JPH0323905B2 - - 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 heat fixing method represented by the heat roller fixer has higher thermal efficiency than the non-contact heating method such as the hot plate fixer. In particular, it has the advantage of being capable of high-speed fixing, 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. becomes.

However, when such a resin is used, the temperature required to fix the toner (hereinafter referred to as the 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 producing a toner by pulverizing a mixture of a colorant and a polymerizable monomer into fine particles in a medium such as water. There are methods of producing toner particles by polymerizing toner particles in a dispersed and suspended state. In particular, a method using suspension polymerization has advantages such as a relatively simple process and the ability to obtain spherical particles.

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.
Usually, the preventive effect is hardly achieved.

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. The colorant is uniformly dispersed by applying force to form a polymerizable composition, and at this time the release agent is also dispersed in the form of extremely fine particles.

A polymerizable composition can undergo a suspension polymerization reaction in an aqueous medium, but mold release agents such as polyolefin waxes are generally lipophilic and strongly hydrophobic, so when suspended, they are buried inside the oil droplets of the polymerizable composition. When the particles are formed into toner particles, they are not exposed on the surface of the toner particles, so their effectiveness as a release agent is significantly reduced. The mold release effect of polyolefin waxes is significantly increased when used in combination with other non-polyolefin waxes, but the effect is inevitably reduced when toners are produced by suspension polymerization, and special treatments are required to fully demonstrate the effect. There is a need for the development of effective means.

[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.

[Structure of the invention]

The above purpose is to create an electrostatic image developing toner (hereinafter simply referred to as toner) obtained by polymerizing a polymerizable composition comprising a colorant, a polyolefin wax, and a non-polyolefin wax other than polyolefin dispersed in a polymerizable monomer. In this method, the polyolefin wax whose surface has been made hydrophilic by sulfonation or chlorosulfonation reaction or organic titanate treatment is used together with a colorant and a non-polyolefin wax other than polyolefin. A method for producing a toner for electrostatic development, comprising a step of dispersing and suspending a polymerizable composition formed by dispersing a monomer in an aqueous medium and polymerizing the same, and a toner produced by the method. will be achieved.

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. Coupled with the coexistence effect with non-polyolefin waxes, toner offset resistance,
This improves the clinging resistance, but the key point is to make only the vicinity of the surface of the polyolefin wax particles hydrophilic, and if the entire polyolefin wax is made hydrophilic, it will not release as much as it should. The effect is lost, and no effect of preventing curling 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 may be mechanically pulverized by any method such as a jet mill, sand mill, etc., or by methods such as spray drying, recrystallization, reprecipitation, etc. It can be obtained by turning the polyolefin into a fine powder and treating its surface with hydrophilic treatment.The hydrophilic treatment can be performed by any method capable of making polyolefin hydrophilic, such as sulfonation with chlorsulfonic acid or chlorsulfonation. Examples include treatment and subsequent amine treatment, hydrolysis, coupling treatment with organic titanates and subsequent hydrolysis, silane coupling agent treatment and subsequent hydrolysis, and introduction of polar groups by ultraviolet irradiation, corona discharge, plasma treatment, etc. However, methods using sulfonation, chlorflufone treatment, or 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.

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.

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, Hiwatux 410P, Hiwatux 405P,
Hiwatukus 400P, Hiwatukus 200P, (or more,
Mitsui Petrochemical Co., Ltd., polyethylene), Sunwax 131-P, Sunwax 151-P, Sunwax
161-P, Sunwax 165-P, Sunwax
171-P (manufactured by Sanyo Chemical Co., Ltd., polyethylene),
Poliwax-400, Poliwax-500, Poliwax-OH-465, Poliwax-1040 (polyethylene manufactured by Toyo Petrolite Co., Ltd.).

Particularly preferable non-polyolefin waxes to be used in combination with the polyolefin wax are:
For example, ceresin, paraffin wax 150, paraffin wax-155, paraffin wax-
140, paraffin wax-135, paraffin wax-130, paraffin wax-125, paraffin wax-120, paraffin wax-115, paraffin wax-SP-0145, paraffin wax-SP-1035, paraffin wax Tsukusu-SP-
1030, Paraffin Wax-SP-3040, Parafine Wax-SP-3035, Parafine Wax-SP-3050 (manufactured by Nippon Seisaku Row Co., Ltd.), Nisseki No. 1 Candle Wax, Nisseki No. 2 Parafin waxes such as candle wax, 145° paraffin, 140° paraffin, 135° paraffin, 130° paraffin, 125° paraffin, paraffin wax (M), 125° special paraffin (all manufactured by Nippon Oil Co., Ltd.) Tsukusu, Petrolite WB-5, Petrolite WB-
16, Petrolite WB-17 (manufactured by Ballet),
NPS-6115, NPS-9210 (all manufactured by Japan Low Co., Ltd.)
hardened paraffin wax, tristearin, Hoechstwax F, Hoechstwax E,
Hoechstwatx KFO, Hoechstwatx KP,
Hoechst Wax KSS (manufactured by Hoechst AG)
fatty acid ester waxes, Hoechst waxes, etc.
Partially saponified fatty acid ester waxes such as OP, Hoechstwax fatty acid amide P,
Fatty acid amide C, fatty acid amide O, fatty acid amide O-3, Kao-wax EB (manufactured by Kao Sekiken Co., Ltd.), Armide C, Armide O, Armide HT, Armide 18, Armowax, Armowax EBS (Lion Akzo) Fatty acid amide wax (manufactured by Co., Ltd.), Nisseki Micro Wax
155, Nippon Oil Microwax 180 (or more, Nippon Oil
Co., Ltd.), Hi-Mic-2095, Hi-Mic-1080, Hi-
Mic-1070, Hi-Mic-2060, Hi-Mic-1045,
Microcrystalline wax such as Hi-Mic-2045 (manufactured by Nippon Seiro Co., Ltd.), other polyamides, and mixed products such as Rice Wax NO1, Rice Wax L-301-J, Rice Wax F-1,
Rice wax M-200, carnauba wax, honey wax, hollow, K-1, POPKO-201,
POPKO-202, POPKO-203 (Noda Watsukusu)
Co., Ltd.), but is not limited to these.

These non-polyolefin waxes can be used alone or in combination of two or more.

The preferred amount of the polyolefin wax and non-polyolefin wax added is in the range of 7 to 50 parts by weight based on 100 parts by weight of the polymerizable monomer used in the toner. If the amount of wax is 2 parts by weight, the release effect of the wax will be insufficient, and if it is more than 50 parts by weight, the viscosity of the polymerizable composition will become extremely high, making production difficult.

The ratio of polyolefin wax to non-polyolefin wax used is preferably 90:10 to 10:90. Even if the ratio of non-polyolefin wax is below or above the above range, the releasability of the resulting toner will be reduced and "offset" and "wrapping" may occur.
is more likely to occur.

Examples of the polymerizable monomer that can be used in the present invention include sterene, 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 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, 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 0.1 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, 2,3-dimethyl-2,5-di t-
Butyl peroxyhexane, t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butyl peroxyhexane, diisopropylbenzene hydroperoxide, Peroxide initiators such as paramenthane 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), Dubon 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 at a sufficient temperature, 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 and diethylene glycol methacrylate. , triethylene glycol dimethacrylate, trimethylolpropane triacrylate, bryl methacrylate, t-
diethylene carboxylic acid esters such as butylaminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, N,N divinylaniline, divinyl ether, divinyl sulfide,
All divinyl compounds such as 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 of water or the like by mechanical stirring as dispersed particles of the required particle size, but as the polymerization progresses, the dispersed particles become sticky. It is necessary to prevent particles from coalescing into large particles due to increase in particles, and a suspension stabilizer is 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 Combinations of sparingly soluble salts and sparingly soluble salts such as barium sulfate, calcium sulfate, barium carbonate, potassium carbonate, and calcium phosphate with surfactants such as sodium hydrodecylbenzenesulfonate and sodium dodecyl sulfate, talc, viscosity, silicic acid, Includes inorganic polymer substances such as diatomaceous earth, metal oxides, and other powders. 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, 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., is suspended and stabilized. It can be effectively used as an agent.

In addition to these, the toner of the present invention may contain a magnetic substance, a charge control agent, a dispersant, etc., if 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. Mention may be made of alloys which become ferromagnetic over time, such as 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 produce the toner according to the present invention, first, a required amount of colorant, previously prepared polyolefin wax particles with a hydrophilic surface, non-polyolefin wax, and other additives are added to the polymerizable monomer. A polymerizable composition is prepared by stirring and dispersing well using a sand stirrer, etc. After adding a polymerization initiator, the mixture is added to an aqueous suspension medium containing a suspension stabilizer, and a high-speed stirrer is used. The polymerization reaction is then dispersed and suspended and maintained at 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 resin particles obtained is determined by the dispersion state of the suspended polymerizable composition, and by adjusting the dispersion conditions and suspending the resin particles to the desired toner particle size, the size of the resin particles obtained is determined by the dispersion state of the suspended polymerizable composition. can be used as is 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.

On the other hand, sterene 90 parts (n) butyl acrylate 10 parts Carbon black "#30" (manufactured by Mitsubishi Kasei Corporation)
10 parts POPKO-201 (manufactured by Noda Wax Co., Ltd.) 8 parts 2,2'-azobis(2,4-dimethylvaleronitrile) 3 parts were mixed and dispersed using a sand stirrer, and the previously obtained surface-hydrophilized viscole was mixed and dispersed. 8 parts of 660P was added and uniformly dispersed to obtain a polymerizable composition. This was combined with 3% by weight of calcium phosphate, sodium dodecylbenzenesulfonate (based on the polymer composition)
in water containing 0.04% by weight (based on the polymerizable composition)
Add only the amount to make 20% by weight (solid content concentration), and
Using a homogeator (manufactured by Tokushu Kika Kogyo Co., Ltd.),
A suspension was obtained by dispersing the particles to a particle size of 7 to 15 μm.

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

2 parts of this toner and hydrophobic silica (manufactured by Degussa)
A developer consisting of 0.016 parts of iron powder carrier and 100 parts of iron powder carrier was prepared and evaluated as follows.

[1] Measuring the temperature at which "winding" occurs Electronic copying machine U-Bix1600 modified for testing so that the temperature of the heat roller for fixing can be set variably
(manufactured by Konishi Photo Industry Co., Ltd.), the transfer paper with a solid black toner image formed on the tip is fixed while lowering the set temperature of the heat roller in steps of 5 °C from 230 °C. Find the temperature at which winding begins to occur on the heat roller (winding temperature). The surfaces of the fixing roller and pressure roller were made of Teflon and silicone rubber "KE-1300R-TV", respectively, and the transfer material passing speed was 120 mm/sec. There is no supply of silicone oil to the fixing section.

[2] Measurement of minimum fixing temperature and offset occurrence temperature Using the same test electronic copying machine as in the previous section, the transfer paper on which the toner image was formed was heated at 146 mm/sec while increasing the set temperature of the fixing heat roller in steps of 5°C. The surface of the resulting image was rubbed with paper to examine its abrasion resistance, and the temperature at which the image attained sufficient abrasion resistance was determined as the lowest fixing temperature. Furthermore, following the transfer paper with an image, a transfer paper without an image is passed through the fixing unit, and it is observed whether or not toner stains have occurred due to the offset phenomenon.
The temperature at which staining occurred was defined as the offset occurrence temperature.

In addition, the "winding" occurrence temperature, minimum fixing temperature, and offset occurrence temperature measured using this method were each 200%.
℃ or lower, 180℃ or lower, and 230℃ or higher, the toner can be said to be practically preferable.

According to the measurement results for the sample toner mentioned above, the temperature was 180℃.
No coiling occurred up to this point, and coiling occurred for the first time at 175°C. Offsets did not occur over the entire range of measurements.

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

Comparative example 1 Finely powdered viscoel whose surface has not been made hydrophilic
A comparison toner was used in the same manner as in Example 1 except that 660P was used and POPKO-201 was not used, and the temperature at which curling occurred was determined in the same manner as in Example 1.
The temperature was 225°C, and an offset phenomenon occurred at 230°C. Furthermore, the minimum fixing temperature was 235°C or higher.

As described above, when only polypropylene whose surface has not been made hydrophilic is used, the wrapping resistance and offset resistance are insufficient, and furthermore, the minimum fixing temperature is too high.

Comparative example 2 Finely powdered viscoel whose surface has not been made hydrophilic
A comparative toner was obtained in the same manner as in Example 1 except that 660P was used. When this comparative toner was evaluated in the same manner as in Example 1, the temperature at which curling occurred was 220°C, and an offset phenomenon occurred at 230°C. Furthermore, the minimum fixing temperature was 230°C.

That is, non-polyalkylene wax POPKO−
Even when 201 was used, if it was used in combination with polypropylene whose surface had not been made hydrophilic, the wrap resistance, offset resistance, and fixing properties were also insufficient.

Thus, it can be seen that the toner of the present invention has remarkable effects on wrap resistance, offset resistance, and fixing properties.

Example 2 Using the finely powdered Viscol 660P obtained in Example 1, it was mixed with 100 ml of sulfuric acid, 50 ml of water, and 15 ml of chromic anhydride.
After stirring for 2 hours, the mixture was poured into ice water, filtered, washed with water, and dried to obtain Viscoel 660P whose surface was made hydrophilic. Using this, POPKO of Example 1
The toner of the present invention was obtained in the same manner as in Example 1 except that ceresin was used in place of -201, and evaluated in the same manner as in Example 1. For the first time, a coiling occurred. The minimum fixing temperature was 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 660P whose surface was made hydrophilic. Using this, the toner of the present invention was obtained in the same manner as in Example 1 except that carnauba wax was used in place of POPKO-201 in Example 1, and the toner of the present invention was evaluated in the same manner as in Example 1. It was 180℃. Minimum fixing temperature is 180
It was warm at ℃. At this time, no offset phenomenon appeared at all.

Example 4 Using the finely powdered Viscoll 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 the surface was made hydrophilic by drying. Obtained Viscole 660P. Using this, Example 1
A toner of the present invention was obtained in the same manner as in Example 1 except that tristearin was used in place of POPKO-201, and evaluated in the same manner as in Example 1. The temperature at which curling occurred was 190°C. Also, the minimum fixing temperature is 185℃
It was hot. At this time, no offset phenomenon appeared at all.

Example 5 The same hydrophilic treatment as in Example 1 was performed using polyethylene "Hiwax 320P" (manufactured by Mitsui Petrochemicals).

On the other hand, styrene 85 parts lauryl methacrylate 15 parts "Mitsubishi Carbon Black #30" (manufactured by Mitsubishi Kasei Corporation)
10 parts Nisseki No. 1 candle wax (manufactured by Nippon Oil Co., Ltd.)
8 parts 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) 2 parts 2,2'-azobisisobutylnitrile 0.5 part were mixed and dispersed using a sand stirrer, and the previously obtained surface hydrophilic 8 parts of Hiwax 320P was added and uniformly dispersed to obtain a polymer composition. Add this to 3% by weight of calcium phosphate (based on the polymer composition)
20% by weight in water containing 0.03% by weight (relative to the polymerization composition) of sodium dodecylbenzenesulfonate
(solid content concentration) was added 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, evaluation was performed in the same manner as in Example 1, and the temperature at which curling occurred was determined from 230°C to 185°C.
No coiling occurred up to 180℃, and coiling occurred for the first time at 180℃. Minimum fixing temperature is 180℃
It was hot. 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 5, except that Hiwax 320P was used without surface hydrophilic treatment.

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

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 "Elftex 8" (manufactured by Cabot Co., Ltd.) 15 parts Rice wax F-1 (manufactured by Noda Wax Co., Ltd.)
After mixing and dispersing 7 parts polyester resin 3 parts 2,2'-azobis(2,4-dimethylvaleronitrile) 5 parts using a sand stirrer, 7 parts of the previously obtained Polywax 500 fine powder whose surface had been made hydrophilic was added. A polymerizable composition was obtained by uniformly dispersing the mixture.
The polyester resin is an unsaturated polyester resin with a softening point of 110° C. obtained by polymerizing bisphenol A, polyethylene glycol (average molecular weight 1000), and terephthalic acid fumaric acid (200:20:100:70 weight ratio).

The obtained polymerizable composition was added to water containing 3% by weight of calcium phosphate (based on the polymeric composition) and 0.03% by weight of sodium dodecylbenzenesulfonate (based on the polymeric composition) to a concentration of 30% by weight (solid content). The desired amount was added and dispersed using a TK homogeator. The suspension thus obtained 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, evaluation was carried out in the same manner as in Example 1 to determine the temperature at which curling occurred. Winding did not occur from 230°C to 180°C, and winding only occurred at 175°C. The minimum fixing temperature was 185°C. On this occasion,
No offset occurred over the entire range of measured temperatures.

Comparative Example 4 A comparative toner was obtained in the same manner as in Example 6, except that Polywax 500 was used without surface hydrophilic treatment.

When this toner was evaluated in the same manner as in Example 1 to determine the temperature at which curling occurred, curling had already occurred at 230° C., so a temperature range that could be evaluated was not obtained.

Example 7 A toner was obtained in the same manner as in Example 1 except that Hoechstwax C was used in place of POPKO-201 in Example 1. Furthermore, the same evaluation as in Example 1 was performed, and the winding occurrence temperature was 175°C, and the minimum fixing temperature was 180°C.
I got it. Note that no offset phenomenon occurred within the measurement range.

Example 8 A toner was obtained and evaluated in the same manner as in Example 1 except that Hoechstwax OP was used in place of POPKO-201 in Example 1. As a result, a winding temperature of 180°C and a minimum fixing temperature of 185°C were obtained.
Note that no offset phenomenon occurred within the measurement range.

The images copied using the toners of Examples 1 to 8 were clear and free of fog.

〔Effect of the invention〕

As is clear from the above examples, the present invention makes it possible to obtain an excellent toner that has high releasability from the fixing roller surface, high offset resistance and wrapping resistance, and can be fixed at low temperatures. . By using the toner of the present invention, "offset" can be achieved without the need to supply lubricating liquid to the surface of the fixing roller.
It has become possible to perform good hot roller fixing without occurrence of "winding".

Claims (1)

[Scope of Claims] 1. A toner for electrostatic image development obtained by polymerizing a polymerizable composition comprising a colorant, a polyolefin wax, and a non-polyolefin wax other than polyolefin dispersed in a polymerizable monomer, A toner for electrostatic image development, wherein the surface of the polyolefin wax is hydrophilized by sulfonation or chlorosulfonation reaction, or organic titanate treatment. 2. A polymerizable composition comprising a polyolefin wax whose surface has been made hydrophilic by sulfonation or chlorosulfonation reaction or organic titanate treatment, dispersed in a polymerizable monomer together with a colorant and a non-polyolefin wax other than polyolefin. 1. A method for producing an electrostatic image developing toner, comprising the steps of dispersing, suspending, and polymerizing in an aqueous medium.