JPS604947A - Toner for electrophotography - Google Patents

Abstract

PURPOSE:To obtain a dry toner suitable for a fixing system using a hot roll coated with no oil by using a resin consisting of nonlinear polyester and linear polyester as a binding resin and by adding an organometallic compound as a cross-linking agent. CONSTITUTION:This toner contains a mixture of nonlinear polyester with linear polyester as a binding resin and an organometallic compound contg. a bivalent metal or higher as a cross-linking agent. The amount of the compound is 0.2- 10wt% basing on the amount of the binding resin. The nonlinear polyester is prepd. by reacting etherified diphenol having >=50% propoxylated groups or ethoxylated propoxy groups with a mixture of bivalent aromatic carboxylic acid with tervalent aromatic carboxylic acid or higher or alkyl substituted dicarboxylic acid with alkyl substituted diol. The linear polyester is prepd. by reacting propoxylated bisphenol with bivalent carboxylic acid. It is preferable that the nonlinear polyester accounts for a higher percentage of the binding resin than the linear polyester. The polyesters have 50-80 deg.C glass transition temp., 60-130 deg.C softening point and 2,000-20,000 number average mol.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner used in electrophotography, electrostatic printing, etc., and particularly to an electrostatic charge developing toner suitable for heat fixing.

Conventionally, as an electrophotographic method, US Pat.
A number of methods are known, such as those described in Japanese Patent No. 24748, but in general, a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means, and then the latent image is The toner image is developed using toner, the toner image is transferred to a transfer material such as paper as required, and then fixed by heat or pressure to obtain a copy.

Furthermore, various developing methods are known in which an electrical latent image is visualized using toner.

For example, the magnetic brush method described in US Pat. No. 2,874,063, the cascade development method described in US Pat. No. 2,618,552, the powder method and fur brush development method described in US Pat. A large number of developing methods are known, including developing properties. As toners used in these developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. Furthermore, it is also known to use fine developing powder to which a third substance is added for various purposes.

The developed toner image is transferred and fixed onto a transfer material such as paper, if necessary.

Methods for fixing toner images include a method in which the toner is heated and melted using a heater or a heated roller, and then fused and solidified on the support; a method in which the binder resin of the toner is softened or dissolved in an organic solvent and then fixed on the support; A method of fixing toner on a support by pressure is known.

Toner materials are selected to suit each fixing method,
Toners used in a particular fusing method generally cannot be used in other fusing methods.

In particular, the toner used in the conventionally widely used heat fusion fixing method using a heater is
It is almost impossible to apply it to pressure fixing methods. Therefore, toners suitable for each fixing method are being researched and developed.

Various magnetic recording methods are also known in which a magnetic latent image is formed and developed with magnetic toner.

Various methods and devices have been developed for the process of fixing toner images on paper, etc., but the most common methods currently are:
This is a so-called hot roll fixing method in which heat and pressure are applied simultaneously, and this is a method in which the toner image is fixed onto the image receiving sheet by bringing the image receiving sheet carrying the toner image into contact with a heated roller. However, when such a fixing method is used, problems such as so-called offset occur with conventional toner. Offset is an undesirable phenomenon in which a portion of the toner carried on the image receiving sheet is transferred to the roller surface.

That is, in recent years, as copying operations have become more efficient, more energy efficient, and copying machines have become smaller, faster, and more sophisticated, heat roll type fixing systems with good thermal efficiency have come to occupy the majority of copying machines on the market. Most of these copying machines use a heated roller to fix the toner on the paper by thermocompression, but a non-contact heating method using a hot wire is used, and the heating element is used to fix toner at a low temperature to achieve satisfactory fixation. Although this method has many advantages such as being able to obtain images and increasing speed, this method also has various drawbacks. One of the major problems is that if the roller is kept at a temperature that requires the toner to be sufficiently fixed to the holding member such as paper, the toner will fuse not only to the paper but also to the heat roll, which will cause copying costs to be increased. As a result, the heat roll becomes dirty, and the blade or cleaning web that is supposed to keep the roll clean is not able to cut it sufficiently, and the paper also becomes dirty, which is a serious problem because it is a so-called offset contact method. .

Various measures have been attempted for fixing devices and toner to solve or alleviate this problem, but it cannot be said that a sufficient solution has been achieved yet.

As the fixing device, a material such as Teflon or silicone having excellent surface releasability is used. Alternatively, efforts have been made to apply oil such as silicone oil to the roller, and most of the thermal roller fixing devices of copying machines currently on the market use some form of oil application. However, oil application causes undesirable problems such as oil stains on the sheet, troubles that tend to occur due to the complexity of the fixing device, and increased costs.

Additionally, in order to increase the releasability of the toner, a method of adding a small amount of wax such as low molecular weight polyethylene or polypropylene that melts sufficiently when heated is also used, but while this is effective in preventing offset, it tends to cause toner aggregation. Adverse effects such as increased charging properties, unstable charging characteristics, and decreased durability are also observed, and it is difficult to say that it is sufficient. As other methods, various attempts have been made to improve the binder resin. Japanese Patent Publication No. 51-23354 proposes a toner using a crosslinked polymer as a binder resin. If that method is followed, there is a remarkable improvement in offset resistance and sticking resistance, but on the other hand, if the degree of crosslinking is increased, the fixing point will rise, and if the fixing temperature is low enough, offset resistance and sticking resistance will be improved.
A product with sufficient fixing properties with good sticking resistance has not been obtained1, and crosslinked polymers are difficult to disperse pigments and are difficult to miscible with other polymers, etc. Toners that use coalescent as a binder resin have drawbacks such as difficulty in obtaining good development characteristics.

As described above, the reality is that a toner that has sufficient separability on a fixing roller without applying oil, is sufficiently fixed at low temperatures, and has storage stability has not yet been obtained.

Recently, low molecular weight amorphous polyester resins and epoxy resins have been attracting attention as materials suitable for low-temperature fixing. An attempt to use a polyester resin as a binder for toner is disclosed, for example, in Japanese Patent Publication No. 46-12680 (USP).

3,590,000), Japanese Patent Publication No. 52-25420 (USP, specification No. 3,681,106), etc. According to these descriptions and the experiments and studies conducted by the inventors, it is true that the fixing temperature of toner containing polyester resin as the main binder can be lower than that of other materials, but the offset phenomenon to the heat roller cannot be adequately prevented. It's not possible.

The main way of thinking to date for preventing offset in toners containing polyester resin as the main (inder) is 3
The aim is to make the polymer non-linear by mixing a polyol or polyacid with a polyol or polyacid having a higher molecular weight and improve its viscoelasticity to improve the offset property during fixing.The present inventors have also studied various examples of these. As I have seen, these non-linearizations are certainly effective in improving offset properties, but this is also the same as the cross-linking measures for styrene-based materials. When implemented, the fixing point rose and the low-temperature fixing properties of the polyester system were almost completely destroyed.Therefore, this attempt at non-linearity only needs to be considered from the point of preventing offset, but it is difficult to fix. It has been found that this is not desirable when considering the point and high-speed fixing properties, and that there is a limit to the non-linearity.

On the other hand, an attempt was made to completely mix a polyvalent metal compound into a polyester resin, give the metal ions a "weak crosslinked structure" and interact with the amount of silver in the polymer, thereby completely changing its melt viscoelasticity and preventing offset. There is also. The present inventors also focused on this technology and attempted various experimental studies, and it was confirmed that adding a metal compound was indeed effective in preventing offset onto the heat roll. For most metal compounds, a fairly large amount of 4 to 25 parts by weight must be added to the binder resin in order to fully bring out their effects. For this reason, similar to the case where a large amount of inorganic filler is added, the defect that the fixing point rises becomes noticeable, probably due to an increase in heat capacity.

Furthermore, it has been found that since an inorganic compound having a lower resistivity than a polymer is included, the charging ability of the toner is considerably reduced, and there is a strong tendency for the developability to be extremely deteriorated. Furthermore, deterioration in moisture resistance was also clearly confirmed, probably due to the same reason. Therefore, the method of adding a metal compound can be considered only from the point of view of improving offset resistance, but it has many defects such as slanting, and it is still difficult to say that it can be used as a commercial product. Since this effect has been recognized, the key point seems to be how to suppress the amount added. The inventors of the present invention have focused on this point and have conducted thorough studies by systematically varying the type of metal compound and the polyester resin to be used. Although the reason is not clear, it has been found that even when the same amount of the same metal compound is added, the effects of improving offset, raising the fixing point, and deteriorating moisture resistance vary greatly depending on the polyester resin to which it is used. It is well known that the acid value of polyester resin has an effect, but when we investigated the above effect on polyesters with the same composition but with various acid values, the results were mixed and no specific direction could be found. There wasn't. After conducting various other studies, it was found that the higher the aromatic component in the polyester resin, the lower the amount of metal compounds, the more noticeable the improvement in offset, and the less the effect of raising the fixing point and deteriorating moisture resistance. did.

The present inventors have also conducted various studies on metal compounds, and found that there are only a limited number of compounds that have a sufficient effect when added in small amounts and have no adverse effects. It turned out that it had to be a metal compound. Among them, acetylacetone metal complexes and salicylic acid metal compounds were particularly effective.

Adding a relatively long-chain alkyl group to the polyester resin core is also effective in lowering the fixation point, and the synergistic effect of the combination of these allows for good overall performance that matches various models. We discovered that it can be used as a toner.

However, the present inventors have developed a non-linear polyester in which a dicarboxylic acid or diol substituted with a relatively long-chain alkyl group, singly or in combination, is added in order to prevent an increase in the fixing point due to non-linearization. When used alone, a sufficiently low fixing point can be obtained, but on the other hand, resin gold combined with linear polyester, which has a problem with offset properties, a binder resin, and an organometallic compound as a crosslinking agent during kneading? After systematically prototyping and examining various types of electrophotographic toner containing this product, and performing a comprehensive evaluation on electrophotography, we found that it was effective in preventing offset.
A binder resin suitable for high-speed fixing was found below the fixing point,
This invention has now been fully completed.

All objects of the present invention are listed below.

(1) An object of the present invention is to provide a dry type l/ner suitable for a hot roll fixing method without applying oil.

(2) The object of the present invention is to achieve sufficient fixation at a very low temperature;
It is an object of the present invention to provide a toner that can be energy-reduced, is particularly suitable for high-speed fixing, sufficiently prevents offset, and has a wide fixable temperature range.

(3) The object of the present invention is to have an acceptable agglomeration temperature;
The objective is to provide a complete toner that does not cause blocking or the like during storage and use.

(4) It is an object of the present invention to provide a highly moisture resistant l.

(5) An object of the present invention is to provide a toner with excellent development characteristics that provides a bright and clear image with sufficient image density, high resolution, and no background blur.

(6) An object of the present invention is to provide a toner that has excellent durability against repeated cycling due to continuous use and that can stably maintain the high-quality images described in the preceding item.

(7) An object of the present invention is to provide a toner that is excellent in various powder properties such as fluidity and cohesiveness, and has good replenishment and storage stability.

(8) An object of the present invention is to provide a toner that has a high degree of abrasion resistance against mechanical loads during the development process and also has excellent impact resistance.

(9) An object of the present invention is to provide a toner that can be easily transferred from an electrostatic image forming surface to an image receiving surface, has a good transfer rate, and has good transferability without image disturbance or unevenness during transfer. It's about doing.

aQ An object of the present invention is to provide a toner that does not adhere to or contaminate the toner holding member or the electrostatic latent image surface.

An object of the present invention is to provide a two-component developer toner that has almost no carrier contamination caused by adhesion to the carrier, fusion, etc.

(b) An object of the present invention is to provide a -component type magnetic toner having good dispersibility of magnetic powder.

01 An object of the present invention is to provide a toner that reduces mechanical abrasion of an electrostatic image forming surface and has good photosensitive surface cleaning properties.

θ Rod An object of the present invention is to provide a toner that is easy to manufacture, can be produced stably, and is low in cost.

α→ An object of the present invention is to provide a toner with high component value and excellent comprehensive conditions that balance various performances required of a toner as described above.

The present invention is characterized by an etherified diphenol containing 50% or more of propoxylated and/or ethoxylated propoxy groups;
A non-linear polyester obtained by reacting an acid, a mixture of trivalent or higher aromatic carboxylic acids, and an alkyl-substituted dicarboxylic acid and/or an alkyl-substituted diol) Propoxylated bisphenol and a divalent carboxylic acid are reacted. As a binder resin, a mixture of linear polyester obtained by
The non-linear polyester used in the present invention further contains an organic metal compound containing 0.2 to 10% by weight of a divalent or higher valent metal based on the binder resin. Among the alcohol components, the acid component is mainly aromatic dicarboxylic acids and aromatic polycarboxylic acids represented by phthalic acids, and the alcohol component is mainly an etherified diphenol mixture. . In particular, the etherified diphenol is mainly a mixture of glopoquinated bisphenol carana and some ethoxylated bisphenol. In addition to these, it particularly contains alkyl-substituted dicarboxylic acids and diols as components.

The advantage of introducing an aromatic group into polyester is the same as conventionally known for vinyl polymers and the like, in terms of the ability to generate and retain triboelectric charges in an insulating electrophotographic toner. Furthermore, the introduction of aromatic polycarboxylic acid has a significant effect on thermal properties during fixing, resulting in an amorphous, non-linear structure that increases the Tr (glass transition point) of polyester, making it useful as a low-melting point blocking-free and offset-free binder for toners. This is a major factor in its use.

At the same time, the non-linearity of the polyester promotes the hardening of the toner and greatly contributes to its durability.

In the linear polyester, divalent carboxylic acids, preferably aliphatic carboxylic acids, are used as the acid component, and propoxylated bisphenols, such as the above-mentioned etherified diphenols, are used as the alcohol component. This linear polyester affects the fixing properties of the toner and has a great effect in lowering the fixing point. The use of a mixture of non-linear polyester and linear polyester as a binder resin for toner has two advantages: on the one hand, the advantages of a high Tt hard resin, such as improved offset resistance and durability, and on the other hand, the advantages of a soft resin, which improves fixing properties. It satisfies both parties. Therefore, selecting the mixing ratio of the resin is particularly important in completing the present invention, and the composition ratio of linear polyester is preferably 5 to 50% by weight, more preferably 7 to 40% by weight.
The content of the non-linear polyester is preferably 50 to 95% by weight, more preferably 60 to 90% by weight. It is always preferable that the proportion of non-linear polyester in the binder resin is higher than that of linear polyester, which gives a more favorable result.

As the carboxylic acids used in the polyester of the present invention, divalent aromatic carboxylic acids include phthalic acid, isophthalic acid,
There are derivatives such as 7-talic anhydride, prephthalic acid, and their esters. Examples of trivalent or higher aromatic polycarboxylic acids include talenttricarboxylic acid, 1,2,4,5benzenetetracarboxylic acid, and their esters. There are anhydrous and esterified products. It is preferable that the amount of trivalent or higher aromatic polycarboxylic acid does not exceed 40 moles of the acid components.

Examples of divalent aliphatic carboxylic acids include maleic acid, fumaric acid, succinic acid, adipic acid, sepatic acid, and itaconic acid. In addition, acid components can be used within a range that does not impair the purpose of the present invention.

The etherified diphenol used in the present invention is mainly an etherified bisphenol obtained by etherifying bisphenol, particularly a propoxylated diphenol and/or an ethoxylated diphenol. These contain 2 to 3 mol of oxypropylene or oxyethylene per mole of bisphenol. Specific examples include polyoxypropylene 2,2-bis(4-hydroxyphenyl)furopane,
Polyoxypropylene 2,2-bis(4-hydroxy,
2,6-dichlorophenyl)propane, polyoxyethylene (1°0)-polyoxypropylene (1,5)-bis(4hydroxyphenyl)propane, and the like.

Particularly useful in the present invention is propoxylated bisphenol, which does not contain ethoxylated bisphenol, but is preferably blended in a molar amount that does not exceed the amount of propoxylated bisphenol, and also contains both propoxylated and ethoxylated alkoxy In the case of treated bisphenol, it is preferred that the amount of ethoxylation does not exceed the amount of propoxylation. That is, in the case of a toner composition using a polyester using an etherified diphenol in which ethoxylated bisphenol accounts for the majority, the properties under high humidity are clearly inferior to those using propoxylated bisphenol. It is presumed that this reflects the difference in hydrophilicity and hygroscopicity of the resulting toner compositions. That is, when etherified bisphenol with an excess of ethoxylated bisphenol is used, the toner has high hygroscopicity at high temperatures, resulting in a decrease in triboelectric charging properties, resulting in poor development performance and, as a result, a decrease in image density.

The etherified diphenols can be obtained by directly adding ethylene oxide or propylene oxide to diphenols or by reacting olefin halohydrins with diphenols.

Other alcohol components may be used, if necessary, within a range that does not interfere with the present invention, such as ethylene glycol, propylene glycol, 1.4-butanediol, 1,5-bentanediol, 1.6-hexanediol, chrycerin, and trimethylol. ethane, trimethylolpropane,
Aliphatic polyols such as pentaerythritol, 1.4-
Alicyclic polyols such as cyclohexanediol and 1,4-cyclohexane dimetatool can be used.

The polyester used in the present invention has a glass transition temperature of 50 to 8
It is desirable that the 0°C softening point is 60 to 130°C. If the glass transition temperature exceeds 80° C. or the softening point exceeds 130° C., excessive thermal energy is required during heat fixing, and high-speed heat fixing performance deteriorates. If the softening point is less than 60° C., the needle offset property during fixing will be poor. In addition, the number average molecular weight is preferably 2,000 to 20,000, more preferably 30
If the molecular weight is less than 2,000, the releasability to the heat fixing roller will be poor and an offset phenomenon will occur, while if it exceeds 20,000, the softening point will increase and the heat fixing power will decrease. The acid number of the polyester still used is preferably from 10 to 100, more preferably from 10 to 60. If the acid value is less than 10, the resulting toner will have insufficient offset during heat fixing and will have poor releasability from the fixing roller. On the other hand, when the number exceeds 100, the obtained toner has poor fixing properties, or is easily affected by humidity, resulting in poor images under high humidity conditions.

As the binder for the toner of the present invention, other known binder resins and gold may be used in combination within a range that does not impair the performance of the present invention. For example, there are polyester resins, epoxy resins, styrene acrylic resins, butyral resins, styrene butadiene resins, etc. which are outside the scope of the present invention.

In addition, the alkyl-substituted dicarboxylic acid has 6 to 1 carbon atoms.
Examples include succinic acid, maleic acid, fumaric acid, and their acid anhydrides in which the alkyl group of No. 8 is substituted.The more carbon atoms in the alkyl group, the more effectively the fixing point can be lowered by adding a small amount, but the effect is If it is too strong, toner blocking will occur in the low temperature range, so the amount must be strictly within the above range.

As the alkyl-substituted diol, glycols substituted with an alkyl group having 6 to 18 carbon atoms can be equally used, and ethylene glycol is particularly preferred. It has the same effects as alkyl-substituted dicarboxylic acids.

Examples of the specific metal compounds used in the toner of the present invention include organic salts or complexes containing divalent or higher-valent metals. Effective metal species include A1. , Ba, Ca, C
d, Co, -Cr, Cu, Fe, Hg.

Examples include multivalent materials such as Mg, Mn, Ni, Pb, Sn, Sr, and Zn. As organometallic compounds, carboxylates, alkoxylates, organometallic complexes, and chelate compounds of the above metals are effective; examples include zinc acetate, magnesium acetate, calcium acetate, aluminum acetate, magnesium stearate, and calcium stearate. , aluminum stearate, dermium improboxide, aluminum acetylacetonate,
Iron (I) acetylacetonate, chromium 3,5 di-tert-butylstearate and the like are preferred, with acetylacetone metal complexes and salicylic acid metal salts being particularly preferred. In order to avoid the adverse effects mentioned above, the amount added must not exceed 10% by weight based on the binder resin, and 0.2%.
Below that, the substantial effect disappears.

A charge control agent, a colorant, and a fluidity modifier may be added to the toner of the present invention as necessary, and the charge control agent and fluidity modifier may be mixed (externally added) with the toner. May be used. Examples of charge control agents include metal-containing dyes and nigrosine, conventionally known dyes and pigments can be used as colorants, and colloidal silica, fatty acid metal salts, etc. can be used as fluidity modifiers. be.

Furthermore, if it is desired to obtain a magnetic toner, magnetic fine particles may be added to the toner. Does it exhibit magnetism as a magnetic substance?
Any material that can be magnetized may be used, such as fine metal powders such as ferrous iron, manganese, nickel, cobalt, and chromium, various ferrites, alloys and compounds of manganese, and other ferromagnetic alloys such as magnetite, which are conventionally known as magnetic materials. You can use what is listed.

Furthermore, polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene may be added to the toner in order to improve the releasability from the heat fixing roll.

The present invention will be specifically explained below with reference to resin production examples, examples, and comparative examples, but these are not intended to limit the present invention in any way. Note that all parts used are parts by weight.

[Production example of non-linear polyester-1] Polyoxypropylene (2,5)-2,2-bis(4-
Put 545 parts of (hydroxyphenyl)propane into a four-loop flask, set a stirrer, condenser, thermometer, and gas inlet tube, and place it in a mantle heater. After purging the inside of the reaction vessel with nitrogen gas and bringing the contents to 50 to 60°C, 135 parts of terephthalic acid and succinic acid (C*a HIIo 04 ) 7 in which the C12 alkyl group was substituted were added.
7 parts and 38 parts of trimellidic acid were added so that 0.1 g of carboxyl group was equivalent to 1 equivalent of hydroxyl group.

This mixture system is heated to 210° C. and stirred. While removing the reaction water, the reaction is monitored by measuring the acid value every hour to check the end point of the reaction after about 5 hours have elapsed. Acid value is about 30
At that point, the reaction is cooled to room temperature.

[Production Example-2 of non-linear polyester] Polyoxypropylene (2
, 5) 545 parts of -2,2-bis(4-hydroxyphenyl)profluorine was placed in a grape flask, and the mixture was purged with nitrogen and heated at 50°C. To this were added 135 parts of isophthalic acid, 77 parts of succinic acid substituted with a C□ alkyl group, and 38 parts of trimellidic acid, and the mixture was heated to 210° C. and stirred to react, and after the reaction was completed, it was cooled to room temperature.

[Production example of non-linear polyester-31 According to the same method as production example 1, polyoxypropylene (
545 parts of 2,5)-2,2-bis(4-hydroxyphenyl)propane? The flask was replaced with nitrogen and heated to 50°C. To this are added 108 parts of terephthalic acid, 24 parts of adipic acid, 77 parts of succinic acid substituted with an alkyl group of CI2, and 38 parts of trime IJ) acid, and the mixture is heated to 210° C. and stirred to react. After the reaction is completed, it is cooled to room temperature.

[Production Example-4 of non-linear polyester] According to the same method as Production Example 1, polyoxypropylene (
2,5)-2,2-bis(4-hydroxypheni/I/
) 436 parts of propane and 18 parts of glycerin are placed in a flask, the flask is purged with nitrogen, and the flask is heated to 50°C. In this, terephthalic acid 1
79 copies, C1! Kono-rirll substituted with an alkyl group of
, 77 parts of gold were added, and the mixture was heated to 210° C. and stirred to react. After the reaction is completed, it is cooled to room temperature.

[Production Example-5 of non-linear polyester] According to the same method as Production Example 1, polyoxypropylene (
436 parts of 2,5)-2,2-bis(4-hydroxyphenyl)propane and 64 parts of ethylene glycol substituted with an alkyl group of Cs (C□.Hya02) were placed in two flasks, replaced with nitrogen, and heated to 50°C. Heat. To this were added 179 parts of terephthalic acid and 38 parts of trimellidic acid, and the mixture was heated to about 210° C. and stirred to react. After the reaction is completed, it is cooled to room temperature.

[Production Example-6 of non-linear polyester] According to the same method as Production Example 1, polyoxypropylene (
2,5) -2,2-bis(4-hydroxyphenyl)
Pour 545 parts of professional fluid into a flask, replace with nitrogen, and heat to 50°C. To this were added 112 parts of terephthalic acid and 95 parts of trimellidic acid, and the mixture was heated to about 210° C. and stirred to react. After the reaction is completed, it is cooled to room temperature.

[Production Example-7 of non-linear polyester] According to the same method as Production Example 1, polyoxypropylene (
2,5)-2,2-bis(4-hydroxypheni#)
7' Lopan 545 parts tPut in a flask and replace with nitrogen 50
Heat to ℃. To this are added 135 parts of terephthalic acid and 155 parts of succinic acid substituted with an alkyl group of C1i, and the mixture is heated to about 210° C. and stirred to react. After the reaction is completed, it is cooled to room temperature.

(Production Example-1 of linear polyester) The acid component of Production Example 1 of non-linear polyester was changed to fumaric acid 1
85 parts, the mixture system was heated and mixed at 210°C, and the reaction water was removed. When the acid value reaches 20, the reaction is terminated and the resin is cooled to room temperature.

(Production Example-2 of Linear Polyester) According to the same method as in Production Example 1 of Linear Polyester, the acid component was placed in 120 parts of maleic anhydride, dehydration condensation was carried out, the reaction was stopped when the acid value was 25, and linear polyester was produced. Polyester was obtained.

(Production Example-3 of linear polyester) The acid component of Production Example 1 of linear polyester was succinic acid 125
A linear polyester was obtained in the same manner as in Production Example 1 except that the amount of polyester was changed. The softening point of the obtained polyester was 112°C.

Example 1 A mixture consisting of 70 parts of the non-linear polyester of Production Example 1, 30 parts of the linear polyester of Production Example 2, 6 parts of magnetite (Fe, 0.0%), 6 parts of low molecular weight polypropylene, 5 parts of iron acetylacetonate, and 2 parts (units are parts by weight). were heated and kneaded with a roll. After this was left to cool, it was made into a coarse pulverized product and was pulverized using an ultrasonic jet mill and classified using an air classifier to obtain toner particles having an average diameter of about 13 μm.

This toner contains colloidal silica (Aerosil R-972).
')t was added and supplied to a one-component development type electrophotographic copying machine (Canon NP-400RE) and a copying test was conducted, and sufficient image density and development durability of over 50,000 sheets were obtained. There were no problems with fixing properties. In addition, in order to take a closer look at the thermal fixing properties, we prepared a separate fixing unit for the copying machine, and performed a fixing test on a separately prepared unfixed image on transfer paper using this separate fixing unit by changing the roller temperature setting. No offset phenomenon occurred in the temperature range, and the fixing performance was also poor. 50 more of this toner
Although it was left in an atmosphere at ℃ for a long time, no blocking or caking was observed. Further, there were no problems in the developability in a high humidity atmosphere and in the developability in a low humidity atmosphere.

Example 2 A toner was obtained in the same manner as in Example 1 except that the nonlinear polyester in Example 1 was replaced with that of Production Example 2. When the obtained toner was subjected to the same tests as in Example 1, it showed sufficient performance in terms of image quality, fixing property, and storage stability.

Example 3 A mixture consisting of 80 parts of the non-linear polyester of Production Example 3, 20 parts of the linear polyester of Production Example 6, 60 parts of magnetite (Fe, 04), 3 parts of polyethylene wax, and 5 parts of iron acetylacetone was heated and kneaded with a roll. This was subjected to a process of coarse pulverization, fine pulverization, and classification to obtain toner particles of 5 to 20 μm. When colloidal silica was added to this toner and the same copying test as in Example 1 was conducted, sufficient performance was confirmed.

There were no problems in the fixing test using an external fixing device and the 50° C. high temperature storage test.

Example 4 In the same manner as in Example 1, except that magnetite, which is a magnetic powder, was removed from the toner formulation and 8.0 parts of carbon black was added, the average particle size was determined through the coarse crushing, pulverizing, and classification steps. A toner of 9.2μ was obtained. Add 20 parts of this toner to 80 parts of carrier iron powder (Japan Iron Powder, EF'V2O0/
300) and supplied to a Canon copier NP-6000 for a development test. As a result, the initial image and the 20,000-sheet durability image were sufficient, and there were no problems with the fixability. Further, the fixing temperature dependence and storage test using a separate fixing device shown in Example 1 also showed sufficient performance.

Example 5 A toner was prepared and evaluated in the same manner as in Example 1 except that 3 parts of 3.5-di-t-butyl chromium salicylate was used instead of 2 parts of iron acetylacetonate, and the initial image and durable image were very good and there were no problems. In addition, good results without any problems were obtained, which were almost the same as in Example 1 in the fixing test using a separate fixing device, the storage test, and the high humidity test.

Example 6 A toner was prepared and evaluated in the same manner as in Example 1, except that 1 part of aluminum impropylate was used instead of 2 parts of iron acetylacetonate. The initial image and durable image were very good and there were no problems. In addition, in a fixing test using a separate fixing device, a storage test, and a high humidity test, almost the same results as in Example 1 were obtained without any problems.

Example 7 In Example 1, 100 parts of the non-linear polyester of Production Example 1 was used as glue, and 100 parts of the non-linear polyester of Production Example 4 was used.
A toner was prepared and evaluated in the same manner as in Example 1, except that the same procedure as in Example 1 was used. Satisfactory results substantially similar to those in Example 1 were obtained.

Example 8 A toner was prepared and evaluated in the same manner as in Example 4, except that 70 parts of the non-linear polyester of Production Example 1 was used in Example 4, and 70 parts of the non-linear polyester of Production Example 5 was used as the glue. However, almost the same satisfactory results as in Example 4 were obtained.

Example 9 In Example 4, instead of using 30 parts of the linear polyester of Production Example 2, 100 parts of the linear polyester of Production Example 3 was used.
<In addition to using this product, it was also made into a toner and evaluated in the same manner as in Example 1. As a result, almost the same satisfactory results as in Example 4 were obtained.

Comparative Example 1 In Example 1, magnesium oxide was used and a toner was made and evaluated in the same manner as in Example 1.
However, the offset phenomenon became noticeable immediately, and the offset toner that could not be removed by the cleaning web of the fuser passed through the web after making 10 copies of the ink, and the image did not appear on the image. It appeared as a black line on the surface, and was completely impractical. When the fixing performance was examined in detail using a separate fixing device, it was found that although the fixing point was slightly lower than that of Example 1, fixing, that is, offset was evident, and the thermal properties were poor, with no practical fixing range at all.

Comparative Example 2 100 parts of the linear polyester of Production Example 3, 60 parts of magnetic powder,
A mixture of 4 parts of low molecular weight polypropylene was kneaded with a heated roll, and a toner was prepared in the same manner as in Example 1. Colloidal silica was added to the obtained toner and it was subjected to a copying test. When the same test as in Example 1 was carried out, the toner of this example had a significant problem, particularly in fixing properties. That is, low-temperature offset during fixing was likely to occur, the transfer paper tended to wrap around the fixing roll, and the melt viscosity characteristics were obviously poor.

Comparative Example 3 A toner was obtained in the same manner as Tip Example 1 except that only the non-linear polyester of Production Example 5 was used as the polyester. Colloidal silica was added to this toner and a test was conducted in the same manner as in Example 1.
It showed sufficient performance in terms of storage stability. However, the fixing point during fixing tended to be clearly too high and could not be put to practical use.

Claims (1)

[Scope of Claims] 1. An etherified dienol having 50% or more of propoxylated and/or ethoxylated propoxy groups, a divalent aromatic carboxylic acid, and a trivalent or higher aromatic carboxylic acid and a mixture of a non-linear polyester obtained by reacting an alkyl-substituted dicarboxylic acid and/or an alkyl-substituted diol, and a linear polyester obtained by reacting ff3) propoxylated bisphenol with a dihydric carboxylic acid. An electrophotographic toner comprising a binder resin and an organic metal compound containing a divalent or higher valent metal in an amount of 0.2 to 10% by weight based on the binder resin. 2 The composition ratio of the binder resin is 5 to 50 for linear polyester.
2. The electrophotographic toner according to claim 1, wherein the weight percent of the nonlinear polyester is in the range of 50 to 95 tons. The electrophotographic toner according to claim 1, wherein the 32-valent carboxylic acid is fumaric acid. 4 Claim 1 containing a magnetic substance in the binder resin
Electrophotographic toner described in Section 1. 5. The electrophotographic toner according to claim 4, which contains 30 to 90% by weight of magnetic material based on the binder resin.