JPH0425535B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc.
In particular, it relates to a toner suitable for heat roller fixing.

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.

The pressure heating method using a heated roller performs fixing by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heated roller whose surface is made of a material that has releasability for toner. . In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be carried out quickly. It 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. A so-called offset phenomenon may occur, and the sheet to be fixed may be stained. One of the essential conditions for the heat roller fixing method is to prevent toner from adhering to the surface of the heat fixing roller.

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, it requires a device to supply a liquid for preventing offset, resulting in problems such as a complicated fixing device. .
Therefore, it is not preferable 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, it may be possible to prevent the offset phenomenon by using a crosslinked resin, but the present inventors have investigated and found that simply creating a crosslinked resin does not necessarily prevent the offset phenomenon. I found out that it wasn't good. In particular, when the degree of crosslinking is increased, the fixing temperature increases, and in the case of magnetic toner, the fixing temperature increases and the offset resistance deteriorates, causing many problems.

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: I 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, when an attempt is made to increase the density of a copied image by increasing the amount of toner adhering to the surface of a photosensitive plate having a latent image, the background density usually increases, resulting in a so-called fog phenomenon. 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 toner having excellent physical and chemical properties that overcomes the above-mentioned toner deficiencies.

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for hot roller fixing which has good fixing properties and particularly good offset resistance.

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

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

A further object of the present invention is to provide a magnetic toner which, when used as a magnetic developer, exhibits good and uniform magnetism and can be fixed by a hot roller.

Its feature is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/
Mn) is greater than 4, Mw is greater than 100000,
A toner for developing electrostatic images contains a vinyl polymer having a carboxyl group crosslinked with an amine represented by the following formula.

In the formula, a and b are integers of 2 to 4, respectively, x and y
are each an integer from 1 to 50, and R is an alkyl group consisting of 8 to 30 carbon atoms (including branched and cycloalkyl groups).

The toner for thermal roller fixing according to the present invention has excellent physical and chemical properties, and by using this toner, no offset occurs even when no offset prevention liquid is applied to the surface of the fixing roller. Since it can perform good heat roller fixing, the fixing device can be simplified and lightened.Furthermore, it has stable and excellent developing characteristics, so it significantly improves the stability and reliability of copying machines. becomes possible.

That is, in the toner of the present invention, although the detailed reaction mechanism is unknown, the binder resin reacts with the amine and undergoes a type of crosslinking, resulting in improved mechanical properties at room temperature and improved impact resistance. It has excellent toughness and toughness, and also has improved charging characteristics, resulting in improved development characteristics as a toner. Furthermore, when the toner of the present invention is fixed with a hot roller fixer, offset resistance at high temperatures is significantly improved. However, the fixing temperature is approximately the same as when the toner is prepared with the corresponding unreacted polymer.

The above fixing characteristics are obtained when the melt index of the toner is in the range of 0.01 to 10 g/10 min (particularly preferably 0.1 to 6 g/10 min) (test conditions are temperature 125°C, load 10 kg, filling amount 5 ~8g),
Shows especially excellent fixing properties. The melt index here was measured by a manual cutting method using an apparatus described in JIS K7210, a flow test method for thermoplastic plastics according to the Japanese Industrial Standards.

In the present invention, particularly preferable results can be obtained when a vinyl polymer having a carboxyl group with a weight average molecular weight/number average molecular weight (Mw/Mn) value of greater than 4.0 (particularly preferably greater than 10) is used. Furthermore, by using a polymer with such a molecular weight distribution, it is possible to easily produce a polymer having a desired melt viscosity through a mild reaction by reaction with an amine, thereby achieving desired fixing characteristics. Therefore, it is possible to stably produce toner having the following properties.

Furthermore, the melt index value of a polymer having a carboxyl group is 125℃, a charge of 2 kg
0.01 to 10 g/min is preferable under the conditions of
Particularly preferred is 0.1 to 5 g/min.

In addition to the above-mentioned fixing properties and mechanical properties, an important electrophotographic property that a toner should have is triboelectric charging properties.To improve the charging properties, a charge control agent is added to the toner. is commonly added. Therefore, if additives such as charge control agents are not uniformly dispersed in the toner,
The triboelectric charging properties of the toner are significantly impaired, making it difficult to obtain clear images.

Therefore, when manufacturing toner, in order to uniformly disperse additives such as charge control agents and colorants in the polymer, raw materials are melt-kneaded at a temperature near the softening point of the polymer, at which the polymer exhibits a high melt viscosity state. It is commonly done. When melt-kneaded in the high melt viscosity region,
Additives such as charge control agents and colorants are uniformly dispersed in the toner by shearing force caused by internal friction of the polymer, and a toner with desired coloring and charging properties is obtained.

However, when a polymer with Mw/Mn > 4 is melt-kneaded in the high melt viscosity region around the softening point, the internal friction in the polymer becomes extremely large and the shearing force becomes too strong, causing molecular chain scission. , which leads to a decrease in melt viscosity and adversely affects offset properties. For example, the softening point (about 135°C) of the polymer whose melt index is about 5 g/10 min was measured by the ball and ring method using a roll mill.
When melt-kneaded at a slightly lower temperature (approximately 120°C), the melt index increases significantly, almost doubling the value, and the fixing temperature range in which the offset phenomenon does not occur is considerably higher than the softening point of the polymer. It becomes much narrower than when melting and kneading at (180℃).

The present inventors believe that in order to solve the problem of offset resistance and additive dispersibility, it is possible to apply some crosslinking when melt-kneading the polymer to cancel out the decrease in viscosity caused by molecular chain scission. I found something good.

According to the above-mentioned method, it is possible to melt and knead the polymer in a high viscosity region near its softening point, so it is possible to obtain a toner in which the additives are dispersed very uniformly, the charging characteristics are stabilized, and the non-offset temperature range is wide. It will be done.

As will be specifically shown later, when a polymer with Mw/Mn<4 is used, in order to obtain a toner having desired fixing characteristics through reaction with an amine, it is necessary to increase Mw/Mn<4.
Compared to when using a polymer with Mn of 4.0 or more, it is necessary to set the amount of diamine and reaction conditions so that the above reaction occurs more actively. It is very difficult to stop the reaction with just the right amount and not enough, making it impossible to stably produce toner with desired fixing characteristics with good reproducibility.

On the other hand, when using a polymer with Mw/Mn > 4, in order to impart offset resistance to the toner, the polymer only needs to be slightly reacted with an amine and crosslinked.
The reaction can be carried out under mild conditions, the reaction can be easily controlled, and toner with excellent fixing properties can be stably produced. Furthermore, when a polymer with Mw/Mn>4, more preferably Mw>100000 is lightly crosslinked,
As the molecular weight distribution becomes wider, it becomes possible to provide the toner with offset resistance while keeping the minimum fixing temperature low.

The value of Mw/Mn is greater than 4.0, preferably
Polymers with Mw greater than 100,000 can be synthesized using well-known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. Methods for adjusting Mw/Mn include methods of melting or mixing several types of resins with different molecular weights in a molten state, changing the reaction temperature during the polymerization reaction, and using initiators, chain transfer agents, etc. There are methods of manufacturing by blending and methods of increasing Mw/Mn and Mw by applying a certain degree of crosslinking when forming a polymer from monomers, among these manufacturing methods, The method most suitable for the present invention is to control the degree of crosslinking within a low range and adjust Mw/Mn, and this is, for example, by adding a trace amount of a polyfunctional monomer to the polymerization reaction system, preferably 0.01 to 10% by weight. achieved by.

On the other hand, as a process for synthesizing the above polymer, a solution polymerization method is preferred. This is because in emulsion polymerization and suspension polymerization, monomers are emulsified or dispersed using additives such as surfactants and dispersion stabilizers in water, which is a continuous phase, and then polymerized by adding salts, etc. The resulting polymer contains the hydrophilic additives mentioned above. When such hydrophilic additives are present in the toner,
Under high humidity conditions, the toner often absorbs moisture, which adversely affects the electrical properties of the toner, such as a decrease in specific resistance. Furthermore, since the polymer used in the present invention has a hydrophilic carboxyl group, it is difficult to obtain a stable reaction. Furthermore, in the bulk polymerization method, problems such as a gel effect occur when the degree of polymerization increases, and it is extremely difficult to control the polymerization reaction when obtaining a polymer with a large Mw/Mn.

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 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 further, according to the present invention, a polymer having a degree of crosslinking created by the solution polymerization method is synthesized by solution polymerization. It is produced by a solution polymerization method that has the above-mentioned excellent properties by reacting a polymer and an amine during the toner 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. It becomes possible to more easily apply the polymer to a toner 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. 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, 10 manufactured by Waters. A combination of ³ , 10 ⁴ , 10 ⁵ or shodex A-802, 803, 804, 805 made by Showa Denko 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 Pressure Chemical Co. or Toryo 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.

Examples of carboxyl group-containing monomers for synthesizing vinyl polymers include acrylic acid, methacrylic acid, α-ethyl acrylic acid, acrylic acid such as crotonic acid and its α- or β-alkyl derivatives, fumaric acid, maleic acid, These include unsaturated dicarboxylic acids such as citraconic acid and their monoester derivatives, and these monomers can be copolymerized alone or in combination with other monomers to create a polymer containing a desired carboxyl group. can.

Examples of monomers copolymerizable with the above carboxyl group-containing monomers include styrene, α-methylstyrene, p-chlorostyrene vinylnaphthalene, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, and acrylic. octyl acid, phenyl acrylate,
Substituted monocarboxylic acids with double bonds such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc.; for example, dibutyl maleate, dimethyl maleate, etc. diester derivatives of dicarboxylic acids having double bonds such as; vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate; such as ethylene, propylene,
Ethylene olefins such as butylene;
Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, etc.; vinyl datals such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc.; aromatic divinyl compounds such as vinylbenzene, divinylnaphthalene, etc.; For example, carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, divinylaniline,
Divinyl compounds such as divinyl ether, divinyl sulfide, and divinyl sulfone and compounds having three or more vinyl groups can be used alone or as a mixture.

The proportion of carboxyl group-containing monomers contained in the carboxyl group-containing polymer is 0.1
~30 wt% gives good results, 0.5-20 wt%
Particularly preferable results can be obtained within the range of .

Next, in the present invention, the amine for crosslinking the carboxyl group-containing polymer has the following general formula.

In the formula, a and b represent integers of 2 to 4 and may be the same or different, x and y represent integers of 1 to 50 and may be the same or different, and R
is an alkyl group consisting of 8 to 30 carbon atoms (however,
(including branched and cycloalkyl groups).

Among the alkoxylated amines having the above general formula, those which are wax-like solid substances under normal pressure and room temperature conditions are excellent. Low-molecular-weight liquid alkoxylated amines crosslink polymers with carboxyl groups in the same way as solid alkoxylated amines, but there are problems such as unreacted liquid alkoxylated amines bleeding out of the toner. Preferred are alkoxylated amines.

In the present invention, the reaction between the polymer and the amine is
Since not all of the amine used will react,
The amount of reactive alkoxylated amine is required in excess, and although it varies depending on the type of amine, it is generally from 0.01 to 100 parts by weight of the polymer, including unreacted amine. Preferably, it is contained in an amount of 20 parts by weight, and particularly good results are obtained when 0.1 to 10 parts by weight are used.

The reaction between the vinyl polymer and the reactive amine in the present invention can be carried out by a method in which the above-mentioned amine is reacted with the reactive polymer in a roll mill,
There is a method of adding an amine to a hot xylene solution of a reactive polymer and causing a reaction. Taking into account post-treatment steps after the reaction, the reaction by melt-kneading method is most suitable for the present invention. A polymer reactant may be first produced through the reaction to form a binder, and then a toner may be produced together with other toner materials.
The above reaction itself may be carried out during heating and kneading of the toner material during the toner manufacturing process, and then finely pulverized to form a toner.

On the other hand, in the toner of the present invention, if the gel content of the polymer after reacting with the amine is 50% or more, the crosslinking of the polymer will proceed too much, and the temperature at which the polymer becomes soft will rise significantly, resulting in the formation of a toner. In this case, the fixing temperature becomes high, which is undesirable. Therefore, the gel content of the crosslinked polymer should be less than 50%;
In particular, if it is 35% or less, the fixing temperature is almost the same as that of an uncrosslinked polymer, and particularly good results can be obtained.
The gel content in the present invention refers to the proportion of the polymer portion that has been crosslinked and is insoluble in a solvent, and can be used as a kind of index representing the degree of crosslinking of a highly crosslinked polymer. Here, gel content is defined as a value measured as follows. That is, a certain weight (W ₁ g) of the polymer after reacting with the diamine was weighed, and the soluble components in the polymer were removed with a solvent using a Soxhlet extractor using a G-3 glass filter. , and the sample that remained unextracted was dried and weighed (W ₂ g). Gel content is W ₂ /W ₁ × 100 (%)
It is calculated as As such a solvent, a nonpolar solvent is preferable, and in this case, extraction was performed using benzene for 50 hours.

Furthermore, among binder polymers crosslinked by reaction with amines, the glass transition temperature is 50%.
℃ or above is excellent because it does not cause problems such as toner aggregation in the developing device or adhesion to the photoreceptor surface, etc., and in particular, one with a glass transition temperature of 50℃ to 80℃ is more preferable. . Thus, in order for the glass transition point of the crosslinked polymer to be 50°C or higher, it is preferable that the glass transition point of the polymer having a carboxyl group before crosslinking is 40°C or higher. Note that the glass transition temperature of the polymer can be measured using a differential scanning calorimeter.

The toner of the present invention has a binder polymer crosslinked by the method described above as a main resin component, but other polymers and resins can be mixed and used as necessary. Other resins that can be used in combination include, for example, polystyrene,
Monopolymers of styrene and its substituted products such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-
Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic ester copolymer, styrene-methacrylic 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-
Styrenic copolymers such as butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyethylene, polypropylene, polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, acrylic ester resin, Methacrylic acid ester resin, polyvinyl acetate, silicone resin, polyurethane, furan resin, epoxy resin, xylene resin,
Polyvinyl butyral, terpene resin, chloroindene 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 10 ⁶ cps 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.
Propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer,
The above copolymers preferably contain 50 mol% to 100 mol% (more preferably 60 mol% to 100 mol%) of olefin monomers.

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, quinacridone, and benzidine yellow.

Furthermore, when the toner of the present invention is a magnetic toner, it contains magnetic powder, which may also serve as a coloring agent. Magnetic powders include ferromagnetic elements, alloys containing these, compounds such as magnetite, hematite, and ferrite, alloys and compounds of iron such as cobalt, nickel, and manganese, and other ferromagnetic alloys. You can use what is provided.

As other additives, carbon black, nigrosine, metal complex salts, colloidal silica powder, fluororesin powder, metal salts of higher fatty acids, etc. may be added for purposes such as charge control and prevention of agglomeration.

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 a fluorine-based resin such as Teflon (manufactured by DuPont), Fluon (manufactured by ICI), and Keru F (manufactured by 3M), silicone rubber, or silicone resin. In some cases, those having a metal surface can be used.

[Example 1] 90 parts by weight of xylene was placed in a separable flask, 75 parts by weight of styrene, 20 parts by weight of butyl methacrylate, 5 parts by weight of maleic acid, and 0.5 parts by weight of divinylbenzene were added, and the gas phase was purged with nitrogen gas. After purging, the temperature was maintained at 80°C, and a solution of 0.8 parts 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.
The mixture was further stirred at 80°C for 10 hours. Next, 5 parts by weight of a toluene solution containing 0.3 parts by weight of benzoyl peroxide was added dropwise, and the temperature was further raised to 90°C and maintained at that temperature for 5 hours to complete polymerization. After cooling, precipitate the polymer in a large amount of methanol, separate the precipitate, and heat at 60°C.
It was dried and collected. Mw/Mn of this polymer is
26, Mw was 243,000.

100 parts by weight of the above polymer, Naimeen S-202 (a condensation product of ethylene oxide of a primary aliphatic amine having an alkyl group having 13 to 17 carbon atoms, commercially available from NOF Corporation, x+y=2) 0.3 parts by weight, 60 parts by weight of magnetite, metal complex dye (product name: Zapon First Black B, CIAcid
4 parts by weight of Black 63 (manufactured by BASF) were melt-kneaded at 150°C for 30 minutes on a roll mill. After cooling, it is finely pulverized using an air jet type pulverizer, and then classified by air to
Particles of 20μ were selected and used as toner. The toner melt index is under the conditions of 125℃ and 10Kg.
It was 1.36g/10min. 0.5 parts by weight of hydrophobic colloidal silica was externally added to 100 parts by weight of this toner to form a developer, and evaluated using a commercially available copying machine (trade name, NP-400RE manufactured by Canon Inc.). The minimum fixing temperature of the above developer is 150℃, and the offset phenomenon is 150℃.
It was not observed from ℃ to 210℃.

Furthermore, we set the temperature of the fixing roller to 170°C and conducted a continuous durability test of 50,000 sheets, but the image reflection density remained stable from the initial stage to after 50,000 sheets, staying around 1.0. Maintained. Even after 50,000 sheets were printed, there was no offset phenomenon to the fixing roller, and no problems such as adhesion to the surface of the photoreceptor drum or agglomeration within the developing device occurred.

[Comparative Example 1] A toner was prepared and used as a developer in the same manner as in Example 1 except that Nymeen S-202 was not added.

Melt index of this toner (125℃, 10
Kg) was approximately equal to the value of the copolymer for toner material, which was 16.86 g/10 min).

The minimum fixing temperature was 150°C, which was the same as the toner of Example 1, but as the temperature increased, the offset became more severe, and at 180°C, permanent image marks were observed on the surface of the fixing roller. .

A continuous durability test was conducted in the same manner as in Example 1, but after about 500 copies, traces of the offset material retransferred from the fixing roller appeared on the image, which became even more severe after 1000 copies, so the durability test was discontinued.

[Example 2] Styrene-butyl acrylate-acrylic acid copolymer (monomer ratio: 80:18:2, Mw/Mn=19,
Mw=188000) 100 parts by weight, Naimeen T ₂ −260
(polyoxyethylene tallow alkylamine commercially available from NOF Corporation, x+y=60) 0.5 parts by weight, 60 parts by weight of magnetite, 4 parts by weight of the metal complex dye of Example 1, polyethylene wax (with a melt viscosity of 2 parts by weight (120 centipoise at 140° C.) was prepared into a toner in the same manner as in Example 1 and evaluated. A toner with excellent offset resistance and stable developability was obtained.

[Example 3] Styrene-butyl acrylate-methacrylic acid copolymer (monomer ratio: 75:15:10, Mw=
310000, Mw/Mn=28) 100 parts by weight, polyoxyethylene octadecylamine (x+y=10) 0.2
A toner prepared in substantially the same manner as in Example 1 using 60 parts by weight of magnetite and 4 parts by weight of the metal complex dye of Example 1 had good fixing properties and stable durability.

[Example 4] Styrene-butyl methacrylate-monobutyl maleate copolymer (monomer ratio: 70:15:15,
Mw=115000, Mw/Mn=8) 100 parts by weight, Naimeen S-220 (ethylene oxide derivative of octadecylamine manufactured by NOF Corporation, x+y=20) 1
Parts by weight, 8 parts by weight of carbon black, and 4 parts by weight of the metal complex dye of Example 1 were melt-kneaded in a small pressure kneader. After cooling, finely pulverize to approximately 5-20μ
The particles were selected and used as toner. 10 parts by weight of this toner and carrier iron powder (product name: EFV250/400,
(manufactured by Nippon Tetsuko Co., Ltd.) was mixed with 90 parts by weight to prepare a developer. This developer is applied to a commercially available copying machine (product name: NP-
5000, manufactured by Canon Inc.), it was fixed at 150°C and no offset was observed at temperatures above 200°C. It also had excellent durability.

[Comparative Example 2] Styrene-butyl methacrylate having no carboxyl group was produced in the same manner as in Example 1 except that 80 parts by weight of styrene, 20 parts by weight of butyl methacrylate and 0.5 parts by weight of divinylbenzene were used. Divinylbenzene copolymer (Mw/Mn=approx. 22,
Mw=about 230000) was prepared.

A toner (melt index: approximately 18 g/10 min under the conditions of 125° C. and 10 kg) was prepared in the same manner as in Example 1, except that the prepared styrene-butyl methacrylate-divinylbenzene copolymer was used. A fixing test was conducted in the same manner as in Example 1. The minimum fixing temperature was 150°C, which was the same as the toner of Example 1, but the offset phenomenon clearly appeared at a temperature of 180°C.

Claims (1)

[Claims] 1. The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is greater than 4, and Mw
A toner for developing electrostatic images containing a vinyl polymer having a carboxyl group having a carboxyl group of greater than 100,000 and crosslinked with an amine represented by the following formula. [In the formula, a and b are each an integer of 2 to 4, x and y are each an integer of 1 to 50, and R is an alkyl group (including branched and cycloalkyl groups) consisting of 8 to 30 carbon atoms. show. 2. The toner for developing electrostatic images according to claim 1, wherein the vinyl polymer has a Mw/Mn of 8 or more. 3. The toner for developing an electrostatic image according to claim 1 or 2, wherein the vinyl polymer is a crosslinked vinyl polymer.