JPS63309968A - Electrostatic latent image developing toner - Google Patents

Abstract

PURPOSE:To obtain good fixability and superior offset resistance by incorporating fine polymer particles obtained by polymerizing a mixture of a monofunctional monomer with a cross-linkable monomer in a state of them dispersed in a nonaqueous medium, in an amount of 1-20wt.%. CONSTITUTION:The mixture of the 80-99wt.% monofunctional monomer, such as a styrene type monomer like styrene and o-methylstyrene, ethylenic unsaturated monoolefines like ethylene and propylene, or vinyl type monomers like vinyl chloride, and the 20-1wt.% cross-linkable monomer, such as one or more kinds of an aromatic divinyl compound like divinylbenzene or divinylnaphthalene, or their derivatives, or a polyfunctional monomer having >=2 unsaturated double bonds like divinyl ether and divinyl sulfite, on the 100wt.% based on the total monomer is dispersed into a nonaqueous medium and polymerized, and the obtained fine polymer particles are contained in an amount of 1-20wt.%, thus permitting the formed electrostatic latent image developing toner to obtain good fixability and to enhance offset resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a toner used for developing electrostatic latent images in electrophotography, electrostatic recording, and the like.

(Prior Art) In electrophotography, electrostatic recording, etc., an electrostatic latent image is developed with toner, and then the developed toner image is transferred to paper or the like to become a semi-permanent visible image. Take root. The fixing method involves passing a toner image carried on paper or the like between pressurized heat rolls.

A hot roll fixing method in which toner is fused to paper using heat and I-force is generally widely used. It goes without saying that this fixing method requires a toner that can provide good fixing properties.

Due to contact fixing, part of the toner image is peeled off to the roll side during fixing, and transferred to the toner image side again after one rotation of the roll, staining the fixed toner image (in the industry, this is called offset). ) is required.

In order to adopt this fixing method, a suitably crosslinked vinyl polymer is used as the toner binder resin. Toners that aim to achieve both fixing properties and anti-offset properties have been known for some time.

(Problems to be Solved by the Invention) However, with this toner, as the degree of crosslinking of the vinyl polymer used increases, offset resistance improves, but fixing performance deteriorates. In addition, reducing the degree of crosslinking improves fixing properties, but
The problem is that offset resistance deteriorates. That is, it has been difficult to achieve both fixing properties and anti-offset properties depending on the degree of crosslinking of the vinyl polymer used as the toner binder resin.

Therefore, an object of the present invention is to provide a toner for developing electrostatic latent images that has good fixing properties and excellent anti-offset properties.

(Means for Solving the Problems) The present invention involves non-aqueous dispersion polymerization by blending monofunctional monomers of 80 to 99% by weight and crosslinking monomers of 1 to 20% by weight to a total of 100% by weight. The present invention relates to a toner for developing electrostatic latent images containing 1 to 20% by weight of polymer fine particles obtained by the above method.

Examples of monofunctional monomers constituting the polymer fine particles in the present invention include styrene, 0-methylstyrene,
m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2.4-f)styrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-
hexylstyrene, p-n-octylstyrene, p-n
-nonylstyrene t p-n-fsilstyrene, p-
Styrenic monofunctional molybdenants such as n-dodecylstyrene, n-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, etc. -, engineering f
ethylenically unsaturated monoolefins such as olefin, propylene, butylene, isobutylene, and vinyl chloride.

Vinylidene chloride, vinyl bromide, vinyl fluoride, vinyl rhodanates, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, methyl acrylate, ethyl acrylate.

Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate.

Dodecyl acrylate, 2-ethylhexyl acrylate,
stearyl acrylate, 2-chloroethyl acrylate,
7') Phenyl lylate, methyl α-chloroacrylate,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl acrylate, α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc., vinyl methyl ether, vinyl ethyl ether, Vinyl ethers such as vinyl imbutyl ether, acrylic acid or methacrylic acid derivatives such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyl methyl ketone, vinyl Vinyl ketones such as xyl ketone and methyl isopropenyl ketone, N-vinylpyrrole, N-
One or more types of N-vinyl compounds such as vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone, vinylnaphthalene salts, etc. are used.

Among these monofunctional monomers, acrylic acid alkyl esters, methacrylic acid alkyl esters, etc. are preferable from the viewpoint of good offset resistance of the toner, and acrylic acid alkyl esters having an alkyl group having 1 to 3 carbon atoms in 9% and Methacrylic acid alkyl esters are preferred.

Examples of crosslinking materials include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and derivatives thereof, and allyl methacrylate.

Ethylene glycol dimethacrylate, ethylene glycol cyacrysate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol triacrylate, trimethylolpropane triacrylate), 1,6-hexanethiol dimethacrylate.

One or more polyfunctional monomers having two or more unsaturated double bonds such as trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, N,N-divinylaniline, divinyl ether, and divinyl sulfite are used.

Among these crosslinking monomers, ethylene glycol dimethacrylate, ethylene glycol diacrylate,
Diethylene glycol dimethacrylate, diethylene glycol diacrylate.

Divinylbenzene is preferred.

The polymer fine particles in the present invention are monofunctional monomers 8
0-99% by weight, preferably 85-985-98 heavy crosslinking monomer 1-20% by weight, preferably 2-15% by weight
It is obtained by blending and polymerizing the total amount of 100% by weight. If the crosslinking monomer exceeds 20% by weight, the particle size of the polymer fine particles becomes too large and the effects of the present invention cannot be achieved, and if the crosslinking monomer is less than 1% by weight, the degree of crosslinking of the polymer fine particles becomes small. Therefore, the effects of the present invention cannot be achieved.

The polymer fine particles in the present invention are prepared by adding the above-mentioned monomers, a polymerization initiator, a dispersant, etc. to a non-aqueous solvent.

Obtained by non-aqueous dispersion polymerization.

The nonaqueous solvent used in this polymerization has an S point of 50 to
Examples include hydrocarbons at 200°C, and preferred ones include n-hexane and n-hebutane.

Examples include isooctane, nonane, decane, and white kerosene.

As a polymerization initiator, azobisin butyronitrile, 2
．． Oil-soluble initiators such as 2'-azobis(4-methoxy-λ4-dimethylvaleronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile) can be used; and preferably 0.5 to 5
Use % by weight.

Further, as a dispersant, there is an affinity for the above-mentioned non-aqueous solvent,
A copolymer or the like having a segment (2) that has no affinity with the polymer fine particles and a segment (2) that has a relatively no affinity with the nonaqueous solvent and has an affinity with the polymer fine particles is used.

Specifically, block copolymers of natural rubber and methyl methacrylate and block copolymers of styrene and methyl methacrylate described in British Patent No. 1,054,241, and polylauryl methacrylate described in British Patent No. 1,122,397. A block copolymer consisting of a segment whose main component is polymethyl methacrylate and a segment whose main component is polymethyl methacrylate.

Adduct of hydroxystearic acid trimer and epoxy resin described in British Patent No. 1,123,611.

Dispersion Poly-m
eration in Organic Medi
a) A comb having a segment containing poly(12-hydroxystearic acid) etc. as a constituent component and a segment containing polymethyl methacrylate etc. as a constituent component, as described in J p. 108 (1975) (published by John Baiso and Sons). Graft copolymers in the shape of a comb are preferred because they exhibit good dispersion stability, and the comb-shaped graft copolymers are particularly preferred.

The polymer particles are prepared by adding a monomer, a polymerization initiator, a dispersant, etc. to the non-aqueous solvent, and performing non-aqueous dispersion polymerization with stirring, preferably at a temperature of 40 to 120°C. The resulting polymer fine particles are:

It is preferable to adjust the average particle size to 50 to 1000 nm. If the average particle size is outside this range, the toner's fixing properties or anti-offset properties tend to deteriorate.

In the present invention, the polymer fine particles are contained in the toner from 1 to 1.
It is contained in an amount of 20 parts by weight, preferably 2 to 15 parts by weight. Even if the amount of polymer fine particles is less than 1% by weight or more than 20% by weight, there is no effect of improving toner fixing properties and anti-offset properties.

Methods for incorporating polymer particles into toner include a method in which polymer particles are dispersed in a monomer serving as a binder resin component to produce a binder resin, and a method in which a binder resin and polymer particles are mixed in a solution.

A method in which the binder resin and polymer fine particles are mixed in advance with the binder resin by melt-kneading, etc., and then mixed with other toner components and melt-kneaded; This can be carried out by a method such as melt-kneading.

Among these mixing methods, it is preferable to mix polymer fine particles with a binder resin in advance and then manufacture the toner because the resulting toner has particularly good fixing properties. A preferred method is to disperse the monomers into the component monomers and then polymerize the monomers.

There are primary binder resins used in the toner for developing electrostatic images according to the present invention.

(1) Monofunctional styrene derivatives such as styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, and propyl acrylate.

Butyl acrylate, hexyl acrylate, octyl acrylate, stearyl acrylate, lauryl acrylate,
Oleyl acrylate, cetyl acrylate, cyclohexyl acrylate, phenyl acrylate, hensyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, hydroxyethyl acrylate.

Monofunctional acrylic acid derivatives such as hydroxypropyl acrylate, hydroxybutyl acrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-diethylamino)ethyl acrylate, morpholinoethyl acrylate, and piperazinoethyl acrylate.

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, stearyl methacrylate,
Lauryl methacrylate, oleyl methacrylate, cetyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate.

Benzyl methacrylate, furfuryl methacrylate.

Tetrahydrofurfuryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate.

Hydroxypropyl methacrylate, hydroxybutyl methacrylate, methacrylic acid (N,N-dimethylamino)
Monofunctional methacrylic acid derivatives such as ethyl, (N,N-diethylamino)ethyl methacrylate, morpholinoethyl methacrylate, piperazinoethyl methacrylate, maleic anhydride, maleic acid, methyl maleate, dimethyl maleate, ethyl maleate, maleic acid Diethyl, butyl maleate, dibutyl maleate, octyl maleate, dioctyl prenate, glycidyl maleate,
Maleic acids such as diglycidyl prenate, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, etc. One or more monofunctional vinyl yarn threaders such as derivatives, vinyl acetate, and vinyl chloride are blended,
In some cases, in addition to these, divinylbenzene.

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, butylene glycol diacrylate.

Butylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate,
Polypropylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate.

2.2-bis(4-acryloxyjethoxyphenyl)
One or more types of bifunctional vinyl monomers such as propane, trifunctional or higher functional vinyl heptomers such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate. is preferably blended in an amount of θ to 1% by weight in all monomers, and polymerized by known polymerization methods such as suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, and non-aqueous dispersion polymerization using a known polymerization initiator. A vinyl polymer obtained by

(2) Bisphenol A, bisphenol F,
Polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as phenol novolak and cresol novolac, or polyhydric alcohols such as polyethylene glycol and hexanediol, or polycarboxylic acids such as hexahydrophthalic acid and terephthalic acid. Epoxy resins such as polyglycidyl ester, commercially available products include Epicor) 1004 (trade name, manufactured by Shell), Epicor) 100'7 (trade name,
(manufactured by Shell), Epicor) 1009 (trade name, manufactured by Shell).

Araldite) GY6084 (trade name, manufactured by Ciba Geigy, hereinafter the same), Araldite) GY6097°, Araldite GY6099, etc.

(31 ethylene glycol, glycerin, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,4-cyclohexane dimetatool, propylene oxide adduct of bisphenol A,) Limethylolethane, Trimethylolpropane, Penta A polyester resin that is polycondensed by appropriately combining polyhydric alcohol components such as erythritol with polybasic acids such as tomaleic acid, fumaric acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, trimellidic acid, and pyromellitic acid.

In addition, known binder resins for toner can be used. The binder resin can be used alone or in combination of two or more. In a two-component toner, the binder resin is preferably blended in a proportion of 30 to 98% by weight based on the total toner components, and in the case of a magnetic toner, it is blended in a proportion of 20 to 69% by weight.
It is preferable that s be blended.

As the binder resin, a vinyl polymer is preferable because the 9-molecule design can be manipulated over a wide range and the toner properties are good.In particular, a vinyl polymer is preferable since the above-mentioned monofunctional styrene derivative and an acrylic acid derivative and/or a methacrylic acid derivative are used as components. styrene
Acrylic resins, acrylic resins containing acrylic acid derivatives and/or methacrylic acid derivatives, and the like are preferred.

It is preferable that the glass transition temperature of the binder resin is adjusted to 40 to 100[deg.] C., since this provides good toner properties.

The toner for developing electrostatic latent images according to the present invention has two colorants and/or
Or contains magnetic powder. As a coloring agent.

Black coloring agents such as carbon black, acetylene black, lamp black, graphite, iron black, aniline black, cyanine black, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, naphthol yellow, Hansa yellow,
pigment yellow.

Yellow coloring agents such as benzidine yellow, permanent yellow, quinoline yellow lake, anthrapyrimidine yellow, permanent orange, palcan fast orange, benzidine orange.

Orange colorants such as indanthrene brilliant orange,
Iron oxide, amber, brown colorants such as permanent brown, red iron oxide, antimony vermilion, permanent red, fire red, brilliant carmine, light fast red toner, permanent carmine, pyrazolone red, Bordeaux, heliobordeaux, rhodamine lake, thio Red coloring agents such as indigo red and thioindigo reddon, purple coloring agents such as cobalt violet, fast violet, and dioxazine violet, cobalt blue, cerulean blue, metal-free phthalocyanine blue, phthalocyanine blue, indanthremble, indigo, etc. Blue colorants, green colorants such as chrome green, cobalt green, green gold, phthalocyanine clean, hollychrome bromine copper phthalocyanine, etc., carbon black, iron black when heat decomposition resistance is required.

Cyanine black, yellow iron oxide, titanium yellow, no-nza yellow, benzidine yellow, permanent orange,
Palkan Fast Orange, iron oxide.

Red red toner, fire red, light fast red toner, permanent carmine, pyrazolone red, Bordeaux, thioindigo maroon, cobalt purple, cobalt blue, cerulean blue, phthalocyanine blue, copal) fIJ-n, phthalocyanine green, polychrome brome steel phthalocyanine, etc. Particularly preferred. These colorants are preferably blended in an amount of 1 to 60% by weight in the total toner components. If it is less than 1% by weight, coloring is insufficient, and if it exceeds 60% by weight, the fixing strength of the toner tends to decrease.

Magnetic powder is blended when the toner is used as a one-component toner. Magnetic powders include metal powders such as iron, manganese, nickel, and cobalt, aluminum, cobalt, steel, lead, magnesium, nickel, and tin.

Zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium.

Metal alloys and mixtures thereof such as tungsten, vanadium, metal oxides such as aluminum oxide, iron oxide, steel oxide, nickel oxide, zinc oxide, titanium oxide, magnesium oxide, chromium oxide, or heat treatment. Alloys 9 that exhibit ferromagnetism when applied, such as whisker alloys such as manganese-copper-aluminum, manganese-copper-tin, etc., can be used. The particle size of the magnetic powder is preferably 10 μm or less, and preferably 1 μm or less for 2%. These magnetic powders are contained in the toner in an amount of 30 to 70% by weight. When using magnetic powder, the above-mentioned colorant may be further added, and the amount thereof is preferably 0 to 10% by weight in the toner.

Additionally, additives such as a charge control agent, a fluidity improver, a cleaning performance improver, an offset inhibitor, and the like can be used in the toner of the present invention, if necessary.

As charge control agents, chromium complexes of salicylic acid derivatives,
Spiron dyes, nigrosine dyes, fatty acid-modified nigrosine dyes, dibutyltin oxide.

Tetraalkylammonium halide, trial
Examples include kylammonium halide, which is preferably added in an amount of 0 to 10% by weight based on the total toner components.

As a fluidity improver, Aerosil R972゜Silica D
-17, R-812, RA200H.

RX-C (manufactured by Nippon Aerosil ■, trade name).

Examples include Taranox 500 (manufactured by Talco, trade name), and these preferably have Fio to 1% of the total toner components.
It is added in an amount of 5% by weight.

Examples of the cleaning property improving agent include fatty acid metal salts such as zinc stearate, calcium stearate, and magnesium stearate, and these are preferably added in an amount of 0 to 10% by weight based on the total toner components.

As anti-offset agents, low molecular weight polyolefins such as polyethylene and polypropylene, casta wax (
Made by Ito Oil Co., Ltd.), Diamond Wax (New Japan Chemical Co., Ltd.)
ester waxes such as), palm acetic acid (manufactured by Nippon Oil & Fats Corporation), Hoechstwax E, Hoechstwax-〇P (all manufactured by Hoechst Akchen Gesellschaft), carnauba wax, Hoechst Wax C (manufactured by Hoechst Akchen Gesellschaft) etc. amide wax.

Examples include fatty acid metal salts, and these are preferably added in an amount of 0 to 30% by weight based on the total toner components.

In addition, any conventionally known additives may be blended.

In the present invention, each of the cage additives described above may be added alone or in combination.

Each of the above toner components is used in a total amount of 100 times i[.

A toner for developing an electrostatic latent image can be produced by mixing the above-mentioned materials, for example, by the following method.

The weighed materials are premixed using a W cone, a blender, a Henschel mixer, etc., and then kneaded using a pressure kneader, a Banbury mixer 9 hot roll, an extruder, etc. at a temperature at which the resin melts. After cooling, it is coarsely ground using a feather mill, pin mill, pulperizer, hammer mill, etc. Next.

The particles are sieved using an Accucut or Alpine classifier to adjust the particle size to preferably 5 to 30 μm.

Incidentally, if the polymer fine particles are not mixed with the binder resin in advance, they are mixed at the time of producing the toner.

When the toner of the present invention is used in a two-component manner, the toner and carrier are combined to prepare a developer.

Examples of carriers include flat, sponge-shaped, coin-shaped, pseudospherical, or spherical iron powder, the surface of the iron powder coated with thermoplastic or thermosetting resin such as Teflon, silicone, vinyl, etc., or the present invention. A one-component toner having the following properties is preferred. Furthermore, the carrier has particle size, electrical resistance value, and
Specific surface area etc. are adjusted.

The toner concentration of a two-component developer generally depends on the specific surface area of the carrier, and when the carrier used is amorphous or has a fine particle size, it is 3 to 10% by weight, and when the carrier is spherical or has a coarse particle size, it is 1%. Preferably, the amount is 5% by weight.

(Function) Since the polymer fine particles used in the present invention have a small particle size, even if they are dispersed in a toner, the melt viscosity is the same as that of a toner that does not contain polymer fine particles.

are not very different. Therefore, a toner in which fine polymer particles are dispersed exhibits good fixing properties.

On the other hand, a toner in which fine polymer particles are dispersed exhibits extremely high elasticity compared to a toner in which fine polymer particles are not dispersed. Therefore, a toner in which fine polymer particles are dispersed has dramatically improved offset resistance compared to a toner that does not contain fine polymer particles.

(Example) Next, the present invention will be explained in detail based on examples.

The present invention is not limited to this.

Preparation example of dispersant for non-aqueous dispersion polymerization (1) Synthesis of poly(12-hydroxystearic acid) Xylene 209, 12-hydroxystearic acid 180
9 and dibutyltin oxide O, 18 g and 1 t were charged into a flask equipped with a stirring device, a nitrogen blowing tube, a thermocouple for temperature control, and a distillation tube for condensed water, and nitrogen was blown into the flask, and the mixture was heated at about 195° C. for 11 hours while stirring. , condensation polymerization was performed. The acid value of the produced poly(12-hydroxystearic acid) is 35.
．． It was KOH/9.

(2) Synthesis of glycidyl methacrylate adduct of poly(12-hydroxystearic acid) Product obtained in (1) above 141.09. xylene 14
0.979. Glycidyl methacrylate 17.559
, hydroquinone 0.159 and N,N-dimethyllaurylamine 0.279 in a stirrer, nitrogen blowing tube.

The mixture was placed in a flask equipped with a thermocouple for temperature control and a cooling tube, nitrogen was blown into the flask, and 9 reactions were carried out at about 140° C. for 12 hours with stirring. The acid value of the reaction solution is 0.2KOH/
It was 9.

(3) Synthesis of dispersant The reaction solution obtained in (2) was distilled under reduced pressure to remove only xylene, resulting in a reaction product of 35.79. Hexane 124.79° Methyl methacrylate 27.759. Methacrylic acid 0.579 and Baroyl IPPC (trade name of peroxide manufactured by NOF ■) 0.689 were mixed with a stirring device and a nitrogen blowing tube.

The mixture was placed in a flask equipped with a thermocouple for temperature control and a cooling tube, and 9 reactions were continued at 60° C. for 5 hours while blowing nitrogen. After cooling, n-hexane was added to the mixture to dilute it until the nonvolatile content reached 30% by weight.

In the following examples, this non-volatile content of 30 weight was used as a dispersant for non-aqueous dispersion polymerization.

Example 1 n-hexane 300.09. Ethyl acrylate 28.8
9. Ethylene glycol dimethacrylate 1.29. The above dispersants xo, og and 2,2'-azobis(2,4-
0.39 of dimethylvaleronitrile) was charged into a flask equipped with a stirring device, a nitrogen blowing tube, a thermocouple for temperature control, and a cooling tube, and while nitrogen was blown into the flask and the mixture was stirred, it was heated to 60°C for 5 hours to form ashes. A dispersion of fine particles in n-hexane was prepared. The polymerization rate at this time was approximately 100% by weight.

This n-hexane dispersion of fine polymer particles was poured into styrene, and n-hexane and the like were azeotropically removed with the styrene under reduced pressure to prepare a styrene dispersion of fine polymer particles. Furthermore, butyl acrylate was added to this to prepare a monomer dispersion of polymer fine particles in which the weight ratio of styrene and butyl acrylate was 80/20 and the content of polymer fine particles was 9 by weight.

9 oz of ion exchange water, 5 oz of polyvinyl alcohol
30g of heavy duty aqueous solution and nitrous acid) IJum 0.12
9 is a nitrogen blowing pipe, a stirring device, and a nitrogen blowing pipe.

The mixture was placed in a flask equipped with a thermocouple for temperature control and a cooling tube, and stirred while blowing nitrogen. Furthermore.

To this, the monomer dispersion liquid 3009 of the above polymer fine particles is added.
Add a solution of benzoyl peroxide 159 to 90
The temperature was raised to 0.degree. C., and 9 reactions were carried out for 5 hours. The polymerization rate at this time was approximately 100% by weight. After cooling, the water was drained and dried to obtain a styrene/acrylic resin containing fine polymer particles.

Styrene/acrylic resin containing polymer fine particles obtained above 2559. Carbon Blackna 44 (trade name, carbon black manufactured by Mitsubishi Chemical Industries ■) 309, Oil Black So (trade name, nigrosine dye manufactured by Orient Chemical Industries ■), and Viscol 660P (trade name, polypropylene manufactured by Sanyo Chemical Industries ■) ) were mixed well and then melt-kneaded.

Next, this mixed material was pulverized using a jet mill, and then classified into 9 parts to obtain toner A having an average particle size of 15 μm.

The above toner A 5% by weight and TSV-20 (1-? rear (
A developer was prepared from 95 weights and 11 pieces of iron oxide powder manufactured by Japan Iron Powder (trade name 1), and SELEX 1200 (trade name, Copia ■) was prepared.
An unfixed solid image of the toner measuring 3 an x 4 am was transferred onto a sheet of paper by reversal development using a copying machine manufactured by Co., Ltd. This toner image is then subjected to varying roll temperatures. The upper side is a Teflon 7 coated roll, T[l is a silicone rubber coated roll, and the pressure between the upper and lower rolls is 0.8 kg f/am''.
The fixing properties and anti-offset properties of the toner image were examined with respect to the roll temperature by passing the toner at a speed of 1/s. The results are summarized in Table 1 together with the physical properties of the toner.

Example 2 In Example 1, except that a monomer dispersion of polymer fine particles having a content of 411 polymer particles was used,
Toner B was prepared in exactly the same manner as in Example 1. In addition,
The polymerization rate of the monomer was approximately 100% by weight. Next, use this toner B.

The fixability and offset resistance of the toner image were examined in exactly the same manner as in Example 1, and the results are summarized in Table 1 together with the toner physical properties.

Example 3 In Example 1, except that a monomer dispersion of polymer fine particles with a polymer fine particle content of 14% by weight was used.
Toner C was prepared in exactly the same manner as in Example 1. In addition,
The polymerization rate of the monomer was approximately 100% by weight. Next, using this Toner C, the toner image fixability and offset resistance were examined in exactly the same manner as in Example 1, and the results are summarized in Table 1 together with the toner physical properties.

Example 4 In Example 1, polymer fine particles were dispersed.

Toner D was prepared in exactly the same manner as in Example 1, except that styrene, a monomer that polymerizes to become a binder resin, was replaced with methyl methacrylate. In addition, the polymerization rate of the monomer is approximately 1
It was 00-Jl Chi. Next.

Using this Toner D, the fixability and offset resistance of the toner image were investigated in exactly the same manner as in Example 1, and the results are summarized in Table 1 together with the physical properties of the toner.

Example 5 Toner E was prepared in exactly the same manner as in Example 2, except that polymer fine particles were dispersed and methyl methacrylate was used instead of styrene, a monomer that polymerized to become a binder resin. In addition, the polymerization rate of the monomer is approximately 100
% by weight. Next.

Using this Toner E, the toner image fixability and offset resistance were examined in exactly the same manner as in Example 2, and the results are summarized in Table 1 together with the toner physical properties.

Example 6 In Example 3, polymer fine particles were dispersed.

Toner F was prepared in exactly the same manner as in Example 3, except that styrene, a monomer that polymerized to become a binder resin, was replaced with methyl methacrylate. In addition, the polymerization rate of the monomer is approximately 1
00% by weight. Next.

Using this Toner F, the toner image fixability and offset resistance were examined in exactly the same manner as in Example 3, and the results are summarized in Table 1 together with the toner physical properties.

Comparative Example 1 Toner G was prepared in exactly the same manner as in Example 1, except that a monomer mixture of styrene and butyl acrylate containing no polymer particles was used.

Note that the polymerization rate of the monomer was approximately 100% by weight.

Next, using this Toner G, the fixability and offset resistance of the toner image were examined in exactly the same manner as in Example 1, and the results are summarized in Table 1 together with the physical properties of the toner.

Comparative Example 2 In Example 1, polymer fine particles were prepared by replacing the entire amount of ethylene glycol dimethacrylate with ethyl acrylate. The polymerization rate at this time was approximately 100% by weight. Toner H was prepared in exactly the same manner as in Example 1 using these polymer fine particles. Note that the polymerization rate of the monomer was approximately 100% by weight. Next, using this toner H,
The fixability and anti-offset properties of the toner images were investigated in exactly the same manner as in Example 1, and the results are summarized in Table 1 together with the physical properties of the toner.

Measurement of toner physical properties and evaluation of characteristics were carried out by the following methods: Melt viscosity of toner: Measured at a shear rate of 100 s-1° and a temperature of 140° C. using a cavilograph (manufactured by Toyo Seiki Seisakusho).

Dynamic shear modulus of toner Nileopexy analyzer 几PX
-705 (manufactured by Wakagi Seisakusho) at 9 frequencies IHz and a temperature of 140°C.

Fixability: Those with an image density ratio before and after peeling off the cellophane tape of 0.9 or more were rated Q, and those less than 0.9 were rated ×.

Offset resistance: Those whose image stain density due to offset was substantially O were evaluated as 0.0.001 or more were evaluated as ×.

In addition, the concentration is Macbeth D-514 (Product name: Image density measurement manufactured by Macbeth Co., Ltd.) The measurement was carried out using a device).

(Effects of the Invention) According to the present invention, a toner for developing electrostatic latent images having good fixing properties and greatly improved anti-offset properties can be obtained.

Claims (1)

[Claims] 1. Polymer fine particles obtained by non-aqueous dispersion polymerization of 80 to 99% by weight of a monofunctional monomer and 1 to 20% by weight of a crosslinking monomer to a total of 100% by weight.
A toner for developing electrostatic latent images containing 20% by weight.