mixing thoroughly with a mixer such as a Henschel mixer or a ball mill, melting, kneading and kneading using a hot kneader such as a heating roll, kneader or extruder to mix the resins into The toner according to the present invention can be obtained by dispersing or dissolving a compound, a pigment, a dye, and a magnetic substance, and solidifying by cooling, followed by pulverization and classification.

Further, if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner for developing an electrostatic image according to the present invention.

Next, the heat fixing structure of the present invention applicable to the fixing method of the present invention will be specifically described.

In the present invention, the heating element has a smaller heat capacity than a conventional heating roll and has a linear heating portion.
The maximum temperature of the heating section is preferably 100 to 300 ° C.

The film located between the heating element and the pressing member is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. Examples of the heat-resistant sheet include polyester, PET, and the like. (Polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, polyamide, etc., as well as metal sheets such as aluminum and metal sheets and polymer sheets The configured laminated sheet is used.

As a more preferable structure of the film, these heat-resistant sheets have a release layer and / or a low-resistance layer.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

FIG. 1 shows a structural diagram of an example of a fixing device for carrying out the method of the present invention.

Reference numeral 11 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus, and has a thickness of 1.0 mm and a width of 10 m as an example.
m, an alumina substrate 12 having a longitudinal length of 240 mm
3 is applied to a width of 1.0 mm, and is energized from both ends in the longitudinal direction. The energization is performed by applying a pulse corresponding to a desired temperature and energy release amount controlled by the temperature detecting element 14 by changing the pulse width in a pulse-like waveform of DC 100 V and a cycle of 20 msec. Approximate pulse width is 0.5 ms
c to 5 msec.

The fixing film 15 moves in the direction of the arrow in the drawing while coming into contact with the heating element 11 whose energy and temperature are controlled in this manner. As an example of this fixing film, a thickness of 20 μm
Heat-resistant film, for example, polyimide, polyetherimide, PES, PFA on at least the image contact surface side PT
This is an endless film in which a release layer obtained by adding a conductive agent to a fluororesin such as FE or PAF is coated by 10 μm. Generally, the total thickness is 100 μm, more preferably less than 40 μm. The film is driven by the driving roller 16 and the driven roller 1
By the drive and the tension by 7, the wrist moves in the direction of the arrow without wrinkles.

Reference numeral 18 denotes a pressure roller having a rubber elastic layer of silicon rubber or the like with good releasability, pressurizing the heating element via the film with a total pressure of 4 to 20 kg, and rotating by pressing against the film.
The unfixed developer 20 on the transfer material 19 is guided to a fixing section by an entrance guide 21 and obtains a fixed image by the above-described heating.

Although the endless belt has been described above, as shown in FIG. 2, a sheet feed shaft 24 and a take-up shaft 27 may be used, and the fixing film may be an edged film.

The image forming apparatus is applicable to all fixing devices such as a copying machine, a printer, and a facsimile, which form an image using a developer.

In the low heat capacity linear heating element 11, when the temperature detected by the temperature detecting element 14 is T ₁ , the surface temperature T ₂ of the film 15 facing the resistance material 13 is substantially equal to T ₁ . Further, the film surface temperature T _{3 at} the portion where the film 15 is peeled off from the developer fixing surface is equal to the temperatures T ₁ and T _2.
Is almost equal to

[0132]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

Resin Synthesis Example 1 200 parts by weight of xylene was charged into a reaction vessel and the temperature was raised to the reflux temperature. In addition, di-tert-
8 parts by weight of butyl peroxide were mixed, and the solution polymerization was completed in 6 hours under reflux of xylene to obtain a low molecular weight resin solution.

On the other hand, styrene 70 parts by weight, butyl acrylate 25 parts by weight, monobutyl maleate 5 parts by weight, divinylbenzene 0.005 parts by weight, polyvinyl alcohol 0.2 parts by weight, degassed water 200 parts by weight, benzoyl peroxide 0.1 part by weight was mixed and dispersed. The suspension was heated and maintained at 85 ° C. for 24 hours under a nitrogen atmosphere to complete the polymerization, thereby obtaining a high molecular weight resin. Next, the resin was washed with an aqueous solution of NaOH equivalent to twice the acid value of the resin for 2 hours. 30 parts by weight of this high-molecular-weight resin was put into a solution of 70 parts by weight of the low-molecular-weight resin described above at the time of completion of the solution polymerization, and completely dissolved in a solvent and mixed. A copolymer composition was obtained.

Resin Synthesis Example 2 Synthesis Example 1 was the same as Synthesis Example 1 except that the mixing ratio of the high molecular weight resin and the low molecular weight resin was 80 parts by weight and 20 parts by weight, respectively.
In the same manner as in the above, a styrenic copolymer composition was obtained.

Resin Synthesis Example 3 Synthesis Example 1 was the same as Synthesis Example 1 except that the mixing ratio of the high molecular weight resin and the low molecular weight resin was 60 parts by weight and 40 parts by weight, respectively.
In the same manner as in the above, a styrenic copolymer composition was obtained.

Resin Synthesis Examples 4 to 7 The styrene copolymer compositions of Synthesis Examples 4 to 7 were obtained by changing the monomer species, the mixing ratio, the initiator, the reaction conditions and the like according to the above Synthesis Example 1.

[0138]

[Table 1]

Comparative Synthesis Examples Resins of Comparative Synthesis Examples 1 to 4 were synthesized in the same manner with the following monomer compositions.

[0140]

[Table 2]

Example 1 100 parts by weight of the copolymer of Resin Synthesis Example 1 100 parts by weight of magnetic fine powder 0.6 part by weight of a negatively chargeable monoazo pigment 4 parts by weight of low molecular weight polypropylene 4 parts by weight The above mixture was heated to 130 ° C. The mixture was melt-kneaded in a twin-screw extruder, and the cooled kneaded material was coarsely pulverized with a hammer mill, and further finely pulverized with a jet mill. The fine powder obtained was air-classified to obtain a magnetic powder having a weight average particle size of 6.7 μm. The resin particles were included.

1.2 parts by weight based on 100 parts by weight of the resin particles.
A magnetic developer was obtained by mixing parts by weight of silica fine powder.

Next, the apparatus used in this embodiment will be described. In this embodiment, a commercially available laser beam printer L
The fixing device of BP-SX (manufactured by Canon) was modified to the following configuration, and the fixing was performed under the following conditions.

An electrostatic latent image is formed by temporarily charging at −600 V, a gap (300 μm) is set without contact between the photosensitive drum and the developer layer on the developer carrier (including magnets), and an AC bias (f = 1800 Hz Vpp = 1200 V) and a direct current bias (VDC = −400 V) were applied to the developing drum.

Next, in the heat fixing apparatus of the present invention shown in FIG.
° C, the total pressure between the heating body 11 and the pressure roller 18 is 6 kg,
The nip between the pressure roller and the film was 3 mm, and the rotation speed of the pressure roller 18 was set to 24 mm / sec (equivalent to LBP-LX).

As the heat-resistant sheet, a 50 μm-thick polyimide film having a low-resistance release layer in which a conductive material was dispersed in PTFE on the contact surface with the transfer material was used.

Under the above setting conditions, 4 sheets (A4) / min
A print test for forming a developer image by a reversal developing method over 3000 sheets continuously at a printing speed of normal temperature and normal humidity (2
(5 ° C., 60% RH), and the obtained images were evaluated for the following items. At the same time, the state of the surface of the fixing film was observed to evaluate its durability.

(Examples 2 to 4) Preparation of a developer was performed in the same manner as in Example 1 except that the resins of Synthesis Examples 2 to 4 were used instead of the resin of Synthesis Example 1 used in Example 1. And a print test.

Table 3 shows the results.

(Comparative Examples 1 to 7) In place of the resin of Synthesis Example 1 used in Example 1, Synthesis Examples 5 to
Preparation of a developer and a print test were performed in the same manner as in Example 1 except that the resin of Comparative Example 7 or the resins of Comparative Synthesis Examples 1 to 4 were used, and the same items were evaluated.

Table 3 shows the results.

[0152]

[Table 3]

[A] Evaluation of Printout Image (1) Fixing Property The fixing property was measured by applying a load of 50 g / cm ² , rubbing the fixed image with soft thin paper, and decreasing the image density before and after rubbing. (%). ◎ (excellent): 0 to 5%, ○ (good): 5 to 10% Δ (acceptable): 10 to 20%, × (impossible): 20% or more (2) Offset resistance A sample image at a rate of about 5% was printed out, and evaluation was made based on the degree of stain on the image after 3000 sheets. ：: very good (no occurrence), ：: good (almost no occurrence) △: practical, ×: impractical (3) Image density Printout of 3000 sheets of ordinary paper for copying machines (75 g / m ² ) Evaluation was made by maintaining the image density at the end of the test. ◎ (excellent): 1.40 or more, ○ (good): 1.35
To 1.40 Δ (acceptable): 1.00 to 1.35, × (impossible): 1.0
0 or more (4) Image quality The scattering of the developer, the roughness and the like were visually evaluated. ◎: very good, ○: good △: practical, ×: impractical

[B] Evaluation of Durability of Fixing Film (1) Surface Condition The surface of the fixing film after the print-out test was scratched or scraped was visually evaluated. ◎: very good (not generated), ：: good (almost no occurrence) △: practical, ×: impractical (2) Status of fixation of residual developer Residual developer on fixing film surface after completion of printout test Was visually evaluated. ◎: very good (not generated), ○: good (almost no occurrence) △: practical, ×: impractical

[0155]

As described above, according to the present invention, the reactive polar group is contained only in the polymer side component constituting the binder resin in the developer, and is crosslinked with the metal-containing compound, whereby the inside of the developer is It is possible to improve the dispersibility of each component and achieve excellent fixing property, anti-offset property and developing property, realize heat fixing with low heat capacity, and enable high durability.

[Brief description of the drawings]

FIG. 1 is a structural diagram of an example of a fixing device for implementing a method of the present invention.

FIG. 2 is a structural diagram of another example of a fixing device for implementing the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Low heat capacity linear heating element 12 Alumina substrate 13 Resistance material 14 Temperature measuring element 15 Fixing film 16 Driving roller 17 Follower roller 18 Pressure roller 19 Transfer material 20 Unfixed developer 21 Inlet guide 24 Sheet feeding axis 27 Winding axis

(72) Inventor Nobuyuki Okubo 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Kiyoko Tsuchiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hiroyuki Suematsu 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-63-94251 (JP, A) JP-A-63-217361 (JP, A) JP-A-62-9356 (JP, A) JP-A-2-160253 (JP, A) JP-A-61-126562 (JP, A) JP-A-3-113463 (JP, A) JP-A-3-288158 (JP, A)

Claims (6)

(57) [Claims] At least a binder resin, a colorant and a metal-containing material.
With compoundThe mixture is obtained through a hot melt kneading process
In heat fixing developer, (A) the binder resin comprises a high molecular weight polymer and a low molecular weight polymer
And a mixture with (b) Measured by GPC of the binder resin
The determined chromatogram has a molecular weight of 2,000 to 30,
000 and 800,000-3,000,000
Have one maximum, and (c)TheHigh molecularamountPolymer only
Can form cross-links by reaction with metal-containing compounds
It has a polar group,(D) having a molecular weight of 800,000 to 3,000,000
Value of the polymer side component that constitutes the maximum value existing in the region
Is greater than 1.0 mg KOH / g,(e) The binding
Heating characterized in that the resin has been treated with alkali
Fixing developer. 2. Only the polymer constituting the polymer-side maximum has a monomer component having two or more polymerizable double bonds in an amount of 0.001 to 100% by weight of the other monomer components.
The heat fixing developer according to claim 1, wherein the developer is synthesized by using 1 to 1% by weight. 3. A fixed image of a developer is heated and fixed on a recording material by a fixedly supported heating element and a pressing member which is in pressure contact with the heating element and is in close contact with the heating element via a film. a developer used in the fixing process, even without less are those containing a binder resin, a colorant and a metal-containing compound, (a) the binder resin comprises a high molecular weight polymer
A mixture of low molecular weight polymer, chromatogram as measured by GPC of (b) the binder resin, molecular weight 2,
Has at least one maximum value in each region of 000～30,000 and from 800,000 to 3,000,000, only (c) the high content <br/> molecular weight polymer, crosslinked by reaction with a metal-containing compound A polar group capable of forming a bond, and (d) a molecular weight of 80
Polymers with maximum values in the range of 10,000 to 3 million
The acid value of the side component is greater than 1.0 mg KOH / g,
( E ) A developer for heat fixing, wherein the binder resin has been subjected to an alkali treatment. 4. Only the polymer constituting the polymer-side maximum has a monomer component having two or more polymerizable double bonds in an amount of 0.001 to 100% by weight of the other monomer components.
The heat-fixing developer according to claim 3, wherein the developer is synthesized by using 1 to 1% by weight. 5. A heating member fixedly supported and a pressure member which is in pressure contact with the heating member and is brought into close contact with the heating member via a film to heat and fix a visible image of the developer on the recording material. in the fixing method are those wherein the developer contains at least a binder resin, a colorant and a metal-containing compound, (a) the binder resin is a polymer
A mixture of an amount the polymer and the low molecular weight polymer, chromatogram as measured by GPC of (b) the binder resin,
Having at least one maximum in each of the molecular weight ranges of 2,000 to 30,000 and 800,000 to 3,000,000,
(C) said high molecular weight polymer only has a polar group capable of forming a crosslinking bond by reaction with a metal-containing compound,
(D) Maximum value existing in the molecular weight range of 800,000 to 3,000,000
Has an acid value of 1.0 mgKOH /
greater than g, (e) the binder resin, heat fixing method characterized by being alkaline treatment. 6. The polymer constituting the polymer-side local maximum value only comprises a monomer component having two or more polymerizable double bonds in an amount of 0.001 to 100% by weight of the other monomer components.
6. The heat fixing method according to claim 5, wherein the composition is synthesized by using 1 to 1% by weight.