JPH0611892A - Electrophotographic toner composition - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic toner compsn. adaptable to a high- speed copying machine and a low-heat fixing copying machine, fixable with a low quantity of heat and excellent in electrostatic chargeability. CONSTITUTION:An ethylenic polymer having <=50,000 wt. average mol. wt. is obtd. using 1-30wt.% multifunctional ethylenic monomer and 30-90 pts.wt. of this polymer is mixed with 70-10 pts.wt. ethylenic unsatd. monomer, 0.01-5 pts.wt. polymn. initiator and 0.05-2 pts.wt. multifunctional ethylenic monomer. This mixture is dispersed in a water system and polymerized and the objective electrophotographic toner compsn. contg. the resulting ethylenic polymer as the principal constituent is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner composition used in electrophotography, electrostatic photography, electrostatic printing or magnetic recording. More specifically, the present invention relates to a toner composition for electrophotography, which is compatible with high-speed machines, has a good balance of fixing and offset properties, and has a small amount of fine powder during toner production.

[0002]

2. Description of the Related Art Generally, in electrophotography in a copying machine or a printer, an electrostatic latent image is formed on a photoconductor, and then the latent image is developed with toner, and then the image is fixed on a fixing sheet such as paper. After the toner image is transferred onto the sheet, a method of heating and pressure bonding with a heat roll (heat roll fixing method) is used. In this method, fixing is performed under heat and pressure, so that the method is quick and the thermal efficiency is very good, and therefore the fixing efficiency is very good. However, when this fixing method is used, in the conventional toner, the heat roll surface and the toner come into contact with each other in a molten state, so that the toner adheres and transfers to the heat roll surface and retransfers to the next sheet to be fixed and becomes dirty (offset). Phenomenon) is not preferable.

On the other hand, the copying machine is directed to the direction of increasing the speed, and the contact time with the fixing roll is inevitably shortened, and a toner that melts by heating for a short time is required. Also,
From the viewpoint of energy saving or safety, there is a demand for a toner that melts at a temperature as low as possible and has good fluidity when melted. In order to obtain a toner having a good melt fluidity, there is a method of reducing the molecular weight of the binder resin, but the decrease in the molecular weight causes an insufficient cohesive force of the binder resin and an offset phenomenon easily occurs, which is not preferable. Further, when attempting to reduce the toner particles in order to cope with high resolution, there is a problem that the generation of unnecessary fine powder as a toner increases during the fine pulverization in the toner manufacturing process, which deteriorates the yield of toner manufacturing. It was

Japanese Patent Publication No. 51-23354 discloses a technique for preventing the offset phenomenon by using a low molecular weight polymer and a crosslinked high molecular weight polymer.
The use of a low molecular weight polymer gives melt flowability of the toner, but an offset phenomenon easily occurs. Therefore, the crosslinked high molecular weight polymer plays a role of preventing the offset phenomenon, but if the amount of the crosslinked high molecular weight polymer used is large, the fixability is poor, and if the amount used is small, it is necessary as a toner. Such properties as anti-blocking property and durability deteriorate.

Japanese Unexamined Patent Publication No. 2-48657 discloses a multifunctional (3
A polymer having a high molecular weight is produced by a suspension polymerization method using a (functional or higher) initiator, and a low molecular weight polymer is further produced in the presence of this polymer. There is disclosed a technique of improving the offset property by a toner using. However, although these techniques have a great effect in the conventional copying machine in which the offset phenomenon becomes a problem, the low heat fixing copying machine cannot obtain sufficient low temperature fixing property and offset resistance. This is because a polymer having a large weight average molecular weight is used in order to achieve the strength improvement and offset resistance of the toner, the toner resin has a high viscosity, the melt flowability of the toner is lowered, and the low heat quantity copying is performed. It is highly probable that it was unsuitable for the aircraft. However, when a material having a small weight average molecular weight is used, the melt fluidity is improved, but the offset resistance or the strength of the toner is insufficient, and the image quality is deteriorated due to the toner cracking or running during long-term running. Was causing problems.

[0006]

SUMMARY OF THE INVENTION The present invention provides an electrophotographic toner composition capable of fixing at a low heat quantity suitable for a high-speed copying machine or a low-heat-fixing copying machine and having excellent strength. is there.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies on the above-mentioned problems, and as a result, these problems are caused by the low fluidity of the low molecular weight polymer having a high fluidity in the toner. Focusing on the lack of strength, an ethylenic polymer (Y) having high fluidity and excellent strength was produced, and in the presence of such a polymer, an ethylenically unsaturated monomer and / or a polyfunctional compound was further added. The above object has been achieved by an electrophotographic toner composition containing an ethylene polymer obtained by polymerizing a volatile monomer as a main constituent.

That is, according to the present invention, the weight average molecular weight (M
w) 30 to 90 parts by weight of an ethylene polymer (Y) having a weight of 50,000 or less, 70 to 10 parts by weight of an ethylenically unsaturated monomer, 0.01 to 5 parts by weight of a polymerization initiator and a polyfunctional ethylene monomer. The present invention relates to an electrophotographic toner composition containing as a main constituent an ethylene-based polymer obtained by dispersing a mixture of 0.05 to 2 parts by weight in water and polymerizing the mixture.

Ethylene polymer (Y) in the present invention
Is an ethylenically unsaturated monomer as a raw material monomer and /
Alternatively, a polyfunctional monomer is used and polymerized by a polymerization method such as solution polymerization, suspension polymerization or emulsion polymerization.

The amount of the polyfunctional monomer used for producing the ethylene polymer (Y) is 1 with respect to the total amount of the monomers.
~ 30% by weight. 1% by weight of polyfunctional monomer
If it is less, the number of branching points will be smaller and the improvement of fluidity due to the branched chain will not be exhibited.If it is more than 30% by weight, the number of branching points will be too much and the branched chains will be entangled with each other, resulting in compatibility with high molecular weight ethylene polymer. Is not good and is not preferable.

The proportion of the ethylene polymer (Y) in the binder resin is preferably 30 to 90 parts by weight. If the proportion of the ethylene-based polymer (Y) is less than 30 parts by weight, the melt flowability as a toner is poor, so that the object to be fixed (paper etc.)
It is not preferable because the adhesiveness with the composition is inferior. Further, the ethylene-based polymer polymerized in the presence of the ethylene-based polymer (Y) is, regardless of the kind of the polyfunctional ethylene-based monomer,
It is used in an amount of 0.05 to 2 parts by weight and can be produced by a conventionally known method, and the suspension polymerization method is particularly preferable. When the amount of the polyfunctional ethylene monomer used is less than 0.05 parts by weight, the cohesive force as a high molecular weight component is insufficient and the offset resistance is poor,
If the amount is more than 2 parts by weight, the weight average molecular weight is large and the crosslinking density is high, so that the fluidity at the time of melting is deteriorated and the fixing property is deteriorated, which is not preferable. Further, as a high molecular weight component in the binder resin, a high molecular weight obtained by polymerizing an unsaturated ethylenic monomer in the presence of the ethylene polymer (Y) in order to have sufficient offset resistance. The weight average molecular weight of the ethylene polymer is preferably 200,000 or more.

To obtain the ethylene polymer of the present invention,
The following unsaturated ethylenic monomers are used alone or in combination. For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-
Ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decyl Styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, 3,4
-Aromatic vinyl monomers such as dichlorostyrene, p-chlorostyrene, α-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, cyclohexyl acrylate, stearyl acrylate , Benzyl acrylate, furfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, isobutyl acrylate, lauryl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic acid esters such as 2-chloroethyl acid, phenyl acrylate, α-chloromethyl acrylate, tetrahydryfurfuryl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl, octyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, benzyl methacrylate,
Furfuryl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, isobutyl methacrylate, dodecyl methacrylate,
Methacrylic acid esters such as 2-ethylhexyl methacrylate, phenyl methacrylate, lauryl methacrylate and tetrahydrofurfuryl methacrylate, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene, vinyl chloride, vinyl bromide,
Vinyl esters such as vinyl fluoride, vinyl acetate, vinyl propionate, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc. Diesters of unsaturated dibasic acids such as vinyl ketones, dimethyl fumarate, dibutyl fumarate, dioctyl fumarate, dioctyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, monomethyl maleate, monoethyl maleate, malein Monobutyl acid, monooctyl maleate, monomethyl fumarate, fumar
Unsaturated dibasic acid monoesters such as monoethyl acetate, monobutyl fumarate, and monooctyl fumarate,
Acrylonitrile, methacrylonitrile, acrylic acid,
Unsaturated carboxylic acids such as methacrylic acid, cinnamic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, acrylamide propane sulfonic acid, vinylnaphthalene, N- Vinyl pyro-
, N-vinylcarbazole, N-vinylindole,
N-vinyl compounds such as N-vinylpyrrolidene and the like, and at least one kind of these monomers is used. Among these, acrylic acid esters, methacrylic acid esters, aromatic vinyl monomers, fumaric acid dialkyl esters, acrylic acid, methacrylic acid, acrylamide, methacrylamide and the like are particularly preferable.

In the present invention, the following polyfunctional (trifunctional or higher) ethylene-based monomer (crosslinking agent) is used together during the polymerization. That is, divinylbenzene, 2,2-bis (4-acryloxypolyethoxyphenyl) propane, 1,
3-butylene glycol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate , Tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, polypropylene glycol diacrylate, N, N'-methylenebis Acrylic acid monomers such as acrylamide, pentaerythritol triacrylate, trimethylolpropane triacrylate, tetramethyl methanetetraacrylate, etc.
1,4-butanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate
1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol
Dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate
Dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) ) Methacrylic acid-based monomers such as propane, aluminum methacrylate, zinc methacrylate, calcium methacrylate, magnesium methacrylate, etc., as well as diallyl phthalate, triallyl cyanurate,
Triallyl isocyanurate, triallyl trimellitate
, Diallyl trolendate, ethylene glycol diglycidyl ether acrylate and the like can be appropriately used in combination.
Particularly preferred polyfunctional (trifunctional or higher) ethylene-based monomers include divinylbenzene, pentaerythritol triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate,
2,2-bis (4-acryloxypolyethoxyphenyl) propane, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate
Acrylic acid such as triethylene glycol diacrylate, N, N'-methylenebisacrylamide, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate
G, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol
Dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate
Polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4- Methacryloxypolyethoxyphenyl) propane, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, and at least one of these polyfunctional ethylene-based monomers and aromatic vinyl vinyl Copolymers with monomers, acrylic acid esters, methacrylic acid esters, fumaric acid dialkyl esters, acrylonitrile, methacrylic acid, cinnamic acid, fumaric acid monoesters, acrylamide, methacrylamide and the like are preferable.

In the present invention, when an ethylene polymer is produced by the suspension polymerization method, a polymerization initiator is usually used. Examples of the polymerization initiator used include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2-
(Carbamoylazo) -isobutyronitrile, 2,2 '
-Azobis (2,4,4-trimethylpentane), 2-
Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane)
Azo initiators, ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, 1,
1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy)
(Oxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, and other peroxyketals, t-butylhydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Hydroper oxides such as butyl hydroper oxide, di-
t-butylperoxide, t-butylcumylperoxide, di-cumylperoxide, 2,5-dimethyl-2,5-di- (di-t-butylperoxy) hexane, α, α′-bis (t- Butylpa-oxyisopropyl) benzene and other dialkylperoxides, isobutyrylperoxide, octanoylperoxide, decanoylperoxide, lauroylperoxide, 3,5,5-trimethylhexanoylperoxide, benzoylperoxide, m-toluoylperoxide.
Diacylperoxides such as oxide, di-isopropylperoxycarbone, di-2-ethylhexylperoxycarbonyl, di-n-propylperoxycarbonyl, dimethoxyisopropylperoxide Oxycarbonates, peroxycarbonates such as di (3-methyl-3-methoxybutyl) peroxycarbonate, sulfanylperoxides such as acetylcyclohexylsulfonylperoxide, t -Butyl per-oxyacetate, t-butyl per-oxyisobutyrate, t-butyl per-oxy neodecanoate, cumylpa-oxy neodecanoate, t-butyl peroxy-2-ethylhexanoate, t -Butyl per-oxylaurate, t-butyl per-oxybenzoate, t-butyl per-oxyiso Ropiruka - Bonnet - DOO, di -t- Buchirujipa - Okishiisofutare - Pas such bets - such as oxy esters can be exemplified. Among these, especially di-t-
Dialkylperoxide-based polymerization initiators such as butylperoxide, t-butylcumylperoxide and dicumylperoxide are preferred. Although the amount thereof depends on the reaction temperature, it is usually used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total amount of the charged ethylenically unsaturated monomer and the low molecular weight ethylene polymer (Y). . In the suspension polymerization method, vinyl chloride resistance is improved by using a crosslinking agent. As the crosslinking agent, the above-mentioned polyfunctional unsaturated monomer is used. The larger the amount used, the larger the gel portion and the better the vinyl chloride resistance. The preferable amount of the crosslinking agent is 0.05 to 2 parts by weight based on 100 parts by weight of the total amount of the charged ethylenically unsaturated monomer and the low molecular weight ethylene polymer (Y). If it is less than 0.05 parts by weight, there is almost no effect, and if it exceeds 2 parts by weight, the thickening effect is severe and the melt fluidity deteriorates, and fixing with a low heat quantity cannot be performed, which is not preferable.

In the present invention, when the low molecular weight ethylene polymer (Y), the polyfunctional unsaturated monomer and the ethylenically unsaturated monomer in which the polymerization initiator is dissolved are dispersed in water, suspended particles are dispersed. In order to stabilize the
Dispersion stabilizer such as gelatin, surfactant, pH adjuster,
Inorganic additives such as calcium phosphate and magnesium carbonate are used.

The thus-dispersed product in water 60
Polymerization is carried out by heating to ~ 90 ° C, and then polymerization for removing residual monomers is carried out at 80-120 ° C. After the completion of the polymerization, the resin is thoroughly washed to remove the dispersion stabilizer, followed by filtration and drying to obtain a binder resin.

The amount of the ethylene polymer (binder resin) of the present invention in the toner composition is usually 50 to 95 parts by weight. Further, if necessary, within a range that does not impair the effects of the present invention, for example, polystyrene resin, polyester resin, polyethylene resin, polypropylene resin, epoxy resin, acrylic resin, polyvinyl chloride, polyvinyl butyral,
Polyurethane, polyamide, rosin, terpene resin, phenol resin and the like may be added. In the electrophotographic toner composition of the present invention, for example, a known charge adjusting agent such as nigrosine, a quaternary ammonium salt, a metal-containing azo dye, a metal salt of a fatty acid, a pigment dispersant, an offset preventing agent, or the like is appropriately selected. Then, the toner can be made into a toner by a known method. That is, after premixing the ethylene polymer of the present invention to which the above-mentioned various additives have been added with a Henschel mixer, kneading in a kneading machine such as a kneader in a heating and melting state, cooling and using a jet grinder. After finely pulverizing, classify with a classifier, usually collect particles in the range of 8 to 20 μ
And Magnetic powder may be contained in order to obtain a magnetic toner. Such magnetic powders include ferromagnetic substances magnetized in a magnetic field, powders of iron, nickel, cobalt, etc.,
Alternatively, there are alloys such as magnetite and ferrite, and the ratio of this magnetic powder is 15 to 70 relative to the weight of the toner.
Parts by weight are preferred.

A colorant is usually used in the electrophotographic toner composition of the present invention. As the coloring agent to be used, for example, a black pigment such as carbon black, acetylene black or lamp black is added. Also, color toner
To obtain, a colorant (dye or pigment) is added as needed. As the colorant, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I.
Modant Red 30, C.I. I. Direct Bull-1,
C. I. Direct Bull-2, C.I. I. Acid Bull-
9, C.I. I. Acid Bull-15, C.I. I. Basic Bull-3, C.I. I. Basic Bull-5, C.I. I. Mode
Dent Bull-7, C.I. I. Direct green 6, C.I.
I. Basic green 4, C.I. I. Basic green
There are dyes such as tincture 6, yellow lead, cadmium yellow, mineral fast yellow, nebul yellow, naft-louiello S, hansa yellow G, permanent yellow NCG, tartrazine lake, red mouth. Yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, eosin lake, manganese purple, fast violet B, methyl violet lake, navy blue, cobalt bull. -, Alkaline Bull Lake,
Victoria Blue Lake, Phthalocyanine Blue, Indanthrene Blue-BC, Chrome Green, Chromium Oxide,
Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like. The amount is usually 5 to 300 parts by weight based on 100 parts by weight of the binder resin.

Further, in the present invention, a releasing agent as described below may be appropriately used during polymerization or during melting / kneading. The releasing agent as referred to herein is a substance which is brought into contact with a fixing roller at the time of fixing to reduce friction, improve releasability, or improve fluidity at the time of melting, for example, polyolefin waxes, Paraffin waxes, higher (saturated straight chain) fatty acids (C12 to C50), higher alcohols (C8 to C32), fatty acid metal salts, fatty acid amides,
Examples include metal soaps and polyhydric alcohols.

In the toner, a charge control agent, a colorant, and a powder fluidity modifier may be mixed (externally added) with the toner particles, if necessary. Examples of the charge control agent include metal-containing dyes and nigrosine, and examples of the powder fluidity modifier include colloidal silica and fatty acid metal salts. Further, for the purpose of increasing the amount, a filler such as calcium carbonate or fine powder silica may be blended in the toner in an amount of 0.5 to 20 parts by weight. Further, a powder flow improver such as Teflon fine powder may be added in order to prevent the toner particles from coagulating with each other and improve the powder flowability.

The toner of the present invention containing an ethylene polymer as a binder resin can be applied to all known developing methods. For example, a two-component developing method such as a cascade method, a magnetic brush method, or a microtoning method; a one-component developing method containing a magnetic material such as a conductive one-component developing method, an insulating one-component developing method, or a jumping developing method. A powder cloud method and a far brush method; a non-magnetic one-component developing method in which the toner is carried on a toner carrier by an electrostatic force and conveyed to a developing section.

[0022]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, “parts” means parts by weight unless otherwise specified. 1. Production Example of Ethylene Polymer (Y) of the Present Invention Production Example 1 A 5 L four-necked flask was equipped with a cooling pipe, a thermometer, a nitrogen introducing pipe and a stirrer, charged with 1000 parts of xylene, and introduced with nitrogen 70 The temperature was raised to ℃ 55, styrene 55 parts, t-butyl peroxyallyl carbonate [trade name Peroma-AC (manufactured by NOF CORPORATION) 3 parts, 2,2'-azobis (2,4-dimethylvalero) 10 parts of nitrile) was continuously added dropwise over 2 hours and polymerized for 4 hours, after which the temperature was raised to 110 ° C., 30 parts of styrene was added continuously for 3 hours and the remaining monomer was polymerized, and the solvent was distilled off. To obtain Resin 1. Production Example 2 Resin 2 was obtained in the same manner as in Production Example 1 except that the amount of t-butylperoxyallyl carbonate was changed to 10 parts.

Production Example 3 Resin 3 was obtained in the same manner as in Production Example 1, except that the amount of t-butylperoxyallyl carbonate was changed to 25 parts. Production Example 4 A 5 L four-necked flask was equipped with a cooling tube, a thermometer, a nitrogen introducing tube and a stirrer, charged with 200 parts of xylene, heated to a reflux temperature while introducing nitrogen, and 100 parts of styrene and 3 parts of divinylbenzene were added. Parts and t-butylperoxy-2-ethylhexanoate (30 parts) were continuously added dropwise over 5 hours, and then 8 parts
The remaining monomer was polymerized at 5 ° C., and the solvent was distilled off to obtain Resin 4.

Production Example 5 Resin 5 was obtained in the same manner as in Production Example 4 except that the amount of divinylbenzene was 10 parts and the dropping time was 8 hours. Production Example 6 Resin 6 was obtained in the same manner as in Production Example 4, except that the amount of divinylbenzene was changed to 20 parts and the dropping time was changed to 12 hours.

Production Example 7 Production Example 4 was repeated except that the composition of the monomers that were continuously dropped was 97 parts of styrene, 10 parts of divinylbenzene, 30 parts of t-butylperoxy-2-ethylhexanoate and 3 parts of maleic acid. Resin 7 was obtained by the same method as described above. Production Example 8 Resin 8 was obtained in the same manner as in Production Example 5 except that the dropping time was 12 hours.

Production Example 9 Resin 9 was obtained in the same manner as in Production Example 4 except that divinylbenzene was not used. Production Example 10 Resin 10 was obtained in the same manner as in Production Example 4 except that the amount of divinylbenzene was 35 parts and the continuous dropping time was 18 hours.

Production Example 11 Resin 11 was obtained in the same manner as in Production Example 5, except that the continuous dropping time was 5 hours. 2. Production Example of Ethylene Polymer (Binder Resin) Production Example 12 A 5 L four-necked flask was equipped with a cooling pipe, a thermometer, a nitrogen introducing pipe and a stirring device, and 72.0 parts of styrene and 27.9 of butyl acrylate.
Part and divinylbenzene 0.1 part were charged, and production example 2 was added thereto.
100 parts of the (resin 2) obtained in Example 1 was dissolved, and 0.5 part of benzoylperoxide was further added to 0.2 part of butyl I (t-butylperoxypropylisopropyl carbonate manufactured by NOF CORPORATION) to obtain a uniform mixture. Dissolved in polyvinyl alcohol
1 part and 5 parts of calcium hydrogen phosphate were added to 1000 CC of water and dispersed in a suspension state. Heat this to 80 ° C for 8
Polymerized for hours. Then, the mixture was heated to 120 ° C under pressure to polymerize the remaining monomer for 3 hours. Next, water was filtered, washed twice with water, and then dried to obtain a resin A.

Production Example 13 0.5 part of divinylbenzene, 27.5 butyl acrylate
Resin B was produced in the same manner as in Production Example 12 except that the resin B
Got Production Example 14 Resin C was obtained in the same manner as in Production Example 12 except that the amount of divinylbenzene was changed to 2 parts and the amount of butyl acrylate was changed to 26 parts.

Production Example 15 Resin D was obtained in the same manner as in Production Example 12 except that polyethylene glycol # 200 dimethacrylate was used instead of divinylbenzene and 0.1 part of the same monomer was used. Production Example 16 The charged monomer composition was 72.0 parts of styrene, 26.9 parts of butyl acrylate, 1.0 part of maleic anhydride and divinylbenzene.
Resin E was obtained in the same manner as in Production Example 12 except that the amount was changed to 0.1 part.

Production Example 17 Resin F was obtained in the same manner as in Production Example 16 except that the amount of divinylbenzene was changed to 0.5 part and the amount of butyl acrylate was changed to 23 parts. Production Example 18 Resin G was obtained in the same manner as in Production Example 16 except that the amount of divinylbenzene was changed to 2 parts and the amount of butyl acrylate was changed to 18 parts.

Production Example 19 Production Example 12 except that Resin 1 was used instead of Resin 2.
Resin H was obtained by the same method as described above. Production Example 20 Production Example 12 except that Resin 3 was used instead of Resin 2
Resin I was obtained by the same method as described above.

Production Example 21 Production Example 12 except that Resin 5 was used instead of Resin 2.
Resin J was obtained by the same method as described above. Production Example 22 0.5 parts of divinylbenzene, 27.5 butyl acrylate
Resin K was produced in the same manner as in Production Example 21 except that the parts were replaced with
Got

Production Example 23 Resin L was obtained in the same manner as in Production Example 21 except that the amount of divinylbenzene was changed to 2 parts and the amount of butyl acrylate was changed to 26 parts. Production Example 24 The charged monomer composition was 72.0 parts of styrene, 26.9 parts of butyl acrylate, 1.0 part of maleic anhydride and divinylbenzene.
A resin M was obtained in the same manner as in Production Example 21 except that the amount was changed to 0.1 part.

Production Example 25 A resin N was obtained in the same manner as in Production Example 21 except that the amount of divinylbenzene was changed to 0.5 part and the amount of butyl acrylate was changed to 23 parts. Production Example 26 Resin O was obtained in the same manner as in Production Example 21 except that the amount of divinylbenzene was changed to 2 parts and the amount of butyl acrylate was changed to 18 parts.

Production Example 27 Production Example 21 except that Resin 4 was used instead of Resin 5.
A resin P was obtained in the same manner as in. Production Example 28 Production Example 21 except that Resin 6 was used instead of Resin 5
A resin Q was obtained by the same method as described above.

Production Example 29 Production Example 21 except that Resin 7 was used instead of Resin 5
A resin R was obtained by the same method as described above. Production Example 30 Production Example 21 except that Resin 8 was used instead of Resin 5
A resin S was obtained by the same method as described above.

Production Example 31 Divinylbenzene was not used and the amount of butyl acrylate was 28
Resin T was obtained in the same manner as in Production Example 12 except that the parts were used. Production Example 32 The amount of butyl acrylate was adjusted to 28 without using divinylbenzene.
Resin U was obtained in the same manner as in Production Example 21 except that the parts were used.

Production Example 33 Production Example 21 except that Resin 9 was used instead of Resin 5.
A resin V was obtained by the same method as described above. Production Example 34 Production Example 21 except that Resin 10 was used instead of Resin 5
A resin W was obtained by the same method as described above.

Production Example 35 Production Example 21 except that Resin 11 was used instead of Resin 5
A resin X was obtained in the same manner as in. Production Example 36 Resin AA was obtained in the same manner as in Production Example 21 except that the amount of Resin 5 used was changed to 1900 parts.

Production Example 37 Resin BB was obtained in the same manner as in Production Example 21 except that the amount of Resin 5 used was changed to 900 parts. Production Example 38 Resin CC was obtained in the same manner as in Production Example 21 except that the amount of Resin 5 used was changed to 233 parts.

Production Example 39 Resin DD was obtained in the same manner as in Production Example 21 except that the amount of Resin 5 used was changed to 66.7 parts. Production Example 40 Resin EE was obtained in the same manner as in Production Example 21 except that the amount of Resin 5 used was changed to 33.3 parts.

The molecular weights of the ethylene polymers obtained in the above Production Examples 1 to 40 were measured by GPC using a commercially available monodisperse standard polystyrene as a standard, tetrahydrofuran as a solvent, and a refractometer as a detector. It was The equipment and measurement conditions are as follows. Detector SHODEX RI SE-31 Column A-80M x 2 + KF-802 Solvent THF (tetrahydrofuran) Discharge rate 1.2 / min Sample 0.25% THF solution In Table 1, the molecular weight of the ethylene-based polymer produced by the above Production Examples 1 to 40 is shown. Indicates.

[0043]

[Table 1] Table-1

Examples 1 to 22 and Comparative Examples 1 to 7 100 parts of the binder resin obtained by the above Production Examples 12 to 40 and carbon black (MA-100 (manufactured by Mitsubishi Kasei Co., Ltd.) 10 parts,
After premixing 5 parts of polypropylene wax and 1 part of nigrosine dye as a charge control agent with a Henschel mixer,
Using a twin-screw kneader, set to 170 ° C, melt and knead, then cool, coarsely pulverize, finely pulverize, and classify with a classifier to obtain 8-2.
A toner of 0 μ was obtained. Using the toner, the fixability, anti-offset property, charging property (charging stability), image quality, blocking property, etc. were evaluated.

The fixing property and the offset property were evaluated by using a machine modified so that the roll temperature of a commercially available copying machine could be arbitrarily changed. Next, an evaluation method will be shown. 70% fixing temperature; 2 cm x 2 cm, the toner layer on the image quality of the solid black part is typewriter with a load of 250 g / cm ^{2 using} a Gakushin-type friction fastness tester (manufactured by Daiei Kagaku Seiki Co., Ltd.). The minimum heat roll temperature necessary for the residual weight ratio of the toner layer after rubbing 50 times with a sand eraser to exceed 70%. High temperature offset temperature: The heat roll temperature was raised to the temperature at which the offset phenomenon began to occur. Non-offset temperature range: The temperature range in which the offset phenomenon does not occur, and was calculated from the following formula. (Non-offset temperature range) = (High temperature offset temperature)-
(70% fixing temperature) Charging property (charging stability): Toner particles and spherical iron oxide powder (charging substance) were mixed at a ratio of 3:97 in a V blender for 30 hours, and after 30 minutes. The Tobori charge amount after 30 hours is expressed by the ratio (absolute value) of the following calculation formula, and this ratio is 1
Within 0% was considered good. [(Charge amount after 30 minutes)-(charge amount after 30 hours)] ÷
(Charge amount after 30 minutes) Image quality (fog): The white background of the 100th sheet and the 10,000th sheet in continuous copying are compared, and the stain on the white background is severe due to the influence of scattering and the like. ○
It was judged to be (good), Δ (stain can be confirmed with a magnifying glass having a magnification of 30), and x (stain can be confirmed with the naked eye). Blocking property: After the toner particles were left in an environment of a temperature of 50 ° C. and a relative humidity of 50% for 1 week, the degree of aggregation of the powder was visually determined as follows. ◎: No blocking at all ○: A little blocking, but practically no problem △: Very blocking ×: Completely agglomerated Fine powder generation amount: 1 μ or less after fine pulverization (before classification) It was evaluated by the value of the weight part which the whole thing occupies. Dirt on the photoconductor; when the 100,000 copies are taken, the photoconductor,
The fixing roll was wiped with cotton, and the cotton was visually evaluated to determine the degree of stain. ⊚: No stain at all ∘: Cotton becomes slightly black Δ: Very black ×: Totally black Table 2 shows the evaluation results.

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[Table 2] Table-2

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[Table 3] Table-2 (continued)

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As is clear from the above results, the toner composition for electrophotography obtained by the present invention has a small amount of fine powder generated during toner production, good fixability, and a non-offset temperature range. It is wide and has excellent chargeability, and is an excellent toner composition for electrophotography.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenji Uchiyama 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals, Inc. (72) Katsuo Uramoto 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. An ethylene-based polymer (Y) having a weight average molecular weight (Mw) of 50,000 or less obtained by using 1 to 30% by weight of a polyfunctional ethylene-based monomer (Y), 30 to 90 parts by weight, and an ethylene-based polymer. Unsaturated monomer 70 to 10 parts by weight, polymerization initiator 0.01 to 5
A toner composition for electrophotography, which comprises, as a main component, an ethylene polymer obtained by dispersing a mixture of 1 part by weight and 0.05 to 2 parts by weight of a polyfunctional ethylene monomer in water and polymerizing the mixture. 2. The ethylenically unsaturated monomer is an aromatic vinyl monomer, acrylic acid ester, methacrylic acid ester, fumaric acid dialkyl ester, acrylonitrile, methacrylic acid, cinnamic acid, fumaric acid monoester, The toner composition for electrophotography according to claim 1, which is at least one selected from acrylamide and methacrylamide.