JPS59174856A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain stably a fine visible image at all times by using a specified styrene polymer as a binder and adding modified polyolefin wax so as to lower the minimum fixing temp. as well as to provide sufficient anti-offsetting properties. CONSTITUTION:A polymer of one or more kinds of styrene monomers having >=3.5 ratio of number average mol.wt./weight average mol.wt. is used as a binder, and about 1-20wt% wax of a polyolefin block- or graft-copolymerized with an aromatic vinyl monomer (modified PO) is added. A copolymer of a styrene monomer with other vinyl monomer may be used. Such styrene resin is effective in preventing offsetting, and by adding the modified PO wax, the minimum fixing temp. is lowered while preventing offsetting. The wax reduces the stickiness and increases the flowability. The resin has high noncoagulability and superior shelf stability. Thus, high developing power and transferability are provided, and a fine visible image can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner for developing an electrostatic charge image formed in the Seiko photography method, electrostatic printing method, electrostatic recording method, etc. This is a step in which fine particles made of Teiden are attracted by static gravity and adhered to the surface of an electrostatic image support, thereby visualizing the electrostatic charge.

Specific methods for accomplishing these 41 techniques include a wet development method using a liquid developer in which pigments or dyes are finely dispersed in an insulating organic liquid, and a binder made of natural or synthetic resin. Dry developing methods such as the cascade method, bristle brush method, magnetic brush method, impression method, and powder cloud method that use a powder developer consisting of a toner containing a fraction of a coloring agent such as carbon black; There is.

The image visualized in the developing process may be fixed on the support as is, but it is usually transferred to another support such as transfer paper. In this way, toner is not only subjected to the development process, but also to the subsequent processes, that is, the transfer process and the fixing process. However, it is required to have good transfer and fixing properties. Among these, the conditions regarding fixability are the most severe.
Research on improving the fixing properties of this toner and its results have been published in numerous documents.

It is generally advantageous to fix the toner image formed in the developing process or the image transferred thereto by a heat fixing method.This heat fixing method includes a non-contact heat fixing method such as oven fixing, There is a contact heating fixing method such as roller fixing. The zero-contact blade heat fixing method is excellent in that it has high thermal efficiency, and is particularly suitable for fast fixing in 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 because during fixing, a portion of the toner forming the threshold is transferred to the surface of the heat roller, and this is transferred again to the transfer paper, etc. that is sent next, and II! ii This is a phenomenon that stains the image. In order to prevent this offset phenomenon, a method of adhering to rice has been proposed, and some of it has been put into practical use.

In one method, fixing is performed while applying a release oil such as silicone oil to the surface of a heated roller, and in the other method, the toner itself is provided with anti-offset properties.

The latter method is advantageous in that the structure of the fixing device is simple because a silicone oil application mechanism or the like is not required, 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 the lower 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 heater, the temperature of the heat roller is The temperature is set to a specific temperature within a fixable temperature range that is higher than the softening point of the toner and lower than the offset generation temperature.

On the other hand, it is naturally desirable that the minimum temperature required for fixing the toner (hereinafter referred to as "minimum fixing temperature") be low, and there is also an increasing demand for OT on both sides of a sheet of transfer paper. In order to achieve image formation, it is necessary that the toner used for development be capable of fixing at low temperatures.

Conventionally, as a technical means to obtain a toner having non-offset properties and a low minimum fixing temperature, for example, the ratio of the weight average molecular weight Mw to the number average molecular weight MnK of the binder resin is increased, and the There are known means for increasing the cohesive force of the toner, or means for incorporating a low softening point wax made of a release agent such as polypropylene wax or polyethylene wax.

However, in the former method, if sufficient non-offset properties are to be obtained, the minimum fixing temperature will rise, and if a binder resin is selected to prevent this, the glass transition point will be lowered and the toner will coagulate. It tends to be easier to do.

Therefore, it is possible to combine the former method with the latter method, but in the method of incorporating a low softening point wax into the toner, the fluidity of the powdered toner decreases, resulting in poor appearance and transferability. As a result, a good visible image cannot be formed, and there is a tendency for agglomeration to occur. Moreover, in order to obtain the effect of adding wax, the content ratio of the wax must be considerably increased, and as a result, the wax component may adhere to the developing sleeve or electrostatic image support and form a film. , and there are drawbacks that impede its 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, but toner containing low softening point wax has sufficient fluidity. 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. This is a serious problem when the support is a photoreceptor, and when the surface of the electrostatic image support is cleaned with a rubber blade, the blade is subject to severe abrasion, and furthermore, when the support is used for development, In image forming apparatuses that have a recycling system in which toner that has been used but did not participate 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. As the fluidity of the toner decreases, the visible image formed will be 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 low Il collection properties, and always stable fixing properties. An object of the present invention is to provide a toner for developing an electrostatic image, which can form an attractive visible image.

The above purpose is to obtain a polymer composed of a styrene monomer or a copolymer of a styrene monomer and another vinyl monomer, so that the ratio of the weight average molecular layer to the number average molecular layer is This is achieved by a toner for developing an electrostatic image, which is characterized by containing a binder resin of 3.5 or more and a wax consisting of polyolefin 9 which is diblock copolymerized or graft copolymerized with an aromatic vinyl monomer.

The present invention will be specifically explained below.

In the present invention, a polymer obtained by polymerizing one or more styrenic monomers, or a copolymer of a styrenic monomer and another vinyl monomer copolymerizable with the styrene monomer is used. The copolymer obtained at least has a ratio of weight average molecular weight Mw to number average molecular weight tlVln Mw/M
A binder resin with an n value of 3.5 or more, preferably 5 or more is used as a binder resin, and the aromatic vinyl monomer and polyolefin are block co-blocked together with the colorant, charge control agent, and other necessary toner components in the particles. A polymer obtained by polymerization or a polymer obtained by graft copolymerizing an aromatic vinyl monomer onto a polyolefin as a chain backbone, that is, a polyolefin modified with an aromatic vinyl monomer (hereinafter referred to as "modified polyolefin") . ) to prepare a toner for developing electrostatic images.

Here, the content of the wax is in the range of 1 to 20% by weight, preferably in the range of 1 to 10% by weight.
It is within. If this proportion is less than 1% by weight, the effect of the wax as a release agent will not be exhibited, and therefore the non-offset property of the toner will not be improved; on the other hand, if it exceeds 20% by weight,
If the fluidity of the toner decreases, the developability and transferability will deteriorate, making it impossible to form a good visible image, and the wax will adhere to the developing sleeve or electrostatic image support, causing a film. formation and come to inhibit its function.

As described above, the toner of the present invention uses a styrene-based polymer or copolymer with a Mw/Mn value of 3.5 or more as the binder resin, and therefore has a high cohesive force when melted. It has a low softening point, that is, the binder resin itself has non-offset properties and has the property of keeping the minimum fixing temperature low, and as mentioned above, it contains a wax consisting of modified polyolefin, which will be described later. As is clear from the description of the embodiments, the offset generation temperature is high and the upper liquid low fixing temperature is low, making it 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 small and the addition of a fluidity agent such as hydrophobic silica fine powder is unnecessary or necessary in order to obtain the necessary fluidity. However, it is sufficient to add only a small amount of the added amount, and therefore, it is possible to avoid the adverse effects caused by adding hydrophobic silica fine powder to the 4-bond.

Furthermore, it has high non-aggregation properties and excellent storage stability. Therefore, the toner of the present invention has high fluidity and non-cohesiveness, and can achieve good development.
It is possible to fix at a low temperature and at high speed, and as a result, visible images with good image density and good quality 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 serving as the toner image support to high temperatures during fixing, and as a result, the occurrence of wrinkles is suppressed. It becomes practically possible to form a visible image section using toner.

The reason why the toner of the present invention has the above-mentioned two different characteristics has not been strictly elucidated, but in relation to the binder resin, the offset generation temperature is high because it is rich in wax consisting of polyolefin. In addition, 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. Part of the reason is thought to be that the modified component has less stickiness and greater fluidity than modified polyolefin waxes.

The binder resin of the toner of the present invention is a polymer or copolymer made of a styrenic single compact, that is, a polymer or copolymer made of one or more styrenic monomers, or a styrenic monomer and others. A styrene resin which is a copolymer with a vinyl monomer and has a MW/Mn value of 35 or more is used.

Specific examples of the styrene monomer include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2+4-dimethylstyrene, p-n-butyl. Styrene, p-tert-butylstyrene 4, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene , p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and the like.

As the copolymer of the styrene monomer and vinyl monomer, styrene-butadiene copolymer or styrene-acrylic copolymer is particularly preferred. Examples of the acrylic monomer for the acrylic component include methyl acrylate, ethyl acrylate, n-butyl acryl, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, iron phenyl acrylate, late methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethyl methacrylate α-methylene aliphatic monocarboxylic acid esters such as aminoethyl and diethylaminoethyl methacrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, and others. These monomers can be used alone or in combination.

The above styrene resin has a Mvv/Mn value of 3.5 or more, but a MW/Mll value of 5 or more is desirable, and its molecular weight is approximately 2000 to 300.
Particularly desirable is one that covers the 1st shift of 00. Furthermore, NIW%
The values of NIn and Mw/NIn can be measured by various methods, and there are slight variations depending on the measurement method. Therefore, in the present invention, the values of Mvt, Mn and tr/Mn are defined as those measured by the following measuring method.

That is, all of these 1' values are values measured by gel permeation chromatography under the conditions described below. The solvent (tetrahydrofuran) was flowed at a flow rate of 1 g/min at a temperature of 25 tll', and the concentration was 0.
8WV with a sample weight of 4 g/dt tetrahydrofuran sample solution! Inject and measure. When measuring the molecular weight of a sample, the measurement conditions are such that the molecular weight distribution of the sample falls within a range where the logarithm of the molecular weight and the count number of the calibration curve prepared using several types of monodisperse polystyrene standard samples are linear. select. In addition, the reliability of this measurement was determined using the NB5706 boristyrene standard sample (Mw = 28J3X10', MH = 13.7) conducted under the above measurement conditions.
x 10', MW/Mn=211), the shoulder n is 2.
Confirm that it is 11±0.10.

In the present invention, NkW A/in is 3. The purpose can be achieved by using a styrene resin on the cape, but a styrene resin with a thickness of 5 or more is particularly effective in preventing offset.

Furthermore, although the styrenic resins mentioned above differ depending on the type of monomers contained as constituent components, those having a softening point of about 100 to 170 C by the ring and ball method are generally particularly effective; Furthermore, those having a glass transition point of 40C or higher are particularly effective. That is, the softening point is 10
If the temperature is below 0C, excessive pulverization is likely to occur, and the photoconductive plate is likely to be contaminated due to toner filming phenomenon. Further, if the softening point exceeds 170C, it is hard and difficult to crush, and a large amount of heat is required during fixing, resulting in poor fixing efficiency. On the other hand, if the glass transition point is 40C or less, the storage conditions for the toner are usually 40C or less.
Since it is less than C, agglomeration is likely to occur due to the cold claw phenomenon.

In addition, the glass transition point of styrene resin is generally M%'r
As the /Mn value increases, there is a tendency to have a wider range and it is difficult to reach a specific value, so it may be difficult to measure the glass transition point for resins with a large Mtw/y> value. be.

The styrene resin can be synthesized by the following method. When using a general polymerization method, the white color of corridor A is 1.5~
A resin of 3.0 is obtained. However, the following method is used to obtain the resin having a coefficient of 3.5 or more used in the present invention. That is, one method is to carry out polymerization by changing the polymerization temperature continuously or intermittently. Another method is to polymerize a divinyl compound and a trivinyl compound* in combination. Still another method is to sequentially separate and polymerize several types of heptads having different initiator concentrations and chain transfer agent concentrations.

In particular, a resin with a large Nk/yn can be easily obtained by mixing a relatively low molecular weight resin with a high molecular weight resin. These methods can be carried out by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. but,
Suspension polymerization is most preferred for reasons such as ease of handling of the resulting resin and reduction in manufacturing costs. Also, Mw/M
One method for increasing n is to dissolve several types of resins with different molecular weights in a solvent and remove the solvent by drying under reduced pressure or spray drying, or to melt and blend them by heating. However, in order to obtain the desired effects of the present invention, it is preferable that the particles be homogeneously dispersed.

A method for producing a styrenic resin according to the present invention is described, for example, in British Patent No. 1,495,428.

The polyolefin component of the modified polyolefin used as the wax contained in the toner of the present invention is a homopolymer type obtained from a single olefin monomer, or a homopolymer type obtained by copolymerizing the olefin monomer with another monomer copolymerizable with it. It may be of any type of copolymer.

The olefin monomers include, for example, ethylene, propylene, butene-1, pentene-1, hexene-1', heptene-1, octene-11 nonene-1, decene-1,
and isomers thereof having different positions of unsaturated bonds, and those having an alkyl group, such as 3-methyl-1-butene, 3-methyl-2-pentene, 3-propyl-5-methyl-2-hexene, etc. This includes all other olefin monomers, including those with branched chains consisting of

In addition, as other monomers copolymerizable with the olefin monomer, other olefin monomers include 7:) h, example j
Vinyl ethers such as C-hahynyl methyl ether, vinyl-n-butyl ether, vinyl phenyl ether, vinyl esters such as vinyl acetate, vinyl butyrate, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinyl chloride, vinylidene chloride,
Haloolefins such as tetrachloroethylene, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate), N,N-dimethylamine ethyl methacrylate, Acrylic acid esters or methacrylic acid esters such as t-butylaminoethyl methacrylate, such as acrylonitrile, acrylic acid derivatives such as N,N-dimethylacrylamide, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itacon Various organic acids such as acids, diethyl fumarate, β-pinene, etc. can be mentioned.

Therefore, when the polyolefin component is a copolymer type, an olefin copolymer type obtained by co-merging at least two or more of the above-mentioned olefin monomers, such as evaporated ethylene-propylene copolymer, ethylene -Butene copolymer, ethylene-pentene copolymer, 7" o H V 7-7" tene copolymer, propylene-pentene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-glo A copolymer type such as a pyrene-butene copolymer, or an olefin copolymer type obtained by copolymerizing at least one of the above olefin monomers and at least one monomer other than the above olefin monomer, For example, ethylene-vinyl acetate copolymer, ethylene-
Vinyl methyl ether copolymer, ethylene-vinyl chloride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-
Acrylic acid copolymer, globylene-vinyl acetate copolymer, propylene-vinylethyl ether copolymer,
Propylene-ethyl acrylate copolymer, propylene-methacrylic copolymer, butene-vinyl methyl ether copolymer, butene-methyl methacrylate copolymer, pentene-vinyl acetate copolymer, hexene-
Vinyl butyrate copolymer, ethylene-propylene-
Vinyl acetate copolymer, ethylene-vinyl acetate f-
)-vinyl methyl ether copolymer.

In the case of making a copolymer type using monomers other than olefin monomers, II of the onfin moiety formed by the olefin monomer in the polyolefin component
It is preferable to use a copolymer type in which the J combination is, for example, 50 molar or more.

This is because if the proportion of the olefin portion becomes small, the effect of improving the fixing properties of the toner will not be sufficiently exhibited.

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

An aromatic vinyl monomer is used as the modifying component, and specific examples thereof include 1-phenylpropene,
Styrene, 0-methylstyrene, m-methylstyrene,
p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dime, tylstyrene, p-n-7'
Chill Stire 7. p-tert-7” tylstyrene, p-
n-hexylstyrene, p-n-octylstyrene, p
-n-nonylstyrene, p-n-decylstyrene, p-
Examples include n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.

A wax consisting of modified polyolefin 9 can be obtained by carrying out block copolymerization or graft copolymerization using the aromatic vinyl monomer as described above and the polyolefin described above according to conventional methods and conditions.

Here, the proportion of the modified component in the modified polyolefin is 0.
．． It is preferably in the range of 1 to 15% by weight, particularly 1 to 10% by weight. If this ratio is too small, the fluidity of the toner will be significantly reduced, and if it is too large, the minimum fixing temperature of the toner will become high.

Further, it is desirable that such modified polyolefin itself has a low softening point, for example, JIS K2
531-1960, the softening point is 80 to 1 soc, preferably 90 to 160
It is desirable that it is C.

The toner of the present invention is a powder or granule material in which a fraction of the above-mentioned modified polyolefin wax is contained in the above-mentioned binder resin together with a colorant, a magnetic material, a property improver, and other necessary additives. The average particle size usually ranges from 5 to 30 microns.

As a coloring agent, carbon black, nigrosine dye (
C,1,A30415B), Aniline Blue (C,1
, A30405), Calco Oil Blue (C6■.

Azoec Blue 3), Chrome x Mouth'
-(C,1,414090), Ultramarine Blue (
C, 1, A77103), DuPont Oil Red (C,
1,A26105), quinoline yellow (C,1,A
47005), methylene blue chloride (C,1,
A52015), Phthalocyanine Blue (C, 1, 74160), Malachite Green Oxale) (
C,1,A4ZO'0・0), lamp black (C,1
, A77266), Rose Bengal (C, 1, A45
435), mixtures thereof, and others.

These colorants need to be contained in a sufficient proportion to form a visible image with sufficient concentration, and usually range from 1 to 20 parts by weight per 100 parts by weight of the binder resin. be done.

The magnetic material may be a ferromagnetic metal or alloy 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 is subjected to appropriate heat treatment. Alloys that exhibit ferromagnetic properties, such as manganese-copper-
Aluminum, a type of alloy called Heusler alloy containing manganese and copper such as manganese-copper-tin, chromium dioxide, and others may be mentioned. These magnetic substances are uniformly dispersed in the binder in the form of fine powder with an average particle size of 0.1 to 1 micron. The content of the toner is 20 to 70 fi, preferably 4
0-70 is a heavy responsibility department.

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 mixed with a carrier made of iron powder, glass beads, etc. to make a two-component developer, but when it contains a magnetic material, it can be used as is for developing electrostatic images as a one-component developer. .

The embodiments of the present invention will be described below, but the present invention is not limited thereto. Note that "1 part" represents parts by weight.

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

[Binder resin]

1) Binder resin A1: Obtained by copolymerizing styrene, methyl methacrylate, and n-butyl methacrylate at a weight ratio of 50:20:30 (7), the ratio of high molecular weight components to low molecular weight components The weight ratio is 40:100, and the weight ratio is 130.0.
00, excitation = 8,000, mausoleum = 16.25, softening point is 1
350 copolymer 2) Binder resin A2 Obtained in the same manner as binder resin A1, Mw = 1
00,000, An = 8,000, Numei Vln = 12
．． 5. Polymer with a softening point of 132C 3) Binder resin A3 Obtained in the same manner as binder resin A1, MW = 9
5,000, Mn= 11,000, M8w/Mn=
B, 6, copolymer with a softening point of 134C 4) Binder resin B Obtained by copolymerizing styrene and acrylic fin-butyl at a weight ratio of 85 = 15, blood = so, ooo, Mn
= 15,000, Mw/Mn = 5.3, softening point is 1
36C copolymer 5) Binder resin C (for comparison) Obtained in the same manner as binder resin AI, Mw = 50
,000, Mn = 25,000, kAVin =
2.0, a copolymer [wax] with a softening point of 135C 1) Wax a Polyethylene wax diblock copolymerized with styrene (styrene component content 4wt%, softening point 112
C) 2) Wax b Sesimeta polyethylene wax diblock copolymerized with 1-phenylpropene (1-phenylpropene content: 4
3) Wax C Polyethylene wax diblock copolymerized with styrene (styrene content 8%, softening point 116C) 4) Wax d Digraft copolymerized with 1-phenylpropene Metapolyethylene wax (]-Pphenylpropene content ratio 4 weight coefficient Softening point 11'2C) 5) Wax e (for comparison) Unmodified polypropylene wax "Viscol 660Pj
(manufactured by Sanyo Kasei Co., Ltd.) 6) Wax f (for comparison) Unmodified polyethylene wax “Hiwax 220PJ
(Softening point 113C1 manufactured by Mitsui Petrochemicals) 7) Wax g (for comparison) Oxidized polyethylene wax [Hiwax 4202E
J (softening point 108 C, manufactured by Mikata Petrochemical Co., Ltd.) In each of the examples and comparative examples, the materials of the indicated formulation were processed in a conventional manner through the steps of melting, kneading, cooling, pulverizing, and classifying. A toner consisting of particles with an average particle size of 10 microns was produced.

Example 1 Binder resin Al 100 evil wax a
3 parts Carbon black "Mogul L" (manufactured by Cabot) 10 parts Example 2 Binder resin A2 100 parts Wax 8
3 parts carbon black "Mogul LJ 10m Example 3 Binder side strength A3 100 parts wax a 3 parts carbon black "Mogul LJ 1 (1 example 4 Binder resin Al 100 parts wax b)
3 parts Carbon black [Mogul LJ 10m Example 5 Binder resin Al 100 parts Wax 0
3 parts carbon black "Mogul LJ 10fJ Example 6 Binder resin Al 100 Evil Wax a
3 parts Carbon black "Mogul L" 10 parts Example 7 Binder resin Al 100 parts Wax 8
Part 6 (29) Carbon black “Mogul LJ 1 (1
Example 8 Binder resin B 100 parts Wax 8
3 parts Carbon black "Mogul LJ" 10 parts Example 9 Binder resin B 100 parts Wax b
3 parts Carbon black "Mogul LJ lo part Example 10 Binder resin B 100 parts Wax 0
3 parts Carbon black "Mogul LJ" 10 parts Example 11 Binder resin B 100 Evil Wax a
6 parts Carbon black [Mogul LJ 10 parts Example 12 Binder resin A1 48 parts Wax 8
3 parts (30) Fine magnetic powder rBL-1004 (manufactured by Titanium Kogyo Co., Ltd.) 52 parts Comparative Example 1 Binder resin Al 100 parts Wax e
3 parts Carbon black "Mogul LJ 10 parts Comparative example 2 Binder resin Al 100 parts Wax f 3 parts Carbon black [Mogul LJ 10 parts Comparative example 3 Binder resin Al 100 parts Wax g
3 parts carbon black "Mogul L" 10 parts Comparative Example 4 Binder resin C100 Jawax a 3 parts Carbon black "Mogul LJ ios Comparative Example 5 Binder resin Al 100 parts Carbon black "Mogul Shi" 10 parts or more Examples 1 to Implementation The toner obtained in Example 12 was
” to “Toner 12”, and the toners obtained in Comparative Examples 1 to 5 were respectively designated as “Comparative Toner 1” to “Comparative Toner 5”.
'' and examined the fluidity of each of these toners. That is, the degree of compaction was measured using a powder compaction tester "Tap Denser" (manufactured by Seishin Enterprise Co., Ltd.), taking advantage of the fact that powders with high fluidity have a low degree of compaction. Specifically, in a container with a diameter of 28 cm and a volume of 100 rILl, 100
The sample was loosely packed through a mesh sieve, the weight was measured to determine the static bulk density A, and the container was then tapped 600 times at a fall height of 5 degrees using an upper tapping device with a lid of the same diameter. The volume of the sample at the time of the test was determined, and the previously determined amount of i was divided by this volume value to determine the bulk density P, and the degree of compaction C was calculated using the following formula.

In addition, by mixing each of the 16 kinds of toners other than toner 12 with a carrier made of resin-coated iron powder, the toner concentration is 2% by weight and the toner charge amount is 20±1 microtron/ Adjust the developer to be g, and each of them will give
Using a Kameko photocopying machine rU-Blx3000J (manufactured by Konishi Roku Photo Industries Co., Ltd.), the electrostatic charge image was developed, one image of toner was transferred to transfer paper, and the toner image was fixed by a heat roller fixing device, and the surface of the photoreceptor drum was developed. The primary adhesion amount of toner to the paper, the transfer rate to the transfer paper, and the image density of the obtained copied image were measured. Here, the toner primary attachment is the toner adhesion amount per unit area at a point where the so-called solid black potential is 800V □ Furthermore, for each of all toners, find the minimum fixing temperature and offset generation temperature, and The storage stability was evaluated. Regarding the minimum fixing temperature, we used a heat roller whose surface layer was made of Teflon (polytetrafluoroethylene manufactured by DuPont) and a heated roller whose surface layer was made of silicone rubber rKE-130.
0RTVJ (manufactured by Shin-Etsu Chemical Co., Ltd.) by a fixing device consisting of a pressure roller and a transfer paper of 6411/m2, the toner image of the sample toner was transferred to a transfer paper of 6411/m2 at a linear velocity of 12
0 Repeat the operation of fixing with a bulletin board at each temperature set at 100C and increasing it step by step by 95C, and apply Kimwipe rubbing to the formed fixed image to ensure sufficient scratch resistance. The lowest setting temperature related to the fixed image showing the above was defined as the lowest fixing temperature.

The fixing device used for each man 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 while the set temperature of the heat roller of the fixing device was successively increased, and the temperature at which offset occurred was determined.

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

The above results are shown in Table 1.

In addition, when we conducted a continuous copying test 20,000 times using each of Toner 1 to Toner 11 using an electrophotographic copying machine rU-Bix 3000j, we found that with each of the toners, the results were clear and good until the end. A duplicate image has been formed.

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 containing conventional unmodified polyolefin waxes, etc. Furthermore, it has high fluidity and uses a fluidity improver. It can be put to practical use even without the addition of , has excellent developability and transferability, and can always form stable and good visible images.

Claims (1)

[Scope of Claims] 1) Ratio of average molecular weight to number average molecular weight of a polymer composed of a styrene monomer or a copolymer of a styrene monomer and another vinyl monomer An electrostatic charge-containing toner comprising a binder resin having a value of 3.5 or more, and a wax made of a polyolefin obtained by block copolymerization or graft copolymerization with an aromatic vinyl monomer. 2) The toner for electrostatic charge one-quadrant development according to claim 1, wherein the content ratio of the wax is 1 to 20:t.