JPH01204059A - Developer - Google Patents

Abstract

PURPOSE:To prevent deterioration of development performance even under environments of high temperature and high humidity by incorporating fine polymer particles comprising structural units each having an amphoteric electrolytic radical and those each having a radical selected from a specified group in a toner. CONSTITUTION:The toner of particle size 11.5mum is prepared by melting, kneading, pulverizing, and classifying a styrene-acrylic copolymer, carbon black, nigrosine, and viscol, and the fine polymer particles having an average particle diameter of 0.01-5mum smaller than that of the toner are added to the toner in an amount of 0.01-10wt.%. The fine polymer particles comprise the structural units each having amphoteric electrolytic radical represented by the formula shown on the right in which A is 1-6C straight or branched alkylene, optionally substituted phenylene, and the structural units each having a radical selected from a group including amino, silicon, an acid radical, and halogen, thus permitting the amphoteric electrolytic radicals to adsorb moisture and to prevent deterioration of development performance even under environments of high temperature and high humidity.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a developer, and particularly to a developer that prevents deterioration of developer properties.

(Prior art and its problems) As a developing method applied to electrophotography or electrostatic recording, toner is charged by triboelectric charging, and this toner forms an electrostatic latent image on a photoconductor or electrostatic recording medium. A method of visualization is known.

The toner electrostatically adhered to the photoreceptor or electrostatic recording medium is transferred to transfer paper and then fixed to form a copy.

Ideally, it is desirable for the toner to be completely transferred to the transfer paper, but in reality, toner that has not been transferred remains on the photoreceptor or electrostatic recording medium.

This residual toner is cleaned by various methods.

As the copying process continues several thousand or tens of thousands of times, toner that cannot be removed gradually accumulates on the surface of the photoreceptor, resulting in inconveniences such as so-called poor cleaning or toner filming.

In order to improve this phenomenon, for example,
Japanese Patent No. 8141 discloses a method of adding an organic polymer having a low surface energy such as polytetrafluoroethylene or polyvinylidene fluoride to toner powder. Also, JP-A No. 52-84741 and JP-A No. 60-18685
In Publication No. 1, polystyrene particles or acrylic resin particles are added to the developer to prevent poor cleaning or toner filming due to a reduction in adhesion or a polishing effect.

Although these methods are useful to some extent in terms of preventing poor cleaning or toner filming, developing materials mixed with such additives have a lower triboelectric charging ability of the toner than those without such additives. This is particularly noticeable under high temperature and high humidity conditions. This causes a decrease in image density and an increase in fog. This is the aforementioned Japanese Unexamined Patent Publication No. 52-
Even the methods disclosed in Japanese Patent Application Laid-open No. 84741 and Japanese Patent Application Laid-Open No. 186851/1987 are not completely satisfactory.

(Means for Solving the Problems) The present inventors provide a developer that can prevent poor cleaning or toner filming without reducing the triboelectric charging ability of toner. That is, the present invention provides a developer containing a toner powder and a fine polymer powder having an average particle size smaller than that of the toner powder, wherein the constituent components of the fine polymer particles are (1) an amphoteric ionic group, (2) an amino group, Provided is a developer characterized by having a group selected from the group consisting of a zircon atom, an acid group, and a halogen element.

Further, the present invention provides a toner powder having a smaller average particle size than the toner powder and whose constituent components are (1) an amphoteric ionic group and (2) an amino group, a zircon atom, an acid group, and a halogen element. A method for controlling the charging characteristics of a toner is provided, characterized in that a fine polymer powder having a selected group is added in an amount of 0.01 to 10% by weight based on the amount of toner powder.

The fine polymer powder used in the present invention can be used in various polymerization methods, such as emulsion polymerization, soap-free emulsion polymerization,
Those polymerized using suspension polymerization, non-aqueous dispersion polymerization, etc. can be used. Further, a fine powder obtained by dissolving a polymer obtained by each of the above polymerization methods, solution polymerization, bulk polymerization, etc. in a solvent and then granulating it by a spray drying method can be used.

However, preferably fine particles obtained by emulsion polymerization or seed emulsion polymerization are used.

Particularly suitable are fine particles that have almost the same particle size, almost uniform electrical characteristics on the surface of the fine particles, homogeneous triboelectric charging ability and uniform charging resistance values, and are nearly perfectly spherical.

The molecular weight of the polymer used in the fine powder according to the present invention is not particularly limited, and a polymer having any molecular weight can be used without departing from the purpose of the present invention.
In some cases, it may be a crosslinked ultra-high molecular weight polymer.

The glass transition temperature of the polymer used in the fine powder of the present invention is preferably at least room temperature, but within the allowable range of toner fluidity and blocking properties, a polymer having a glass transition temperature at or below room temperature is used. be able to.

The zwitterionic groups present in the constituent components of the fine polymer powder of the present invention are -N-A-9o, H1-N-A-Cool-1 or [
In the formula, A represents a C1 to C8 linear or branched alkylene group, phenylene group or substituted phenylene group]. Introduction of amino (sulfonic) acid type zwitterionic group is described in JP-A-57-139111.
Formula as described in the publication: %Formula% [] [In the formula, R1 is a substituent containing a radically polymerizable ethylenically unsaturated group, and R3 is H or various substituents. R3 is a substituent mainly composed of C2 to C5 hydrocarbons, which may also contain, R3 is a substituent mainly composed of C8 to C8 hydrocarbons, and B is a 100000 group or - It is SO3H group. ] You may use at least one type selected from the polymerizable amino acid compounds shown as the polymerizable monomer. The polymerizable amino acid compound mentioned above is a monomer that can be produced by an addition reaction between benzyl halide and an aminosulfonic acid compound having a primary or secondary amino group (for example, N-(vinylbenzyl)taurine, N-
-methyl-N-(vinylbenzyl)taurine, N-(isopropenylbenzyl)taurine, etc.); Monomers that can be produced by reacting an oxirane compound with an amino acid compound having a primary or secondary amino group (e.g.
N-(2-hydroxy-3-allyloxypropyl) taurine, 2-[N-(2-hydroxy-3-allyloxypropyl)] taurine, N-(2-hydroxy-3-allyloxypropyl) alanine, etc. ).

The aminosulfonic acid type zwitterionic group represented by the formula: % formula % [wherein A represents a straight chain or branched alkylene group, phenylene group or substituted phenylene group of CI''Ca] Containing polymer compounds (for example, JP-A-55-5
No. 6048 discloses polyester resin, JP-A-57-4
No. 0522 discloses epoxy resin, JP-A-54-243
No. 57 discloses an acrylic resin) may be used as a dispersion stabilizer or an emulsion stabilizer.

The polyester resin containing an aminosulfonic acid type zwitterionic group has the following formula as an alcohol component in the reaction component: % Formula % [In the formula, R4 has at least one hydroxyl group, and 10- or 10- or C+-C*o alkyl group that may include -COO-, R6 is a hydrogen atom, 01-
a C2° alkyl group, an alkyl group or a cyclic group having at least 61 hydroxyl groups and/or sulfonic acid groups, and A is a C6 to C0 linear or branched alkylene group, phenylene group or substituted phenylene group; represent. ] The hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by
%, and by reacting this with a polybasic acid compound and, if necessary, a polyhydric alcohol and/or an oxirane compound. Examples of hydroxyl group-containing aminosulfonic acid type zwitterionic compounds include hydroxyethyltaurine, dihydroxyethyltaurine,
Examples include hydroxybrobyltaurine and the like.

The epoxy resin containing an aminosulfonic acid type zwitterionic group has the following formula: [wherein Re and R7 represent hydrogen or a methyl group. ]
An epoxy resin having a terminal group represented by the formula: % formula % [wherein R8 is hydrogen or a C0 to C2° alkyl group or a substituted alkyl group, R11 is a C1 to C6 alkylene or substituted alkylene group, and M is Represents an amine, an alkali metal or ammonia. It is produced by reacting an aminosulfonate of ] and then treating the reaction product with an acid.

Examples of aminosulfonates with the formula: % are taurine, 2-aminopropanesulfonic acid, 3-aminobutanesulfonic acid, l-amino-2-methylpropanesulfonic acid, N-ethyltaurinia, and other alkali sulfonates. Includes metal salts, amine salts and ammonium salts.

The acrylic resin containing an aminosulfonic acid type zwitterionic group has the above-mentioned formula: [wherein R1 is a substituent containing a radically polymerizable ethylenically unsaturated group, and R1 is I] or or a substituent mainly composed of 01 to C30 hydrocarbons that may contain various substituents, R3 is a substituent mainly composed of C, -C, hydrocarbons, and B is -COOH group or -5O38 group. ] It is obtained by polymerizing or copolymerizing at least one monomer selected from the polymerizable amino acid compounds represented by the following.

The sulfobetaine type zwitterionic group is described, for example, in JP-A-53-
The formula as disclosed in Publication No. 72090: [wherein R1° is a hydrogen atom or a methyl group, R11 and RI! are the same or different and represent an alkyl group of 01 to C6; A is 0 or N I-1, +111 and nl are the same or different and represent an integer of 1 to 12; ] Compounds or formulas represented by: [wherein R11 is a hydrogen atom or a methyl group, ILa is a hydrogen atom or a CI-C3 alkyl group, m is an integer of O to 6, and n is an integer of 1 to 6. The expressions and A have the same meanings as above. ] Introducing by a method of using a resin obtained by polymerizing or copolymerizing the compound represented by as a dispersion stabilizer or a surfactant, or by a method of copolymerizing these compounds as a polymerizable monomer with other polymerizable monomers. I can do it.

Examples of compounds represented by the above formula include N.

N-dimethyl-N-methacryloxyethyl-N-(3-
Sulfopropyl)-ammonium betaine, N,N-dimethyl-N-methacrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, I-(3-sulfopropyl)-2-vinylpyridinium betaine, and the like.

The fine polymer powder of the present invention has a group selected from the group consisting of an amino group, a zircon atom, an acid group, and a halogen element in addition to the amphoteric ionic group.

The method of introducing each group will be explained.

The amino group is introduced by copolymerizing an amino group-containing polymerizable monomer during the synthesis of the polymer fine powder. Examples of amino group-containing polymerizable monomers include N,N-dimethylaminomethyl (
meth)acrylate, N,N-dimethylaminoethyl (
meth)acrylate, N.

N,N-dialkylaminoalkyl (meth)acrylates such as N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, etc. -Dialkylaminoalkyl (meth)acrylamide and the like. Furthermore, amino groups may be introduced by using amino group-containing polyester or amino group-containing acrylic as a dispersion stabilizer or surfactant during synthesis of the polymer fine powder. Amino group-containing polyester is produced by a known polyester synthesis reaction using alkanolamines such as ethanolamine, jetanolamine, and triethanolamine as one of the components, and amino group-containing acrylic is produced by using the above-mentioned amino group-containing polymerizable monomers. manufactured by polymerization or copolymerization using

The introduction of silicon atoms is achieved by copolymerizing a silicon atom-containing polymerizable monomer or by using a silicon atom-containing acrylic copolymerized with this as a dispersion stabilizer or surfactant during the synthesis of a polymer fine powder. The silicon atom-containing polymerizable monopolymer has the formula: [wherein R15 is H or CH3, Le is an alkylene group, R17 is an alkyl group or a phenyl group, and n is 1
Indicates an integer between ~5. ]. A specific example thereof is as follows.

The introduction of acid groups is carried out by copolymerizing acid group-containing polymerizable monomers such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, etc. during the synthesis of the polymer fine powder.

Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, and monobutyl maleate.

Examples of the phosphoric acid group-containing monomer include acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, and 3-chloro-2-acid phosphooxypropyl methacrylate.

Furthermore, examples of the sulfonic acid group-containing monomer include 2-acrylamido-2-methylpropanesulfonic acid and 2-sulfoethyl methacrylate. Acid groups may also be introduced by using polyester, acrylic, polyvinyl alcohol, epoxy, or the like containing the above-mentioned acid groups as a dispersion stabilizer or surfactant during the synthesis of the fine polymer powder. These can be produced by polymerization or copolymerization of the above-mentioned acid group-containing monomers, or polyester synthesis using sulfophthalic anhydride as a raw material.

Halogen elements can be introduced by copolymerizing a halogen element-containing polymerizable monomer or by using a halogen-containing acrylic copolymerized with this as a dispersion stabilizer or surfactant during the synthesis of polymer fine powder. can.

Examples of halogen element-containing monomers include 2.2.
2-)-Rifluoroethyl acrylate, 11-1.
I! -Reaction products of fluorine-containing monomers such as 1,5H-octafluoropentyne acrylate, IH, IH, 2H, 2H-hebutadecafluorodecyl acrylate and hydroxyl group-containing monomers and tetrachlorophthalic anhydride. Examples include chlorine-containing monomers. Further, examples of vinyl compounds include vinyl acetate and vinyl propionate.

Furthermore, examples of diene compounds include butadiene, isoprene, and the like.

In addition to the above-mentioned polymerizable monomers, a multi-ethylenic monomer may be blended in order to adjust the glass transition temperature and molecular weight of the obtained particles. Examples of polyethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1
．． 3-butylene glycol dimethacrylate, trimedylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate,
1.6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol acroxy Examples include dimethacrylate, 1.1°1-trishydroxymethylethane diacrylate, divinylbenzene, meta-diisopropenylbenzene, para-diisopropenylbenzene, or mixtures thereof. These polyethylene monomers are usually used in an amount of 0 to 50% by weight based on the monomer, but may be used in an amount exceeding 50% by weight.

Polymerization is usually carried out using a polymerization initiator. As the polymerization initiator, ordinary ones may be used.

For example, peroxides such as benzoyl peroxide, di-butyl peroxide, cumene hydroperoxide, t-butyl peroxy 2-ethylhexanoate, azobisisobutyronitrile, 2.2°-azobis(2,4- dimethylvaleronitrile), 2゜2゜-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2
, 2'-azobisisobutyrate and the like are used in solution polymerization, bulk polymerization, suspension polymerization, and the like. In addition, in emulsion polymerization and seed emulsion polymerization, 2.2
Such as ゜-azobis(2-amidinopropane) dihydrochloride, 2.2゛-azobis(N,N'-dimethyleneisobutyramidine), 2,2''-(N,N'-dimethyleneisobutyramidine) dihydrochloride By using a polymerization initiator, amino groups can be introduced into 4.4'-
Introduction of acid groups is possible by using a polymerization initiator such as azobis (4-cyanopentanoic acid), potassium persulfate, or ammonium persulfate. These may be used alone or in combination of two or more.

The fine powder according to the present invention is not limited to using only one type, but a plurality of types can be used in combination. Further, the fine powder according to the present invention can be used in combination with other additives.

The average particle size of the fine powder according to the present invention needs to be smaller than the average particle size of the toner powder, but is preferably 0.01 to 5 μm.
A particle size of m, more preferably 0.02 to 2 μx gives good results.

The amount of fine powder added according to the present invention is 0°01-
10% by weight, preferably 0.05-2.0% by weight gives good results.

The developer of the present invention is made by mixing a known toner in addition to the above-mentioned polymer or copolymer additive, and the binder resin used in this toner includes a styrene resin and an olefin resin. , acrylic resin, vinyl ketone resin, or polyester resin. The above toner may be colored if necessary. Furthermore, a magnetic toner containing a magnetic material can also be used. The toner may have an average particle size of less than about 30 μl, preferably 3 to 20 μl, but is not particularly limited.

The developer of the present invention mixed with the above-mentioned additives may be a so-called two-component developer having a carrier and a toner, or a so-called two-component developer not using a carrier.

The developer of the present invention can develop an electrostatic latent image formed on a photoreceptor or an electrostatic recording medium.

That is, an electrostatic latent image is electrophotographically formed on a photoreceptor made of an inorganic photoconductive material such as selenium, zinc oxide, cadmium sulfide, or amorphous silicon, or an organic photoconductive material such as a phthalocyanine pigment or a bisazo pigment, or an electrostatic latent image is formed on a photoreceptor made of an organic photoconductive material such as a phthalocyanine pigment or a bisazo pigment. An electrostatic latent image is formed on an electrostatic recording medium having a dielectric material such as terephthalate using a needle-like electrode, and the electrostatic latent image is coated with the electrostatic latent image according to the present invention by a developing method such as a magnetic brush method, a cascade method, or a touchdown method. A developer is applied to form a toner image. After this toner image is transferred to a transfer material such as paper, it is fixed and becomes a copy, and the toner remaining on the surface of the photoreceptor etc. is cleaned. As the cleaning method, various methods such as a blade method, a brush method, a web method, and a roll method can be used.

(Effects of the Invention) The developing ability of a developer, particularly the triboelectric charging ability, gradually decreases, and this decrease is particularly likely to occur in developers using conventional additives. However, the developer according to the present invention is less likely to cause a decrease in developing ability, and even when 50,000 copies are made, there is almost no decrease in the density of the copied image. In particular, it has the characteristic that it is unaffected by high temperature and high humidity environments, and this is thought to be because the zwitterionic group adsorbs moisture under high humidity conditions and has a buffering effect that does not reduce the function of the charge control group. Furthermore, when cleaning toner remaining on a photoreceptor, etc., the developer containing the fine powder of the present invention will not cause cleaning defects even if 50,000 copies are made. On the other hand, developers using conventionally known additives can perform sufficient cleaning at the initial stage, but the cleaning performance gradually decreases and the cleaning performance gradually decreases.
If the number of sheets exceeds 30,000, toner remains in the form of an image on the photoreceptor,
Afterimages or band-like black streaks will appear on the next copy. Particularly under high temperature and high humidity conditions, a similar phenomenon occurs even when the number of copies is smaller.

Furthermore, the photoreceptor is less likely to be damaged, and toner filming does not occur.

(Example) The present invention will be explained in more detail with reference to Examples. The present invention is not limited to these examples.

Reference Example 1 (Manufacture of fine particles) 400 parts by weight of deionized water was added to an IQ separable flask equipped with a stirrer, a thermometer, N, an inlet tube, a condenser, and a dropping port, and the temperature was raised to 80°C. After adding 2.2 parts by weight of an aqueous solution prepared by dissolving 0.2 parts by weight of dimethylethanolamine and 2 parts by weight of azobiscyanovaleric acid in 20 parts by weight of deionized water and leaving it for 10 minutes, add N prepared separately from the aqueous solution. .

N-dimethyl-N-methacryloxyethyl-N-(3-
sulfopropyl)-ammonium-betaine dissolved in 48 parts by weight of deionized water, and further 104 parts by weight of methyl methacrylate and 6 parts by weight of n-butyl acrylate.
A liquid mixture of 8 parts by weight and 16 parts by weight of ethylene glycol dimethacrylate was added dropwise over 2 hours. After the dropwise addition was completed, the emulsion was kept at the same temperature for 2 hours to obtain an emulsion with a nonvolatile content of 29.6% and an average particle size of 0.3 microns. Water was removed from this using a freeze dryer to produce sulfobetaine-containing acrylic resin particles.

Reference Example 2 (Production of Fine Particles) Using the same synthesis apparatus as in Reference Example 1, 370 parts by weight of deionized water was added and the temperature was raised to 80°C. An aqueous solution of 2 parts by weight of 2,2-azobis(2-amidinopropane) dihydrochloride dissolved in 20 parts by weight of deionized water was added and left to stand for 5 minutes, followed by separately prepared 1-(3-sulfopropyl)-
15 parts by weight of a solution of 22 parts by weight of 2-vinylpyridinium betaine dissolved in 198 parts by weight of deionized water, 122 parts by weight of styrene, 16 parts by weight of n-butyl methacrylate, 36 parts by weight of n-butyl acrylate, dimethylaminoethyl methacrylate. Of the 4 parts by weight of the mixed liquid, 12 parts by weight were added. After keeping it for 10 minutes, the above two liquids were added dropwise separately over 1 hour, and the temperature was kept at the same temperature for another 3 hours.
An emulsion with a nonvolatile content of 25.2% and an average particle size of 0.1 micron was obtained.

Water was removed from this using a freeze dryer to produce acrylic resin particles containing a sulfobetaine group, an amino group, and an amidino group.

Reference Example 3 (Manufacture of fine particles) 213 parts by weight of dihydroxyethyl taurine, 208 parts by weight of neopentyl glycol, 296 parts by weight of phthalic anhydride, 404 parts by weight of sebacic acid, and 34 parts by weight of xylene were mixed with an acid value of 164 by a conventional polyester synthesis method. m9K O
After the reaction reaches H/IF, 500 parts by weight of Cardura E (manufactured by Shell Chemical Co., Ltd., persatic acid glycidyl ester) is added and the reaction is carried out until the acid value reaches 49 ygK OHI3, thereby converting the aminosulfonic acid type zwitterionic group. A containing polyester resin was obtained. This polyester resin 22.
5 parts by weight, 2.3 parts by weight of dimethylethanolamine, and 440 parts by weight of deionized water were added to the same synthesis apparatus as in Reference Example 1, and the temperature was raised to 83°C. To this, 127 parts by weight of styrene, n-
A mixed solution of 69 parts by weight of butyl acrylate and 84 parts by weight of ethylene glycol dimethacrylate and a solution obtained by dissolving 2.8 parts by weight of ammonium persulfate prepared separately in 28 parts by weight of deionized water were each added dropwise over 2 hours. After completion of the dropwise addition, the reaction was kept at the same temperature for 2 hours to complete the reaction, and an emulsion with a nonvolatile content of 38.7%, an average particle size of 0, and an OS micron was obtained. Remove moisture from this using a freeze dryer,
Acrylic resin particles containing an aminosulfonic acid type zwitterionic group, a sulfonium group, and a carboxyl group were produced.

Reference Example 4 (Production of Fine Particles) Using the same synthesis apparatus as in Reference Example 1, 464 parts by weight of deionized water and 13 parts by weight of N-octadecyl-2-alanine were added, and the temperature was raised to 80°C. An aqueous solution of 0.3 parts by weight of dimethylethanolamine and 2.6 parts by weight of azobiscyanovaleric acid dissolved in 60 parts by weight of deionized water was added dropwise over 2 hours. 10 minutes after dropping the aqueous solution, a separately prepared mixed solution of 150 parts by weight of methyl methacrylate, 64 parts by weight of 2-ethylhexyl acrylate, 7 parts by weight of dimethylaminopropyl methacrylamide, and 39 parts by weight of neopentyl glycol dimethacrylate was added dropwise. It started dropping and was added dropwise after 1 hour and 30 minutes. Thereafter, the reaction was completed by keeping at the same temperature for 2 hours. An emulsion with a nonvolatile content of 32.2% and an average particle size of 0.25 microns was obtained. Water was removed from this in a freeze dryer to produce acrylic resin particles containing an amino acid type zwitterionic group, an amino group, and a carboxyl group.

Reference Example 5 (Manufacture of Fine Particles) Using the same synthesis apparatus as in Reference Example 1, 434 parts by weight of isopropyl alcohol, 214 parts by weight of deionized water, and 5.6 parts by weight of mercapto polyvinyl alcohol were added, and the temperature was raised to 75°C. To this, a solution prepared by dissolving 2.4 parts by weight of benzoyl peroxide in 67 parts by weight of styrene and a solution obtained by dissolving 3 parts by weight of N-methyl-N-(vinylbenzyl)taurine in 30 parts by weight of deionized water were added, After being left for 2 hours, the temperature was raised to 85℃ and the reaction was continued for 16 hours, resulting in a non-volatile content of 10℃.
%, and an average particle size of 0.8 microns was obtained. After filtering and washing with water, water was removed using a freeze dryer to produce styrene resin particles containing aminosulfonic acid type zwitterionic groups.

Reference example 6 (manufacture of fine particles) 213 parts by weight of dihydroxyethyl taurine, l.

After reacting 320 parts by weight of 9-nonanediol, 308 parts by weight of hexahydrophthalic anhydride, 376 parts by weight of azelaic acid, and 36 parts by weight of xylene to an acid value of 14619K OH/9 by a conventional polyester synthesis method, Cardura E (shell (manufactured by Kagaku Co., Ltd., persatic acid glycidyl ester) 250 parts by weight and allyl glycidyl ether 11
4 parts by weight were added and reacted until the acid value reached 41m9KOH/9, thereby synthesizing a polyester resin having an allyl group and an aminosulfonic acid type zwitterionic group. A solution was prepared by dissolving 29 parts by weight of this polyester resin in 3 parts by weight of dimethylethanolamine and 203 parts by weight of deionized water, and while stirring, 106 parts by weight of styrene, 21 parts by weight of methyl methacrylate, and n-diptylacrylate were added. A pre-emulsion was prepared by adding a mixture of 48 parts by weight, 60 parts by weight of trimethylolpropane trimethacrylate, and 5 parts by weight of diethylaminoethyl methacrylate. Reference example 1
Using the same synthesis apparatus as above, 368 parts by weight of deionized water was added and the temperature was raised to 78°C. A solution prepared by dissolving 2.4 parts by weight of 2°2°-azobis[N-(4-aminophenyl)-2-methylpropionamidine cotetrahydrochloride in 36 parts by weight of deionized water and the previously prepared precipitate] After dropping the emulsion for 45 minutes, at the same temperature
When the reaction was completed after leaving it for a while, the non-volatile content was 30.3.
% and an average particle size of 0.06 microns was obtained.

This was dried using a freeze dryer (a trowel) to remove moisture and produce acrylic resin particles having an aminosulfonic acid type zwitterionic group, an amino group, and an amidino group.

Example 1 Styrene-acrylic copolymer resin (manufactured by Sanyo Chemical Industries, Ltd., T
B-1000) 90 parts by weight of carbon black (manufactured by Cabot Corporation, R330) 8 parts by weight of nigrosine, and 5 parts by weight of Viscol 660P (manufactured by Sanyo Chemical Industries, Ltd., polypropylene wax) were melt-kneaded, pulverized, and classified by conventional methods. I used it as a toner. The volume average particle size measured by Coulter Counter was 2.5 microns. To 100 parts of this toner, 1.5 parts by weight of the sulfobetaine-containing acrylic resin particles obtained in Reference Example 1 were added and dispersed for 10 minutes using a Henschel mixer.

When this was observed using an electron microscope, fine particles were found to be attached to the toner surface. 10 parts of iron powder per 3 parts by weight of this developer.
Table 1 shows the results of chargeability measurements such as average charge amount and charge distribution by the pro-off tribo method when 0 parts by weight were mixed. Further, when a continuous running test of 10,000 copies was conducted using a copying machine, no image quality defects due to poor cleaning were observed, and no deterioration of the developer was observed.

Example 2 To 100 parts by weight of the same toner as in Example 1, 0.8 parts by weight of the acrylic resin particles containing amino acid type zwitterionic groups, amino groups, and carboxyl groups obtained in Reference Example 4 were added, and the mixture was placed in a Henschel mixer. and dispersed for 5 minutes. When this was observed using an electron microscope, it was found that fine particles were attached to the toner surface. Table 1 shows the measurement results of the average charge amount and chargeability when 100 parts by weight of iron powder was mixed with 3 parts by weight of this developer.

Further, when a continuous running test of 10,000 copies was conducted using a copying machine, no image quality defects due to poor cleaning were observed, and there was no deterioration of the developer.

Example 3 A toner was prepared in the same manner as in Example 1, using 2 parts by weight of E-81 (chromium-containing metal dye) manufactured by Orient Chemical Co., Ltd. in place of the nigrosine used in Example 1. The volume average particle size measured by Coulter Counter was 12 microns. This toner 10
To 0 parts by weight, 1 part by weight of the acrylic resin particles containing aminosulfonic acid type zwitterionic groups obtained in Reference Example 5 was added and dispersed for 10 minutes using a Henschel mixer. When this was observed using an electron microscope, fine particles were found to be attached to the toner surface. Table 1 shows the measurement results of the average charge amount and chargeability when 100 parts by weight of iron powder was mixed with 3 parts by weight of this developer. Further, when a continuous running test of 10,000 copies was conducted using a copying machine, no image quality defects due to poor cleaning were observed, and no deterioration of the developer was observed.

Example 4 A toner was made in the same manner as in Example 1 except that the nigrosine was removed. To 100 parts by weight of this toner, 1.8 parts by weight of the acrylic resin particles containing an aminosulfonic acid type amphoteric ionic group, a sulfonium group, and a carboxyl group obtained in Reference Example 3 were added and dispersed in a Henschel mixer for 15 minutes. . When observing this with an electron microscope,
Fine particles were attached to the toner surface. Table 1 shows the measurement results of the average charge amount and chargeability when 100 parts by weight of iron powder was mixed with 3 parts by weight of this developer. Also, 1 by copying machine
When a continuous running test of 00,000 sheets was conducted on an actual machine, no image quality defects due to poor cleaning were observed, and there was no deterioration of the developer.

Example 5 Reference Example 6 was added to 100 parts by weight of the toner used in Example 4.
Two parts by weight of the acrylic resin particles containing the aminosulfonic acid type amphoteric ionic group, amino group, and amidino group obtained in step 1 were added and dispersed for 15 minutes using a Henschel mixer. When this was observed using an electron microscope, it was found that fine particles were attached to the toner surface. Table 1 shows the results of measuring the average band in and chargeability of a mixture of 3 parts by weight of this developer and 100 parts by weight of iron powder.

Further, when a continuous running test of 100,000 copies was conducted using a copying machine, no image quality defects due to poor cleaning were observed, and there was no deterioration of the developer.

Example 6 Reference example! 4 parts by weight of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-M2O3) and 0 parts by weight of sodium dialkyl sulfosuccinate (manufactured by Kao Corporation, Perex TR) were added to the same synthesis apparatus.
．． 04 parts by weight and 400 parts by weight of deionized water at 65°C.
The temperature rose to . To this were added 85 parts by weight of styrene, 15 parts by weight of 2-ethylhexyl acrylate, 1. After adding a mixed solution of 10 parts by weight of C. Solvent Red 24 and 2 parts by weight of lauroyl peroxide and reacting for 12 hours, the mixture was filtered, washed with water, water was removed using a freeze dryer, and classified to obtain a toner.

The volume average particle size measured by Coulter Counter was 7 microns. To 100 parts by weight of this toner, 1.7 parts by weight of the acrylic resin particles containing sulfobetaine groups, amino groups, and amidino groups obtained in Reference Example 2 were added and dispersed for 300 minutes in a Henschel mixer.

When this was observed using an electron microscope, it was found that fine particles were attached to the toner surface. 10 parts of iron powder per 1.8 parts by weight of this developer.
Table 1 shows the measurement results of the average charge amount and chargeability when 0 parts by weight were mixed. Further, when a continuous actual running test was conducted using a copying machine with 10,000 copies, no image quality defects due to poor cleaning were observed, and there was no deterioration of the developer.

Comparative example! 100 parts of iron powder was added to 3 parts by weight of the toner prepared in Example 1.
Table 1 shows the measurement results of the average charge amount and chargeability of mixed parts by weight.
It was shown to. In addition, although a running test was conducted on an actual machine, there were frequent cleaning failures and satisfactory image quality could not be obtained.

Comparative Example 2 1 part by weight of polyethylene powder was added to 1 part by weight of 100 parts of the toner prepared in Example 3, and 5 parts by weight were added using a Henschel mixer.
Table 1 shows the measurement results of the average charge amount and chargeability of three parts of the developer dispersed for minutes and 100 parts by weight of iron powder mixed therein. When we conducted an actual driving test,
Although there were no image quality defects caused by cleaning, capri occurred after about the 50,000th print, and the toner inside the machine was heavily stained and the image quality was unstable.

Comparative Example 3 Characteristics were measured in the same manner as in Comparative Example 2 except that the toner prepared in Example 4 was used, and the results are shown in Table 1. In actual machine running tests, there was a lot of fog and satisfactory image quality could not be obtained.

Comparative Example 4 80 parts by weight of methyl methacrylate, 20 parts by weight of R-butyl acrylate, 4 parts by weight of dimethylaminoethyl methacrylate, 200 parts by weight of distilled water, 0.6 parts by weight of potassium persulfate.
Parts by weight, 4 parts by weight of polyoxyethylene nonylphenol, and 1 part by weight of sodium lauryl sulfate were polymerized for 4 hours by a conventional emulsion polymerization method. After the polymerization was completed, the reaction solution was cooled to 20° C., and acrylic resin fine particles with an average particle size of 0.1 μm were obtained using an ultrafiltration device and a freeze dryer. To 100 parts by weight of the toner prepared in Example 1, 1 part by weight of these fine particles was added and dispersed for 10 minutes using a Henschel mixer.

When this was observed using an electron microscope, fine particles were found to be attached to the toner surface. 100 parts of iron powder per 3 parts by weight of this developer.
Table 1 shows the measurement results of the average charge amount and chargeability of mixed parts by weight.
It was shown to. In addition, when we conducted a continuous running test of 100,000 sheets using a copying machine, we found that although no image quality defects were found due to poor cleaning, the developer stored in an environment of 80% at 30°C deteriorated and was not satisfactory. Image quality could not be obtained.

Comparative Example 5 Acrylic resin fine particles were obtained in exactly the same manner as in Comparative Example 4, except that dimethylaminoethyl methacrylate was used. 1.3 parts by weight of these fine particles were added to 100 parts by weight of the toner prepared in Example 3, and dispersed for 10 minutes using a Henschel mixer.

When this was observed using an electron microscope, fine particles were found to be attached to the toner surface. Iron powder for 3 parts by weight of this developer! 00
Table 1 shows the measurement results of the average charge amount and chargeability of the mixed heavy parts.
It was shown to. In addition, when we conducted a continuous running test of 100,000 sheets using a copying machine, we found that although no image quality defects were found due to poor cleaning, the developer stored in an environment of 80% at 30°C deteriorated and was not satisfactory. Image quality could not be obtained.

(2) Values measured after mixing in a ball mill for 200 minutes are shown.

2) Regarding the amount of blow-off charge measured after mixing for 1 minute in a ball mill, based on the value measured after mixing for 200 minutes, O: 75% or more, △Near 5-50%, ×: 5
Shown as 0% or less.

3) The measurement results of the toner composition mixed for 1 minute in a ball mill using a Q/D meter manufactured by Ebbing Co., Ltd. are shown as O: 2% or less, Δ: 2 to 1O%, and ×: 10% or more.

Patent applicant Nippon Paint Co., Ltd.

Claims (1)

[Claims] 1. A developer containing a toner powder and a fine polymer powder having an average particle size smaller than that of the toner powder, wherein the constituent components of the fine polymer particles are (1) a zwitterionic group and (2) A developer characterized by having a group selected from the group consisting of an amino group, a zircon atom, an acid group, and a halogen element. 2. Zwitterionic group ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, A represents a C_1 to C_8 linear or branched alkylene group, phenylene group, or substituted phenylene group. ] The developer according to claim 1, which is an amino(sulfonic) acid type amphoteric ionic group. 3. The zwitterionic group is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A has the same meaning as above. The developer according to claim 1, which is a sulfobetaine type amphoteric ionic group represented by the following formula. 4. The developer according to claim 1, wherein the average particle size of the polymer particles is 0.01 to 5 μm. 5. The developer according to claim 1, wherein the polymer fine particles are added in an amount of 0.01 to 10% by weight based on the toner powder. 6. The toner powder has an average particle size smaller than that of the toner powder, and its constituent components are (1) a zwitterionic group and (2)
) Fine polymer powder having a group selected from the group consisting of an amino group, a zircon atom, an acid group, and a halogen element is added in an amount of 0.0% based on the amount of toner powder. A method for controlling the charging characteristics of a toner, characterized in that the toner is added in an amount of 01 to 10% by weight. 7. The zwitterionic group is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is a C_1 to C_6 linear or branched alkylene group, phenylene group, or Represents a substituted phenylene group. ] The method according to claim 6, which is an amino(sulfonic) acid type zwitterionic group. 8. Zwitterionic groups are ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A has the same meaning as above. ] The method according to claim 6, which is a sulfobetaine type zwitterionic group represented by the following.