JPS59189346A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To provide a toner for developing an electrostatic charge image having high flowability and noncoagulability and forming stably a fine visible image at all times by adding a specified polyester type binder resin and specified polyolefin wax. CONSTITUTION:Polyester resin contg. >=5wt% chloroform-insoluble component is used as a binder resin. To particles of the binder resin is added wax of polyolefin block- or graft-copolymerized with an alpha-methylene aliphatic monocarboxylate monomer together with a coloring agent, an electrostatic charge controller and other necessary toner components. Thus, a toner for developing an electrostatic charge image is prepd. The amount of the wax to be added is 1-20wt%, preferably 1-10wt% of the amount of the binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, and the like.

In the process of developing an electrostatic image, charged fine particles are attracted by electrostatic attraction and attached to the surface of an electrostatic image support.
This is the step (2) of visualizing the electrostatic charge image.

The specific method for carrying out such a developing process is as follows:
It consists of a wet development method using a liquid developer in which pigments or dyes are finely dispersed in an insulating organic liquid, and a toner in which a coloring agent such as carbon black is dispersed in a binder made of natural or synthetic resin. There are dry developing methods that use a powder developer, such as a cascade method, a bristle brush method, a magnetic brush method, an impression method, and a powder cloud method.

The image visualized in the developing step may be fixed on a support as it is, but usually it is transferred to another support such as transfer paper and then fixed. In this way, the toner is not only subjected to the development process, but also to the subsequent processes, that is, the transfer process and the fixing process.

Therefore, toners are required to have not only good developability but also good transferability and fixing properties. Among these, the conditions related to fixing properties are the most severe, and many studies and results have been published in the past on improving the fixing properties of toners.

(3) It is generally advantageous to fix the toner image formed in the developing process or the image to which it is transferred by a heat fixing method.This heat fixing method includes a non-contact heat fixing method such as open fixing, Contact heat fixing methods such as heat roller fixing are prohibited. The contact heating fixing method is excellent in that it has high thermal efficiency, and is particularly capable of high-speed fixing and is suitable for fixing in °C high-speed copying machines. Furthermore, since a relatively low-temperature heat source can be used, this method requires less power consumption, making it possible to downsize the copying machine and save energy. Further, even if paper accumulates in the fixing device, there is no risk of fire, which is also preferable.

Although the contact heating fixing method is preferable in various respects as described above, this method has a serious problem of occurrence of an offset phenomenon. This is a phenomenon in which a portion of the toner constituting the image is transferred to the surface of the heat roller during fixing, and this is transferred again to the transfer paper or the like that is fed next, staining the image. In order to prevent this offset phenomenon, various proposals have been made and some of them have been put into practical use. One is to perform fixing while applying a release oil such as silicone oil to the surface of a heated roller, and the other is to provide the toner itself with anti-offset performance. The latter method is
Since no silicone oil application mechanism is required, the structure of the fixing device is simple, and maintenance such as replenishment of silicone oil is not required.

Therefore, the offset phenomenon occurs when the temperature of the heat roller increases, and therefore, the higher the minimum temperature at which the offset phenomenon occurs (hereinafter referred to as "offset occurrence temperature"), the better the non-offset property. However, in order for the toner to be fixed, it must be heated to a temperature above its softening point. Therefore, in an actual heat roller fuser, the temperature of the heat roller is lower than the temperature of the toner. The temperature is set to a specific temperature within the fixable temperature range, which is higher than the softening point of and lower than the offset generation temperature.

However, in practice, it is not possible to maintain the temperature of the heat roller completely uniformly at the set temperature, and there are also temperature-related circumstances (5) that must be taken into consideration. It is desirable to have a toner that does not impair the advantages of the contact heat fixing method.

Vinyl polymers have been widely used as binders for toners, and in order to obtain non-offset properties in toners using vinyl polymers as binders, it has been proposed to use high molecular weight polymers. However, high molecular weight vinyl polymers have a high softening point,
Therefore, even if the offset generation temperature is high, it is difficult to obtain a wide fixable temperature range, and it is impossible to obtain a suitable number of sheets.

On the other hand, polyester resin can be relatively easily obtained in the form of a low molecular weight material, so it is possible to use it as a binder to obtain a toner with a low softening point. Compared to , it has better "wetting" to a support such as transfer paper when melted,
(6) It is preferable in that sufficient fixing can be performed at a lower temperature than toners made of vinyl polymers having approximately the same softening point.

Furthermore, since toner is attached to an electrostatic image support using electrostatic attraction, or is further transferred to another support, it is generally necessary to have uniform and stable triboelectric charging properties. . A common method for imparting triboelectric charging properties to toner is to incorporate a charge control agent such as a dye into resin particles constituting the toner. Therefore, in the production of such toners, strict conditions must be met to ensure that the charge control agent is uniformly dispersed in the resin.

However, polyester resin itself has appropriate triboelectrification properties, so it is not necessary to include a charge control agent, or even if it is necessary, a small amount is sufficient.
After all, if polyester resin is used as a binder, toner production can be achieved very easily.

However, toner that uses polyester resin as a binder,
The disadvantage is that the temperature at which offset occurs is usually low.

(7) In order to increase the temperature at which offset occurs in a toner, it is effective to include a high molecular weight component in the binder resin of the toner. Since the resin has a high softening point, the minimum temperature required for fixing the toner (hereinafter referred to as "minimum fixing temperature") becomes high, and the advantage of the contact heat fixing method is lost. It is naturally desirable that this minimum fixing temperature be low, and in order to achieve the formation of visible images on both sides of a single sheet of transfer paper, which has recently become a high demand, the toner used for development must be It is necessary that the material can be fixed at a low temperature.

In view of the above-mentioned background, a means has been developed for lowering the minimum fixing temperature by incorporating a low softening point wax made of a release agent such as polypropylene wax or polyethylene wax into toner particles. However, in this method, the fluidity of the powdered toner is reduced, so the developability and transferability are reduced, and a good visible image cannot be formed. There is a tendency to Moreover, in order to obtain the effect of adding wax, the content ratio of the wax must be considerably large, and as a result, the wax component adheres to the developing sleeve or electrostatic image support and forms a film. There are drawbacks that impede this function.

In order to improve the fluidity of toner, it is effective to add a fluidity improver made of fine hydrophobic silica powder to toner powder. In order to obtain this, it is necessary to add a large amount of hydrophobic silica fine powder, and as a result, the surface of the electrostatic image support is damaged by the highly hard hydrophobic silica fine powder, and the support is This becomes a serious problem when the photoreceptor is a photoconductive photoreceptor, and when surface cleaning of the electrostatic charge image is carried out using a rubber blade, the blade becomes severely worn, and even though the image is subjected to development, In an image forming apparatus (9) that has a recycling system in which toner that has not participated in the formation of a toner image is returned to the developing device for reuse, fine particles of hydrophobic silica are embedded in the surface of the toner particles. The fluidity of the toner decreases, resulting in a visible image of low quality.

The present invention has been made based on the above-mentioned circumstances, and its objects are to have sufficient non-offset properties, a low minimum fixing temperature, high fluidity and non-cohesiveness, and always stable fixing properties. An object of the present invention is to provide a toner for developing an electrostatic image that can form a good visible image.

The above purpose is to use a binder resin made of polyester resin containing 5% by weight or more of chloroform-insoluble matter, and α
This is achieved by a toner for developing an electrostatic image, which is characterized by containing a wax made of a polyolefin block copolymerized or graft copolymerized with a methylene aliphatic monocarboxylic acid ester monomer.

The present invention will be specifically explained below.

In the present invention, a polyester resin having a chloroform-insoluble content of 5% by weight or more is used as the binder resin (10), and α-methylene A polymer obtained by block copolymerizing an aliphatic monocarboxylic acid ester monomer and a polyolefin, or a polymer obtained by graft copolymerizing an α-methylene aliphatic monocarboxylic acid ester monomer onto the polyolefin, That is, a toner for developing electrostatic images is prepared by containing a wax made of a polyolefin modified with an α-methylene aliphatic monocarboxylic acid ester monomer (hereinafter referred to as "modified polyolefin").

Here, the content of the wax is within the range of 1 to 20% by weight, preferably 1 to 1% by weight based on the binder resin.
It is within the range of 0% by weight. If this proportion is less than 1% by weight, the effect of the wax as a release agent will not be exhibited and the non-offset property of the toner will not be improved, while if it exceeds 20% by weight, the fluidity of the toner will decrease. 9,
As a result, the developability and transferability deteriorate, and a good visible image cannot be formed (11), and the wax adheres to the developing sleeve or electrostatic image support, forming a film and inhibiting its function. It becomes like this.

As described above, in the toner of the present invention, the binder resin is composed of a polyester resin containing a high molecular weight component that is insoluble in chloroform above a certain level. In addition to providing excellent non-offset properties with a high However, the minimum fixing temperature is low and it is suitable for high-speed fixing using a heat roller fixing device. In addition, when the degree of decrease in fluidity due to the addition of wax is slight and the addition of a fluidity improver such as hydrophobic silica fine powder is not necessary or necessary in order to obtain the necessary fluidity. Even if the amount of hydrophobic silica fine powder added is very small, it is sufficient, and therefore, the adverse effects caused by adding a large amount of hydrophobic fine silica powder can be avoided. Furthermore, it has a high cohesive property and excellent preservability. Therefore, according to the toner of the present invention, by having good fluidity and non-aggregation property, it is possible to achieve a good fixation rate (W), and also by being able to fix at a low temperature and high speed, it is possible to achieve t! As a result, excellent visible images with high artist density can always be stably formed. In addition, since the toner of the present invention has a low minimum fixing temperature, it is possible to avoid exposing the paper, which is the toner (8) support, to high temperatures during fixing, and this suppresses the occurrence of wrinkles. It is practically possible to form visible images on both sides using toner.

The reason why the toner of the present invention has the above-mentioned excellent properties has not been strictly elucidated, but in relation to the binder resin, it contains a wax consisting of polyolefin, so the offset generation temperature remains high and the minimum fixation temperature remains high. As the temperature decreases, the polyolefin is a modified polyolefin that has a modifying component in its molecular structure that has an affinity for the binder, and therefore has high compatibility with its own binder resin, and moreover, the polyolefin is a modified polyolefin ( 18
) Part of the reason is thought to be that the modified components have less stickiness and greater fluidity compared to reflex wax.

The polyester resin used as the binder resin in the present invention is obtained by condensation polymerization of alcohol and carboxylic acid. Examples of alcohols used include ethylene glycol, diethylene glycol, triethylene glycol, 1°2-propylene glycol, 1, 8
-Propylene glyco-”% 1 # Diols such as 4-butanediol, neopentyl glycol, 1,4-butynediol, 1,4-bis(hydroxymethyl)
Cyclohebyusan, Bisphenol A, Hydrogenated Bisphenol A, Poliothodiethylenated Bisphenol A
, etherified bisphenols such as poliocybropyre/bisphenol A, and other dihydric alcohol monomers.

Examples of carboxylic acids include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, and isophthalic acid.

(14) Terephthalic acid, cyclohexane dicarboxylic powder, succinic acid, adipic acid, sepatic acid, malonic acid, anhydrides of these acids, dimers of lower alkyl esters and liluic acid, other divalent Mention may be made of organic acid monomers.

As the polyester resin used in the present invention, it is preferable to use not only a polymer made only of one or more difunctional monomers, but also a polymer containing a component made of trifunctional or more polyfunctional monomers. Such a polyfunctional monomer is a trihydric or higher polyhydric alcohol monomer, or, for example, sorbitol% 112.8.6-1,000 santetrol, 1.4
-Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1°z,
4-butanetriol, 1,2.5-pentanetriol, glycerol, 2-methylpropanetriol, 2
-Methyl-1,2,4-butane trio-/I/, trimethyloleta/, trimethylolpropane, 1,3.5
-1-lihydro dimethylbenzene, and others.

(15) Also, examples of trivalent or higher polycarboxylic acid monomers include, for example, 1
, 2.4-benzene+, +carboxylic acid, 1°2.5-
Benzenetricarboxylic acid, 1,2,4-cyclohexantricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid 1,1. Z, 4-naphthalenetricarboxylic acid, 1. Z
, 4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1゜3-dicarboxyl-2-methyl-
Examples include 2-methylenecarbocypropane, tetra(methylenecarbocyl)methane% 1,2,7.8-octanetetracarboxylic acid, embol trimer acid, acid anhydrides thereof, and others.

It is desirable that the above trifunctional or higher polyfunctional monomer component is contained in a proportion of 30 to 8 mol A/% in each of the alcohol component or acid component as a structural unit in one polymer.

The polyester resin used in the present invention has a chloroform-insoluble content of 5% by weight or more.

Here, the chloroform-insoluble content refers to the content that permeates through the paper process when the sample is dissolved in chloroform, and is
−189346 (5) It is obtained as follows.

Sample powder obtained by finely pulverizing the resin sample and passing it through a 40-mesh sieve5. Collect the OOg, and use the r superassistant radiolite (+
700)5. Capacity 150 with OOg? Place it in a Fll container and pour 100 g of chloroform into the container.

The sample was placed on a ball mill stand and rotated for 5 hours or more to sufficiently dissolve the sample in chloroform.

- A piece of paper with a diameter of 7 crn in the actual pressurizer (from the 2nd rod)
5.00 g of Radiolite was uniformly precoated on top of the container, 9 mouthfuls of small amounts of chloroform were added, one piece of paper was brought into close contact with the filter, and the contents of the container were poured into the filter. 100 more containers? F! Thoroughly wash with J chloroform and pour into a filter to prevent any deposits from remaining on the walls of the container. Then close the top lid of the filter,
Perform filtration. The first filtration is carried out under a pressure of 447 cm2 or less, and after the outflow of chloroform has stopped, 100 ffl/chloroform is newly added to wash the residue on the first paper, and the pressure filtration is carried out again.

After completing the above operations, all of the paper and its residue (17) and radiolite were placed on aluminum foil and placed in a vacuum dryer at a temperature of 80-100C.

Dry for 10 hours under a pressure of 100 mmHg,
The total weight a (g) of the dried product thus obtained is measured, and the cycloform insoluble content X (weight %) is determined by the following formula.

X (wt%) The chloroform-insoluble content determined in this way is a high molecular weight polymer component or a crosslinked polymer component in the polyester resin, and its molecular weight is approximately 2.
00,000 or more.

The above-mentioned chloroform-insoluble components can be reduced by appropriately selecting reaction conditions in the polymerization reaction between alcohol and carboxylic acid, or by allowing an appropriate crosslinking agent to exist in the reaction system. Can be formed at controlled rates.

In the present invention, a polyester resin having a chloroform-insoluble content of (18) 5% by weight or more is used as a binder, but if a polyester resin having a chloroform-insoluble content of not more than 5% by weight is used, the resulting toner has an offset generation temperature. It becomes low.

The polyolefin component of the modified polyolefin used as the wax contained in the toner of the present invention is a homopolymer obtained from a single olefin monomer, or a copolymer obtained by copolymerizing the olefin monomer with another monomer copolymerizable with it. It is of the current type of collapse, and 1 is also good.

Examples of the olefin monomer include ethylene.

Propylene, butene-1, pentene-1, hesensen-1
．． Heptene-1, Octe/-1, Nonene-1, Decene-
1, and their isomers with different positions of unsaturated bonds,
Examples include 3-methyl-1-butane, 8-methyl-2
- pentene, 8-propyl-5-methyl-2-hexane, etc., which have a branched chain consisting of an alkyl group;
All other olefin monomers are included.

In addition, other (1,9
) Monomers include other olefin monomers, such as vinyl ether M such as vinyl methyl ether, vinyl-n-methyl ether, vinyl phenyl ether, etc.
For example, t is a vinyl ester such as vinyl acetate or vinyl butyrate, such as vinyl fluoride, vinylidene fluoride, tetraflumeroethylene, vinyl chloride, vinylidene chloride,
Haloolefins such as tetrachloroethylene, such as methyl acrylate, ethyl acrylate, n-butyl acrylate-1., methyl methacrylate, ethyl methacryle-1., n-butyl methacrylate-1., stearyl methacryle-1. -,N,N-dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, and other acrylic acid esters or methacrylic dispersion esters; for example, acrylonitrile, N,N-dimethylacrylamide, and other acrylic acid derivatives; Organic acids such as ethyl acrylate, methacrylic acid, maleic acid, fumaric acid, itaconic acid, diethyl fumarate,
You can make sweet potatoes such as β-Bio and Plum.

Therefore, when the polyolefin component is a copolymer type, an olefin copolymer type obtained by copolymerizing at least two or more of the above-mentioned olefin monomers, such as an ethylene-propylene copolymer, Ethylene-butene copolymer, ethylene-pentene copolymer, propylene-butene copolymer propylene-pentene copolymer, ethylene-8-methyl-1-
A copolymer-type glaze such as a butene copolymer, an ethylene-propylene-butene copolymer, or a glaze obtained by copolymerizing at least one olefin monomer as described above and at least one monomer other than the olefin monomer as described above. olefin copolymer types such as ethylene-vinyl acetate copolymers, ethylene-vinyl methyl ether copolymers, ethylene-vinyl chloride copolymers, ethylene-methyl acrylate copolymers, ethylene-vinyl acrylate copolymers,
Methyl methacrylate copolymer, ethylene-acrylic acid copolymer, propylene-vinyl acetate copolymer,
Propylene-vinylethyl ether (21) copolymer, propylene-ethyl acrylate copolymer,
Propylene-methacrylic acid copolymer, butene-vinyl methyl ether copolymer, buty/-methyl methacrylate copolymer, pentene-vinyl acetate copolymer, vinyl-vinyl butyrate copolymer, ethylene/- Copolymer types such as propylene-vinyl acetate copolymer and ethylene-vinyl acetate-vinyl methyl ether copolymer can be used.

When a copolymer type is used using a monomer other than an olefin monomer, it is preferable to use a copolymer type in which the proportion of the olefin portion of the olefin monomer in the polyolefin component is, for example, 50 mole or more.

This is because if the ratio of the olefin y portion becomes small, the effect of improving the fixing properties of the ]-ner cannot be sufficiently exhibited.

The modified polyolefin is composed of the above-mentioned polyolefin component and a modifying component, and the polyolefin component is diblocked or grafted by the modifying component.

Acrylate monomers are used as the modifying component, and specific examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, and acrylate. lauryl acid, acrylic acid 2-
1,000 syl to ethyl, stearyl acrylate, acrylic &2
-Chlorethyl, γ-phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n- methacrylate
Butyl, n-butyl methacrylate, methacrylic [n
-Octyl, dodecyl methacrylate, lauryl methacrylate, methacrylic acid? - Ethyl to 1,000 syl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and others.

By carrying out block copolymerization or graft copolymerization using the above-mentioned acrylate monomer and the polyolefin described above according to conventional methods and conditions (28), it is possible to obtain a wax consisting of a modified polyolefin. can.

For example, for block copolymerization, a method using a living polymer or a method in which a block copolymer is obtained by reacting an acrylate monomer with radicals generated by mechanochemically splitting wax, etc. can be used. For graft copolymerization, a method in which ozonized polyethylene is reacted with an acrylate monomer (polymer initiator method), a method in which grafting is performed using radiation, etc. can be used. Specific examples of preferred acrylate monomers as modifying components include methyl acrylate, methyl methacrylate, and n-butyl methacrylate. Here, the ratio of the modifying component in the modified polyolefin is 0.1 to
It is preferably within the range of 15% by weight, particularly from 1 to 10% by weight.

If this ratio is too small, the fluidity of the toner will be severely reduced, and if it is too large, the minimum fixing temperature of the toner will increase.

In addition, it is desirable that the modified polyolefin itself has a low softening point, for example JIS K2
531-1960, the softening point is 80 to 180t; preferably 090 to 16
0t:' is desirable.

The toner of the present invention is powder particles made by dispersing the above-mentioned modified IJ rufin wax in the above-mentioned binder resin together with a coloring agent, a magnetic substance, a property improver, and other necessary additives. body, its average particle size Fi
Usually in the range of 5 to 80 microns.

As a coloring agent, carbon black, nigrosine dye (
C, 1, Limited 50415B), Aniline Blue (c-1,
h 50405), Calcomale Blue (C,I.

1% azoec Blue 8), Chrome Yellow (
C, 1, 14090), Ultramarine Blue (C
, 1, 7710B), DuPont Oil Red (C,
1,1426105), Sennorin Yellow (C,1,
NQ47005), methylene blue chloride (CIJ
&152015).

(25) Phthalocyanipple (C, 1, number 74160), malachite green off-salate (CI 111kL420)
00), Lamp Black (C, 1, Floor 77266),
Mention may be made of rose bengal (C,I 45435), mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a visible image with sufficient acidity, and are usually added in an amount of 1 to 20 parts by weight per 100 parts by weight of the binder resin. Ru.

The magnetic material 'C' is a metal or alloy exhibiting ferromagnetism such as ferrite, magnetite, iron, cobalt, or nickel, or a compound containing these elements, or a material that does not contain a ferromagnetic element but has been subjected to suitable heat treatment. Alloy 1 which becomes ferromagnetic by applying
aluminum.

Examples include a known alloy called Heusler alloy containing manganese and copper, such as manganese-copper-tin, chromium dioxide, and others. These magnetic materials have an average particle size of 0
．． It is uniformly dispersed in the binder in the form of a fine powder of 1 to 1 micron. The content (26) is 20 to 70 parts by weight per 100 parts by weight of toner.

Preferably it is 40 to 70 parts by weight.

Examples of the property improving agent include a charge control agent, an anti-offset agent, a lubricant for improving fluidity, and others.

The toner of the present invention is made into a two-component developer by mixing 9% iron powder, glass peas, etc., but when it contains a magnetic material, it is used as a single-component developer and the electrostatic charge image appears. served.

Examples of the present invention will be described below, but the present invention is not limited to these. Note that "parts" represent parts by weight.

The binder resin and wax used in the following examples are as follows.

[Binder resin]

l) Binder resin A1: 299 g of terephthalic acid and polyethylene dipropylene (2,
2) 211 g of -2,2-bis(4-hydrothousandiphenyl)furopane and 82 g of pentaerythritol,
Place it in a round bottom flask equipped with a thermometer, a stainless steel stirrer, a crow rope gas conductor, and a flow container (27), set the flask on a mantle heater, and introduce nitrogen gas.11. D Nitrogen gas was introduced to raise the temperature while keeping the inside of the flask in an inert atmosphere, and 0.05 g of dibutyltin was added, followed by reaction at a temperature of 200 C while monitoring the reaction at the softening point. 17% by weight of chloroform insoluble matter,
Polyester resin with a softening point of 181 tr 2) Contains binder resin 2 A chloroform-insoluble content of 6% by weight, obtained in the same manner as in the production of binder resin AI, except that the weight of pentaerythritol was changed to 40g.

Polyester resin with a softening point of 125C 8) Binder resin A8 In the production of binder resin Al, obtained in the same manner except that the weight of pentaerythritol was changed to 100g, chloroform insoluble content 22% by weight, softening point 184t
ll' polyester resin 4) Binder resin B Using 800 g of triethylene glycol, 182 g of isophthal 1N 189346 (8) acid, and 188 g of benzene-1,2,4-tricarboxylic acid, in the case of binder resin A1. A polyester resin with a chloroform insoluble content of 17% by weight and a softening point of 180t obtained by reacting at a temperature of 200C in the same manner as 5) Binder resin C (for comparison) Etherified bisphenol A, Polyester resin [wax] with a chloroform-insoluble content of 0% by weight and a softening point of 112C l) Wax a Block copolymerized with n-butyl methacrylate Polyethylene wax made by block copolymerization with n-butyl methacrylate (methacrylic 1 ln-butyl content ratio 8 weight ratio, softening point 11 (1) 2) Wax b Polyethylene wax block copolymerized with n-butyl methacrylate (methacrylate (29) lyric acid 8) Wax C Polyethylene wax copolymerized with methyl methacrylate (methyl methacrylate content 7)
Weight %, softening point 118'C) 4) Wax d (for comparison) Unmodified polypropylene wax [Viscol 660PJ
(Manufactured by Sanyo Chemical Co., Ltd.) 5) Wax e (for comparison) Unmodified polyethylene wax [Hiwax 220PJ
(Softening point 118C, manufactured by Mitsui Petrochemicals) 6) Wax f (for comparison) Oxidized polyethylene wax "Hiwax 4202E
J (softening point 108G, manufactured by Mitsui Petrochemicals) In each of the Examples and Comparative Examples, the materials with the indicated formulations were processed in a conventional manner through the steps of melting, kneading, cooling, pulverizing, and classifying to obtain an average particle size. A toner consisting of particles having a diameter of lOμ was produced.

(30) Example 1 Binder resin Al 100 parts Wax a 3 parts Carbon black "Mogul LJ (manufactured by Cabot) 10 parts Example 2 Binder resin A2 100 parts Wax a 3 parts Carbon black [Mogul LJ lo part Example 3 □ Binder resin A3 100 parts Wax a 3 parts Carbon black [Mogul L4 10
Part Example 4 Binder resin Al 100 parts Wax b 3 parts Carbon black "Mogul LJ 1
tl Example 5 Binder resin Al 100 parts Wax c 3 parts Carbon black "Mogul LJ 10
Part (31) Example 6 Binder resin AI 100 parts Wax 8 6 parts Carbon black [Mogul LJ 10%Example 7 Binder resin B 100 parts Wax a 3 parts Carbon black "Mogul LJ 1 o!
Example 8 Binder resin B 100 parts Wax b 3 parts Carbon black "Mogull LJ 10"
9 Example 9 Binder resin B 100 parts Wax 1 6 parts Carbon black "Mogul Lj" 10% Example 10 Binder resin A1 48 parts Wax a 3 parts Magnetic fine powder 1
'-BL-100J (manufactured by Titan Kogyo Co., Ltd.) 52 parts JP-A No. 59-189346 (9) Comparative Example 1 Nono Inder Resin Al 100 parts Wax d 3 parts Car 4
``Mogul LJ''
Lo part comparative example 2 No2 Ingu resin Al 100
Part wax 8 3 parts Carbon black "Mogul LJ 10i Comparative example 3 Nono Inder resin Al 100 Miyako wax f 8 parts Carbon black "Mogul LJ 10 parts Comparative example - Binder resin 0 100 parts Wax a 8 parts Carbon black "Mogul LJ lO @ Comparison example 5 Nononingu resin Al 10
Part 0 Carmen Black "Mogul L" 10
Example 1 to implementation f! Toner obtained in 110 (
88) as "Toner 1" to "Toner 10", respectively.

The toners obtained in Comparative Examples 1 to 5 were designated as "Comparative Toner 1" to "Comparative Toner 5," respectively, and the fluidity of each of these toners was examined. That is, taking advantage of the fact that powders with high fluidity have a low degree of compaction, the degree of compaction was measured using a powder compaction tester "Tapdenser" (manufactured by Seishin Kokudo Co., Ltd.). Specifically, the diameter is 28W and the volume is 100? Fl
The sample was loosely packed into a 1-liter container from above through a 100-mesh sieve, the weight was measured to determine the static bulk density A, and the container was then placed with a top tapping device with a lid of the same diameter.
The volume of the sample when tapped 600 times under the conditions of fi was determined, the previously determined weight was divided by this volume value to determine the bulk density P, and the degree of compaction C was calculated using the following formula.

-A C-□ Toner charging (84) Prepare a developer with an amount of 20±1 micron/g, and apply each toner to an electrophotographic copying machine 1'-U-Bix.
8000J (manufactured by Konishiroku Photo Industry Co., Ltd.), the electrostatic charge image is developed, one toner image is transferred to the transfer paper, and the toner image is muddied using a heated roller fixing device, and the toner is primarily attached to the photoreceptor drum interface. The amount, transfer rate to transfer paper, and sharpness of the resulting copied image were measured. Here, the primary adhesion amount of toner is the amount of toner adhesion per unit area at a location where the so-called petablack potential is 800V.

Furthermore, for each k of all toners, the minimum fixing temperature and offset occurrence temperature were determined, and the storage stability was evaluated. Regarding the minimum fixing temperature, a heat roller whose surface layer is made of Teflon (polytetrafluoroethylene manufactured by DuPont) and a heat roller with a surface layer of
1800RTVJ (manufactured by Shin-Etsu Chemical Co., Ltd.) A toner image of a sample toner transferred onto a transfer paper of 64 g/m 2 is fixed at a linear speed of 1201 m/s using a heat roller. The set temperature was increased stepwise from (35) 1001Z' to 5C, and Kimwipe rubbing was applied to the formed fixed image. The set temperature was taken as the minimum fixing temperature. Note that the fixing device used here does not have a silicone oil supply mechanism.

In addition, to measure the offset occurrence temperature, the toner image is transferred and fixed to the above-mentioned fixing device, and then a blank transfer sheet is sent to the fixing device under the same conditions. The operation of observing whether or not toner stains occur was repeated with the set temperature of the heat roller of the fixing device being increased by one limit, and the temperature at which offset occurred was determined.

Regarding storage stability, each sample was left for 48 hours at a temperature of 55°C and a relative humidity of 40°C, and the presence or absence of aggregation and its degree were evaluated.

The above results are shown in Table 1.

Special opening R59-189346 (10) 1st clothing
(36) (87) Also, each of Toner 1 to Toner 9 has stains on the side photocopier.
When a continuous copying test was carried out 20,000 times using U-Bix 8000j, a clear and good copy image was formed until the end even when the toner was falling down.

As is clear from the above results, the toner according to the present invention has
It has excellent non-offset properties, has a very low minimum fixing temperature, and has a wider fixable temperature range than toners that use conventional unmodified polyolefin wax, and has improved fluidity. It can be put to practical use even without the addition of agents, and has excellent acupuncture and transferability.

It is possible to always form stable and good visual clarity.

Japanese Patent Publication No. 59-189346 (11) 309-

Claims (1)

[Scope of Claims] 1) Block copolymerization or graft copolymerization of a binder resin consisting of a polyester resin containing 5 weight or more of chloroform-insoluble matter and an α-methylene aliphatic monocarboxylic acid ester monomer. A toner for developing an electrostatic image, comprising a wax made of polyolefin. 2) The toner for developing electrostatic images according to claim 1, wherein the wax content is 1 to 20% by weight.