JPH0323904B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, etc., and a method for manufacturing the same.

[Prior art]

An electrostatic image formed on an electrostatic image carrier such as a photoconductive photoreceptor is generally developed with a toner comprising fine particles of binder resin containing a coloring agent and the like. The obtained toner image is usually transferred onto an image support such as paper and fixed by a fixing process to obtain a desired recorded matter.

Various methods are known for fixing toner images, but the contact heating fixing method, represented by hot roller fixing, has higher thermal efficiency than non-contact heating methods such as hot plate fixing, and is particularly fast. It has the advantage of being fixable and is widely used.

However, in this method, the toner is brought into direct pressure contact with the high-temperature fixing roller surface and becomes thermally molten, so that the molten toner adheres to the fixing roller surface.

The toner adhering to the fixing roller transfers onto the next image support and stains it, causing a so-called "offset" phenomenon, and the image support adheres to the fixing roller via the toner. It is necessary to prevent this from happening as it can cause the so-called "winding" phenomenon.

Various proposals have been made in the past to solve this problem, such as Japanese Patent Application Laid-open No. 134652/1983;
JP-A-50-144446 and JP-B-50-3304 disclose toner resins and toners that are less likely to cause offset development, but even with these means, the problem cannot be sufficiently solved. I haven't reached it yet.

Generally, vinyl resins are widely used as binders for toners, but in order to improve the offset resistance of toners using vinyl resins as binders, it is necessary to use high molecular weight resins with a high softening point. Become.

However, when such a resin is used, the temperature required for fixing the toner (hereinafter referred to as minimum fixing temperature) inevitably increases, and the advantages of the contact heat fixing method are lost. Naturally, it is desirable that the minimum fixing temperature be low, and the toner used in the recently developed method of forming toner images on both sides of a sheet of transfer paper is required to be able to be fixed at a low temperature. Improvements are desired.

In addition, in order to reduce the adhesion force between the fixing roller surface and toner, the fixing roller is coated with a fluororesin or the like, and a lubricating liquid such as silicone oil is supplied to the surface to form a liquid layer on the fixing roller surface. A method is currently in use that provides a mold release effect.

However, in this method, the lubricating liquid may be heated and emit an odor, or a high-precision device is required to stably supply the liquid, making the image recording device as a whole complicated and expensive. There were flaws.

Furthermore, as a method for preventing "offset" and "wrapping" without supplying a lubricating liquid to the surface of the fixing roller, Japanese Patent Application Laid-Open No. 153944/1983 discloses a method of containing polyolefin wax as a release agent in the toner. has been disclosed, and excellent improvement effects have been recognized.

On the other hand, various methods are used to manufacture toner, such as kneading molten resin and colorant, cooling and solidifying it, and pulverizing it to form a toner, and further spraying and heating. A method of obtaining a spherical toner, a method of polymerizing a mixture of a colorant and a polymerizable monomer and then finely pulverizing it to obtain a toner, or a method of pulverizing a mixture of a colorant and a polymerizable monomer in a medium such as water. There are methods of producing toner particles by dispersing the toner particles in a suspended state and polymerizing them in a suspended state. In particular, a method using suspension polymerization is a relatively simple process. It has advantages such as being able to obtain a spherical shape.

The effect of the release agent added to the toner varies depending on the method of manufacturing the toner as described above. For example, when producing toner by suspension polymerization, even if a release agent such as polyolefin wax is added to the polymer monomer, "offset" and "wrapping" may occur.
It turns out that it cannot be prevented sufficiently.

To produce toner containing a release agent using the suspension polymerization method, colorants and release agents such as wax are usually added to liquid polymerizable monomers, and the mixture is subjected to strong shearing using a mixer such as a sand stirrer. This is thought to be due to the fact that the coloring agent is uniformly dispersed by applying force to form a polymerizable composition, and at this time the mold release agent is also dispersed in the form of extremely fine particles.

Polymerizable compositions can undergo a suspension polymerization reaction in an aqueous medium, but mold release agents such as polyolefin waxes generally have small surface energy and strong hydrophobicity, so when suspended, the inside of the polymerizable composition oil droplets It is buried in the toner particles and does not appear on the surface of the toner particles, making it ineffective as a release agent.

As can be seen from this example, the effect of the release agent added to the toner depends on the state in the toner, so the toner always exhibits the effect of the release agent regardless of the manufacturing method. There is also a need for the development of a method for producing such an excellent toner.

[Purpose of the invention]

An object of the present invention is to provide a toner for electrostatic image development that has excellent releasability from the surface of a fixing roller, does not cause "offset" or "wrap," and can be fixed at a low fixing temperature, and a method for producing the same. It is in.

Another object of the present invention is to provide a toner for electrostatic image development that has excellent fluidity, agglomeration resistance, and powder properties.

Another object of the present invention is to provide an electrostatic image developing toner that can be fixed by a hot roller without supplying a lubricating liquid such as silicone oil.

Another object of the present invention is to provide a toner for developing electrostatic images that does not adhere to or contaminate the inside of a developing machine, a photoreceptor, etc.

Another object of the present invention is to provide a one-component electrostatic image developing toner that exhibits good fixing properties even when magnetic powder is contained therein.

Another object of the present invention is to provide a toner for developing electrostatic images which is free from carrier contamination in a two-component system.

Another object of the present invention is to provide a manufacturing method that incorporates mechanically and physically weak substances into toner.

Another object of the present invention is to provide an electrostatic image developing toner that is easy to manufacture, can be produced stably, and is inexpensive, and a method for manufacturing the same.

[Structure of the invention]

The above-mentioned purpose is to provide an electrostatic image developing toner (hereinafter sometimes simply referred to as toner) obtained by polymerizing a polymerizable composition comprising a colorant and a polyolefin wax dispersed in a polymerizable monomer. A polymerizable composition comprising a polyolefin wax whose surface has been made hydrophilic by sulfonation or chlorosulfonation reaction or organic titanate treatment and dispersed in a polymerizable monomer together with a coloring agent is used as an aqueous polymerizable composition. This is achieved by a method for producing a toner for electrostatic development, which is characterized by including a step of dispersing and suspending in a medium and polymerizing, and a toner produced by the method.

As mentioned above, normally the polyolefin added to the toner particles becomes fine particles and is buried inside the toner particles, but the present invention can prevent suspension polymerization by making the surface of the polyolefin wax particles hydrophilic. At the same time, the polyolefin wax particles are easily exposed to the interface between the polymerizable composition oil droplets and the aqueous medium, and toner particles with exposed polyolefin wax on the surface are formed to exhibit the effects of the polyolefin wax and toner particles. This improves offset resistance and wrapping resistance, but the key point is to make only the vicinity of the surface of the polyolefin wax particles hydrophilic; if the entire polyolefin wax is made hydrophilic, The original mold release effect is lost, and no effect of preventing hofset or curling can be obtained.

When only the surface is made hydrophilic, no deterioration in the mold release effect of the polyolefin wax is observed, and the desired effect of preventing offset and curling can be obtained.

The polyolefin wax whose surface has been made hydrophilic according to the present invention can be obtained by mechanically pulverizing the polyolefin wax by any method such as a jet mill, sand mill, etc., or by spray drying, recrystallization, reprecipitation, etc. The hydrophilic treatment can be performed by any method capable of making polyolefin hydrophilic, such as sulfonated powder with chlorsulfonic acid. is chlorsulfonation treatment followed by amine treatment, hydrolysis, coupling treatment with organic titanate and subsequent hydrolysis, silane coupling agent treatment and subsequent hydrolysis, and other polar groups by ultraviolet irradiation, corona discharge, plasma treatment, etc. Although methods such as sulfonation, chlorosulfonation treatment, and organic titanate treatment are most preferably used.

The polyolefin wax preferably used in the present invention may be either a homopolymer obtained from a single olefin monomer or a copolymer obtained by copolymerizing the olefin monomer with another monomer copolymerizable therewith.

Examples of the olefin monomer include ethylene, propylene, butene-1, pentene-1,
Hexene-1, heptene-1, octene-1, nonene-1, decene-1, and their isomers with different positions of the unsaturated bond, as well as e.g. 3-methyl-1-butene, 3-methyl-2 -Penen, 3
-Propyl-5-methyl-2-hexene, which have a branched chain consisting of an alkyl group, and all other olefin monomers are included, but ethylene and propylene are particularly preferred.

Other monomers copolymerizable with the olefin monomer include other olefin monomers, such as vinyl methyl ether, vinyl-n-
Vinyl ethers such as butyl ether and vinyl phenyl ether; vinyl esters such as vinyl acetate and vinyl butyrate; haloolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinyl chloride, vinylidene chloride, and tetrachloroethylene; For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate,
Acrylic acid esters or methacrylic acid esters such as stearyl methacrylate, N,N-dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, acrylic acid derivatives such as acrylonitrile, N,N-dimethylacrylamide, etc. acrylic acid,
Organic acids such as methacrylic acid, maleic acid, fumaric acid, itaconic acid, diethyl fumarate, β-
Various pinenes can be mentioned.

Further, as a useful wax, a modified polyolefin obtained by blocking or grafting the above polyolefin wax with other components can also be used.

Examples of modification components in this case include styrene, p-methylstyrene, α-methylstyrene,
Aromatic vinyl monomers such as 3,4-dichloro-styrene, unsaturated fatty acid monomers such as acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate, and their esters are useful.

Specific examples of polyolefin waxes useful in the present invention are listed below, but it goes without saying that the mold release agent used in the present invention is not limited to these.

Viscole 330-P, Viscole 550-P, Viscole 660-P (manufactured by Sanyo Chemical Co., Ltd., polypropylene), Hiwax 320P, Hiwax 310P,
Hiwax 410P, Hiwax 405P, Hiwax 400P, Hiwax 200P, (polyethylene manufactured by Mitsui Petrochemical Co., Ltd.), Sanwax 131-
P, Sanwax 151-P, Sanwax 161-
P, Sunwax 165-P, Sunwax 171-P
(Polyethylene manufactured by Sanyo Chemical Co., Ltd.), Polywax 400, Polywax 500, Polywax-OH
-465, Polywax -1040 (manufactured by Toyo Petrolite Co., Ltd., polyethylene).

These polyolefin waxes can be used alone or in combination of two or more. The preferred amount of polyolefin wax used is the polymerizable monomer
Preferably 3 to 40 parts by weight per 100 parts by weight, and 5 parts by weight.
It is particularly preferred that the amount is from 35 parts by weight.

Examples of the polymerizable monomer that can be used in the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
α-methylstyrene, p-ethylstyrene, 2,
4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n
-nonylstyrene, p-n-decylstyrene, p
Preferred examples include styrene monomers such as -n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene. In addition, for example, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, and vinyl benzoate. ,
Vinyl esters such as vinyl butyrate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid 2
-Chlorethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-octyl ethacrylate, 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, and acrylamide; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc. Vinyl ethers; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes, Others can be mentioned. These monomers can be used alone or in combination, or can be polymerized to form a copolymer.

For the polymerization of vinyl monomers as described above, a polymerization initiator is usually used in an amount of 0.5 to 10% by weight based on the polymerizable monomer. Specific examples of typical polymerization initiators include acetylcyclohexylsulfonyl peroxide, isodibutyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, t -butyl peroxypivalate, 3,
5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, succinic acid peroxide,
Acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobutyrate, t-
Butyl peroxymale acid, t-butyl peroxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoyl peroxyhexane, t-butyl peroxy acetate , t-butyl peroxybenzoate, diisobutyl diperoxy phthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di t-
Butyl peroxyhexane, t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, diisopropylbenzenehydro Peroxide initiators such as peroxide, paramethane hydroperoxide, pinane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide,
2,2'-azobisisobutyronitrile, 1,1'-
Azobis(cyclohexane-1-carbonitrile), 2,2'-azobis4-methoxy-2,4-
Dimethylvaleronitrile, 2,2'-azobis-
Examples include azo initiators such as 2,4-dimethylvaleronitrile.

In carrying out the method of the present invention, a plurality of polymerization initiators having different radical half-lives can be used. In this case, at a certain polymerization temperature, a polymerization initiator with a short half-life forms a so-called rapid initiation system, and a polymerization initiator with a long half-life forms a so-called slow initiation system, and a rapid initiation system is formed with a polymerization initiator with a long half-life. In the initiation system, a polymer with a low degree of polymerization and a low molecular weight is formed, and at the same time, in the slow initiation system, a polymer with a high degree of polymerization and a high molecular weight is formed. According to a toner made of a polymer consisting of a low molecular weight polymer portion and a high molecular weight polymer portion, the minimum fixing temperature is low due to the low molecular weight polymer portion, and offset occurs due to the high molecular weight polymer portion. The temperature becomes high.

A preferred example of a polymerization initiator with a short half-life is 2,2'-azobis-4-methoxy-2,4-
Dimethylvaleronitrile, 2,2'-azobis-
Examples include 2,4-dimethylvaleronitrile, and preferred examples of polymerization initiators with a long half-life include 1,1'-azobis(cyclohexane-1-carbonitrile).

Coloring agents include carbon black, nigrosine dye (CI No. 50415B), and aniline blue (CI No.
50405), Calco Oil Blue (CINo.azoic Blue)
3), Chrome Yellow (CINo.14090), Ultramarine Blue (CINo.77103), Dupont Oil Red (CINo.26105), Quinoline Yellow (CINo.
47005), methylene blue chloride (CINo.
52015), Phthalocyanine Blue (CINo.74160),
Malachite Green Oxalate (CINo.
42000), lampblack (CI No. 77266), rose bengal (CI No. 45435), mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a visible image of sufficient concentration, and are usually used in binder resins.
The proportion is about 1 to 20 parts by weight per 100 parts by weight.

Although the molecular weight of the polymer according to the present invention is arbitrary,
Preferably, the weight average molecular weight is 50,000 to 1,000,000, and the number average molecular weight is 1,000 to 100,000.

The polymer according to the present invention may be polymerized in the presence of a crosslinking agent to form a crosslinked polymer. Preferably used crosslinking agents are mainly compounds having two or more polymerizable double bonds, such as aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof, such as ethylene glycol dimethacrylate, diethylene glycol, etc. Diethylenic carboxylic acid esters such as dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, N,N divinyl All divinyl compounds such as aniline, divinyl ether, divinyl sulfide, divinyl sulfone, and compounds having three or more vinyl groups are selected singly or as a mixture.

The amount of such crosslinking agent added to the monomer is 0.005 to 20
% by weight, preferably in the range from 0.1 to 5% by weight. If the amount added is too large, the toner will not melt and will tend to lose its fixing properties as a toner. In addition, if the amount is too low, it becomes difficult to impart toner properties such as durability, storage stability, and abrasion resistance.Especially in hot roll fixing copiers, etc., the molecular weight distribution of the polymer expands due to crosslinking, and as a result, Due to the properties of the toner itself, it becomes difficult to achieve the effect of preventing the offset phenomenon during fixing.

Further, the toner of the present invention may contain a low molecular weight olefin polymer known as a so-called mold release agent.

A prepolymer (especially a reactive prepolymer) may be added to the toner of the present invention during the polymerization process for the purpose of improving fixing performance such as offset prevention effect. The reactive prepolymer has a reactive group in the main chain and/or side chain of the prepolymer, and examples of such prepolymers include unsaturated polyesters, unsaturated polybutadiene, and the like.

When carrying out suspension polymerization, the polymer composition is dispersed and suspended in a dispersion medium such as water as dispersed particles of a required particle size by mechanical stirring, and polymerization is carried out. However, as the polymerization progresses, the dispersed particles become sticky. It is necessary to prevent particles from coalescing into large particles by increasing the particle size, and suspension stabilizers are used for this purpose.

The suspension stabilizers used as such suspension stabilizers are generally divided into water-soluble polymeric substances and fine powders of poorly soluble inorganic compounds.The former includes gelatin, starch, polyvinyl alcohol, and others, and the latter includes Barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, calcium phosphate, and other sparingly soluble salts, combinations of sparingly soluble salts and surfactants such as sodium dodecylbenzenesulfonate and sodium dodecyl sulfate, talc, viscosity, silicic acid, and diatomaceous earth. Inorganic polymer substances such as metal oxides and other powders are included. In addition, when the polymer composition contains an ionic substance, for example, a cationic substance or anionic substance such as a nitrogen-containing polymerizable monomer or poorly water-soluble amines, the dispersed particles have a positive effect when dispersed in water. Or, in the case of being charged to one negative polarity, use an ionic dispersant that is charged to the other polarity when dispersed in water, such as negatively charged colloidal silica, positively charged aluminum oxide, etc., as a suspension stabilizer. It can be effectively used as

In addition to these, the toner of the present invention may contain a magnetic substance, a charge control agent, a dispersant, etc., as necessary.

Magnetic materials include ferrite, magnetite, iron, cobalt, nickel, and other ferromagnetic metals or alloys, or compounds containing these elements, or materials that do not contain ferromagnetic elements but can be made by applying appropriate heat treatment. Alloys which become ferromagnetic, for example alloys of the type called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, among others.

To manufacture the toner according to the present invention, first, a required amount of colorant, pre-prepared polyolefin wax particles whose surface has been made hydrophilic, and other additives are added to the polymerizable monomer, and then a sand stirrer or the like is added. A polymerizable composition is prepared by stirring and dispersing the mixture well, and after adding a polymerization initiator, it is added to an aqueous suspension medium containing a suspension stabilizer, and then dispersed and dispersed using a high-speed stirrer or the like.
The suspension is maintained under appropriate temperature conditions to allow the polymerization reaction to proceed. The polymerizable composition suspended as fine oil droplets in the medium is directly polymerized and solidified to obtain spherical resin particles containing colorant, wax, etc. The size of the resulting resin particles is determined by the dispersion state of the suspended polymerizable composition, so if you adjust the dispersion conditions and suspend the toner to the desired particle size, the resin particles obtained will remain as they are. Can be used as a toner.

The toner of the present invention is mixed with a carrier consisting of iron powder, glass beads, etc. to form 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.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Note that the numbers in this example represent parts by weight unless otherwise specified.

Example 1 Polypropylene "Viscol 660P" (manufactured by Sanyo Chemical Co., Ltd.) was reprecipitated from a toluene solution into methanol to obtain a fine powder.

Next, a mixed solution of 100 ml of sulfuric acid, 50 ml of water, and 15 g of potassium dichromate was prepared, and after adding Viscoll 660P to the fine powder obtained earlier and stirring for 3 hours,
It was poured into ice water, filtered, washed with water, and dried to obtain Viscoel 660P whose surface was made hydrophilic.

The weight average particle size of the obtained powder was measured using a Coulter counter and was found to be approximately 3 μm.

On the other hand, sterene 85 parts (n)butyl methacrylate 15 parts ethylene glycol dimethacrylate 0.4 parts carbon black "MONARCH880" (manufactured by Cabot Corporation) 6 parts 2,2'-azobis(2,4-dimethylvaleronitrile) 3 parts Mix and disperse with a sand stirrer, and add
10 parts of Viscoel 660P, whose surface had been made hydrophilic, obtained previously was added and uniformly dispersed to obtain a polymerizable composition.
This was added in an amount of 20% by weight to water containing 2% by weight of calcium phosphate and 0.02% by weight of sodium dodecylbenzene sulfonate, and using a TK homogiator (manufactured by Tokushu Kika Kogyo Co., Ltd.), 7 to 15 μm thick was added.
A suspension was obtained by dispersing the particles so as to have the same particle size.

Thereafter, this suspension was polymerized by heating at 60° C. for 20 hours, treated with hydrochloric acid, filtered, washed, and dried to obtain the toner of the present invention.

A developer consisting of 2 parts of this toner and 100 parts of iron powder carrier was prepared and evaluated as follows.

First, a solid black toner image is created on the leading edge of the transfer paper that is the image support, and this is transferred between a heated roller whose surface layer is made of Teflon (polytetrafluoroethylene manufactured by Dupont) and a heated roller whose surface layer is made of silicone rubber "KE".
-1300RTV" (manufactured by Shin-Etsu Chemical Co., Ltd.) at a linear speed of 120 mm/sec through a fixing device consisting of a pressure roller made of I did it by changing it. In other words, the set temperature of the heat roller was lowered in steps of 5 degrees Celsius from 230 degrees Celsius, and the above operation was performed at each temperature to find the highest temperature at which the transfer paper began to wrap around the heat roller (the temperature at which wrapping occurred). 230℃
No coiling occurred from 180℃ to 180℃, and coiling occurred for the first time at 175℃. At this time, the offset phenomenon did not occur over the entire range of measured temperatures.

Comparative Example 1 Finely powdered viscoll obtained in Example 1
A comparative toner was obtained in the same manner as in Example 1, except that 660P was used without being subjected to hydrophilic treatment. Using this comparative toner, the temperature at which curling occurred was determined in the same manner as in Example 1, and it was found to be 225°C. but,
An offset phenomenon occurred at 230°C.

In this way, the toner of the present invention has excellent curling resistance and
It can be seen that this has a remarkable effect on offset resistance.

Example 2 Using the finely powdered Viscoll 660P obtained in Example 1, it was mixed with 100 ml of sulfuric acid, 50 ml of water, and 15 g of anhydrous chromium.
After stirring for 2 hours, the mixture was poured into ice water, filtered, washed with water, and dried to obtain Viscoel 660P whose surface had been made hydrophilic. Using this, a toner of the present invention was obtained in the same manner as in Example 1, and the temperature at which curling occurred was determined in the same manner as in Example 1. It was found that curling did not occur up to 180°C, and curling only occurred at 175°C. . At this time, no offset phenomenon appeared at all.

Example 3 Using the finely powdered Viscol 660P obtained in Example 1, it was mixed with 2 ml of chlorosulfonic acid and 1,1,1-
The mixture was added to a solution of 100 ml of trichloroethane, stirred for 1 hour, filtered, washed with trichloroethane, and treated with a dioxane solution of butylamine to obtain Viscoel 600P whose surface was made hydrophilic. Using this,
A toner of the present invention was obtained in the same manner as in Example 1, and the temperature at which curling occurred was determined in the same manner as in Example 1, and was found to be 180°C.

At this time, no offset phenomenon appeared at all.

Example 4 Using the fine powder of Viscol 660P obtained in Example 1, it was added to a solution of 4 g of tetrabutyl titanate in 150 ml of isopropanol, and after ultrasonic dispersion, the solvent was distilled off and dried to make the surface hydrophilic. Obtained Viscoel 660P. Using this, the toner of the present invention was obtained in the same manner as in Example 1, and Example 1
In the same manner as above, the temperature at which the coiling occurred was determined.
It was 190℃.

At this time, no offset phenomenon appeared at all.

Example 5 Polyethylene "Hiwax 320P" (manufactured by Mitsui Petrochemicals) was used and subjected to the same hydrophilic treatment as in Example 1.

On the other hand, sterene 85 parts lauryl methacrylate 15 parts "Mitsubishi Carbon Black #30" (manufactured by Mitsubishi Kasei Corporation)
10 parts 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) 2 parts 2,2'-azobisisobutyronitrile 0.5 part were mixed and dispersed using a sand stirrer, and the previously obtained 8 parts of Hiwax 320P whose surface had been made hydrophilic was added and uniformly dispersed to obtain a polymer composition.

This was added in an amount of 20% by weight to an aqueous solution containing 3% by weight of calcium phosphate and 0.03% by weight of sodium dodecylbenzene sulfonate, and dispersed using a TK homogiator. The thus obtained suspension was polymerized by heating at 65° C. for 25 hours, treated with hydrochloric acid, filtered, washed, and dried to obtain the toner of the present invention. Using this toner, the temperature at which curling occurred was determined in the same manner as in Example 1.
From 230°C to 185°C, no curling occurred and a good fixed image was obtained, and curling occurred for the first time at 180°C. At this time, no offset occurred over the entire range of measured temperatures.

Comparative Example 2 A comparative toner was obtained in the same manner as in Example 5, except that Hiwax 320P was used without surface hydrophilic treatment.

Using this comparative toner, the temperature at which curling occurred was determined in the same manner as in Example 1, and it was found to be 230°C.
Since coiling had already occurred in the test, a temperature range that could be evaluated could not be obtained. It was not possible to evaluate the offset performance due to the occurrence of winding.

Example 6 Polyethylene "Polywax 500" (manufactured by Toyo Petrolite Co., Ltd.) was pulverized and hydrophilized in the same manner as in Example 1. On the other hand, styrene 82 parts 2-ethylhexyl acrylate 18 parts Carbon black " After mixing and dispersing 5 parts of 2,2' azobis(2,4-dimethylvaleronitrile) using a sand stirrer, 15 parts of polyester resin (manufactured by Kyabot Co., Ltd.), and 5 parts of 2,2' azobis(2,4-dimethylvaleronitrile) were mixed and dispersed, and then the surface obtained earlier was subjected to a hydrophilic treatment. 10 parts of polyethylene wax fine powder was added and uniformly dispersed to obtain a polymerizable composition.

The polyester resin of the above formulation contains bisphenol A, polyethylene glycol (average molecular weight
1000), terephthalic acid, fumaric acid (weight ratio 200:
20:100:70) is an unsaturated polyester resin with a softening point of 110°C.

The obtained polymerizable composition was mixed with 2% by weight of calcium phosphate and sodium dodecylbenzenesulfonate.
It was added in an amount of 30% by weight to water containing 0.02% by weight, and dispersed using a TK homogetter.
The thus obtained suspension was heated at 60° C. for 20 hours to polymerize, then treated with hydrochloric acid, filtered, washed, and dried to obtain the toner of the present invention. Using this toner, the temperature at which curling occurred was determined in the same manner as in Example 1. From 230°C to 180°C, curling did not occur and a good fixed image was obtained, and curling only occurred at 175°C. .

At this time, no offset occurred over the entire range of measured temperatures.

Comparative Example 3 A comparative toner was obtained in the same manner as in Example 6, except that finely powdered Polywax 500 was used without surface hydrophilic treatment.

When the temperature at which curling occurred was determined for this toner in the same manner as in Example 1, curling had already occurred at 230° C., so no temperature range that could be evaluated was obtained.

Example 7 For each of the toners of the present invention obtained in Examples 1 to 6, an electrophotographic copying machine "U-Bix3000" was used.
(manufactured by Konishiroku Photo Industry Co., Ltd.) to evaluate the fixation, it was found that no offset phenomenon or curling phenomenon occurred, and a good copied image was obtained. Continuous copying was then repeated 20,000 times, and a good, clear copy image was obtained without causing any offset or curling phenomena.

〔Effect of the invention〕

As is clear from the above examples, the present invention makes it possible to obtain a toner that has high releasability from the surface of the fixing roller and has excellent offset resistance and wrapping resistance. By using the toner of the present invention, it has become possible to perform good hot roller fixing without the occurrence of "offset" or "wrapping" without the need to supply a lubricating liquid to the surface of the fixing roller.

Claims (1)

[Scope of Claims] 1. A toner for electrostatic image development obtained by polymerizing a polymerizable composition comprising a colorant and a polyolefin wax dispersed in a polymerizable monomer, wherein the surface of the polyolefin wax is composed of sulfonate. 1. A toner for electrostatic image development, characterized in that the toner is made hydrophilic by a chlorosulfonation reaction, a chlorsulfonation reaction, or an organic titanate treatment. 2. A polymerizable composition prepared by dispersing a polyolefin wax whose surface has been made hydrophilic by sulfonation or chlorosulfonation reaction or organic titanate treatment in a polymerizable monomer together with a colorant in an aqueous medium. A method for producing a toner for electrostatic image development, comprising a step of suspending and polymerizing.