JPH0117579B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., and in particular, a method for producing a toner suitable for hot roller fixing. It is related to.

Conventionally, as an electrophotographic method, U.S. Patent No. 2297691
Specification of No. 42-23910 and Special Publication No. 1973
Many methods are known, as described in Japanese Patent No. 24748, etc., but in general, a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means, and then the A latent image is developed using toner, and after the toner image is transferred to a transfer material such as paper as necessary, it is fixed by heat, pressure, solvent vapor, etc. to obtain a copy.

Various methods and devices have been developed for the above-mentioned final step, which is the step of fixing the toner image on a sheet such as paper. The most common method at present is the compression heating method using a heated roller.

In the press-heating method using a hot roller, fixing is performed by passing the toner image surface of the sheet to be fixed under pressure on the surface of a hot roller whose surface is made of a material that has releasability to the toner. . In this method, the surface of the heated roller and the toner image on the fixing sheet come into contact with each other under pressure.
It has extremely good thermal efficiency when fusing a toner image onto a sheet to be fixed, allows rapid fixing, and is very effective in high-speed electrophotographic copying machines. However, in the above method, since the surface of the heat roller and the toner image contact each other under pressure in a molten state, a portion of the toner image adheres to and transfers to the surface of the fixing roller, and this is transferred again to the next sheet to be fixed. One of the essential conditions for the heated roller fixing method is to prevent toner from adhering to the surface of the heat fixing roller, which may cause a so-called offset phenomenon and stain the sheet to be fixed.

Conventionally, in order to prevent toner from adhering to the fixing roller surface, for example, the roller surface is made of a material that has excellent releasability for toner, such as silicone rubber or fluorine-based resin, and the surface is also coated with anti-offset and roller surface coatings. In order to prevent fatigue, the surface of the roller is coated with a thin film of a liquid with good mold releasability, such as silicone oil. However, although this method is extremely effective in preventing toner offset, the offset prevention liquid evaporates due to heating, giving the user an unpleasant odor, and requires a device to supply the offset prevention liquid. Therefore, there are problems such as a complicated fixing device. Therefore, it is not desirable to prevent offset by supplying an offset-preventing liquid, but rather the development of a toner with high offset resistance over a wide fixing temperature range is currently desired.

As described in Japanese Patent Publication No. 51-23354, such an offset phenomenon tends to occur when a low molecular weight resin is used. Therefore, as described in the same publication, a method for preventing the offset phenomenon by using a crosslinked resin is proposed. The inventors of the present invention have investigated and found that simply creating a crosslinked resin is not necessarily satisfactory. In particular, when the degree of crosslinking is increased, the dispersion of pigments and the like into the binder resin deteriorates, the pigments and the like are exposed on the toner surface, the development characteristics of the toner deteriorates, and the fixing temperature also rises.

Further, in the case of magnetic toner, there are problems such as an increase in fixing temperature and poor offset resistance.

Of course, in addition to fixing properties, toners also need to be excellent in anti-blocking properties, development properties, transferability, cleaning properties, etc., but conventional toners must have the following defects: had one or more. That is, many toners that are easily melted at relatively low temperatures by heating tend to cake or aggregate during storage or in a copying machine. Many toners have poor triboelectric and rheological properties due to environmental humidity changes. In addition, with many toners, the density of the resulting image decreases due to mutual deterioration of the toner, carrier particles, and photosensitive plate due to collisions between toner particles and carrier particles due to repeated development due to continuous use and contact between them and the photosensitive plate surface. or increase the background density, reducing the quality of the copy.
Furthermore, with many toners, if an attempt is made to increase the density of a reproduced image by increasing the amount of toner adhering to the surface of the photosensitive plate having a latent image, the background density usually increases;
A so-called fog phenomenon occurs. Therefore, there is a need for a toner that has excellent various toner properties and is suitable for hot roller fixing.

Therefore, it is an object of the present invention to provide a method for producing a toner having excellent physical and chemical properties that overcomes the above-mentioned toner defects.

An object of the present invention is to provide a method for producing a toner for hot roller fixing which has a good fixing method and particularly good offset resistance.

A further object of the present invention is to provide a method for producing a toner for hot roller fixing that has good chargeability and always shows stable chargeability during use, and provides clear and fog-free images.

A further object of the present invention is to provide a method for producing a toner for hot roller fixing that has excellent fluidity, does not cause aggregation, and has excellent impact resistance.

A further object of the present invention is to provide a method for producing a toner for thermal roller fixing that causes less deposits on the surface of a toner holding member or photoreceptor.

A further object of the present invention is to provide a method for producing a magnetic toner that, when used as a magnetic latent image agent, exhibits good and uniform magnetism and can be fixed by a hot roller.

The feature of the present invention is that 1 to 50 parts by weight of a decomposable metal compound is mixed with 100 parts by weight of a polymer having no carboxyl groups to prepare a mixture containing the above-mentioned metal compound. The above degradable metal compound is added to 100 parts by weight of the polymer.
The above mixture and a colorant in an amount of 0.01 to 20 parts by weight are added and melt-kneaded to cause the carboxyl group-containing polymer and the degradable metal compound to react during the manufacturing process.

The toner for hot roller fixing produced using the present invention is physically and chemically superior, and even when no offset prevention liquid is applied to the surface of the fixing roller, it can be fixed well with a hot roller without causing offset. This makes it possible to simplify and lighten the fixing device. Furthermore, since it has stable and very excellent developing properties, it is possible to significantly improve the stability and reliability of copying machines.

That is, in the toner manufactured according to the present invention, the carboxyl group-containing polymer in the binder resin reacts with the decomposable metal compound to undergo a type of crosslinking, resulting in poor mechanical properties at room temperature. The toner has improved impact resistance and toughness, and also has improved charging characteristics, resulting in improved development characteristics as a toner. Furthermore, in the manufacturing method of the present invention,
When the reaction between the carboxyl group-containing polymer in the binder resin and the decomposable metal compound has hardly progressed, and the melt viscosity of the binder polymer is low, toner particles such as dyes, pigments, and charge control agents are removed. Since the material is dispersed in the binder polymer, it can be more uniformly dispersed than when dyes, pigments, etc. are dispersed in a crosslinked polymer with a high degree of crosslinking. Thereafter, the binder polymer is crosslinked to a desired degree by a gentle reaction between the carboxyl group-containing polymer in the binder and the dispersible metal compound. Therefore, in the toner manufactured based on the method of the present invention, toner components such as dyes, pigments, and charge control agents are uniformly dispersed in the toner, so that electrical properties such as specific resistance and chargeability of the toner can be improved. Characteristics are stabilized and toner development characteristics are significantly improved. Furthermore, in the toner according to the present invention, the crosslinking reaction of the polymer proceeds gradually due to the reaction between the carboxyl group-containing polymer in the binder and the decomposable metal compound, making it easy to control the crosslinking reaction during the manufacturing process. Therefore, it is easy to obtain a toner having a desired melt viscosity.

The toner melt index meets the Japanese Industrial Standards JISK 7210 flow test method for thermoplastic plastics.
0.01 to 0.01 when measured using the manual cutting method under test conditions of temperature 125℃ and load 10Kg using the described device.
When the toner is in the range of 10g/10min., the toner has excellent fixing properties, and when fixed with a heated roller fixer, the offset resistance in high temperature areas is significantly improved.
The fixing temperature is approximately the same as that of toners made from corresponding unreacted polymers. In particular, the toner melt index is 0.1 to 6g/10min.
Within this range, better results can be obtained.

Furthermore, the value of weight average molecular weight/number average molecular weight (Mw/Mn) is larger than 4.0 (particularly preferably larger than 10), and the weight average molecular weight (Mw)
100,000 or more, it is possible to easily produce a polymer having a desired melt viscosity through a mild reaction by reaction with a degradable metal compound, and having the desired fixing properties. It is possible to stably produce toner. As will be specifically shown later, when a polymer with Mw/Mn of less than 4.0 is used, Mw/Mn must be increased in order to obtain a toner having desired fixing properties through reaction with a decomposable metal compound.
Compared to the case where a polymer of 4.0 or more is used, the formulation and manufacturing conditions must be set so that the above reaction occurs more actively, and it is difficult to stably produce a toner having the desired fixing characteristics with good reproducibility. It becomes difficult.

The value of Mw/Mn is greater than 4.0, and Mw
Polymers larger than 100,000 can be synthesized using well-known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization, in which several resins with different molecular weights are dissolved or molten. How to mix with. A method of manufacturing by changing the reaction temperature during the polymerization reaction, a method of manufacturing by mixing an initiator, a chain transfer agent, etc., and a method of manufacturing by applying a certain degree of crosslinking when forming a polymer from monomers to increase Mw. /Mn and
There are methods of increasing Mw, but among these manufacturing methods, the method of adjusting Mw/Mn by suppressing the degree of crosslinking within a low range is the most suitable method for the present invention. This is achieved by adding a small amount of a polyfunctional monomer to.

On the other hand, a solution polymerization method is suitable as a process for synthesizing a polymer for a binder. This is because in emulsion polymerization and suspension polymerization, monomers are polymerized by emulsifying or dispersing them using additives such as surfactants and dispersion stabilizers in water, which is the continuous phase, and then adding salts etc. to form the polymer. Since the polymer is recovered, the resulting polymer contains the hydrophilic additives mentioned above.
When such a hydrophilic additive is present in a toner, the toner often absorbs moisture under high humidity, resulting in a decrease in specific resistance, which adversely affects the electrical properties of the toner. Furthermore, in the bulk polymerization method, problems such as a gel effect occur when the degree of polymerization increases, making it extremely difficult to control the polymerization reaction.

On the other hand, in the solution polymerization method, the polymerization reaction is generally carried out in a hydrophobic organic solvent, so a hydrophilic additive is not required, and furthermore, the presence of a solvent makes it relatively easy to control the polymerization reaction. However, the solution polymerization method has a problem in that when the degree of crosslinking is increased, a gel is formed that is insoluble in the solvent, making it difficult to control the polymerization reaction and to recover the polymer after polymerization. Therefore, a polymer having a degree of crosslinking within a range that does not cause the above-mentioned problems is synthesized by solution polymerization, and based on the present invention, a polymer having a slight degree of crosslinking made by solution polymerization is synthesized. Synthesized using a solution polymerization method that has the above-mentioned excellent properties by reacting the coalescent with a decomposable metal compound during the manufacturing process and increasing the degree of crosslinking to the extent that it provides a melt viscosity suitable for the fixing characteristics of the toner. This makes it possible to more easily apply the resulting polymer to toners for hot roller fixing.

In the present invention, the value of Mw/Mn was calculated from the value measured by gel permeation chromatography. The measurement conditions are as follows: Tetrahydrofuran is flowed as a solvent at a flow rate of 1 ml per minute at a temperature of 25° C., and 0.5 ml of a sample solution of tetrahydrofuran with a sample concentration of 8 mg/ml is injected for measurement. In addition, in order to accurately measure the molecular weight range of 10 ³ to 2 × 10 ⁶ as a column, it is recommended to combine multiple commercially available polystyrene gel columns, such as μ-Styragel 500 manufactured by Waters, A combination of 10 ³ , 10 ⁴ , 10 ⁵ or a combination of Showa Denko's Shodex A-802, 803, 804, 805 is good. When measuring the molecular weight of a sample,
The molecular weight distribution of the sample was calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples. For example, standard polystyrene samples for creating a calibration curve include:
Manufactured by PressureChemical CO. or Toyo Soda Kogyo Co., Ltd., with a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ ,
1.75×10 ⁴ , 5.1×10 ⁴ , 1.1×10 ⁵ , 3.9×10 ⁵ , 8.6×
It is appropriate to use at least 10 standard polystyrene samples of 10 ⁵ , 2×10 ⁶ , and 4.48×10 ⁶ . In addition, an RI (refractive index) detector is used as a detector. Furthermore, among polymers crosslinked with metal compounds, those with a glass transition temperature of 50°C or higher are superior because they do not cause problems such as toner aggregation in the developing device or adhesion to the photoreceptor surface. In particular, those having a glass transition temperature between 50°C and 80°C are more preferable. Note that the glass transition temperature of the polymer can be measured using a differential scanning calorimeter.

Examples of the polymer that reacts with the decomposable metal compound of the present invention include polymers containing carboxyl groups, such as polymers synthesized from vinyl monomers having carboxyl groups.
Examples of carboxyl group-containing monomers for vinyl polymers include acrylic acid, methacrylic acid,
These include acrylic acid and its α- or β-alkyl derivatives such as α-ethyl acrylic acid and crotonic acid, and unsaturated dicarboxylic acids and their monoester derivatives such as fumaric acid, maleic acid, citraconic acid, and itaconic acid. A desired polymer can be produced by copolymerizing the monomers alone or in combination with other monomers. As for the proportion of the carboxyl group-containing monomer contained in the polymer, 0.1 to 30% by weight gives good results, and 0.5 to 30% by weight gives good results.
Particularly favorable results are obtained in the range of ~20% by weight. Examples of monomers copolymerizable with the above carboxyl group-containing monomers include:
Styrene, α-methylstyrene, p-chlorostyrene, vinylnaphthalene, methyl acrylate, ethyl acrylate, butyl acrylate, dotesyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate Substituted monocarboxylic acids with double bonds, such as octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc.: diester derivatives of dicarboxylic acids with double bonds, such as dibutyl maleate, dimethyl maleate, etc. : Vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate, etc.; Ethylene olefins such as ethylene, propylene, butylene, etc.; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, etc.; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc.; aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, etc.; e.g. ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate 2 double bonds such as
Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, and compounds having three or more vinyl groups can be used alone or as a mixture.

As mentioned above, the glass transition temperature of a polymer crosslinked by reaction with a decomposable metal compound is 50°C.
In order to achieve the above, it is preferable that the unreacted polymer has a glass transition temperature of 40°C or higher.

Further, as the decomposable metal compound used in the present invention, those containing the following metal ions can be used. Suitable monovalent metal ions include Ha ⁺ , Li, ⁺ ,
There are Cs ⁺ , Ag ⁺ , Hg ⁺ , Cu ^{+ ,} etc., and divalent metal ions include Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Hg ²⁺ , Sn ²⁺ ,
These include Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , and Zn ²⁺ . In addition, trivalent ions include Al ³⁺ , Sc ³⁺ , Fe ³⁺ ,
Examples include Co ³⁺ , Ni ³⁺ , Cr ³⁺ , and Y ³ . Among the compounds containing metal ions as mentioned above, the more decomposable the compound, the better the results. This is presumed to be because metal ions in the decomposable compound more easily bond to carboxyl groups in the polymer through thermal decomposition. This decomposable metal compound has a temperature range of 100°C to 600°C (particularly preferably 160°C).
It is preferable to have a decomposition temperature between ℃ and 400℃.

In the present invention, metal compounds having the decomposition temperature as described above are reacted at a temperature below the decomposition temperature. If the reaction occurs above the decomposition temperature, the metal compound will rapidly decompose and react violently with the carboxyl group-containing polymer, making it difficult to control the reaction, and the degree of crosslinking formed by the reaction will become too large, resulting in lower fixing temperatures. This is not desirable as it causes an increase in the temperature. However, when a metal compound and a polymer are reacted at a temperature below the decomposition temperature, a portion of the metal compound gradually decomposes, so the reaction proceeds slowly, making it easier to control the reaction and achieving the desired fixing performance. It is possible to stably produce toner with

Among the decomposable metal compounds, organometallic compounds have excellent compatibility and dispersibility with the polymer, and crosslinking by reaction with the metal compound proceeds more uniformly in the polymer, giving better results.

Among the decomposable organometallic compounds mentioned above, those containing organic compounds with high vaporizability and sublimation properties as ligands and counterions are particularly useful.
Examples of organic compounds having the above-mentioned properties that form coordinates or counterions with metal ions include salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicyrosalicylic acid, ditertiarybutylsalicylic acid, Examples include salicylic acid and its derivatives such as, for example, β-diketones such as acetylacetone and propionacetone, and low molecular weight carboxylic acid salts such as acetate and propionic acid.

In the present invention, since the temperature at which the polymer and the decomposable metal compound are reacted is lower than the decomposition temperature of the decomposable metal compound (preferably 50°C or higher), most of the decomposable metal compound is Does not react with coalescence. Therefore, the amount of the decomposable metal compound contained in the toner of the present invention is necessary in excess, and although it varies depending on the type of compound, it generally includes the unreacted metal compound. , 0.01 to 20 parts by weight of reactive polymer
Parts by weight are preferably included, and particularly good results are obtained when 0.1 to 10 parts by weight are used.

Further, since the temperature at which the polymer and the decomposable metal compound are reacted is lower than the decomposition temperature of the decomposable metal compound, most of the decomposable metal compound does not react with the polymer. Therefore, if the decomposable metal compound is not uniformly dispersed in the carboxyl group-containing polymer, the reaction between the decomposable metal compound and the polymer will proceed unevenly in the toner binder resin. Resin crosslinking is uneven,
It becomes difficult to obtain a toner with desired fixing properties.

Therefore, a decomposable metal compound is thoroughly mixed and dispersed in a non-reactive polymer in advance, and a predetermined amount of fine powder of this dispersion is added to a reactive polymer and melt-kneaded. By reacting a decomposable metal compound with a polymer, the reaction can be carried out uniformly, making it easy to produce a toner with desired fixing characteristics.

Taking into consideration problems such as fixing properties, it depends on the molecular weight and molecular weight distribution of the polymer for pre-dispersion, but if the amount of the polymer mixed in the toner is too large, it will have a negative effect on the fixing properties, so It is preferable to disperse 1 to 50 parts by weight of a degradable metal compound to 100 parts by weight of the polymer (particularly preferably 5 to 30 parts by weight), and further disperse 1 to 50 parts by weight of the above dispersion to 100 parts by weight of the reactive polymer. parts (more preferably 1 to 30 parts by weight)
It is appropriate to add 0.01 to 20 parts by weight (particularly preferably 0.1 to 10 parts by weight) of the decomposable metal compound per 100 parts by weight of the reactive polymer.

As the predispersion polymer, a polymer containing no carboxyl group is used. Such polymers include, for example, polystyrene, poly-p
- Homopolymers of styrene and its substituted products such as chlorostyrene and polyvinyltoluene, styrene-p
- Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer,
Styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer Polymers, styrenic copolymers such as styrene-isobrene copolymers, styrene-acrylonitrile-indene copolymers: polystyrene, polypropylene, polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, Acrylic acid ester resin, methacrylic acid ester resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene resin, petroleum resin, etc. are used. can.

Preliminary dispersion methods include melt-kneading a decomposable metal compound and a non-reactive polymer using a roll mill, kneader, extruder, etc., and then pulverizing the mixture; There are a method of mixing a compound with a compound in a solution, followed by drying and pulverizing, and a method of spray drying a mixed solution to obtain a fine powder.

Furthermore, in the present invention, as a method for producing a toner in which a polymer having a carboxyl group and a decomposable metal compound in a predispersion are reacted during the manufacturing process, a method for producing a toner containing a polymer having a carboxyl group and a predispersion is a method for producing a toner in which a polymer having a carboxyl group and a decomposable metal compound in a predispersion are reacted. Roll mill, kneader,
There is a method in which the toner is made to react by melting and kneading using an extruder or the like, and then being pulverized to form a toner.

In the present invention, some of the above-mentioned polymers are used as the main resin component, and other polymers and resins can be mixed and used as necessary within a range that does not impair the fixing properties. . Other resins that can be used include, for example, polystyrene, poly-p-
Monopolymers of styrene and its substituted products such as chlorostyrene and polyvinyltoluene, styrene-p
- Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer,
Styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer Polymers, styrenic copolymers such as styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers: polyethylene, polypropylene, polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, Acrylic ester resin, methacrylic ester resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron indene resin, petroleum resin, etc. Can be used.

In particular, by adding 0.1 to 10% by weight (more preferably 0.2 to 5% by weight) of an ethylene olefin monopolymer or ethylene olefin copolymer having a melt viscosity of 10 to ¹⁰⁶ eps at 140°C to the toner. The dispersibility and compatibility of the pigment and magnetic fine particles with the toner are improved, and the adverse effects on the photoreceptor surface, cleaning member, etc. are reduced. Examples of the ethylene-based olefin monopolymer or ethylene-based olefin copolymer include polyethylene, polypropylene, and ethylene-olefin copolymer.
There are propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, etc. In the above polymers, olefin monomers are contained in an amount of 50 mol% to 100 mol% (more preferably 60 mol%).
% to 100 mol%) is preferred.

The Brookfield method was used to measure the melt viscosity, and here a B-type viscometer equipped with a small sample adapter was used.

Any suitable pigment or dye can be used as a colorant in the toner of the present invention. For example, there are known dyes and pigments such as carbon black, iron black, phthalocyanine blue, ultramarine blue, quinacridon, and benzidine yellow.

Furthermore, when the toner of the present invention is a magnetic toner, it may also serve as a coloring agent, but ferromagnetic elements and alloys and compounds containing them such as iron, cobalt, and ferrite such as magnetite, hematite, and ferrite, It may also contain magnetic powders conventionally known as magnetic materials, such as alloys and compounds of manganese, and other ferromagnetic alloys.
Further, carbon black, nigrosine, metal complex salts, colloidal silica powder, fluororesin powder, etc. may be added for the purpose of charge control, prevention of aggregation, etc.

The toner of the present invention can be applied to various developing methods.
For example, magnetic brush development method, cascade development method, method using conductive magnetic toner described in U.S. Pat. No. 3,909,258, and JP-A-53-31136
A method using a high-resistance magnetic toner described in Japanese Patent Publication No. 54-42141, a method described in Japanese Patent Application Laid-Open No. 55-18656, etc., a fur brush development method,
There are powder cloud method, impression method, etc.

The toner image formed on a fixing sheet such as paper using the toner according to the present invention does not cause the toner offset phenomenon even when a fixing roller that does not supply offset prevention liquid to the surface of the toner image is used. Fixing can be done with a heated roller. The fixing roller has a smooth surface made of fluorine-based resin such as Teflon (manufactured by Dekopon), Fluon (manufactured by ICI), and KEL-F (manufactured by 3M), silicone rubber, or silicone resin. It is possible to use a metal surface or, in some cases, a metal surface.

Example 1 70 parts by weight of xylene was placed in a separable flask, and further 75 parts by weight of styrene, 15 parts by weight of butyl acrylate, 10 parts by weight of monobutyl maleate, and 0.5 parts by weight of divinylbenzene were added, and the gas phase was replaced with nitrogen gas. 1 part by weight of benzoyl peroxide dissolved in 10 parts by weight of xylene was added dropwise over 30 minutes using a dropping funnel purged with nitrogen gas, stirred at 85°C for 10 hours, and then heated to 95°C. Raise the temperature to 3
The polymerization was completed after a certain period of time. After cooling, the polymerization solution was poured into a large amount of methanol to separate the precipitate, which was sufficiently dried at 50°C and collected. The Mw/Mn of the polymer is 24.
Mw was 276,000.

Next, 100 parts by weight of styrene-butyl methacrylate copolymer (trade name, Me-230, manufactured by Ionatsuk Co., Ltd.) and cobalt acetylacetone () (decomposition temperature
310°C) were thoroughly melted and kneaded on a roll mill, cooled, and pulverized.

100 parts by weight of the polymer synthesized by the above melt polymerization method,
20 parts by weight of the above-mentioned pulverized premix and 60 parts by weight of magnetite were melt-kneaded at 105°C using a roll mill, then finely pulverized, and particles of approximately 5 to 20 μm were selected to form a toner. The melt index of this toner was 1.25 under the conditions of 125° C. and 10 kg.

0.4 parts by weight of hydrophobic colloidal silica was externally added to 100 parts by weight of the above toner to prepare a developer.

Apply this developer to a commercially available copying machine (product name: NP-
400RE, manufactured by Canon Inc.). The minimum fixing temperature of the above toner was 150°C, and no offset phenomenon was observed from 150°C to 210°C.

Furthermore, when we set the temperature of the fixing roller to 170℃ and conducted a continuous durability test of 50,000 sheets, the image reflection density remained almost constant from the initial stage to after 50,000 sheets, and remained around 1.0. Maintained. Even after 50,000 copies, there was no offset phenomenon to the fixing roller, no adhesion to the surface of the photosensitive drum, no aggregation within the developing device, etc.

Comparative Example 1 Carboxyl group-containing polymer synthesized in Example 1
100 parts by weight, 16 parts by weight of the styrene-butyl methacrylate copolymer used for preliminary dispersion in Example 1, and 60 parts by weight of magnetite were melt-kneaded in a roll mill, and a developer was prepared in the same manner as in Example 1.

The melt index of this toner is 18,
The minimum fixing temperature was approximately 145°C, but a slight offset phenomenon was observed even at this temperature, and as the fixing temperature increased, the offset phenomenon became more severe.
℃, the surface of the fixing roller reached a point where clear image marks were observed.

Further, continuous durability was started in the same manner as in Example 1, but after about 500 sheets, traces of the toner offset from the fixing roller being retransferred onto the paper appeared on the images, and the durability was discontinued.

Example 2 Example 1 except that the monomers were 70 parts by weight of styrene, 25 parts by weight of butyl methacrylate, 5 parts by weight of acrylic acid, and 0.8 parts by weight of divinylbenzene.
A reactive polymer was synthesized in almost the same manner. The Mw/Mn of the polymer was 34.5 and the Mw was 327,000.

Next, 10 parts by weight of iron acetylacetonate (decomposition temperature: 340°C) was added to 100 parts by weight of styrene polymer (trade name D-125, manufactured by Hercules) and melt-kneaded in a roll mill. 100 parts by weight of reactive polymer,
10 parts by weight of the pulverized preliminary mixture and 60 parts by weight of magnetite were kneaded in the same manner as in Example 1, and a developer was further prepared and evaluated.

The melt index of the toner was 0.76, the minimum fixing temperature was 160°C, there was no offset from this temperature to 200°C or higher, and the durability was good.

Example 3 Styrene-butyl acrylate-maleic acid copolymer (monomer ratio: 80:17:3, Mw/Mn=
12.4, Mw=12800) was synthesized in substantially the same manner as in Example 1.

Next, 100 parts by weight of the styrene of Example 2 and 40 parts by weight of a chromium complex salt of ditertiary butylsalicylic acid were added.
parts by weight were dissolved in 100 parts by weight of toluene and dried to prepare a premix.

Furthermore, 100 parts by weight of the reactive polymer, 25 parts by weight of the pulverized product of the above premix, 60 parts by weight of magnetite, and 3 parts by weight of polyethylene wax (solution viscosity at 140°C: about 120 centipoise) were added in the same manner as in Example 1. A developer was produced and evaluated. It showed very good fixing properties.

Example 4 In Example 1, acetylacetone cobalt () was converted into acetylacetone aluminum (decomposition temperature 193°C).
A premix was made in place of 20 parts by weight.

Next, 100 parts by weight of the reactive polymer of Example 1, 5 parts by weight of the pulverized product of the above premix, and magnetite
60 parts by weight, polypropylene wax (melt viscosity approx.
A toner was prepared as described in Example 1 using 5 parts by weight (400 centipoise). A toner having good fixability and developability was obtained.

Example 5 100 parts by weight of the styrene polymer of Example 2 was melt-kneaded with 30 parts by weight of a zinc complex of ditertiary butylsalicylic acid.

100 parts by weight of the reactive polymer of Example 2, 20 parts by weight of the pulverized product of the above premix, 8 parts by weight of carbon black, metal complex dye (trade name, Pomelo First Black B, CIAcid Black 63, manufactured by BASF)
4 parts by weight were thoroughly melted and kneaded using a small pressure kneader. After cooling, it was finely pulverized, and particles of approximately 5 to 20 μm were classified and used as toner. 10 parts by weight of this toner and carrier iron powder (product name, EFV, 250/
400 (manufactured by Nippon Tetsuko Co., Ltd.) and 90 parts by weight to prepare a developer. Apply this developer to a commercially available copying machine (product name,
NP-5000, manufactured by Canon Inc.), but 150
It was fixed at a temperature of 200°C and no offset was observed at temperatures above 200°C. Moreover, the durability was also very good.

Claims (1)

[Claims] 1 Prepare a mixture containing the above metal compound by mixing 1 to 50 parts by weight of a degradable metal compound with 100 parts by weight of a polymer not having a carboxyl group, and add the above-mentioned mixture to 100 parts by weight of a polymer having a carboxyl group. The above mixture containing 0.01 to 20 parts by weight of a decomposable metal compound and a colorant are added and melt-kneaded to cause the polymer having a carboxyl group and the degradable metal compound to react during the manufacturing process. A method for manufacturing a toner characterized by the following.